JPH0391127A - Information recording medium - Google Patents

Abstract

PURPOSE:To enhance the stability to oxidation, etc., by forming a reflecting film layer for which a phthalocyanine dyestuff is used on the information record ing surface of a transparent resin substrate imparted with information. CONSTITUTION:The phthalocyanine dyestuff having a good adhesive property to the transparent resin substrate is formed as the reflecting film and the film is formed by an ordinary coating device, such as ordinary spin coater, without using a large-sized apparatus, such as vapor deposition device or sputtering device. Namely, the reflecting film layer for which the phthalocyanine dyestuff, such as phthalocyanine or napthalocyanine is used, is formed on the information recording surface of the transparent resin substrate imparted with the informa tion. The long-term preservable stability of CDs, or CD-ROMs, etc., is improved in this way and the apparatus and process for production are simplified. The information recording media, such as CDs, or CD-ROMs, are inexpensively obtd. in this way.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to an information recording medium such as a CD or CD-ROM that optically reads out information recorded in groove or bit-like uneven patterns. It is related to.

(Prior Art) Among information recording media using focused laser light, compact discs (CDs) are widely used for reproducing music such as audio.

This CD is manufactured by: (1) information is added to the surface of a transparent resin substrate, usually made of polycarbonate resin or acrylic resin, by injection molding using a stamper, or by the so-called 2P method using a photopolymer, using a stamper to attach a bit string having a CD format signal; It is manufactured by a method in which a reflective film such as aluminum or gold is provided by vapor deposition or sputtering on the reflective film, and then a photopolymer is applied and cured as a protective film.

In CD or CD-ROM optical discs (information recording media) manufactured in this manner, aluminum or gold is used as the reflective film, but in the case of aluminum, the reflectance decreases due to oxidation.

There is a problem with long-term storage of information. On the other hand, in the case of gold, the reflective film has excellent oxidation resistance, but has poor adhesion to the resin and there is a risk that the reflective film will peel off. Also.

The only way to form such a gold rlI thin film is by vapor deposition or sputtering, and the manufacturing equipment is expensive and large-scale equipment, requiring a large area for the manufacturing line. Therefore, the size of the clean room for the production line becomes large, and the running cost for production becomes extremely high, which is currently a major problem in the production of inexpensive CDs.

(Problem to be solved by the invention) The present invention solves the above problems.

In addition to improving the long-term storage stability of CDs and CD-ROMs, we have also simplified the manufacturing equipment and manufacturing process.
Alternatively, information recording media such as CD-ROMs can be provided at low cost.

[Structure of the Invention] (Means for Solving the Problems) The present invention provides an inexpensive CD or CD-ROM information recording medium with excellent oxidation resistance and adhesion to resin.
This is achieved by the following means. That is, this is a method in which a reflective film is made of a phthalocyanine dye that has good adhesion to a transparent resin substrate, and the film is formed using a typical coating device such as a spin coater without using large equipment such as a vapor deposition device or a sputtering device.

First, the first invention is an information recording medium in which information is recorded as a groove or a bit-like uneven pattern, and a phthalocyanine dye such as phthalocyanine or naphthalocyanine is coated on the information recording surface of a transparent resin substrate to which information is imparted. An information recording medium characterized by forming a reflective film layer using the above-mentioned reflective film.

Next, the second invention is an information recording medium characterized in that the phthalocyanine dye used in the reflective film layer 9 is represented by the following general formula [1].

(Left below) [In the formula, rings A1 to A4 each independently represent a benzene ring,
Represents a naphthalene ring or anthracene ring.

M represents AI, Ga, in, St, Ge or Sn, and X may be the same or different.

Alkyl group which may have a substituent, aryl group which may have a substituent, heterocyclic residue which may have a substituent, halogen atom, nitro group, cyano group, sulfonic acid group, -OR
'-3R', -COOR', -NR'R'
, -5Ox NR'R' , C0NR" R
'.

