JP2007293975A - Optical disk substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical disk having a low water absorption and small change of a tilt by environmental change. <P>SOLUTION: In the optical disk which has: a support substrate; a reflection layer formed on the support substrate; and a light transmissible cover layer formed on the reflection layer and comprising a curing resin, wherein a laser beam is made incident from the cover layer side to perform recording and reproduction, and the support substrate is formed by compounding 0.5 to 10 pts.wt. polycaprolactone to 100 pts.wt. polycarbonate resin having a specified recurring unit, and using a thermoplastic resin having ≤0.3% saturated water absorption measured by immersion in water at 23°C. When the optical disk is exposed to a hot and humid environment at 30°C and 95% humidity until a saturated water absorption is attained and then returned in a normal temperature and humidity state at 23°C and 50% humidity, the change of the warpage angle of the optical disk is within 0.9°. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a molding material for an optical disc substrate, an optical disc substrate molded from the material, and an optical disc formed therefrom. Furthermore, it comprises a support substrate, a reflective layer formed on the substrate, and a light-transmitting cover layer made of a curable resin formed on the reflective layer. In the optical disk of the system for performing reproduction, the support substrate is made of a thermoplastic resin composition made of a polycarbonate resin and polycaprolactone, and the resin has a low water absorption, and the above structure made of the support substrate The present invention relates to an optical disk substrate for a support substrate, characterized in that there is little warpage change due to environmental changes. In particular, the present invention relates to an optical disk substrate for a support substrate in a high density optical disk having a very large recording capacity.

  The recording density of optical discs is continuously improving from 0.6 GB for CD to 4.7 GB for DVD and 15 to 25 GB for BD and HD-DVD. For example, the capacity of 4.7 GB is realized in DVD-R, DVD-RW, and DVD-RAM that can be recorded / reproduced as well as a read-only DVD-ROM. Also, Blu-ray Disc (hereinafter referred to as BD) and HD-DVD, which are recording media compatible with digital high-definition broadcasting, realize 15 to 25 GB.

  Conventionally, a polycarbonate resin (hereinafter referred to as PC-A) obtained by reacting a carbonate precursor with 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) is transparent, heat resistant, mechanical It has been widely used in many fields as an engineering plastic because of its excellent characteristics and dimensional stability. Furthermore, in recent years, utilization of the transparency as an optical material in the fields of optical discs, optical fibers, lenses and the like has been developed, and in particular, in the field of optical discs, it is widely used as a material for information recording medium substrates.

  However, it has been an important issue that an optical disk substrate is small in deformation due to environmental changes (for example, moisture absorption and dehumidification processes). In particular, in the BD, in order to realize a large capacity with an optical disc of almost the same size as a CD or DVD, the thickness of the light-transmitting cover layer is reduced to about 0.1 mm, and the NA is about 0.85. The laser wavelength is set to about 400 nm. The reason why the light-transmitting cover layer is made thin is that the thinner the recording / reproducing side substrate, the larger the allowable value of the warp angle (hereinafter referred to as tilt) of the disc, and the NA is about 0.85. When the wavelength of the light is about 400 nm, it is said that the allowable value of tilt can be made the same as that of DVD by setting the light-transmitting cover layer to about 0.1 mm. However, by maintaining the thickness of the optical disk at 1.2 mm in order to maintain compatibility with the DVD, the signal recording layer is sandwiched between the 0.1 mm light-transmitting cover layer and the 1.1 mm support substrate. An optical disc configuration. Since the disk configuration is asymmetrical, environmental changes, especially moisture absorption, moisture absorption difference and dehumidification rate difference (or difference in water absorption expansion coefficient due to different materials) in the moisture absorption and dehumidification process become large, and a large tilt change Occurs, which greatly affects the recording / reproducing characteristics. For example, since the wavelength of the laser is shortened and the pickup lens has a high NA, coma aberration increases even if the substrate is warped, causing a focus error and a tracking error. In addition, since the distance between the pickup lens and the substrate approaches as the NA increases, it is important that the warpage change due to the substrate warpage and the environmental change is small in order to avoid contact between the lens and the substrate. In particular, when the vehicle is in operation, the room temperature is high and the humidity is low. Therefore, a rapid change is likely to occur, and a focus error such as a signal being unreadable due to disk deformation is likely to occur.

  In order to suppress such deformation due to environmental changes, in order to suppress water absorption deformation, it has “a substrate, a recording layer arranged on this substrate for recording information signals, and a transparent protective layer laminated on the recording layer. , A disc-shaped information recording medium for recording / reproducing information signals by making light incident from the transparent protective layer side. This substrate is integrated with a resin core layer and a core layer, Is an information recording medium characterized in that the recording layer side has irregularities in the information signal on the surface of the recording layer, and is composed of a resin surface layer that is more fluid than the core layer. A substrate using a resin with a rate of 0.3% or less has been proposed, and a direction to solve the problem by a complicated substrate configuration by two-color molding or sandwich molding is shown. (For example, refer to Patent Document 1) Further, it includes a support substrate, a reflective layer formed on the substrate, and a light-transmitting cover layer formed on the reflective layer, and laser light is incident from the cover layer side. In an optical disc of a recording and / or reproducing type, a method of suppressing the moisture absorption amount by forming a moisture absorption preventing film on the main surface of a support substrate has been proposed. (For example, refer to Patent Document 2) At that time, the moisture absorption preventing film is formed in an island shape or a donut shape, and the size of the inner diameter is optimized, whereby the recording / reproducing side substrate and the base material are formed. Balances expansion due to moisture absorption. Thus, it is said that tilt change due to moisture absorption can be suppressed, but the number of manufacturing steps is increased for forming a moisture absorption preventing film. Further, it has been proposed to suppress a change in warp due to an environmental change by using a material having a low saturated water absorption rate for the thermoplastic resin used for the support substrate. In particular, it has been proposed to use an alloy of polycarbonate resin and polycaprolactone as a substrate material for optical disks. (For example, Patent Documents 3, 4, 5, 6, and 7) In Patent Document 3, 1) 0.1 to 40 parts by weight of a biphenyl terphenyl compound with respect to 100 parts by weight of a polycarbonate resin, and 2) a number average molecular weight of 2 A method has been proposed in which 0 to 20 parts by weight of polycaprolactone of 1,000,000 to 100,000 is added to improve the rigidity of the substrate material and to reduce the saturated water absorption rate, thereby suppressing warpage during the molding of the substrate. . In the material, the heat resistance is greatly reduced by adding a low molecular weight compound, and thus the change in warp becomes large in an environmental change, particularly in a high temperature state such as in an automobile interior. Moreover, in patent document 4, resin for optical disk substrates formed by mixing 50 to 5 parts by weight of a styrene polymer with a thermoplastic resin comprising 80 to 98 parts by weight of a polycarbonate resin and 20 to 2 parts by weight of polycaprolactone. Proposed. However, the purpose of this proposal is to reduce the birefringence of the optical disk by adding a styrene polymer. Furthermore, the heat resistance is reduced by adding the styrene resin, and thus the warpage change is increased in an environmental change, particularly in a high temperature state such as an automobile room. In Patent Document 5, two optical disk substrate resins containing 200 to 10,000 ppm of polycaprolactone having a number average molecular weight of 10,000 to 50,000 per 100 parts by weight of polycarbonate resin may be bonded. Proposed. Since the disk configuration is symmetric, the change in environment, especially the difference in moisture absorption and dehumidification rate in moisture absorption and dehumidification processes (or the difference in water absorption expansion due to different materials) becomes equivalent, and the tilt change can be suppressed. No mention is made of an asymmetrical optical disc. Furthermore, since the water absorption rate does not decrease with the blending amounts used in the examples, it is not expected to improve the warp change due to environmental changes in an asymmetric optical disk. Patent Document 6 proposes a resin composition obtained by blending 0.1 to 50 parts by weight of polycaprolactone having a number average molecular weight of 5,000 to 10,000 with respect to 100 parts by weight of a polycarbonate resin. The material has been studied for the purpose of improving the releasability by improving the adhesion to metal, and the warpage change of the environmental change has not been studied. Further, in Patent Document 7, A) 0.1 to 20 parts by weight of a sulfonic acid phosphonium salt, B) 0.1 to 1 part by weight of a phosphite, and 0.01 to 0.01% of a sulfur-containing ester with respect to 100 parts by weight of a polycarbonate resin. A resin composition comprising 3 parts by weight, C) 0.1 to 10 parts by weight of a caprolactone polymer has been proposed. The material has been studied for the purpose of improving the retention stability by adding a heat stabilizer and preventing coloration by adding polycaprolactone, but when applied to an optical disk, it is a phosphonium sulfonate salt that is an antistatic agent during molding. Adheres to the mold and causes poor appearance of the molded product, resulting in a decrease in yield.

