JPH08287523A - Tape-like optical information recording medium - Google Patents

Abstract

PURPOSE: To improve recording performance and preservable stability by providing an information recording medium having at least one layer of recording layers and incorporating a laser beam responsive compd. and a high-polymer compd. as a binder into these recording layers. CONSTITUTION: A coating liquid of a liquid compsn. 1 is applied on a polyethylene terephthalate base 4 by a wire coater 1 to form a first layer. The coating liquid is fed by a liquid feed pump from a coating liquid stock tank 3 and is supplied through a filter 14 to the wire coater 1. The wire coater 1 rotates in the same direction as the transporting direction of a web to transfer the coating liquid to the web. The coating is dried with hot air of 40 deg.C first, then 80 deg.C after the coating and the web is taken up. A coating liquid of a liquid compsn. 2 is applied at the speed of 20m per minute by using the similar wire bar coater on the first layer formed by the coating in such a manner, by which the second layer is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical recording medium, and more particularly to a long tape-shaped optical recording medium for recording or reproducing information by irradiating a laser beam.

[0002]

2. Description of the Related Art As an optical recording medium for recording or reproducing information by irradiating a laser beam, a digital audio disc (so-called compact disc), an optical video disc (so-called laser disc), a CD-
Disc-shaped recording media such as a read-only recording medium such as a ROM and a write-once optical disc (so-called WORM, CD-R, etc.) capable of additional recording have been widely used.

In an optical recording medium for recording or reproducing information by irradiating laser light, a recording layer made of a dye or the like for absorbing the laser light is usually formed on a substrate, and the laser light is signal-modulated. Then, by focusing on this recording layer, a signal recording pattern (so-called pit or mark) is formed on the recording layer.

Further, the recorded information is reproduced by detecting the difference in reflectance between the signal recording pattern portion and the portion where the signal recording pattern is not formed.

Such an optical recording medium can be narrowed in track pitch and enables high-density recording as compared with a magnetic recording medium, so that it has attracted attention as a medium for storing a large amount of information and many studies have been conducted. Has been done. In order to increase the amount of information recorded on such a disc-shaped recording medium, the signal recording density on the disc is increased, or the diameter of the disc itself is increased to provide an area where a signal recording pattern can be formed. It is necessary to increase it. However, if the signal recording pattern formation density is too high, the track pitch becomes too narrow compared to the resolution of the optical system for signal reproduction, crosstalk may occur during reproduction, and good information detection may not be possible. On the other hand, if the diameter of the disc itself is increased, it is inconvenient to carry or store, and a device for reproducing information becomes large in size. Therefore, it is difficult for the disk-shaped optical recording medium to improve the amount of recorded information more than the current situation.

As an optical recording medium suitable for recording a larger amount of information than a disc-shaped optical recording medium, tape-shaped optical recording media are disclosed in JP-A-1-286130, 4-163736, and JP-A-4-163736.
-163737, 6-89464, 6-739.
No. 58, No. 6-251425 and the like.

A tape-shaped optical recording medium can record much more information than a disc-shaped recording medium. This is because even if it is long, it can be wound in a coil shape to increase the area for recording information for its volume. Therefore, the tape-shaped optical information recording medium has a preferable characteristic that it has both a large recording capacity and practicality such as portability and storability.

When information is recorded on or reproduced from a tape-shaped optical information recording medium, the tape is mechanically conveyed at a high speed, and laser light is emitted from the optical head in a non-contact state with the tape. There is a need to. Also, during storage, the tape is wound so that the front and back sides contact each other. Therefore, unlike a disc-shaped recording medium, it is necessary to devise a device that is not damaged by various tensions and frictions during transportation and winding. Alternatively, scraps that fall off from the recording medium due to friction during transportation should not accumulate in the recording / reproducing apparatus and interfere with normal functions. Therefore, the recording layer must be stably supported on the support even under such conditions.

On the other hand, various dyes are used as the light absorbing substance, but the optical properties of the coating film are insufficient, the solubility is low and a coating solution having a sufficient concentration cannot be prepared, and a polymer bond is used. There is a problem that phase separation occurs due to low compatibility with the agent, and it is difficult to obtain an optically uniform coating film by crystallization after coating. However, the coating film using a dye having a high solubility has a problem that its properties are likely to change when it is stored under high temperature and high humidity conditions. In addition, an example in which a perchlorate of a cyanine dye is used is conventionally known, but there is a problem that perchlorate is not preferable in production because it has a property of decomposing with a large amount of heat generation.

[0010]

SUMMARY OF THE INVENTION The object of the present invention was made in view of the above-mentioned circumstances, and it is less susceptible to damage during the winding and transportation of a tape, and the optical characteristics at the wavelength of the laser light used for recording or reproduction. It is an object of the present invention to provide a large capacity tape-shaped optical information recording medium which has good properties, enables high-sensitivity recording / reproduction, has excellent storage stability, and has excellent coating and manufacturing suitability.

[0011]

The object of the present invention has been solved by the following means (1) to (14).

(1) At least one recording layer capable of recording or reproducing information by using a laser beam is provided on a tape-shaped support, and the recording layer has a high function as a laser beam responsive compound and a binder. A tape-shaped optical information recording medium containing a molecular compound.

(2) The laser beam responsive compound is
Cyanine dye, merocyanine dye, oxonol dye,
The tape-shaped optical information recording medium according to (1) above, which is at least one selected from azomethine dyes, azo dyes, phthalocyanine dyes, and metal complexes in which these dye structures serve as ligands.

(3) The laser beam responsive compound is
The tape-shaped optical information recording medium according to the above (1) or (2), which contains at least one compound represented by the following general formula (1).

General formula (1):

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In the formula, R ¹ and R ² independently represent an alkyl group or an aryl group, Z represents an atomic group for forming an aromatic ring, and L represents a linking group for forming a cyanine dye.

(4) The tape-shaped optical information recording medium according to any one of (1) to (3) above, wherein the recording layer contains a singlet oxygen quencher.

(5) The tape-shaped optical information recording medium according to any one of (1) to (4) above, which contains a laser beam responsive compound as a solid dispersion.

(6) The tape-shaped optical information recording medium as described in any one of (1) to (5) above, wherein a metallic reflection layer is provided between the tape-shaped support and the recording layer.

(7) The back layer composed of a polymer layer is supported on the side opposite to the recording layer via a support.
A tape-shaped optical information recording medium according to any one of (1) to (6).

(8) The thickness of the recording layer is an integral multiple of 1 / 4n (where n represents the refractive index of the dye recording layer) of the wavelength of the laser beam used for recording or reading, and (1) ) To (7), the tape-shaped optical information recording medium according to any one of items.

(9) The antireflection layer for absorbing a laser beam used for recording or reading is provided on the opposite side of the recording layer via a support, as described in any one of (1) to (8) above. Tape-shaped optical information recording medium.

(10) The thickness of the recording layer has a wavelength of 780 n
m infrared light, reflectance 15% or more, transmittance 30%
The tape-shaped optical information recording medium according to any one of (1) to (9) below, which is as follows.

(11) Dye / binder weight ratio> = 1.
The tape-shaped optical information recording medium according to any one of (1) to (10) above, wherein the recording layer has a thickness of 0 to 50 nm.

(12) The surface resistance SR of the tape is log
(SR) is 10 or less, and the half-life of charge leakage from the surface is 60 seconds or less when 8 KV is applied. (1)
(11) A tape-shaped optical information recording medium according to any one of (1) to (11).

(13) The tape-shaped optical information recording medium as described in (7) above, wherein a layer containing carbon black and a specific fluorine-containing surfactant is coated as a back layer.

(14) The tape-shaped optical information recording medium as described in any one of (1) to (13) above, wherein the recording layer contains a cyanine dye and a polyamic acid.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

In the general formula (1), R ¹ , R ² and Z may further have a substituent. Preferred of these substituents are C.I. The hydrophobicity parameter, π, proposed by Hansch et al. Is for values in the range -0.5 to 15. The hydrophobic parameter can be calculated according to the following documents. 1) C.I. Hans
ch et al. Med. Chem. , Volume 16, 1207
Page (1973), 2) C.I. Hansch et al.,
Volume 20, p. 304 (1977).