CHt NHCOCHz NR”R”, NHCO
6 R' representing "R", -N=NR13, -N=CHR"
R'', R3, R4, R5, R6R', R11, R9R1
+1 and Rl may be the same or different and represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group, an acyl group, a cycloalkyl group, or a polyether group. or with R6 and R″
R1 and R9 or Rlo and R may form a 4- to 7-membered ring, and these 4- to 7-membered rings may be a heterocycle containing a heteroatom such as a nitrogen atom. . R”,
R'3 and R14 may be the same or different and represent an alkyl group, a cycloacrylic group, or an aryl group that may have a substituent. Y is a hydrogen atom, a halogen atom, or a hydroxyl group.

An alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, -05iRISR1&R'7 or 10PR"R". RIs, R16, RI? , RI8OyobiR
``represents an alkyl group, aryl group, or acyl group that may be the same or different and may have a substituent.

Cycloalkyl group, alkoxy group, aryloxy group.

Represents a polyether group, hydroxyl group, or halogen atom.

k, 1. m and n each independently represent an integer of 0 to 8. p represents an integer of 1 or 2. ] The transparent substrate used in the present invention preferably has a light transmittance of 85% or more for signal reading and has small optical anisotropy. For example, acrylic resin, polycarbonate resin.

Polyester resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, polystyrene resin, polyolefin resin (poly-4-methylpentene, etc.).

Examples include substrates made of thermoplastic resins such as polyether sulfone resins, thermosetting resins such as epoxy resins, and allyl resins. Among these, ease of molding.

Particularly preferred are acrylic resins and polycarbonate resins from the viewpoint of ease of imparting signals, optical properties, and mechanical properties.

In addition, the signal can be applied using a stamper or the like when molding the thermoplastic resin (injection molding, compression molding), or
Alternatively, a so-called 2P method using a photopolymer is preferred.

In the present invention, the method for forming the phthalocyanine dye used in the reflective film 1 includes a wet process, such as a spin code method, a date coating method, a roll coating method, or an LB (
(Langmuir-Blodgett) method, etc.If the phthalocyanine dye used for the zero-reflection film is soluble in general-purpose organic solvents (alcohol, ketone, cellosolve, halogenated hydrocarbon, etc.), It is preferable to form a film using the spin code method. When forming a film using the so-called coating method, a polymer binder may be added as necessary. Examples of the polymer binder include vinyl chloride resin, acrylic resin, etc. resin, polyester resin, polyamide resin, polycarbonate resin, epoxy resin.

Examples include methacrylic resin, vinyl acetate resin, nitrocellulose, ferrite, and nol resin. When using a polymer binder, the ratio of the polymer binder to the organic dye system is preferably 10% by weight or less. It is also possible to use a dry process, such as a vacuum evaporation method or a sputtering method. Further, an overcoat layer may be provided on the second reflective film to protect the reflective film from chemical deterioration (for example, water absorption, etc.) and physical deterioration (for example, scratches, scratches, etc.). A method using a UV curable resin as the overcoat material is common, but the method is not limited to this.

The present invention will be specifically explained below with reference to examples, but the present invention is not limited to the following examples. [Example 1] CD formatting by 2P method using a stand bar and UV curable resin A naphthalocyanine compound represented by formula [2] was dissolved in dichloroethane as a reflective film on a polycarbonate resin substrate having a thickness of 1.2 mm, an outer diameter of 120 mm, and an inner diameter of 15 mm, onto which the signal was transferred.

The zero-order film was formed using a spin code method with a film thickness of 740,
A protective layer was provided on top of this using a UV curable resin to produce a CD optical disc.

The reflectance of the CD optical disc thus manufactured at 780 nm when incident on the substrate surface was 72%.

A reflectance of 70% or more, which is the standard for CDs, was obtained.

In addition, the signal from this CD optical disc was played using a commercially available CD player at a linear velocity of 1.3 m/sec and a reproduction laser output of 0.
．． When reproduction was performed at 5 mW, the reproduced signal obtained was good.

(The following is a blank space) [Example 2] A reflective film as shown in formula 1 [3] was formed on a polycarbonate resin substrate with a thickness of 1.2 mm and an inner diameter of 15 mm onto which a CD formant signal was transferred by injection molding using a stand bar. A film thickness of 800 mm is obtained by vacuum deposition of phthalocyanine compound.
After the film was formed manually, a protective layer was provided thereon using a UV curable resin to produce a CD optical disc.