  As described above, any of the methods specifically shown shows good characteristics as an optical disk with a small warp change due to the environment, but it is not always sufficient. In addition, various studies have been made by using an alloy material of polycarbonate resin and polycaprolactone for the optical disk substrate material, but no study has been conducted to suppress the warpage change due to environmental changes, and this is a new concept. I can say that.

JP 2000-11449 A JP 2003-173571 A JP 2000-195099 A JP-A 63-90555 JP-A-9-332781 JP-A-7-102166 JP-A-9-194711

An object of the present invention is to solve the above-mentioned problems and to provide an optical disk molding material made of a thermoplastic resin having low water absorption and an optical disk formed from the material and less deformed due to environmental changes.
As a result of intensive research on optical disk substrate materials in order to achieve the above object, the present inventor used a molding material for optical disk substrates consisting of a specific polycarbonate resin and polycaprolactone and having a saturated water absorption of 0.3% or less. The optical disk substrate and the optical disk formed in this manner have been found to have little warpage change due to moisture absorption and dehumidification processes, and the present invention has been achieved.

Hereinafter, the present invention will be described in detail.
A support substrate, a reflective layer formed on the substrate, and a light-transmitting cover layer made of a curable resin formed on the reflective layer, and recording and / or recording with laser light incident from the cover layer side Alternatively, it is a supporting substrate in an optical disc of a reproduction type, and the supporting substrate contains 0 polycaprolactone with respect to 100 parts by weight of a polycarbonate resin having at least one repeating unit represented by the following formula [1] as a repeating unit. 0.5 to 10 parts by weight and a support substrate formed using a thermoplastic resin having a saturated water absorption measured by immersion in water at 23 ° C. of 0.3% or less, and the temperature of the optical disk The change in the warp angle of the optical disk when the saturated water absorption is reached in a humid heat environment of 30 ° C. and a humidity of 95% is returned to normal humidity at a temperature of 23 ° C. and a humidity of 50%. It is an optical disk substrate for supporting the substrate, characterized in that is within degrees.

［式中、Ｒ^１及びＲ^２はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２０のシクロアルキル基、炭素数６〜２０のシクロアルコキシ基、炭素数６〜１０のアリール基、炭素数７〜２０のアラルキル基、炭素数６〜１０のアリールオキシ基、および炭素数７〜２０のアラルキルオキシ基からなる群より選ばれる基を表し、Ｒ^１及びＲ^２が複数ある場合はそれぞれ同一若しくは異なっていてもよく、ｍ及びｎは夫々１〜４の整数であり、Ｗは下記式［２］で表される構造単位である。

（Ｒ^３、Ｒ^４はそれぞれ独立して、水素原子または炭素数１〜１０の炭化水素基を表し、Ｒ^５及びＲ^６はそれぞれ独立して水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^５及びＲ^６が複数ある場合はそれぞれ同一もしくは異なっていてもよく、ｐは４〜１２の整数、Ｒ^７及びＲ^８はそれぞれ独立して水素原子、ハロゲン原子又は炭素数１〜３のアルキル基を表す。）］

[Wherein, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or a carbon number. From the group consisting of a 6-20 cycloalkoxy group, an aryl group having 6-10 carbon atoms, an aralkyl group having 7-20 carbon atoms, an aryloxy group having 6-10 carbon atoms, and an aralkyloxy group having 7-20 carbon atoms. In the case where a plurality of R ¹ and R ² are present, they may be the same or different, m and n are each an integer of 1 to 4, and W is a structure represented by the following formula [2] Unit.

(R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. , R ⁵ and R ⁶ may be the same or different from each other, p is an integer of 4 to 12, R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 3 Represents an alkyl group.)]

  According to the present invention, the content of polycaprolactone is 0.5 to 10 parts by weight with respect to 100 parts by weight of the polycarbonate resin, more preferably 1 to 9 parts by weight, and even more preferably 2 to 8 parts by weight. 3 to 7 parts by weight is most preferable. In that case, a thermoplastic resin having a satisfactory saturated water absorption rate and good melt fluidity, and an optical disk substrate and an optical disk formed therefrom are provided. When the proportion of polycaprolactone is less than 0.5 parts by weight, the saturated water absorption is hardly lowered, and when it is more than 10 parts by weight, the glass transition temperature is lowered and the heat resistance is lowered.

［式中、Ｒ^１及びＲ^２はそれぞれ独立して水素原子、および炭素数１〜５のアルキル基からなる群より選ばれる基を表し、Ｒ^１及びＲ^２が複数ある場合はそれぞれ同一若しくは異なっていてもよく、ｍ及びｎは夫々１〜２の整数であり、Ｗは下記式［４］で表される構造単位である。

（Ｒ^３、Ｒ^４はそれぞれ独立して、水素原子または炭素数１〜５の炭化水素基を表し、Ｒ^５及びＲ^６はそれぞれ独立して水素原子又は炭素数１〜２のアルキル基を表し、Ｒ^５及びＲ^６が複数ある場合はそれぞれ同一もしくは異なっていてもよく、ｐは４〜８の整数、Ｒ^７及びＲ^８はそれぞれ独立して水素原子、炭素数１〜３のアルキル基を表す。）］
で表される繰り返し単位を少なくとも１種類有するポリカーボネート樹脂からなることが好ましく、前記一般式［１］が２，２−ビス（４−ヒドロキシフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン、４，４’−（ｍ−フェニレンジイソプロピリデン）ジフェノール及び９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンから選ばれる少なくとも一種から誘導された繰り返し単位であるポリカーボネート樹脂であることがさらにより好ましい。特に２，２−ビス（４−ヒドロキシフェニル）プロパンより誘導される繰り返し単位であるポリカーボネート樹脂、若しくは４，４’−（ｍ−フェニレンジイソプロピリデン）ジフェノール及び９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンより誘導される繰り返し単位であり、その構成比が１０：９０〜９０：１０の範囲（モル比）であるポリカーボネート樹脂であることが好ましい。更にその構成比が３０：７０〜７０：３０の範囲（モル比）であるポリカーボネート樹脂であることがより好ましい。 The polycarbonate resin contained in the thermoplastic resin composition of the present invention is represented by the following formula [3].