Preferred as the group represented by R ¹ or R ² is a substituted or unsubstituted lower alkyl group (having 1 to 8 carbon atoms), and further the above-mentioned C.I. Hans
a hydrophobicity parameter proposed by ch et al., π,
May have a substituent having a value in the range of -0.5 to 15. When R ¹ or R ² has a substituent, a particularly preferable substituent is a halogen atom (F, Cl, B
r, I), a substituted or unsubstituted phenyl group (eg phenyl, m-chlorophenyl, p-methylphenyl etc.), an alkylthio group (eg methylthio, butylthio etc.), a substituted or unsubstituted phenylthio group (eg phenylthio, p- Chlorophenylthio, m-methylphenylthio, etc.).

Particularly preferred among the groups represented by R ¹ or R ² are unsubstituted alkyl groups having 1 to 4 carbon atoms, and among them, a methyl group is particularly preferred.

Examples of the atomic group represented by Z include an atomic group for completing a benzene ring, a naphthalene ring and an anthracene ring, and a preferable group is an atomic group for completing a benzene ring or a naphthalene ring. And may further have the above-mentioned substituents. When Z has a substituent, a particularly preferable substituent is a halogen atom (F, Cl, Br, I), a substituted or unsubstituted phenyl group (eg, phenyl, m-chlorophenyl, p-methylphenyl, etc.), alkylthio. Group (eg, methylthio, butylthio, etc.), substituted or unsubstituted phenylthio group (eg, phenylthio, p-chlorophenylthio, m-methylphenylthio, etc.), substituted or unsubstituted alkyl group (eg, methyl, trifluoromethyl, etc.)
tert-amyl), a cyano group, an alkoxycarbonyl group (eg, propoxycarbonyl, butoxycarbonyl, benzyloxycarbonyl, decyloxycarbonyl, 2-ethylhexyloxycarbonyl, etc.).

Among the atomic groups represented by Z, particularly preferable are those having a Hammett sigma constant of -0.2 to +0.7.
Is a group of atoms for forming a benzene ring having a substituent having a relatively weak electron donating property in the range of, among them, for forming a benzene ring substituted with a halogen atom such as F, Cl, Br, I. Are preferred.

The linking group represented by L represents a linking group for forming a mono-, di-, tri-, or tetracarbocyanine dye, and those represented by the general formulas (a) to (i) are particularly preferable. .

[0035]

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[0036]

[Chemical 4]

[0037]

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In formulas (a) to (i), Y represents a hydrogen atom or a monovalent group. In this case, the monovalent group includes a lower alkyl group such as a methyl group, a substituted or unsubstituted phenyl group, an aralkyl group such as a benzyl group, a lower alkoxy group such as a methoxy group, a dimethylamino group, a diphenylamino group, a methylphenyl group. Amino group, morpholino group, imidazolidino group, di-substituted amino group such as ethoxycarbonylpiperazino group, acyloxy group such as acetoxy group, alkylthio group such as methylthio group, cyano group, nitro group, halogen such as F, Cl, Br It is preferably an atom or the like.

Among the linking groups represented by L, a particularly preferred linking group is a linking group necessary for forming a di- or tricarbocyanine dye, and more specifically, general formulas (b) and (c ), (D), (e), (f), (g), and (h).

Specific examples of the compound represented by formula (1) used in the present invention are shown below, but the scope of the present invention is not limited to these.

[0041]

[Chemical 6]

[0042]

[Chemical 7]

[0043]

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[0044]

[Chemical 9]

[0045]

[Chemical 10]

[0046]

[Chemical 11]

The polymer compound contained in the recording layer of the present invention is used for easily maintaining the amorphous state without crystallization of the dye compound represented by the general formula (1) and the anti-fading agent. . Examples of such polymer compounds include natural polymer substances such as gelatin, dextran, rosin and rubber, cellulose derivatives such as nitrocellulose, cellulose acetate and cellulose acetate butyrate, polyethylene, polystyrene, polypropylene and polyisobutylene. Hydrocarbon resins, vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride-polyvinyl acetate copolymer, acrylic resins such as polyacrylamide, polymethyl acrylate, polymethyl methacrylate, polyvinyl alcohol, chlorine Examples thereof include synthetic polymer substances such as prepolymerized thermosetting resins such as modified polyolefin, epoxy resin, butyral resin, rubber derivative, and phenol-formaldehyde resin.

In the present invention, a tape-shaped optical information recording medium containing a laser beam responsive compound as a solid dispersion is preferable.

The solid dispersion used in the present invention may be called a pigment dispersion. In the dye solution, the dye exists as a molecule isolated in a medium such as a solvent, but in the solid dispersion, fine solids (microcrystals) of the dye are contained or dispersed in the medium. The difference between the two can be determined, for example, by the presence or absence of diffraction originating from the molecular arrangement in a regular crystal when irradiated with X-rays.

The laser beam responsive compound used in the present invention may be not only a dye of the compound represented by the general formula (1) but also a dye which is not dissolved in a medium. As the classification of the dye, for example, a cyanine dye such as a compound represented by the general formula (1), a merocyanine dye, an oxonol dye, an azomethine dye, an azo dye, a phthalocyanine dye, or a dye structure of these becomes a ligand. It may be a metal complex or the like.

It is important not to include particles having a particle size of 0.1 micron or more because noise increases when the size of the dispersed dye particles is about the same as or larger than the laser beam used for recording information. .

The laser applied to the tape-shaped optical recording medium of the present invention is a solid-state laser (160n) such as YAG.
m), a gas laser such as an argon laser (488 nm) and a helium-neon laser (633 nm), a semiconductor laser (for example, 830 nm, 780 nm, 680 n).
m, 635 nm, 410 nm) and the like are preferable.

The laser power for recording information is preferably 2 mW or more, and the laser power for reading information is preferably 1 mW or less.

A semiconductor laser is preferable in that the device can be made compact, and a preferable example is a semiconductor laser having a wavelength of 780 nm for writing with a power of 6 to 15 mW and reading with a power of 1 mW or less.

The beam diameter is preferably about 0.4 to 2 microns. The relative linear velocity between the recording medium and the laser beam is 1 to 20 m / sec, preferably 5 to 15
m / sec.

In the present invention, a tape-shaped optical information recording medium having a back layer composed of a polymer layer on the side opposite to the recording layer via a support is preferable.

In the present invention, the thickness of the recording layer is an integral multiple of 1 / 4n (where n represents the refractive index of the dye recording layer) of the wavelength of the laser beam used for recording or reading information. It is preferably a tape-shaped optical information recording medium.

In the present invention, the thickness of the recording layer containing the laser beam responsive compound represented by the general formula (1) has a reflectance of 15 with respect to infrared light having a wavelength of 780 nm.
It is preferably a tape-shaped optical information recording medium having a transmittance of 30% or more and a transmittance of 30% or less. If the reflectance is low, the read signal is weak and the C / N is low. If the absorption and transmission is high, the recording sensitivity is low.

In the present invention, further, the dye / binder weight ratio> = 1.0 and the recording layer thickness is 50 to 15
A tape-shaped optical information recording medium having a thickness of 0 nm is preferable.

The dye here is of course a dye having an absorption spectrum capable of absorbing a laser used for recording information.

The binder used in the present invention is a polymer compound that does not substantially absorb the light of a laser used for recording information, such as a polypeptide such as gelatin, cellulose, diacetyl cellulose, cellulose acetate butyrate and the like. Preferred are modified celluloses, acrylic resins such as polyacrylic acid and polymethyl acrylate, polyimides, polyimide acids obtained by partially hydrolyzing these, polystyrenes, and epoxy resins.

In the present invention, the reason for defining the dye / binder weight ratio> = 1.0 will be described below. The absorption amount of light energy increases as the amount of dye increases. When the amount of the binder increases, the film thickness increases, the energy required to deform the recording layer at the time of recording information increases, and the sensitivity decreases. Alternatively, as the film thickness increases, the smoothness of the coating film decreases and noise increases. Therefore, the amount of the binder is preferably as small as possible as long as the fixability of the dye is not impaired, and thus the dye / binder weight ratio> = 1.0 is defined.

Next, the reason for defining the recording layer thickness to be 50 to 150 nm will be described. The reflected light used for reading the signal is light in which the reflection from the incident surface and the reflection from the support surface overlap. Therefore, they interfere with each other depending on the wavelength of light and the film thickness. When the recording layer is deformed by irradiating it with a laser beam, it is preferable that the signal strength becomes large if the relationship of the interference changes greatly. Therefore, the film thickness is the wavelength of light used for reading, for example, 1 at around 780 nm.
If it is set to / 4 or less, the change in the degree of light interference due to the deformation of the recording layer becomes large.
It is preferably 150 nm. Also, from the viewpoint of easily imparting smoothness, it is not so thick and a thickness of this level is preferable.

