JP2009066935A - Optical recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical recording medium which can prevent a recording material from developing a deflection power with data unrecorded and induce the development of the deflection power after recording, with a significant quantity of signal fluctuation, and deal with a rapid writing operation. <P>SOLUTION: This optical recording medium is characterized in that: at least, one of the constituent materials of a recording layer is a polymer material with a chainlike structural part. Further, the main chain of the polymer material is a block copolymer having a repeating unit of A-b-[B-C], and either one of the [B-C] parts of the polymer main chain has a light absorber grafted which assumes an order or a disorder state, provided, wherein A, B and C represent a repeating monomer unit, -b- represents a diblock copolymer (A-b-[B-C]) of A and [B-C], and [B-C] represents a random copolymer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a write-once optical recording medium.

  Conventionally, a method for forming a recording medium by incorporating a liquid crystal material in a recording layer and controlling the orientation direction thereof has been proposed for a long time. In the case of a low-medium molecular liquid crystal material, a method of changing the alignment direction by an external force such as an electric field is often used. In this case, the problem is that the memory property is unstable, and a method of polymerizing a polymerizable liquid crystal material with laser light has been proposed (Patent Documents 1 and 2).

In addition, a liquid crystal polymer in which mesogenic groups are randomly bonded to the polymer main chain (Patent Document 3), a polysiloxane-based side chain polymer liquid crystal compound (Patent Document 4), a photocrosslinked liquid crystal poly (meth) acrylate PP (patent document 5), polymer material showing cholesteric liquid crystallinity and photochromism (patent document 6), polymer liquid crystal material polymerized with acrylic acid derivative compound (patent documents 7 and 8), polymer liquid crystal having glass transition point Material (patent document 9), copolymer of nematic monomer and cholestic monomer (patent documents 10 and 11), liquid crystal having a group that undergoes photo-induced conformational change and a group having mesogenic properties in the side chain Polymer (Patent Document 12), polymer liquid crystal having mesogenic group to be photoisomerized (Patent Documents 13 and 14), aliphatic dicarboxylic acid or And a propanediol-based polyester having a mesogenic substituent at the central carbon containing two rings, either alicyclic or aromatic (Patent Document 15), can cause a reversible photoisomerization reaction A photoreactive component capable of controlling the molecular orientation by light and having a urethane group, a urea group or an amide group in the polymer repeating unit and using a polymer material (Patent Document 16) Recording media have been proposed.
However, in optical recording media using these polymer liquid crystal materials, the orientation direction is often changed by heat, and the main chain itself of all the polymer liquid crystal materials in the heated place moves. The problem is that the response speed is slow to align and change direction.

  In order to solve these problems, it has been proposed to use a mixed system of a polymer liquid crystal material and a medium / low molecular weight liquid crystal material (Patent Document 17). By confining the medium- and low-molecular liquid crystal material in the mesh space formed by the polymer material, the instability of the memory property of the medium- and low-molecular liquid crystal material is eliminated, and the high mobility of the medium and low-molecular liquid crystal material is incorporated Although the response speed of polymer liquid crystal materials has been increased, it is necessary to carry out polymerization and crosslinking reactions in the product liquid crystal cell in order to create a net-shaped structure. The problem is that the work of mixing the cross-linking agent into the liquid crystal cell and that some of these foreign substances that lower the performance remain after the polymerization / cross-linking reaction.

  Also, an optical recording medium having a uniform organic dye film has been proposed, and DVD + R and DVD-R have been commercialized as large-capacity optical disks. DVD-based optical discs can also be easily assumed that the market demands high-speed writing as found in CD-Rs, but optical recording media that support high-speed writing have not yet been developed.

The conventional optical recording medium having the uniform organic dye film has a large thermal conductivity of the recording layer, so that heat is transferred to the outside of the spot diameter of the recording / reproducing light, and the recording mark spreads beyond the diameter of the laser beam. The problem is that the edge of the recording mark becomes dull and the jitter increases.
In order to solve this problem, organic dyes (regions with high thermal conductivity) are scattered in non-recording materials (regions with low thermal conductivity) to form a recording layer in which organic dyes are discontinuous, It is conceivable to prevent the organic dye from absorbing the laser light and transferring the generated heat.
However, when the recording layer in this discontinuous state is formed, the density of the recording material is smaller than that of a normal recording medium having a recording layer formed only of a recording dye material, and accordingly, the amount of signal change is reduced accordingly. Problem arises.