[Wherein, R ¹ and R ² each independently represent a hydrogen atom and a group selected from the group consisting of alkyl groups having 1 to 5 carbon atoms, and when there are a plurality of R ¹ and R ² , they are the same or different, respectively. M and n are each an integer of 1 to 2, and W is a structural unit represented by the following formula [4].

(R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. , R ⁵ and R ⁶ may be the same or different, p is an integer of 4 to 8, R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. To express.)]
Preferably, the general formula [1] is 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl). Cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4 ′-(m-phenylenediisopropylidene) diphenol and 9,9-bis (4-hydroxy-3) Even more preferred is a polycarbonate resin which is a repeating unit derived from at least one selected from -methylphenyl) fluorene. In particular, polycarbonate resins which are repeating units derived from 2,2-bis (4-hydroxyphenyl) propane, or 4,4 ′-(m-phenylenediisopropylidene) diphenol and 9,9-bis (4-hydroxy) It is preferably a polycarbonate resin which is a repeating unit derived from -3-methylphenyl) fluorene and whose constitution ratio is in the range (molar ratio) of 10:90 to 90:10. Further, the polycarbonate resin is more preferably in the range of 30:70 to 70:30 (molar ratio).

  The polycaprolactone contained in the thermoplastic resin composition of the present invention preferably has a number average molecular weight of 5,000 to 100,000, more preferably 7,000 to 50,000, Most preferably, it is 000-30,000.

  The glass transition temperature of the thermoplastic resin composition of the present invention is preferably 110 ° C to 180 ° C, more preferably 120 ° C to 170 ° C, and further preferably 130 ° C to 160 ° C. When the glass transition temperature is lower than 110 ° C., the heat resistance is insufficient in the environment inside the automobile and thermal deformation occurs, which is not preferable. On the other hand, if the glass transition temperature is higher than 180 ° C., the melt fluidity is poor and a molding defect is caused, and the precision transferability to the mold becomes inferior.

  The glass transition temperature was measured using DSC-2910 (trade name: DSC2910, manufactured by TA Instruments) in accordance with differential scanning calorimetry (DSC) defined in JIS K7121. The measurement conditions are a heating rate of 20 ° C./min, a nitrogen flow rate of 40 ml / min, and a measurement temperature of 20 ° C. to 250 ° C.

The thermoplastic resin composition of the present invention is preferably at least ^{5 cm} 3/10 min is the value of MVR, more preferably 20 cm ^3/10 minutes or more, still more preferably at least 30 cm ^3/10 min. And 70 cm < ³ > / 10 minutes or more is the most preferable. The upper limit of the value of such MVR is preferably 100 cm ^3/10 min, more preferably 90cm ^3/10 minutes.

  If this range is exceeded, the transfer rate in forming the optical disk substrate will be affected. That is, the transfer rate is lowered and the moldability of the optical disk substrate is impaired. Further, it is not preferable because a focus error and a tracking error are likely to occur.

The melt volume rate (MVR) was measured using a semi-auto melt indexer (trade name: L251, manufactured by Toyo Seiki Co., Ltd.) having an orifice (die) having a length and a diameter defined in ISO1133. The measurement conditions are a test temperature of 300 ° C., a test load of 11.77 N (1.2 kgf), the time of a sample passing through a certain section is measured, and the flow rate (capacity) per unit time is calculated, and the unit is cm It is shown in ^3/10 minutes.

  The thermoplastic resin provided in the present invention has a saturated water absorption measured by immersion in water at 23 ° C. of 0.3% or less, and more preferably 0.25% or less. If the saturated water absorption exceeds 0.3%, it is not preferable because warpage of the optical disk is likely to change during the moisture absorption and dehumidification process, and a focus error and a tracking error are likely to occur.

This saturated water absorption was measured by the rate of change in weight due to immersion in water at 23 ° C. as defined in ASTM D570. That is, this measurement sample was molded with a circular mold having a diameter of 45 mm and a thickness of 30 mm (vacuum press molding machine (manufactured by Shin-Fuji Metal Industry Co., Ltd., product name: SFV-10), mold temperature 300 ° C., primary pressure 0.5 MPa, After melting at a holding time of 1.5 minutes, compression was performed at a secondary pressure of 1.5 MPa and a holding time of 5 minutes). This was dried at 120 ° C. for 4 hours or more and weighed to obtain an initial weight (W ₀ ). Then, it was immersed in water at 23 ° C., taken out from the water every 24 hours, weighed after removing water, and the water absorption was calculated by the following formula. Water absorption rate = {(measured weight every 24 hours) −W ₀ } / W ₀ × 100 (%)

  The change in warpage in the process of moisture absorption and dehumidification of the optical disk was transferred to the environment of 23 ° C. and humidity 50% RH after the disk was exposed to reach the saturated water absorption rate in the environment of temperature 30 ° C. and humidity 90% RH. This is a comparison of the difference (Δtilt) between the maximum value of the tilt change at 58 mm from the center and the value when the steady state is reached. At this time, the Δtilt is within 0.9 degrees, preferably within 0.75 degrees, and more preferably 0.5 degrees or less.

  This measuring method is as follows. A protection film formed by sputtering a reflective film on the signal surface side of an optical disk substrate having a diameter of 120 mm and a thickness of 1.1 mm, and then adjusting the ultraviolet curable resin with a coating thickness of 100 μm by a spin coater and then irradiating with ultraviolet rays. The optical disk with the film is sandwiched between the spacers and left in a temperature 23 ° C, humidity 50% RH environment for 2 days or more, then measured periodically every 12 hours. The rate of change before and after radial tilt is 5% or less. At that time, the radial tilt was evaluated with a three-dimensional shape measuring instrument DLD-3000U manufactured by Japan EM Co., Ltd. to obtain an initial radial tilt (measured 58 mm from the center of the optical disk substrate). Next, the optical disk for which the initial radial tilt was evaluated was left for 72 hours in a constant temperature and humidity chamber at 30 ° C. and a humidity of 90% RH. Thereafter, the optical disk was moved to an environment of 23 ° C. and humidity 50% RH, and the radial tilt of the optical disk was measured with the above apparatus over time (every 30 minutes). The value indicating the maximum value of the measured values obtained was taken as the maximum value of radial tilt. The difference between the measured maximum value of the radial tilt and the initial radial tilt was taken as Δradial tilt.