A singlet oxygen quencher is preferably added to the recording layer of the present invention for the purpose of preventing photobleaching of the dye represented by formula (1) contained in the recording layer. Examples thereof include US Pat. No. 4,999,281,
Examples thereof include quenchers described in JP-A-59-178295 and aminium compounds described in JP-A-6-321872.

The heat generated at the time of recording information is used for deformation of the recording layer and the adjacent layer (including thermal decomposition of dye). It is preferable that the thermal conductivity of the component is low, because heat is effectively used. In general, air has a lower thermal conductivity than solid, so that the efficiency of heat utilization is higher and the recording sensitivity is higher when a protective layer or the like is not provided. However, it is better to provide a protective layer in consideration of mechanical strength such as scratch resistance.

The tape-shaped optical information recording medium of the present invention may have a protective layer. As the material, a polymer such as cellulose ester-based, vinylidene chloride-based, vinyl chloride-based, norbornene-based, acrylic-based, polycarbonate-based, polyvinyl alcohol, gelatin, or the like can be used. Further, for the purpose of improving slipperiness, a polymer containing silicon or fluorine, a surfactant, or inorganic compound particles such as calcium carbonate or silicon dioxide may be contained.

The tape-shaped optical information recording medium of the present invention may have a back coat layer in order to secure the running property of the medium. The material may be one generally used for tape-shaped recording media such as audio tapes and video tapes, and examples thereof include resins in which conductive carbon is dispersed and conductive polymers. The back coat layer preferably comprises two layers, one layer being an antistatic layer provided in contact with the support, and the other layer being a protective layer.
As the antistatic layer, carbon, an electron conductive metal oxide (for example, tin oxide, antimony oxide, vanadium pentoxide), or a conductive polymer (for example, polypyrrole, polyacetylene, polyaniline) can be used. Further, as the polymer binder, the same polymer compound as that of the above-mentioned protective layer can be used. As the protective layer of the back coat layer, the same composition as the above-mentioned protective layer can be used, and in order to keep the shape of the optical information recording medium flat according to the temperature and humidity conditions, the curl on the recording layer side is offset. It is preferable to adjust the thickness so that

The tape-shaped optical information recording medium of the present invention may have a reflective layer between the recording layer and the support. That is, in the present invention, it is preferable that the tape-shaped optical information recording medium has a back layer made of a polymer layer supported on the side opposite to the recording layer via a support.

The material of the reflective layer may be a metal such as gold or aluminum, or a reflective layer made of an organic compound as described in JP-A-4-3345.

In addition, a layer of materials having different refractive indexes may be laminated to form a reflective layer.
It may be a reflective layer made of a non-metallic dye as described in No.

A metal reflective film is preferable from the viewpoint of manufacturing cost or the possibility of mixing with other layers. The material is preferably aluminum, which can be easily installed by vapor deposition and is inexpensive, but other metals having a high reflectance in the near infrared region such as gold and silver can also be preferably used.

In the present invention, the tape-shaped optical information recording medium has an antireflection layer which absorbs a laser beam used for recording or reading information on the opposite side of the dye recording layer through the support. preferable.

The material and layer structure of the antireflection layer that can be used in the present invention are a combination of carbon black and a suitable binder, or a dye or pigment that absorbs light of a laser wavelength used for recording or reproducing information. And a binder are preferred.

It is preferable to arrange the reflective layer and the recording layer in this order on the support. The reason is that a commercially available aluminum vapor deposition film can be used as it is, which is advantageous in terms of cost.

As the support used in the tape-shaped optical information recording medium of the present invention, any support can be used as long as it is excellent in flexibility and dimensional stability. Thickness is 1 to 100 microns,
It is preferably 5 to 50 microns. Polyester (for example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate), polystyrene, and aramid are preferably used, but metal foil such as aluminum and copper, or polymer film obtained by vapor deposition or plating of metal such as aluminum can also be used.

Coating is preferred as a method for providing the above layers on the support of the tape-shaped optical information recording medium of the present invention. In particular, from the viewpoint of productivity and accuracy of film thickness, a slide coater, a curtain coater, an extension coat, which is widely used in the production of photographic light-sensitive materials, is a method capable of coating a thin layer and forming a sufficiently uniform coating film. A coating method using a rouge coater, a wire bar coater, or a gravure coater is preferable. The coating of a plurality of layers can be performed one by one using a slide coater, a curtain coater, or an extrusion coater, or a plurality of layers can be simultaneously coated. The coating speed can be selected within a wide range of, for example, 1 meter to 1000 meters per minute, and is preferably 10 meters to 200 meters per minute because it is easy to maintain the uniformity of the coating surface quality and the stability of the coating speed.

In the present invention, the coating solution prepared when the above-mentioned layers are applied is prepared by dissolving or dispersing the material to be applied in water, an organic solvent or a mixture thereof. For example, as a solvent when applying a mixture mainly composed of an organic dye and a polymer compound, ketones (for example, methyl ethyl ketone, cyclohexanone, acetone), alcohols (for example, ethanol, butanol, cyclohexanol, diacetone alcohol, 2, 2,3,3-
Tetrafluoro-1-propanol), halogenated hydrocarbons (dichloromethane, 1,2-dichloroethane) and the like. The viscosity of the coating solution is 0.5 to 1000
cP, particularly 0.5 to 100 cP is preferable for performing thin layer coating at high speed. Covalently bond a surfactant and a thickener to the coating solution in order to improve the coating property, and a crystal nucleating agent and a gelling agent, preferably a polymer chain, for suppressing uneven flow due to the dry air after coating. It is also possible to add a polyfunctional compound (for example, alkylene diisocyanates, dichlorotriazines, bisvinyl sulfones, etc.) for crosslinking with.

The means for stably coating the recording layer on the support will be further described.

1) An undercoat layer may be provided on the support. It is preferable to provide an undercoat layer because the adhesion between the support and the recording layer is improved and peeling and cissing can be prevented. The composition of the undercoat layer is preferably a component having an affinity with the recording layer coating liquid. In particular, it is preferable to set by applying a polymer binder. In addition, a metal (such as aluminum) may be vapor-deposited.

2) The dye and the binder may be connected by a covalent bond. For example, it is preferable to use a reactive dye as a pigment and a cellulose-based polymer or a polymer containing a hydroxyl group or an amino group such as gelatin as a binder. Alternatively, it is preferable that a dye having a hydroxyl group or an amino group and a binder containing a hydroxyl group or an amino group are mixed and applied in the presence of a crosslinking agent such as diisocyanate.

A slip agent is preferably used in the tape-shaped optical information recording medium of the present invention.

Next, the slip agent preferably used in the present invention will be described.

When the optical tape is run in a series of manufacturing process steps, for example, a slit step and a recording / reproducing apparatus, the sensitive material is damaged due to the contact of the tape with the equipment or the contact of the front and back sides of the tape, and binder scrap is generated. The binder waste is a very serious problem such as being caught between the device and the optical tape, further damaging the surface of the optical tape, and adhering to the surface of the recording layer to cause noise during signal input / output.

The slip agent of the present invention is used for suppressing the scratching of the optical tape and the generation of binder scraps generated during the running of the optical tape in a series of optical tape systems and for improving the tape running property.

The slipping agent preferably used in the present invention is, for example, polyorganosiloxane disclosed in Japanese Patent Publication No. 53-242, US Pat. No. 4,275,275.
Higher fatty acid amides as described in Japanese Patent No. 146, Japanese Patent Publication No. 58-33541, British Patent No. 927,446.
Or JP-A-55-126238 and 58-
Higher fatty acid esters (esters of fatty acids having 10 to 24 carbon atoms and alcohols having 10 to 24 carbon atoms) as disclosed in 90633, and US Pat.
Higher fatty acid metal salts as described in JP-A No. 3,516, and esters of linear higher fatty acids and linear higher alcohols as described in JP-A-58-50534, WO 90108115.8. And higher fatty acid-higher alcohol ester containing a branched alkyl group as described in 1.