The reflectance of the CD optical disc thus produced at 780 nm when incident on the substrate surface was 74%.

A reflectance of 70% or more, which is the standard for CDs, was obtained.

Further, when the signal from this CD optical disc was reproduced using a commercially available CD player at an &I speed of 1.3 m/sec and a reproduction laser output of 0.5 mW, the reproduction signal obtained was good.

[Example 3] A phthalocyanine compound represented by formula 2 [4] was deposited as a reflective film on a polycarbonate resin substrate with a thickness of 7.2 mm and an inner diameter of 15 mm, onto which a CD format signal was transferred by injection molding using a stand bar, by vacuum evaporation. After forming a film with a thickness of 860 layers, a protective layer was provided thereon using a UV curable resin to produce a CD optical disc.

The reflectance of the CD optical disc thus produced at 780 nm when incident on the substrate surface was 71%.

A reflectance of 70% or more, which is the standard for CDs, was obtained.

In addition, the signal from this CD optical disc was played using a commercially available CD player at a linear velocity of 1.3 m/sec and a reproduction laser output of 0.
．． In addition, Example 1 was obtained when regeneration was performed at 5 mW. Example 2. In order to examine the adhesion of the CD optical disk obtained in Example 3, a cross-cut cellophane tape peeling test was conducted at 10 locations, and no peeling was observed in any of the cases.

Also, Example 1. Example 2. In order to examine the storage stability of the CD optical discs obtained in Example 3, they were stored for 3000 hours in an environment with a temperature of 70°C and a humidity of 90%, and the signals of these CD optical discs were recorded using a commercially available CD player.
When reproduction was performed at a linear velocity of 1.3 m/sec and a reproduction laser output of 0.5 mW, reproduction signals equivalent to those before storage in the environment were obtained in both cases.

[Effects of the Invention] The tank bottom of the present invention makes it possible to provide an inexpensive CD or CD-ROM that is highly stable against oxidation and the like.

Claims (1)

[Claims] 1. In an information recording medium in which information is recorded as a pattern of grooves or pits, a reflective film layer using a phthalocyanine dye is provided on the information recording surface of a transparent resin substrate to which information is provided. An information recording medium characterized by being formed. 2. The information recording medium according to claim 1, wherein the phthalocyanine dye used in the reflective film layer is represented by the following general formula [1]. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, rings A1 to A4 are each independently a benzene ring,
Represents a naphthalene ring or anthracene ring. M represents Al, Ga, In, Si, Ge or Sn. X may be the same or different, and is an alkyl group that may have a substituent, an aryl group that may have a substituent, a heterocyclic residue that may have a substituent, Halogen atom, nitro group, cyano group, sulfonic acid group, -OR^1, -
SR^2, -COOR^3, -NR^4R^5, -SO
_2NR^6R^7, -CONR^8R^9, -CH_
2NHCOCH_2NR^1^0R^1^1, -NHC
OR^1^2, -N=NR^1^3, -N=CHR^1
Representing ^4, R^1, R^2, R^3, R^4, R^5
, R^6, R^7, R^8, R^9, R^1^0 and R^1^1 may be the same or different from each other, and have a hydrogen atom and a substituent. represents an optional alkyl group, aryl group, acyl group, cycloalkyl group or polyether group, or R^6 and R^7 represent R^8
and R^9, or R^1^0 and R^1^1, 4
R^1^2, R^1^3 and R^ may form ~7-membered rings, and these 4- to 7-membered rings may be heterocycles containing heteroatoms such as nitrogen atoms. 1^4 represents an alkyl group, a cycloacryl group, or an aryl group, which may be the same or different and may have a substituent. Y is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, -OSiR^
1^5R^1^6R^1^7 or -OPR^1^8R
Represents ^1^9. R^1^5, R^1^6, R^1^7
, R^1^8 and R^1^9 may be the same or different from each other and are an alkyl group, an aryl group, an acyl group, a cycloalkyl group, an alkoxy group, an aryloxy group which may have a substituent. group, polyether group, hydroxyl group, or halogen atom. k, l, m and n each independently represent an integer of 0 to 8; p represents an integer of 1 or 2; ]