  When preparing the thermoplastic resin of this invention, arbitrary methods are employ | adopted. For example, after mixing polycarbonate resin and polycaprolactone into a mixed solution, the solvent is distilled off, the solvent is distilled off and then melted into pellets using a vent-type extruder, or the polycarbonate resin and polycaprolactone are mixed into a super mixer or tumbler. A method of mixing with a Nauta mixer or the like and pelletizing with a twin screw ruder or the like is used. Moreover, additives, such as a stabilizer, antioxidant, a light stabilizer, a coloring material, a sliding material, a mold release agent, can also be added as needed. Furthermore, in the extrusion process (pelletizing process) for obtaining a pellet-like polycarbonate resin for use in injection molding, compression molding, and injection compression molding, foreign matters are removed by passing through a sintered metal filter having a filtration accuracy of 10 μm in the molten state. Is preferred. In any case, it is necessary for the raw material resin before injection molding to keep the content of foreign matters, impurities, solvents, etc. as low as possible.

  If necessary, the thermoplastic resin composition forming the support substrate is blended with at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, and esters thereof. be able to. The amount of the phosphorus compound is preferably 0.0001 to 0.05% by weight, more preferably 0.0005 to 0.02% by weight, and 0.001 to 0.01% by weight in the thermoplastic resin composition. Particularly preferred. By blending this phosphorus compound, the thermal stability of the thermoplastic resin composition is improved, and a decrease in molecular weight and a deterioration in hue during molding are prevented.

［式中、Ｒ^９〜Ｒ^２２は、それぞれ独立して、水素原子、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ドデシル、ヘキサデシル、オクタデシルなどの炭素原子数１〜２０のアルキル基、フェニル、トリル、ナフチルなどの炭素原子数６〜１５のアリール基またはベンジル、フェネチルなどの炭素原子数７〜１８のアラルキル基を表し、また１つの化合物中に２つのアルキル基が存在する場合は、その２つのアルキル基は互いに結合して環を形成していてもよい。］
よりなる群から選択された少なくとも１種のリン化合物である。 The phosphorus compound is at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, and esters thereof, preferably the following general formula

[Wherein, R ^{9 to} R ²² are each independently a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl. Represents an alkyl group having 1 to 20 carbon atoms such as octadecyl, an aryl group having 6 to 15 carbon atoms such as phenyl, tolyl and naphthyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl and phenethyl; When two alkyl groups are present in one compound, the two alkyl groups may be bonded to each other to form a ring. ]
At least one phosphorus compound selected from the group consisting of:

  Examples of the phosphorus compound represented by the above formula [5] include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, and trioctyl phosphite. , Trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, and the like.

  Examples of the phosphorus compound represented by the above formula [6] include tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like. Examples of the phosphorus compound represented by the above formula [7] include tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite. Examples of the compound represented by the formula [8] include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like. Examples of the compound represented by the formula [9] include bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butyl). Phenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.

  Among these phosphorus compounds, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylene Phosphonite is preferably used.

Furthermore, higher fatty acid esters of mono- or polyhydric alcohols of 1 ppm or less of sodium metal can be added to the thermoplastic resin composition of the present invention as necessary.
The higher fatty acid ester having 1 ppm or less of sodium metal is preferably a partial ester or total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Further, partial esters or total esters of such monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, propylene glycol. Examples thereof include monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate and the like. Of these, stearic acid monoglyceride and pentaerythritol tetrastearate are preferably used. The compounding amount of the ester of the alcohol and higher fatty acid is preferably 0.01 to 2% by weight, more preferably 0.015 to 0.5% by weight, and 0.02 to 0.2% by weight in the thermoplastic resin composition. % Is more preferable. If the blending amount is within this range, it is preferable that the release property is excellent and the release agent does not migrate and adhere to the metal surface. On the other hand, when the sodium metal content exceeds 1 ppm, the manufactured disk substrate deteriorates in hue, and the quality deteriorates due to an increase in white defects due to hydrolysis of PC.

  To the thermoplastic resin composition of the present invention, an antioxidant generally known for the purpose of preventing oxidation can be added. Examples thereof include phenolic antioxidants, specifically, for example, triethylene glycol-bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate), 1,6 -Hexanediol-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl) -4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydride) Cinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis {1 , 1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, etc. Is mentioned. The range of the preferable addition amount of these antioxidants is 0.0001 to 0.05 weight% in a thermoplastic resin composition.

  When manufacturing an optical disk substrate from the thermoplastic resin composition, an injection molding machine (including an injection compression molding machine) is used. Although generally used as this injection molding machine, from the viewpoint of suppressing the generation of carbides and improving the reliability of the disk substrate, the adhesion to the resin as a cylinder or screw is low, and the corrosion resistance and resistance It is preferable to use a material made of a material that exhibits wear.

  As conditions for injection molding, the cylinder temperature is preferably 260 to 450 ° C, more preferably 280 to 380 ° C, and the mold temperature is preferably 50 to 180 ° C, more preferably 70 to 135 ° C. Can be obtained.

  The environment in the molding process is preferably as clean as possible in view of the object of the present invention. It is also important to take into consideration that the material used for molding is sufficiently dried to remove moisture, and that no retention that causes decomposition of the molten resin occurs.

  In the optical disk substrate of the present invention, it is necessary to form a reflective layer and / or a recording layer on one side. As a method for producing the inorganic thin films of the recording layer and the reflective layer, various thin film forming methods such as a known vacuum deposition method, PVD method such as sputtering method, or CVD method can be applied. However, it is preferable that the optical disk medium is manufactured under conditions where adhesion to the polymer substrate is particularly high in order not to cause peeling that occurs in a high temperature and high humidity environmental resistance test. For this purpose, sputtering is preferred.

  Further, a light transmissive cover layer is formed on the reflective layer and / or the recording layer. As a method of forming a light-transmitting cover layer, an ultraviolet curable resin is dropped on the substrate, and the ultraviolet curable resin is applied to the entire substrate while rotating the substrate at a predetermined rotational speed by spin coating, and then irradiated with ultraviolet rays. Then, a method of curing the ultraviolet curable resin is used. At that time, it is difficult to produce a uniform thickness from the inner periphery to the outer periphery by the spin coating method, and the inner periphery tends to be thin and the outer periphery tends to be extremely thick. In order to prevent this, a method of producing a uniform light-transmitting layer by irradiating and curing ultraviolet rays while rotating at a higher speed than the coating rotation number after applying the ultraviolet curable resin can be mentioned. Furthermore, this light-transmitting cover layer is limited to a thickness of 3 to 200 μm in order to keep coma aberration considerably small. As the ultraviolet curable resin to be used, an ultraviolet curable resin using a (meth) acrylate-based material cured by a radical polymerization reaction, a cationic curable material using a material such as epoxy, vinyl ether, oxetane, or the like is used.

  The optical disk substrate of the present invention comprises a support substrate, a reflective layer formed on the substrate, and a light-transmitting cover layer formed by applying an ultraviolet curable resin on the reflective layer by spin coating and then curing the resin. Further, it is also suitably used as an optical disc of a type that performs recording and / or reproduction by entering laser light from the cover layer side, for example, a high-density optical disc substrate typified by a Blu-ray Disc (BD) or a hologram disc. In particular, in the case of Blu-ray Disc (recording type), it is created by forming a light reflecting layer, a recording layer consisting of a recording film and a recording film protective film, and a light transmissive cover layer on a 1.1 mm thick substrate. Is done. A plurality of these layers may be formed.