Examples of the polyorganosiloxane include polyalkylsiloxanes such as polydimethylsiloxane and polydiethylsiloxane, polyarylsiloxanes such as polydiphenylsiloxane and polymethylphenylsiloxane, and Japanese Patent Publication No. 53-292. As described in JP-B-55-49294 and JP-A-60-140341, an organopolysiloxane having a C5 or higher alkyl group, an alkylpolysiloxane having a polyoxyalkylene group in the side chain, and a side chain A modified polysiloxane such as an organopolysiloxane having an alkoxy group, a hydroxy group, a hydrogen group, a carboxyl group, an amino group, or a mercapto group may be used, or a block polymer having a siloxane unit or JP-A-60-19.
It is also possible to use a graft copolymer having a siloxane unit in the side chain as described in 1240. Preferred specific examples include KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.), SF1023, SF1054, SF1079 (Ge.
(Neral Electric), DC190, DC200, DC
510, DC1248 (manufactured by Dow Corning), BYK3
00, BYK310, BYK320, BYK322, B
YK330, BYK370 (made by BYK Chemie), etc. are mentioned.

Examples of higher fatty acids and their derivatives, higher alcohols and their derivatives include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, higher fatty acid polyhydric alcohol esters, and higher aliphatic alcohols. Use of higher aliphatic alcohol monoalkyl phosphite, dialkyl phosphite, trialkyl phosphite, monoalkyl phosphate, dialkyl phosphate, trialkyl phosphate, higher aliphatic alkyl sulfonic acid, amide compound or salt thereof, etc. be able to.

As represented by the general formulas (2) and (3),
The long-chain alkyl compound is preferable in that sufficient scratch resistance and slipperiness can be obtained under various environmental conditions before and after the development processing.

General formula (2) R ³ X ¹ R ⁴ General formula (3) R ⁵ X ² R ⁶ X ³ R ^{7 In} this general formula (2), R ³ and R ⁴ are aliphatic hydrocarbon groups. . The total carbon number of this compound is preferably 20 or more and 120 or less. In order to obtain sufficient slipperiness, the total number of carbon atoms is preferably 20 or more, and when the total number of carbon atoms is more than 120, the solubility in an organic solvent is poor and the application becomes difficult. The total carbon number is more preferably 25 or more and 100 or less, further preferably 30 or more and 80 or less. R ³ ,
It is preferable that each R ⁴ is an aliphatic hydrocarbon group having 10 to 70 carbon atoms. When the carbon number is less than 10, it is difficult to obtain sufficient scratch resistance and slipperiness. In addition, the aliphatic compound functionalized at one end with more than 70 carbon atoms is
Not generally known. This aliphatic hydrocarbon group may have a linear structure, may contain an unsaturated bond, may partially have a substituent, or may have a branched structure. Of these, the linear structure is particularly preferable.
The number of carbon atoms of R ³ and R ⁴ is more preferably 15
It is 50 or more and 50 or less.

In the general formula (3), R ⁵ , R ⁶ , and R ⁷
Is an aliphatic hydrocarbon group. The total carbon number of this compound is 3
It is preferably 0 or more and 150 or less. In order to obtain sufficient scratch resistance and slipperiness, a total carbon number of 30 or more is required. If the total carbon number is more than 150, the solubility in an organic solvent is poor and the application becomes difficult. The total carbon number is more preferably 40 or more and 130 or less, further preferably 50 or more and 120.
It is the following. In order to obtain sufficient scratch resistance and slipperiness, R ⁵ and R ⁷ are each an aliphatic hydrocarbon group having 10 to 70 carbon atoms, and R ⁶ is an aliphatic hydrocarbon group having 10 to 50 carbon atoms. It is preferably a group. Regarding R ⁵ and R ⁷ , if the number of carbon atoms is less than 10, it is difficult to obtain sufficient scratch resistance and slipperiness, and one end functionalized aliphatic compound having more than 70 carbon atoms is generally used. unknown.
This aliphatic hydrocarbon group may have a linear structure, may contain an unsaturated bond, may partially have a substituent, or may have a branched structure. Of these, the linear structure is particularly preferable. The carbon number of R ⁵ and R ⁷ is particularly preferably 15 or more and 50 or less. Further, R ⁶ has sufficient scratch resistance when the carbon number is 10 terminals,
It is difficult to obtain slipperiness, and an aliphatic compound functionalized with less than both ends having more than 50 carbon atoms is not generally known. This aliphatic hydrocarbon group may also have a linear structure, may contain an unsaturated bond, may have a partial substituent, or may have a branched structure.
Of these, the linear structure is particularly preferable. The carbon number of R ⁶ is preferably 10 or more and 30 or less, and particularly preferably 12 or more and 25 or less.

In the general formulas (2) and (3), X
¹ , X ² and X ³ are divalent linking groups. Specifically, −
C (O) O -, - C (O) NR -, - SO 3 -, - OS
_{O 3 -, - SO 2 NR} -, - O -, - S -, - NR-,
-OC (O) NR- and the like (R represents H or an alkyl group having 8 or less carbon atoms).

Specific examples of the compounds represented by the general formulas (2) and (3) are shown above, but the compounds are not limited thereto.

(1-1) n-C ₁₅ H ₃₁ COOC ₃₀ H ₆₁ -n (1-2) n-C ₁₇ H ₃₅ COOC ₄₀ H ₈₁ -n (1-3) n-C ₁₅ H ₃₁ COOC _{50 H 101 -n (1-4) n-} C 27 H 55 COOC 28 H 57 -n (1-5) n-C 21 H 43 COOCH 2 CH (CH 3)
_{-C 9 H 19 (1-6) n} -C 21 H 43 COOC 24 H 49 -iso (2-1) n-C 29 H 59 OCO (CH 2) 2 COOC
₂₄ H _49- n (2-2) n-C ₁₈ H ₃₇ OCO (CH ₂ ) ₄ COOC
₄₀ H ₈₁ -n (2-3) n-C ₁₈ H ₃₇ OCO (CH ₂ ) ₁₈ COOC
_{18 H 37 -n (2-4) iso} -C 24 H 49 OCO (CH 2) 4 CO
_{OC 24 H 49 -n (2-5)} n-C 40 H 81 OCO (CH 2) 2 COOC
₅₀ H ₁₀₁ -n (2-6) n-C ₁₇ H ₃₅ COO (CH ₂ ) ₆ OCOC
₁₇ H ₃₅ -n (2-7) n-C ₂₁ H ₄₃ COO (CH ₂ ) ₁₈ OCOC
₂₁ H ₄₃ -n (2-8) iso-C ₂₃ H ₄₇ COO (CH ₂ ) ₂ OC
_{OC 23 H 47 -n (2-9)} iso-C 15 H 31 COO (CH 2) 6 OC
OC ₂₁ H _43- n In addition, candelilla wax, carnauba wax, auri curly wax, rice wax, sugar wax, wood wax, beeswax, whale wax, sina insect wax, shellac wax,
Natural waxes such as montan wax can also be preferably used.

R ³ , R in the above general formulas (2) and (3)
A slip agent having a polar substituent on at least one of ⁴ or at least one of R ⁵ , R ⁶ and R ⁷ is more preferable. The polar substituent as used herein means a substituent capable of forming a hydrogen bond or a substituent that produces an ion by dissociating. The polar substituent is not particularly limited, -OH, -COOH, -COOM, -NR 5, -N
_{^{R 6+ A -, - CONH 2}} , -SO 3 H, -SO 3 M are preferable. Here, M is a cation such as an alkali metal, an alkaline earth metal or a quaternary ammonium salt, R is H or a carbon-hydrogen group having 8 or less carbon atoms, and A ⁻ is an anion such as a halogen atom. Moreover, -OH is especially preferable among these substituents. There may be any number of these polar substituents in one molecule. Specific examples will be given below, but the present invention is not limited thereto.