  In the case of a write-once optical disk, the recording film is a recording film on which a irreversible optical characteristic is changed or a concavo-convex shape is formed by irradiation with laser light. For example, the recording film is decomposed by heating by laser light irradiation, A cyanine-based, phthalocyanine-based, azo-based organic dye or the like that changes the optical constant and causes deformation of the substrate due to a volume change is used.

  In the case of a rewritable optical disc, the recording film is a material (phase change recording type) in which a reversible phase structure change between the amorphous state and the crystalline state of the substance caused by laser light irradiation, or perpendicular to the film surface This is a magnetic thin film (magneto-optical recording type) having a magneto-optic effect that has an easy magnetization direction in any direction and can record, reproduce, and erase information by creating an arbitrary inversion magnetic domain. Examples of the phase change recording film include GeSbTe, InSbTe, InSe, InTe, AsTeGe, TeOx-GeSn, TeSeSn, FeTe, SbSeBi, and BiSeGe that are chalcogenide materials. Although it is used, a film made of GeSbTe is preferable because of its stable operation during repeated recording / erasing. Examples of magneto-optical recording films include amorphous alloy thin films of rare earth elements and transition metal elements such as TbFe, TbFeCo, GdTbFe, NdDyFeCo, NdDyTbFeCo, NdFe, PrFe, and CeFe, and those utilizing exchange coupling. A two-layer film, an artificial lattice multilayer film such as Co / Pt or Co / Pd, or a CoPt alloy can be used.

In addition, it is preferable to use a dielectric material as the recording film protective film for sandwiching the recording film. Thereby, the difference in reflectance between the crystalline phase and the amorphous phase as a medium, and the magneto-optical effect can be enhanced. In this case, the dielectric material is preferably a material having a high refractive index n, that is, a material satisfying n ≧ 1.6, more preferably a material satisfying n ≧ 1.8. Eg, SiO-based, _{SiON-based, Ta 2 O 3, TiO 2} , Al 2 O 3, Y 2 O 3, CeO, La 2 O 3, In 2 O 3, GeO, GeO 2, PbO, SnO, SnO 2, Bi ₂ O ₃ , TeO ₂ WO ₂ , WO ₃ , Sc ₂ O ₃ , ZrO _{2 and} other oxides, nitrides such as TaN, AlN, SiN and AlSiN, ZnS, Sb ₂ S ₃ , CdS and In ₂ It is preferable to use a sulfide such as S ₃ , Ga ₂ S ₃ , GeS, SnS ₂ , PbS, Bi ₂ S ₃ , a mixed material thereof, a laminate thereof, or the like as the protective film.

  The light reflecting layer is preferably a material having higher reflectivity than the recording layer with respect to the laser beam of the drive head used for evaluation. Specifically, it is preferable to select a material in which the refractive index n and the extinction coefficient k, which are optical constants at the used laser light wavelength, satisfy n ≦ 3.5 and k ≧ 3.5. More preferably, n ≦ 2.5 and 4.5 ≦ k ≦ 8.5. With a medium manufactured under these conditions, the reproduction signal characteristics can be further improved.

  On the other hand, when recording a signal by heating with laser light, if the thermal conductivity of the light reflecting layer is too high, thermal diffusion is large and strong laser power is required. For this reason, in order to enable signal recording with a semiconductor laser having a power of 15 mW or less that is widely used at present, the thermal conductivity of the material used for the light reflection layer is 100 [W / (m · K)] or less. It is more preferable that it is 80 [W / (m · K)] or less.

As a material satisfying such conditions, one or more elements such as Au, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Tc, Re, Ru, Os, Ir, etc. as Al or Ag An alloy to which is added. In these alloys, if the amount of the additive element is less than 0.5 atomic%, the effect of the above-described decrease in heat conduction is small. This is disadvantageous. Therefore, the content of the additive element is preferably within the range of 0.5 to 20 atomic%. In particular, Ti, Zr, Hf, Ta, Cr, and Re are preferable in the specific element group in terms of enhancing durability of the metal reflective film itself. The film thickness range of these reflective layers is 10 to 500 nm, but preferably 30 to 200 nm, particularly in order to suppress the deterioration of the reproduction signal characteristics due to the decrease in reflectance and to enable recording at a laser power of 15 mW. Preferably it is 40-100 nm.
In the case of a read-only optical disc medium, only the light reflecting layer described above is formed on the substrate, but the same materials can be used.

  Since the thermoplastic resin composition comprising the specific polycarbonate resin and polycaprolactone of the present invention is excellent in low water absorption and moldability, the optical disk substrate, particularly an optical disk for a high-density optical disk, is small in warpage change due to environmental changes. It is suitably used as a substrate, and its industrial effect is exceptional. In particular, the result of signal characteristics (jitter value) after an environmental change of an optical disc using this optical disc substrate is very good, and it is clear that the optical disc is effective as an optical disc.

  Hereinafter, although an example is given and explained in detail, the present invention is not limited to this unless it exceeds the purpose. In the examples and comparative examples, “parts” is parts by weight. Evaluation was according to the following method.

(1) Glass transition temperature The glass transition temperature was measured using DSC-2910 (trade name: DSC2910, manufactured by TA Instruments) in accordance with differential scanning calorimetry (DSC) defined in JIS K7121. The measurement conditions are a heating rate of 20 ° C./min, a nitrogen flow rate of 40 ml / min, and a measurement temperature of 20 ° C. to 250 ° C. The measurement sample was weighed 4 to 8 mg, put in an aluminum sample pan, covered with a sample, and sealed with a press forming tool. The glass transition temperature is calculated from the obtained DSC curve (vertical axis: calorie (W / g), horizontal axis: temperature (° C)), a straight line equidistant from the extended straight line of each baseline in the vertical axis direction, and glass The temperature at the point where the curve of the step-like change part of the transition intersects was taken. The measured value was rounded off to the first decimal place.

(2) Fluidity (MVR)
Melt volume rate (MVR) was carried out using a semi-auto melt indexer (trade name: L251, manufactured by Toyo Seiki Co., Ltd.) having an orifice (die) having a length and a diameter defined in ISO1133. The measurement conditions are a test temperature of 300 ° C. and a test load of 11.77 N (1.2 kgf). As a measurement sample, a polycarbonate resin was melt-kneaded with an extruder and pelletized. At the apparatus, to measure the time of the sample that passes through a constant interval, to calculate the amount of flow per unit time (capacity), the unit is shown in cm ^3/10 min. The measured value was rounded off to the first decimal place.

(3) Saturated water absorption rate The water absorption rate was measured by the weight change rate by immersion in water at 23 ° C as defined in ASTM D570. As a measurement sample, a vacuum press molding machine (product name: SFV-10, manufactured by Shin-Fuji Metal Industry Co., Ltd.) was used, and pellets 5 to 5 in which a polycarbonate resin was melt-kneaded in an extruder with a diameter of 45 mm and a thickness of 30 mm 7 g was added, melted at a mold temperature of 300 ° C., a primary pressure of 0.5 MPa, and a holding time of 1.5 minutes, then compressed at a secondary pressure of 1.5 MPa and a holding time of 5 minutes, cooled to room temperature, and taken out from the mold. A molded product was used. The molded product dried at 120 ° C. for 4 hours or more is weighed to obtain an initial weight (W ₀ ). The molded product is immersed in water at 23 ° C., and the molded product is taken out from the water every 24 hours. After removing water adhering to the surface, the weight was weighed, and the water absorption was calculated by the following formula. Moreover, the value at which the change with time of the water absorption calculated by the following formula every 24 hours was less than 5% was defined as the saturated water absorption. The measured value was rounded off to the first decimal place.
Water absorption rate = {(measured weight every 24 hours) −W ₀ } / W ₀ × 100 (%)

(4) Initial radial tilt A spacer is put between the optical discs so that they do not come into contact with each other. After being left in an environment of 23 ° C. and humidity of 50% RH for 2 days or more, it is measured periodically every 12 hours. At the time of the following, radial tilt was evaluated by a three-dimensional shape measuring instrument DLD-3000U manufactured by Japan EM Co., Ltd., and an initial radial tilt was obtained.

(5) Maximum amount of radial tilt change (△ radial tilt)
The optical disk for which the initial radial tilt was evaluated was left for 72 hours in a constant temperature and humidity machine at 30 ° C. and a humidity of 90% RH. Thereafter, the optical disk was moved to an environment of 23 ° C. and humidity 50% RH, and the radial tilt of the optical disk was measured over time (every 30 minutes) with a 3D shape measuring instrument DLD-3000U manufactured by Japan EM Co., Ltd. . The difference (Δradial tilt) between the measured maximum value of radial tilt and the initial radial tilt was evaluated.

(6) Initial signal characteristics (initial jitter)
Jitter measurement was performed on an optical disc evaluated for initial radial tilt using ODU-1000 manufactured by Pulstec Industrial. The case where the measured jitter value was 6.5% or less was indicated by ◯, the value by 6.5 to 8.0% or less was indicated by Δ, and the value exceeding 8.0% was indicated by ×.

(7) Signal characteristics after environmental test (jitter after environmental change)
The optical disk for which the initial radial tilt was evaluated was left for 72 hours in a constant temperature and humidity machine at 30 ° C. and a humidity of 90% RH. Thereafter, the optical disk was moved to an environment of 23 ° C. and humidity 50% RH, and the radial tilt of the optical disk was measured over time (every 30 minutes) with a 3D shape measuring instrument DLD-3000U manufactured by Japan EM Co., Ltd. . Jitter measurement was performed with ODU-1000 manufactured by Pulstec Industrial Co., Ltd. using the disk having the maximum radial tilt value. The case where the measured jitter value was 6.5% or less was indicated by ◯, the value by 6.5 to 8.0% or less was indicated by Δ, and the value exceeding 8.0% was indicated by ×.

(8) Transferability The depth of the groove transferred from the stamper to the substrate was measured at a position with a radius of 40 mm using an atomic force microscope (SPI3800N manufactured by Seiko Denshi Kogyo). Transferability was determined by using a transfer rate represented by the following formula as an index, with transfer rates of 80% to 100% being ◯, 50% to less than 80% being Δ, and less than 50% being ×.
Transfer rate (%) = 100 × disc groove depth / stamper groove depth

[Example 1]
100 g of polycaprolactone (polycaprolactone H1P, manufactured by Daicel Chemical Industries, Ltd.) was added to 10 kg of polycarbonate resin (Teijin Chemicals, Panlite AD-5503) obtained from 2,2-bis (4-hydroxyphenyl) propane. And then dry blended and mixed uniformly. Subsequently, the composition was melt-kneaded while degassing at a cylinder temperature of 260 ° C. with a vented twin-screw extruder [KTX-46, manufactured by Kobe Steel Co., Ltd.] to obtain thermoplastic resin composition pellets. The pellet was measured for glass transition temperature, MVR, and saturated water absorption.

Next, the pellets were dried at a predetermined drying temperature (= glass transition temperature−20 ° C.) for 5 hours, and then a stamper was attached to an injection molding machine [SD-40E manufactured by Sumitomo Heavy Industries, Ltd.] An optical disk substrate having a diameter of 120 mmφ and a thickness of 1.1 mm was injection-molded at the described cylinder temperature and mold temperature. With a high frequency magnetron sputtering apparatus (ILC3102 type manufactured by Anelva) on the signal surface side of the obtained optical disk substrate, an Ag alloy sputtering target containing 5.0 atomic% Nd and 1.0 atomic% Bi was used with a discharge power of 500 W. A 100 nm thin film was deposited by DC sputtering. (Deposition conditions are substrate temperature: 22 ° C., argon gas pressure: 2 mTorr, film formation rate: 5 nm / sec, back pressure: <5 × 10 ⁻⁶ Torr.) Type epoxy acrylate 15 parts, polytetramethylene glycol (molecular weight 850) 1 mole and tolylene diisocyanate 2 moles were reacted with urethane ethyl acrylate 40 parts, tricyclodecane dimethanol diacrylate 19 Parts, tetrahydrofurfuryl acrylate 11 parts, 2-ethoxyethoxyethyl acrylate 10 parts, 1-hydroxycyclohexyl phenyl ketone 5 parts, IRGANOX 1520L (Ciba Specialty Chemicals Co., Ltd., compound of formula (III)) 0.2 Part, and mix by heating at 60 ° C for 1 hour After adding a light yellow transparent ultraviolet curable composition prepared by dissolving the solution, the thickness of the coating film is adjusted to 100 μm with a spin coater, and the irradiation amount is set using a metal halide lamp with a cold mirror 120 W / cm. An optical disk was produced by irradiating with ultraviolet rays of 500 mJ / cm ² (light meter UVPF-36 manufactured by Eye Graphics Co., Ltd.). The initial radial tilt, Δradial tilt, initial jitter, and jitter after environmental change of the optical disc were measured.