(3-1) HOCO (CH ₂ ) ₁₀ COOC ₂₁ H ₄₃ -n (3-2) n-C ₁₇ H ₃₅ COOCH ₂ CH (OH) C
_{12 H 25 -n (3-3) n} -C 9 H 19 C (OH) (C 9 H 19) CH
₂ COOC ₂₅ H ₅₁ -n (3-4) n-C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ C
_{OOC 40 H 81 -n (3-5)} n-C 14 H 29 CH (NH 2) COO (CH
_{2) n CH (CH 3)} (CH 2) m -CH 3
(N + m = 15) (3-6) CH ₃ (CH ₂ ) ₂ CH (COONa) (C
_{H 2) 6 COOC 40 H 81} -n (3-7) HOCH 2 (CH 2) 6 CH (OH) CH
_{(OH) (CH 2) 4} COO-C 50 H 101 -n (3-8) n-C 17 H 35 COO (CH 2) 16 OH (3-9) CH 3 (CH 2) 2 CH (OH) (CH ₂ )
₆ CONHC ₂₁ H ₄₃ -n (3-10) n-C ₇ H ₁₅ -φ-COOCH (CONH
_{2) C 16 H 33 -n (} 3-11) n-C 27 H 55 COOCH 2 CH (OH) C
_{H 2 OH (3-12) HOCO (} CH 2) 5 COOC 40 H 81 -n (3-13) CH 3 (CH 2) 15 CH (SO 3 Na) C
_{OOCH 2 CH (C 13 H 27} ) -C 10 H 21 -n (4-1) n-C 14 H 29 CH (OH) COO (C
_{H 2) 5 OCOCH (OH)} -C 14 H 29 -n (4-2) n-C 10 H 21 COOCH (C 2 H 5) (CH
₂ ) ₇ CH (C ₂ H ₄ COOH) -OCOC ₁₀ H ₂₁ -n (4-3) NaOCO (CH ₂ ) ₁₁ COO (CH ₂ )
_{10 OCO (CH 2) 11 -COOH} (4-4) n-C 9 H 19 C (OH) (C 9 H 19) CH 2
_{COO (CH 2) 15 CONH-} C 10 H 21 -n (4-5) H 2 NCO (CH 2) 10 COOCH (C 6
_{H 13) (CH 2) 10} COO-C 30 H 61 -n (4-6) n-C 14 H 29 CH (N + (CH 3) 3 C1
^{_{-) COO (CH 2) 10}} OCO-C 17 H 35 -n (4-7) n-C 6 H 13 CH (OH) (CH 2) 10 CO
_{O (CH 2) 8 OCO- (} CH 2) 10 CH (OH) C 6
_{H 13 -n (4-8) n-} C 15 H 31 COOCH 2 CH (OH) C
_{H 2 OCOC 15 H 31 -n (} 4-9) n-C 8 H 17 NHCO (CH 2) 10 COO
(CH ₂ ) ₁₅ OH (4-10) n-C ₄₀ H ₈₁ OCO (CH ₂ ) ₅ COO
(CH ₂ ) ₅ COOH (4-11) n-C ₄₀ H ₈₁ OCO (CH ₂ ) ₇ CH (O
_{H) CH (OH) C 8} H 17 -n (4-12) n-C 40 H 81 OCO (CH 2) 18 COOH (4-13) n-C 40 H 81 OCO (CH 2) 18 COOC
_{H 2 CH (OH) CH 2} OH (4-14) n-C 40 H 81 OCO (CH 2) 18 COOC
_{H 2 CH 2 OCH 2 CH 2} CH (4-15) n-C 40 H 81 OCOCH 2 N (CH 3) C
_{OC 11 H 23 -n (4-16)} CH 3 (CH 2) 15 CH (SO 3 Na) C
_{OO (CH 2) 2 CH (} CH 3) - (CH 2) 2 OCO
_{C 17 H 35 -n (4-17)} HOCH 2 CH (OH) CH 2 OCO (C
_{H 2) 3 CH (C 2} H 5) - (CH 2) 9 COOC 50 H
_{101 -n φ: -C 6 H 4} - formula of the present invention (2), (3) a lubricant of often have low solubility in solvents. Therefore, it is preferable to disperse and use it in water or an organic solvent. As a method of dispersing in water, a method of dissolving in an organic solvent and then emulsifying in water,
Examples thereof include a method of melting a lubricant at a high temperature and emulsifying in water, a ball mill, a solid dispersion method using a sand grinder, and the like. For such emulsification dispersion method, cutting rice, pebbles,
It is described in publications such as "Handbook of Emulsification and Dispersion Technology Application" (Science Forum Edition) edited by Hidaka.

As a method of dispersing the lubricant in the organic solvent, a method of solid-dispersing the lubricant in the organic solvent by a ball mill, a sand grinder, or the like, or by heating and dissolving the lubricant in the organic solvent with stirring A method of cooling and precipitating and dispersing, a method of heating and dissolving a lubricant in an organic solvent, and adding it to an organic solvent at room temperature or a temperature of cold to precipitate and disperse, and mutually Examples include a method of emulsifying with incompatible organic solvents. Of these, the preferred method is to dissolve the lubricant by heating in an organic solvent,
This is a method in which this is added to an organic solvent at room temperature or cooled, cooled, precipitated, and dispersed. Specifically, use 6
It is a method in which it is melted by heating at 0 ° C to 150 ° C and dispersed in a cooling medium in which the solubility of the lubricant at room temperature is 1% or less. The organic solvent used for dispersion is not particularly limited, but as the cooling medium, a solvent having a high polarity, particularly, a solvent having a solubility of 1% or less at room temperature of the lubricant of the present invention is preferably ketones or alcohols. Further, as the disperser used in this dispersion, an ordinary stirrer can be used, but an ultrasonic disperser or a homogenizer is particularly preferable.

As the dispersion stabilizer of the lubricants of the general formulas (2) and (3) of the present invention in an organic solvent, those which do not deteriorate the scratch resistance and the slipperiness are preferable. The dispersion stabilizer of the following general formula (4) is preferable in that it can exert the stabilizing effect of the lubricant of the general formulas (2) and (3) of the present invention in most organic solvents.

General Formula (4) R ⁸ YBD In the general formula (4), R ⁸ is an aliphatic hydrocarbon group having 20 to 70 carbon atoms. This hydrocarbon group may have a linear structure, may contain an unsaturated bond, may be substituted with various substituents, and may have a branched structure. Particularly preferred is a straight-chain aliphatic hydrocarbon group. In the hydrocarbon group having less than 20 carbon atoms, the general formula (2),
The effect of stabilizing the dispersion of the slip agent (3) in the organic solvent is not exhibited. Further, as a hydrocarbon compound having a functional group of less than 70 carbon atoms, a straight chain or branched aliphatic alcohol is known, but a compound having a hydrocarbon group having more than 70 carbon atoms is generally known. Little known. The carbon number is more preferably 30 to 60, and particularly preferably 40 to 60.

Y is a divalent linking group, specifically-
C (O) O-, -OCO-, -C (O) NR'-, -N
_{R'CO-, SO 2 NR '-,} - NR'SO 2 -, - O
-, -S-, -NR-, -OCOR "COO-, -OC
Examples thereof include OR "O- and the like (R 'represents H or a hydrocarbon group having 8 or less carbon atoms, and R" represents a hydrocarbon group having 8 or less carbon atoms). Is B, - (CH ₂ CH ₂
O) _a -, or _{- (CH 2 CH (OH)} CH 2 O) b
-, or _{- ((CH 2) c CH} (R) CH 2 O)
_d -, or _{- (CH 2 CH 2 O)} e - (CH 2 CH
_{(OH) CH 2 O) f} - ((CH 2) c CH (R) CH
₂ O) _g- , and a is 3 to 8
0, b, d is 3 to 60, c is 1 to 3, e is 0 to 80,
f and g are 0 to 60, e + f + g is 3 to 140, and D
Are H, CH ₃ and phenyl groups. If B is too long, scratch resistance and slipperiness are deteriorated. Particularly preferred among the above nonionic group _{- (CH 2 CH 2 O)} a - a and, a
Is preferably 15 to 70, particularly preferably 30 to 60. The amount of the dispersion stabilizer (4) used with respect to the slip agent of the general formulas (2) and (3) of the present invention may be 5 to 90% by weight, preferably 20 to 70% by weight, and particularly preferably 30. -60% by weight.

Specific examples of the dispersion stabilizer represented by the general formula (4) are shown below, but the invention is not limited thereto.