Further, an optical molding machine having a diameter of 120 nm and a thickness of 1.2 mm using an injection molding machine M35B-D-DM manufactured by Meiki Seisakusho, using a stamper with grooves 200 nm deep, 0.5 μm apart and 0.2 μm wide. A substrate was molded. The cylinder temperature was fixed at 360 ° C., and the mold temperature was set for each resin as shown in Table 1. The transfer rate of the optical disk substrate was measured.
Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Example 2]
A thermoplastic resin composition pellet was obtained in the same manner as in Example 1 except that 500 g of polycaprolactone (polycaprolactone H1P) was added to 10 kg of polycarbonate resin (Panlite AD-5503), and the glass transition temperature of the pellet, MVR, The saturated water absorption was measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Example 3]
In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 929.2 parts of ion-exchanged water and 61.3 parts of 48% aqueous sodium hydroxide solution were added, and 1,1-bis (4-hydroxyphenyl) -3, 3, 5 was added. -After dissolving 39 parts of trimethylcyclohexane, 43.6 parts of 4,4 '-(m-phenylenediisopropylidene) diphenol and 0.17 part of hydrosulfite, 1.51 parts of p-tert-butylphenol and methylene chloride After adding 637.9 parts and 0.09 part of triethylamine, 32.4 parts of phosgene was blown in at a temperature of 15 to 25 ° C. with stirring for 40 minutes. After completion of the phosgene blowing, 15.6 parts of a 48% aqueous sodium hydroxide solution was added, and the reaction was terminated by stirring at 28 to 33 ° C. for about 1 hour. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, the methylene chloride is evaporated to give 1,1-bis A colorless polymer having a molar ratio of structural units of (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 4,4 ′-(m-phenylenediisopropylidene) diphenol of 50:50 is obtained. It was. (Yield 97%)

  A thermoplastic resin composition pellet is obtained in the same manner as in Example 1 except that 500 g of polycaprolactone (polycaprolactone H1P) is added to 10 kg of the aromatic polycarbonate copolymer, and the glass transition temperature, MVR, and saturation of the pellet are obtained. The water absorption was measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Example 4]
In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 31,500 parts of ion-exchanged water and 1,730 parts of a 48% sodium hydroxide aqueous solution were placed, and 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene 2 , 040 parts, 2,4 '-(m-phenylenediisopropylidene) diphenol 2,802 parts, and hydrosulfite 10 parts, p-tert-butylphenol 81 parts and methylene chloride 13,770 parts were added. After adding 4 parts of triethylamine, 1,670 parts of phosgene was blown in for 60 minutes at 15 to 25 ° C. with stirring. After the completion of phosgene blowing, 270 parts of a 48% aqueous sodium hydroxide solution was added, and the reaction was terminated by stirring at 28 to 33 ° C. for about 1 hour. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, the methylene chloride is evaporated to 9,9-bis. A colorless polymer having a molar ratio of structural units of (3-methyl-4-hydroxyphenyl) fluorene and 4,4 ′-(m-phenylenediisopropylidene) diphenol of 50:50 was obtained. (Yield 96%)

  A thermoplastic resin composition pellet is obtained in the same manner as in Example 1 except that 500 g of polycaprolactone (polycaprolactone H1P) is added to 10 kg of the aromatic polycarbonate copolymer, and the glass transition temperature, MVR, and saturation of the pellet are obtained. The water absorption was measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 1]
A thermoplastic resin composition pellet was obtained in the same manner as in Example 1 except that 1,500 g of polycaprolactone tree (polycaprolactone H1P) was added to 10 kg of polycarbonate resin (Panlite AD-5503). Temperature, MVR, and saturated water absorption were measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 2]
A thermoplastic resin composition pellet was obtained in the same manner as in Example 1 except that 20 g of polycaprolactone (polycaprolactone H1P) was added to 10 kg of polycarbonate resin (Panlite AD-5503), and the glass transition temperature of the pellet, MVR, The saturated water absorption was measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 3]
A thermoplastic resin composition pellet was obtained in the same manner as in Example 1 except that only the polycarbonate resin (Panlite AD-5503) was used, and the glass transition temperature, MVR, and saturated water absorption rate of the pellet were measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 4]
A thermoplastic resin composition pellet was obtained in the same manner as in Example 3 except that only the polycarbonate copolymer polymerized in Example 3 was used, and the glass transition temperature, MVR, and saturated water absorption rate of the pellet were measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured.
Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 5]
A thermoplastic resin composition pellet was obtained in the same manner as in Example 3 except that 1,500 g of polycaprolactone (polycaprolactone H1P) was added to 10 kg of the polycarbonate copolymer polymerized in Example 3, and a glass transition of the pellet was obtained. Temperature, MVR, and saturated water absorption were measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured.
Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 6]
A thermoplastic resin composition pellet was obtained in the same manner as in Example 3 except that 20 g of polycaprolactone (polycaprolactone H1P) was added to 10 kg of the polycarbonate copolymer polymerized in Example 3, and the glass transition temperature of the pellet was obtained. MVR and saturated water absorption were measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 7]
A thermoplastic resin composition pellet was obtained in the same manner as in Example 4 except that only the polycarbonate copolymer polymerized in Example 4 was used, and the glass transition temperature, MVR, and saturated water absorption rate of the pellet were measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured.
Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 8]
A thermoplastic resin composition pellet was obtained in the same manner as in Example 4 except that 1,500 g of polycaprolactone (polycaprolactone H1P) was added to 10 kg of the polycarbonate copolymer polymerized in Example 4. The glass transition temperature, MVR, and saturated water absorption of the pellet were measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 9]
A thermoplastic resin composition pellet was obtained in the same manner as in Example 4 except that 20 g of polycaprolactone (polycaprolactone H1P) was added to 10 kg of the polycarbonate copolymer polymerized in Example 4, and the glass transition temperature of the pellet was obtained. MVR and saturated water absorption were measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 10]
A thermoplastic resin composition pellet was obtained in the same manner as in Example 1 except that only the polycarbonate resin (Panlite AD-5503) was used, and the glass transition temperature, MVR, and saturated water absorption rate of the pellet were measured. Furthermore, an optical disk and a substrate were prepared in the same manner as in Example 1, and a ZnS—SiO ₂ (molar fraction 80:20) dielectric material was used as a moisture absorption preventing film on the surface of the support substrate of the obtained disk. The film formation on the light transmission layer is set to 10 nm so that the decrease in the transmittance of recording / reproducing light can be suppressed to about several percent, and the film is formed from the diameter of 60 mm to 119 mm so as to be substantially concentric with the optical information recording medium. Filmed. Initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 11]
A thermoplastic resin composition in the same manner as in Example 1 except that 100 g of metaterphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of polycaprolactone (polycaprolactone H1P) were used for 10 kg of the polycarbonate resin (Panlite AD-5503). Pellets were obtained, and the glass transition temperature, MVR, and saturated water absorption rate of the pellets were measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 12]
To 9 kg of the polycarbonate resin (Panlite AD-5503), 1 kg of polycaprolactone (polycaprolactone H1P) was dry-blended and mixed uniformly. Subsequently, the composition was melt kneaded while degassing at a cylinder temperature of 220 ° C. using a vented twin-screw extruder [KTX-46 manufactured by Kobe Steel Co., Ltd.] to obtain pellets. The thermoplastic resin was used in the same manner as in Example 1 except that 8 kg of the thermoplastic resin was used and 2 kg of styrene-acrylonitrile copolymer polymer (27% by weight of acrylonitrile manufactured by Daicel Chemical Industries, Ltd.) was dry-blended again. A composition pellet was obtained, and the glass transition temperature, MVR, and saturated water absorption rate of the pellet were measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

[Comparative Example 13]
All of 1,4-cyclohexanedimethanol (hereinafter sometimes referred to as CHDM) contained in the container was placed in a melting tank and uniformly melted at 70 ° C. in a nitrogen atmosphere. From this molten CHDM, 72.0 parts by weight was weighed with a meter, and charged into a reaction vessel equipped with a stirrer, a distiller and a decompressor. Thereafter, 114 parts by weight of bisphenol A (hereinafter sometimes referred to as BPA), 220 parts by weight of diphenyl carbonate, 0.18 parts by weight of tetramethylammonium hydroxide, and 8 × 10 ⁻⁴ parts by weight of sodium hydroxide were added to the reaction vessel. The mixture was purged with nitrogen and purged with nitrogen, and then melted at 140 ° C. After stirring for 30 minutes, the pressure was gradually reduced while the internal temperature was raised to 180 ° C., and the mixture was reacted at 13.3 kPa for 30 minutes to distill off the produced phenol. Next, the temperature was continued while maintaining the same pressure, and the reaction was carried out at 190 ° C. for 30 minutes and at 200 ° C. for 40 minutes, and the amount of distilled PhOH was 124 parts by weight (65% distillation, theoretical amount: 191 parts by weight). The temperature was further raised, and the reaction was carried out by distilling off phenol at 210 ° C. for 30 minutes, 220 ° C. for 30 minutes, and further 240 ° C. for 30 minutes. Thereafter, the pressure was slowly reduced to 133 Pa or less at 240 ° C. The reaction was carried out with stirring for 4 hours after full vacuum was reached. After adding 8 × 10 ⁻⁴ parts by weight of tetrabutylphosphonium dodecylbenzenesulfonate as a deactivator, the mixture was stirred at 240 ° C. and 13.3 kPa for 20 minutes, and then discharged from the bottom of the reaction tank under nitrogen pressure. The pellet was cut with a pelletizer while cooling. A thermoplastic resin composition pellet is obtained in the same manner as in Example 4 except that 500 g of polycaprolactone (polycaprolactone H1P) is added to 10 kg of the polymerized polycarbonate copolymer, and the glass transition temperature, MVR, saturation of the pellet are obtained. The water absorption was measured. Further, an optical disk and a substrate were prepared in the same manner as in Example 1, and initial radial tilt, Δradial tilt and initial jitter, jitter after environmental test, and transfer rate were measured. Table 1 shows the measured glass transition temperature, MVR, saturated water absorption, initial radial tilt, Δradial tilt, initial jitter, jitter after environmental test, and transfer rate.

Claims (13)

A support substrate, a reflective layer formed on the substrate, and a light-transmitting cover layer made of a curable resin formed on the reflective layer, and recording and / or recording with laser light incident from the cover layer side A support substrate in an optical disc of a reproduction type, wherein the support substrate has a polycaprolactone in an amount of 0. 10 parts by weight with respect to 100 parts by weight of a polycarbonate resin having at least one repeating unit represented by the following formula [1] as a repeating unit. 5 to 10 parts by weight, and a support substrate formed using a thermoplastic resin having a saturated water absorption measured by immersion in water at 23 ° C. of 0.3% or less. The warp angle change of the optical disc is 0.9 after exposure to a saturated water absorption rate in a humid heat environment of 95 ° C. and humidity of 95% and then returning to a normal humidity state of 23 ° C. and 50% humidity. Optical disc substrate for supporting the substrate, characterized in that within it.

[Wherein, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or a carbon number. From the group consisting of a 6-20 cycloalkoxy group, an aryl group having 6-10 carbon atoms, an aralkyl group having 7-20 carbon atoms, an aryloxy group having 6-10 carbon atoms, and an aralkyloxy group having 7-20 carbon atoms. In the case where a plurality of R ¹ and R ² are present, they may be the same or different, m and n are each an integer of 1 to 4, and W is a structure represented by the following formula [2] Unit.

(R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. , R ⁵ and R ⁶ may be the same or different from each other, p is an integer of 4 to 12, R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 3 Represents an alkyl group.)] The optical disk substrate according to claim 1, wherein the polycarbonate resin is a polycarbonate resin having at least one repeating unit represented by the following formula [3] as a repeating unit.

[Wherein, R ¹ and R ² each independently represent a hydrogen atom and a group selected from the group consisting of alkyl groups having 1 to 5 carbon atoms, and when there are a plurality of R ¹ and R ² , they are the same or different, respectively. M and n are each an integer of 1 to 2, and W is a structural unit represented by the following formula [4].

(R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. , R ⁵ and R ⁶ may be the same or different, p is an integer of 4 to 8, R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. To express.)]   The general formula [1] is 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5. A repeating unit derived from at least one selected from trimethylcyclohexane, 4,4 ′-(m-phenylenediisopropylidene) diphenol and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene Item 3. The optical disk substrate according to any one of Items 1 and 2.   The optical disk substrate according to claim 1, wherein the general formula [1] is a repeating unit derived from 2,2-bis (4-hydroxyphenyl) propane.   The general formula [1] is a repeating unit derived from 4,4 ′-(m-phenylenediisopropylidene) diphenol and / or 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. Item 4. The optical disk substrate according to any one of Items 1 to 3.   6. The optical disk substrate according to claim 1, wherein the thermoplastic resin is a thermoplastic resin obtained by blending 1 to 9 parts by weight of polycaprolactone with respect to 100 parts by weight of the polycarbonate resin.   6. The optical disk substrate according to claim 1, wherein the thermoplastic resin is a thermoplastic resin obtained by blending 3 to 7 parts by weight of polycaprolactone with respect to 100 parts by weight of the polycarbonate resin.   The optical disk substrate according to claim 1, wherein the thermoplastic resin has a glass transition temperature of 110 to 180 ° C.   9. The optical disk according to claim 1, wherein the light-transmitting cover layer made of the curable resin is formed by applying an ultraviolet curable resin on the reflective layer by a spin coating method and then curing the resin. substrate.   A light-transmitting material comprising the optical disk substrate according to claim 1 as a support substrate, comprising a support substrate, a reflective layer formed on the substrate, and a curable resin formed on the reflective layer. An optical disc comprising a cover layer and recording and / or reproducing by entering laser light from the cover layer side.   The optical disk according to claim 10, wherein the light-transmitting cover layer made of the curable resin is formed by applying an ultraviolet curable resin on the reflective layer by a spin coating method and then curing it.   A support substrate, a reflective layer formed on the substrate, and a light-transmitting cover layer made of a curable resin formed on the reflective layer, and recording and / or recording with laser light incident from the cover layer side A support substrate in an optical disc of a reproduction type, wherein the support substrate has 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- From bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4 ′-(m-phenylenediisopropylidene) diphenol and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene Polycaprolactone with respect to 100 parts by weight of polycarbonate resin represented by a repeating unit derived from at least one selected from 0.5 to 10 parts by weight, and a support substrate formed using a thermoplastic resin having a saturated water absorption measured by immersion in water at 23 ° C. of 0.3% or less, and the optical disc The warp angle change of the optical disk is within 0.9 degrees when it is exposed to a saturated water absorption rate in a humid heat environment with a temperature of 30 ° C. and humidity of 95% and then returned to a normal humidity state of 23 ° C. and humidity of 50%. A polycarbonate resin molding material for an optical disk substrate for a support substrate.   13. The polycarbonate for an optical disk substrate for a support substrate according to claim 12, wherein the light-transmitting cover layer made of the curable resin is formed by applying an ultraviolet curable resin on the reflective layer by spin coating and then curing the resin. Resin molding material.