(5-1) n-C ₂₀ H ₄₁ O (CH ₂ CH ₂ O) ₃₀ H (5-2) n-C ₃₀ H ₆₁ O (CH ₂ CH ₂ O) ₁₀ H (5-3) _{n-C 30 H 61 O (} CH 2 CH 2 O) 40 H (5-4) n-C 30 H 61 O (CH 2 CH 2 O) 50 H (5-5) n-C 30 H 61 O ( _{CH 2 CH 2 O) 60 H} (5-6) n-C 40 H 81 O (CH 2 CH 2 O) 15 H (5-7) n-C 40 H 81 O (CH 2 CH 2 O) 30 H _{(5-8) n-C 40 H} 81 O (CH 2 CH 2 O) 50 H (5-9) n-C 40 H 81 O (CH 2 CH 2 O) 60 H (5-10) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (5-11) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₃₀ H (5-12) n-C ₅₀ H ₁₀₁ O (CH ₂ CH _{2 O) 50 H (5-13)} n-C 50 H 101 O (CH 2 CH 2 O) 60 H (5-14) n _{C 50 H 101 O (CH 2} CH 2 O) 70 H (5-15) n-C 50 H 101 - (CH (CH 3) CH 2
_{O) 3 (CH 2 CH 2} O) 16 -H (5-16) n-C 50 H 101 - (CH 2 CH (OH) C
_{H 2 O) 3 - (CH} (OH) CH 2 O) 3 - (CH 2 C
H ₂ O) ₁₅ H (5-17) n-C ₄₀ H ₈₁ OCOCH ₂ CH ₂ COO
(CH ₂ CH ₂ O) ₁₆ H (5-18) n-C ₅₀ H ₁₀₁ OCOCH = CHCOO
(CH ₂ CH ₂ O) ₁₆ H (5-19) n-C ₅₀ H ₁₀₁ OCOCH ₂ CH ₂ COO
_{- (CH 2 CH (OH)} CH 2 O) 3 - (CH 2 CH 2
O) ₁₅ H Coating the slip agent represented by the general formulas (2) and (3) of the present invention with a binder capable of forming a film improves the surface state on which the slip agent is applied and the film strength of the slip agent-containing layer. It is particularly preferable in terms of improvement. As such a binder, a known thermoplastic resin, thermosetting resin, radiation-curable resin, reactive resin, water-soluble binder of the present invention, or the like can be used, or these can be mixed and used. May be.

The layer containing the slip agent of the present invention may be coated anywhere, and may be added to, for example, an undercoat layer, an antistatic layer or a layer containing the water-soluble binder of the present invention. . A particularly preferred additive layer is a layer containing the water-soluble binder of the present invention.

The amount of the slip agent represented by the general formulas (2) and (3) of the present invention is not particularly limited, but sufficient slip resistance,
Long to express lubricity at 1-500 mg / m ^2, it is preferably 3-200 mg / m ^2, particularly preferably 5 to 100 mg / m ^2.

The surface slipperiness imparted by the slip agent of the present invention is a dynamic friction coefficient before and after the development treatment evaluated using a stainless ball having a diameter of 5 mm at 25 ° C. and 60% RH, both of which is 0.03 to 0. 25, preferably 0.04 to
0.20, more preferably 0.04 to 0.15, and particularly preferably 0.04 to 0.13. Dynamic friction coefficient is 0.
If it is larger than 25, the generation of binder waste becomes remarkable when the photographic system is running, and the frequency of signal input / output failures increases.

The layer containing the lubricant of the present invention may be coated on the emulsion side, preferably an emulsion protective layer, and particularly preferably the outermost layer on the emulsion side.

Various additives can be added to the lubricant-containing layer of the present invention. For example, monobasic fatty acids having 10 to 22 carbon atoms (saturated, unsaturated, Li, Na, K,
(Including Cu salt), 1-6 having 2-22 carbon atoms
Dihydric alcohols (including saturated and unsaturated), alkoxy alcohols having 12 to 22 carbon atoms (including saturated and unsaturated), esters of monobasic fatty acids having 12 to 22 carbon atoms (saturated, unsaturated) (Including saturated), fatty acid amides having 8 to 22 carbon atoms, and the like. Specific examples of these compounds include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linolenic acid, butyl stearate, octyl stearate, isooctyl stearate, amyl stearate, butoxyethyl stearate. , Oleyl alcohol, lauryl alcohol and the like.

Further, in order to improve cissing of the developing solution of the light-sensitive material due to the slip agent of the present invention, a surfactant having a sulfonic acid or a sulfuric acid ester as a hydrophilic group represented by the following general formula (5) is added. Is preferred.

General formula (5) R ⁹ Z ¹ EM ^{1 In the} general formula (5), R ⁹ is an aromatic or aliphatic hydrocarbon group. The hydrocarbon group is not particularly limited, but specifically, straight-chain alkyl, branched alkyl, substituted or unsubstituted phenyl group, naphthalene group, succinic acid ester of alkyl group, phosphonic acid ester, and the like. can give.

Z ¹ is a divalent linking group. This linking group may be omitted. The linking group is not particularly limited, but specifically, -R-, -OR-, -COOR-, -O.
COR- and the like, and R is an alkyl group having 0 to 10 carbon atoms, a polyoxyethylene group, a polyoxypropylene group, or the like. Further, E _{is, -OSO 3 -, - SO 3} - is. M ¹ is H or an alkali metal, an alkaline earth metal,
It is a cation such as a quaternary ammonium salt.

Specific examples of the additive represented by the general formula (5) are shown below, but the present invention is not limited thereto.

(6-1) C ₁₂ H ₂₅ OSO ₃ Na (6-2) C ₁₆ H ₃₃ OSO ₃ Na (6-3) C ₁₈ H ₃₇ φSO ₃ Na (6-4) C ₈ H ₁₇ φSO ₃ Na (6-5) C ₁₂ H ₂₅ φSO ₃ Na (6-6) C ₆ H ₁₃ OCOCH ₂ CH (C ₆ H ₁₃ OC
O) SO ₃ Na φ: —C ₆ H ₄ — Further, the addition amount of the additive represented by the general formula (5) of the present invention is 0.1 mg / m ₂ or more up to the solid content of the lubricant of the present invention. Well, preferably 0.5 mg / m ₂ or more
2 solids content, particularly preferably 1 mg / m ₂ or more and 1/3 solids content of the slip agent.

The diluting solvent used in the lubricant dispersion or solution of the present invention may be any one that does not deteriorate the dispersion stability or solubility of the lubricant, such as water and various surfactants. Contained water, alcohols (methanol, ethanol, isopropanol, butanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), esters (acetic acid, formic acid, oxalic acid, maleic acid, succinic acid, etc., methyl, ethyl, propyl) , Butyl ester, etc.), hydrocarbon type (hexane,
Cyclohexane, etc.), halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, toluene, xylene, benzyl alcohol, benzoic acid, anisole, etc.), amides (dimethylformamide, dimethyl) Acetamide, n-
Methylpyrrolidone, etc.), ethers (diethyl ether, dioxane, tetrahydrofuran, etc.), ether alcohols such as propylene glycol monomethyl ether, glycerin, diethylene glycol, dimethyl sulfoxide, etc. Among these, water, water containing various surfactants, alcohols, ketones, and esters are preferable.

In the present invention, it is preferable to manufacture a tape-shaped optical information recording medium by coating a layer containing carbon black and a specific fluorine-containing surfactant as a back layer of the optical recording tape.

The fluorine-containing compound used in the present invention will be described.

Various rubbers (eg emulsion waste, cartridge waste, etc.) are used during cutting of the optical tape and during running of the system.
Equipment wear debris) is likely to occur. If such dust adheres to the back surface of the photosensitive material of the present invention, signal input / output failure may occur. The fluorine-containing compound of the present invention is used for the purpose of preventing the dust thus generated from adhering to the surface of the optical tape.

The fluorine-containing compound used in the present invention is
Any compound containing at least three fluorine atoms may be used, and it may be a surfactant or a polymer. Those containing a nonionic, anionic, cationic, or betaine hydrophilic substituent are preferable, and a fluorine-containing compound containing an anionic substituent is particularly preferable.

The fluorine-containing compound particularly preferably used in the present invention is a fluorine-containing surfactant represented by the following general formula (6).

General formula (6) Rf-A-X ⁴ wherein Rf is a partially fluorinated or fully fluorinated substituted or unsubstituted alkyl group, alkenyl group, or at least 3 fluorine atoms, or Represents an aryl group. A represents a divalent linking group, and X ⁴ represents a hydrophilic substituent.

A is preferably an alkyl group, an aryl group or an alkylaryl group, and is, for example, -C.
(O) O -, - C (O) NR -, - SO 3 -, - OSO
_{3 -, - SO 2 NR -} , - O -, - S -, - NR -, -
It may be a divalent substituted or unsubstituted linking group such as OC (O) NR-.

In the present invention, the recording layer is preferably a tape-shaped optical information recording medium containing a cyanine dye and a polyamic acid represented by the following structural formula.

[0121]

[Chemical 12]

In the present invention, the surface resistance SR of the tape is
Is 10 or less in log (SR), and the half-life of charge leakage from the surface is 60 seconds or less when 8 KV is applied, and it is preferable to use a tape-shaped optical information recording medium.

Next, the antistatic layer used in the present invention will be described.

Excessive electrification of the web in the process of manufacturing the optical tape, for example, in the process of coating the organic solvent, is not desirable because it may cause uneven coating and may cause ignition due to discharge. Furthermore, even in the slitting process for cutting the tape, cutting dust generated during cutting adheres to the tape, and especially when the tape is thin, the electrostatic discharge between the tapes may cause jamming during running. Cause problems.
The antistatic layer may be on the recording layer side or the reflecting surface, and may be the recording layer or the undercoat layer.

Therefore, it is desirable to impart an antistatic function to the optical tape. The antistatic function required for the optical tape includes the surface resistance value SR and the charge leakage rate. The surface resistance value is 10 ¹⁰ or less, preferably 10 ⁸
As for the charge leakage rate, the charge half-life Th when applying 8 KV is 60 seconds or less, preferably 10 seconds or less.

[0126]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. .

(Example 1) A coating solution having a liquid composition 1 was applied to a polyethylene terephthalate support 4 having a width of 18 cm and a thickness of 15 μm with a wire bar coater 1 as shown in FIG. 1 at a speed of 20 m / min for the first layer. Was applied. The coating liquid is fed from the coating liquid stock tank 3 by the liquid feed pump 2 and is supplied to the wire bar coater 1 through the filter 14. The wire bar coater 1 rotates in the same direction as the web conveying direction and transfers the coating liquid onto the web. The diameter of the wire is 0.15 mm, and the peripheral speed of the wire bar is 20 m / min.
A 10 micron wet coating was obtained. After application, the coating was first dried with hot air at 40 ° C and then at 80 ° C, and then wound. On the thus-applied first layer, the same wire bar coater was used to apply the coating solution of the liquid composition 2 at a rate of 20 m / min to form a second layer. The wire used had a diameter of 0.3 mm and a peripheral speed of 15 m / min to obtain a 20 μm wet coating film. Similarly, it was dried with warm air and wound up to obtain Sample 1. The liquid compositions 1 and 2 had viscosities of 20 degrees Celsius and 3 cP and 10 cP, respectively.

Liquid composition 1: Compound I-1: 1 part by weight IRG-022 (manufactured by Nippon Kayaku): 0.1 part by weight Cellulose acetate butyrate (manufactured by Eastman Chemical Co.): 1 part by weight Coronate (Nippon Polyurethane Industry Co., Ltd.) Co., Ltd.): 0.1
Parts by weight 1,2-dichloroethane: 100 parts by weight Liquid composition 2: Polyvinyl alcohol: 3 parts by weight Formaldehyde: 0.5 parts by weight Sodium laurylbenzenesulfonate: 0.2 parts by weight Distilled water: 100 parts by weight (Example 2) Sample 2 was prepared in the same manner as in Example 1 except that the liquid composition 3 was applied to the first layer instead of the liquid composition 1.
The viscosity of the coating liquid was 5 cP at 20 degrees Celsius.

Liquid composition 3: Compound I-15: 1 part by weight IRG-022 (manufactured by Nippon Kayaku): 0.1 part by weight Cellulose diacetate (manufactured by Daicel Corp., acetylation degree 5)
5.5%): 1 part by weight Coronate (manufactured by Nippon Polyurethane Industry Co., Ltd.): 0.5
Parts by weight Methyl ethyl ketone: 50 parts by weight Cyclohexanone: 50 parts by weight (Example 3) Sample 3 was prepared in the same manner as in Example 1 except that the liquid composition 4 was applied to the first layer instead of the liquid composition 1.
The viscosity of the coating liquid was 0.6 cP at 20 degrees Celsius.

Liquid composition 4 Compound I-1: 1 part by weight IRG-022 (manufactured by Nippon Kayaku): 0.1 part by weight Dichloromethane: 100 parts by weight (Example 4) Instead of the liquid composition 2, the liquid composition 5 was used. Sample 4 was prepared in the same manner as in Example 1 except that it had two layers. The viscosity of the coating liquid was 3 cP at 20 degrees Celsius.

Liquid composition 5 Cellulose diacetate (manufactured by Daicel Corp., degree of acetylation 5)
5.5%): 1 part by weight Coronate (manufactured by Nippon Polyurethane Industry Co., Ltd.): 0.5
Parts by weight Methyl ethyl ketone: 50 parts by weight Cyclohexanone: 50 parts by weight (Example 5) Sample 5 was prepared in the same manner as in Example 1 except that the liquid composition 5 was used as the second layer instead of the liquid composition 2. The viscosity of the coating liquid was 15 cP at 20 degrees Celsius.

Liquid composition 6 Cellulose triacetate: 2 parts by weight Dichloromethane: 90 parts by weight Cyclohexanone: 10 parts by weight (Example 6) Liquid composition 7 was applied to the first layer and liquid composition 8 was applied to the back surface of the sample of Example 1. Sample 2 was applied as two layers.

Liquid composition 7: Tin oxide fine particles (average particle size 0.2 micron): 5 parts by weight Antimony oxide (average particle size 0.2 micron): 5 parts by weight Acid-treated gelatin (isoelectric point 7.0): 1 part by weight p-chlorophenol: 10 parts by weight Acetic acid: 1 part by weight Polyoxyethylene nonylphenyl ether: 0.02
Parts by weight Water: 6 parts by weight Methanol: 72 parts by weight Liquid composition 8: Cellulose triacetate (manufactured by Daicel Corporation, degree of acetylation 60.9%): 1 part by weight Acetone: 70 parts by weight Methanol: 15 parts by weight Dichloromethane: 10 Parts by weight p-chlorophenol: 4 parts by weight Liquid compositions 7 and 8 had viscosities of 2.5 cP and 0.9 cP at 20 degrees Celsius, respectively. For coating, the same wire bar coating as in Example 1 was used to successively form coating films. The coating speed of the first layer is 20 m / min, the outer diameter of the wire is 0.15 mm, and the peripheral speed of the wire bar is 20 m / min.
A wet film thickness of 0 micron was obtained. The coating speed of the second layer was 20 m / min, the outer diameter of the wire was 0.3 mm, the peripheral speed of the wire bar was 20 m / min, and a wet film thickness of 20 microns was obtained. The coating was first dried with warm air at 60 degrees Celsius and then 120 degrees Celsius.

(Example 7) Sample 7 was obtained by applying the same composition as in Example 3 except that the liquid composition 7 was used as the first layer and the liquid composition 9 was used as the second layer on the back surface of the sample of Example 3. did. 2 degrees Celsius
The viscosity of liquid composition 9 at 0 degrees was 2.3 cP.

Liquid composition 9: Cellulose diacetate (manufactured by Daicel Corporation, degree of acetylation 5)
5.5%): 1 part by weight Acetone: 70 parts by weight Methanol: 15 parts by weight Methylene chloride: 10 parts by weight p-Chlorophenol: 4 parts by weight (Example 8) In the first layer on the back surface of Example 6, Liquid composition 7
The liquid composition 10 was used in place of, and the second layer was not applied to be the sample 8. The coating conditions are the same as in Example 6.

Liquid composition 10: carbon black (manufactured by Mitsubishi Chemical Corporation, type 40)
B): 0.5 parts by weight Cellulose derivative (FA21 manufactured by Shin-Etsu Chemical Co., Ltd.):
0.5 parts by weight Cellulose derivative (FA22, manufactured by Shin-Etsu Chemical Co., Ltd.):
0.5 parts by weight Acetone: 50 parts by weight Propylene glycol monomethyl ether: 30 parts by weight Methanol: 18.5 parts by weight Sodium hexadecyl sulphate: 0.2 parts by weight (Example 9) Sample 9 was prepared by simultaneously applying the liquid composition 11 as one layer and the liquid composition 12 as the second layer by the slide coater shown in FIG.
The adjusted coating liquid is used as the coating liquid stock tanks 10 and 11.
Is supplied to the slide coater 7 through gear pumps 8 and 9, respectively. The supplied coating liquid is laminated while flowing down on the slide surface, and is applied to the web 13 on the backup roll 12. The viscosities of liquid compositions 11 and 12 at 20 degrees Celsius were both 25 cP.

Liquid composition 11: Compound I-1: 0.5 parts by weight IRG-022 (manufactured by Nippon Kayaku): 0.05 parts by weight Cellulose diacetate (manufactured by Daicel, degree of acetylation 55.5)
%): 2.5 parts by weight Coronate (manufactured by Nippon Polyurethane Industry Co., Ltd.): 0.5
Parts by weight Methyl ethyl ketone: 50 parts by weight Cyclohexanone: 50 parts by weight Liquid composition 12: Cellulose diacetate (manufactured by Daicel, acetylation degree 55.5)
%): 2.5 parts by weight Coronate (manufactured by Nippon Polyurethane Industry Co., Ltd.): 0.5
Parts by weight Methyl ethyl ketone: 50 parts by weight Cyclohexanone: 50 parts by weight
Was fed so that the thickness of each of the wet coatings would be 20 microns, and after being laminated on the slide surface, it was applied to the support through the beads. The coating speed is 80 m / min,
The lower part of the coating bead was decompressed by 20 mmAq with respect to atmospheric pressure. The inclination angle of the slide was 5 degrees, the slide length was 25 mm, and the bead clearance was 150 μm. The drying conditions were 40 ° C. for the first 10 seconds and a wind speed of 0.5 m, and thereafter 90 ° C. for drying.

(Example 10) Coating of water-soluble binder-containing layer (back third layer) The following slip agent and dispersion stabilizer were mixed in a ratio of 1: 1,
An equal weight of xylene was added, and the mixture was heated and dissolved at 100 ° C., and then added to cyclohexanone to prepare a lubricant dispersion having a solid content of 1.5% by weight. The slip agent dispersion was inserted into an ultrasonic disperser to crush the slip agent.

[0139] _{n-C 6 H 13 CH (} OH) C 10 H 20 COOC 40 H 81 -n ( slip agent) 1 part by weight of _{n-C 50 H 101 O (} CH 2 CH 2 O) 16 H ( dispersion stabilizer Agent) 1 part by weight A coating solution having the following composition was applied onto the second back layer so that the coating amount of the water-soluble binder was 25 mg / m ² .
The drying conditions were 115 ° C. and 3 minutes.

15 parts by weight of the above-mentioned lubricant / dispersion-stabilized solid content Hydroxypropylcellulose (water-soluble binder) 25 parts by weight BYK-310 (silicone by BYK, lubricant) 6 parts by weight C ₉ F ₁₇ SO ₂ N ( _{C 3 H 7) (CH 2} CH 2 O) 4 (CH 2) 4 SO 3 Na ( fluorine surfactant) 1.5 parts by weight of xylene 15 parts by weight cyclohexanone 1250 parts by weight of isopropyl alcohol 6750 parts by weight of methanol 240 parts by weight (Comparative Example 101) A comparative sample 10 was prepared in the same manner as in Example 1 except that the dye A obtained by replacing the hexafluorophosphate ion of the compound I-1 with a perchlorate ion was used instead of the compound I-1.
Created in 1.

[0141]

[Chemical 13]

(Comparative Example 102) NK-1 used in the examples of JP-A-6-251425 instead of the compound I-2.
Comparative sample 102 in the same manner as in Example 2 except that 25 is used.
It was created.

<Evaluation of Tape-like Optical Information Recording Medium> The sample prepared as described above was attached to a smooth polymethylmethacrylate plate with the recording layer facing outside, and recording was performed by irradiating a semiconductor laser from the recording layer side. And played. The evaluation conditions were as follows.

Semiconductor laser: GaAlAs, wavelength 780 nm Beam diameter: 1.6 μm Linear velocity: 5 m / sec Recording power: 8 mW Recording frequency: 2.5 MHz Recording duty: 50% Reproduction power: 0.4 mW Further, each sample was 70 degrees Celsius After storing at 90% humidity for 2 weeks, it was regenerated and the degree of deterioration was evaluated. The results of these evaluations are shown in Table 1.

[0145]

[Table 1]

From the results shown in Table 1, the optical recording medium of the present invention has a recording performance equal to or higher than that of Comparative Example, is excellent in storage stability, and has no fear of explosive property such as perchlorate. It turns out that it is especially excellent in using.

Further, Examples 8 and 10 and Comparative Example 101
For Nos. 102 and 102, the recording layer surface and the back surface were brought into close contact with each other and rubbed under a load of 500 g / cm ² , as a result, Comparative Example 1
In Nos. 01 and 102, the recording surface was markedly scratched, whereas in Example 8, there was only a slight scratch, and in Example 10, no scratch was visually observed. This shows that the slipperiness of the back surface affects the occurrence of scratches when it comes into contact with the recording layer, and the slip agent of Example 10 has an effect of preventing scratches. (Example 11) Measurement of surface resistance Hivesta manufactured by Mitsubishi Petrochemical Co., Ltd. was used for measurement of surface resistance.
MCP-TESTER was used. In addition, SHISHIDO CO. LTD made of STAT
IC HONESTO METER Type S-4
101, applied voltage 8KV, atmospheric humidity 55% R
Performed in H at 25 ° C. The measurement results are shown in Table 2 below. In Table 2, ◯ means no adhesion, Δ means slight adhesion, and X means adhesion.

[0148]

[Table 2]

From the results shown in Table 2, it can be seen that the dust-prevented sample has a good dust adhesion state and a good adhesion behavior between the tapes.

[0150]

EFFECT OF THE INVENTION The tape-shaped optical information recording medium of the present invention has a recording performance equal to or higher than that of the comparative example, is excellent in storage stability, and has no fear of explosive property such as perchlorate. Is particularly excellent in that it is used, and the antistatic product exhibits excellent effects such as the adhesion state of dust and the adhesion behavior between tapes.

[Brief description of drawings]

FIG. 1 is a schematic view of a wire bar coater used in Example 1 and the like.

FIG. 2 is a schematic view of a slide coater used in Example 9.

[Explanation of symbols]

1 ... Wire bar coater, 2 ... Liquid feed pump, 3 ... Coating liquid stock tank, 4 ... Support feeding roll, 5 ... Support winding roll, 6 ... Drying duct, 7 ... Slide coater, 8, 9 ... Fixed amount feeding Liquid pump (gear pump), 1
0, 11 ... Coating solution stock tank, 12 ... Backup roll, 13 ... Support base, 14 ... Filter.

Claims (14)

[Claims] 1. A tape-shaped support having at least one recording layer capable of recording or reproducing information using a laser beam, the recording layer comprising a laser beam responsive compound and a polymer as a binder. A tape-shaped optical information recording medium containing a compound. 2. The laser beam responsive compound is at least one selected from cyanine dyes, merocyanine dyes, oxonol dyes, azomethine dyes, azo dyes, phthalocyanine dyes, and metal complexes in which these dye structures serve as ligands. The tape-shaped optical information recording medium according to claim 1, which is a seed. 3. The tape-shaped optical information recording medium according to claim 1, wherein the laser beam responsive compound contains at least one compound represented by the following general formula (1). General formula (1): In the formula, R ¹ and R ² independently represent an alkyl group or an aryl group, Z represents an atomic group for forming an aromatic ring,
L represents a linking group for forming a cyanine dye. 4. The tape-shaped optical information recording medium according to claim 1, wherein the recording layer contains a singlet oxygen quencher. 5. The tape-shaped optical information recording medium according to claim 1, which contains a laser beam responsive compound as a solid dispersion. 6. The tape-shaped optical information recording medium according to claim 1, further comprising a metallic reflection layer provided between the tape-shaped support and the recording layer. 7. The tape-shaped optical information recording medium according to claim 1, wherein a back layer composed of a polymer layer is supported on the side opposite to the recording layer via a support. 8. The thickness of the recording layer is 1 / 4n (where n is the wavelength of a laser beam used for recording or reading).
Represents the refractive index of the dye recording layer. 8. The tape-shaped optical information recording medium according to claim 1, which is an integral multiple of 9. The tape-shaped optical element according to claim 1, wherein an antireflection layer for absorbing a laser beam used for recording or reading is provided on the opposite side of the recording layer via a support. Information recording medium. 10. The tape shape according to claim 1, wherein the recording layer has a thickness of 15% or more and a transmittance of 30% or less for infrared light having a wavelength of 780 nm. Optical information recording medium. 11. The tape-shaped optical information recording medium according to claim 1, wherein the weight ratio of dye / binder> = 1.0, and the thickness of the recording layer is 50 to 150 nm. 12. The surface resistance SR of the tape is log (S
The tape-shaped optical information recording medium according to any one of claims 1 to 11, wherein R) is 10 or less, and the half-life of charge leakage from the surface is 60 seconds or less when 8 KV is applied. 13. The tape-shaped optical information recording medium according to claim 7, wherein a layer containing carbon black and a specific fluorine-containing surfactant is coated as a back layer. 14. The tape-shaped optical information recording medium according to claim 1, wherein the recording layer contains a cyanine dye and a polyamic acid.