Both problems having the above trade-off relationship are obtained by using a dye polymer (light absorber) exhibiting liquid crystal properties in the recording dye of the optical recording medium in which the recording dye and the material having low thermal conductivity are microphase-separated, There has been proposed an optical recording medium in which molecules are aligned in one direction in an island-shaped portion of a recording layer, signal intensity is increased, and high-speed writing can be supported (Patent Document 18).
However, research on such light absorbers has not been sufficient.
* Corresponded to claim 1.

Japanese Patent No. 3803770 Japanese Patent No. 3690061 JP-A 63-66229 JP-A-2-193115 JP-A-3-170597 Japanese Patent Laid-Open No. 11-256147 JP 2001-270848 A JP 2001-89529 A Japanese Patent No. 251566 Japanese Patent No. 2630044 Japanese Patent No. 2630045 Japanese Patent No. 3056249 Japanese National Patent Publication No. 10-50433 Japanese National Patent Publication No. 11-501359 JP-A 64-86338 JP-A-6-297854 Japanese Patent No. 3347763 JP 2004-358728 A

  The present invention prevents a recording material from exhibiting a deflection capability in an unrecorded state, exhibits a deflection capability after recording, has a large amount of signal change, and is suitable for high-speed writing. It is an object of the present invention to provide an optical recording medium having a recording layer made of a polymer material having

  The above problem is (1) of the present invention. At least one of the materials constituting the recording layer has a portion that cannot take an order-disorder state by light and a light absorber that can take an order-disorder state. An optical recording medium wherein the body is a polymer material containing at least one compound represented by the following general formula (I);

上記一般式（Ｉ）中、Ｒ１〜Ｒ５はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。また、Ｒ１とＲ２、Ｒ２とＲ３、Ｒ３とＲ４、Ｒ４とＲ５は、連結して環を形成していても良い。Ｒ１〜Ｒ５の何れか１つは高分子主鎖と連結している。ＡはＮとＢが連結して成る環を表し、ＢはＯ、Ｓ、Ｎ、ＮＲ７、ＣＲ８、ＣＲ９Ｒ１０の何れかを表し、Ｒ７〜Ｒ１０はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。」、（２）「前記光吸収体は下記一般式（Ｉ）で示される化合物を少なくとも１種類以上含有していることを特徴とする前記（１）項に記載の光記録媒体；

In the general formula (I), R1 to R5 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group. Substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted A substituted arylcarbonylamino group, a carbamoyl group, a substituted or unsubstituted alkylcarbamoyl group, and a substituted or unsubstituted arylcarbamoyl group are represented. R1 and R2, R2 and R3, R3 and R4, and R4 and R5 may be linked to form a ring. Any one of R1 to R5 is linked to the polymer main chain. A represents a ring formed by linking N and B, B represents any of O, S, N, NR7, CR8, CR9R10, and R7 to R10 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano Group, hydroxyl group, carboxy group, amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkyl Amino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, carbamoyl group, substituted or unsubstituted alkylcarbamoyl group, substituted or unsubstituted aryl Represents a rucarbamoyl group. ", (2)" The optical recording medium according to item (1), wherein the light absorber contains at least one compound represented by the following general formula (I);

上記一般式（ＩＩ）中、Ｒ１’〜Ｒ５’はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。また、Ｒ１’とＲ２’、Ｒ４’とＲ５’は、連結して環を形成していても良い。Ａ’はＮとＢ’が連結して成る環を表し、Ｂ’はＯ、Ｓ、Ｎ、ＮＲ７’、ＣＲ８’、ＣＲ９’Ｒ１０’の何れかを表し、Ｒ７’〜Ｒ１０ ’はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。−Ｘ−は−Ｏ−、−Ｓ−、−（ＮＲ１１）−、−（ＣＲ１２Ｒ１３）−、−（Ｃ＝Ｏ）−、−（Ｏ−Ｃ＝Ｏ）−、−（Ｃ＝Ｏ−Ｏ）−、−（ＮＨ−ＣＯ）−、−（ＣＯ−ＮＨ）−の何れかを表す。−Ｙ−は−（ＣＨ_２）ｓ−、−（Ｃ_６Ｈ_４）ｔ−の何れかを表し、ｓ及びｔは０を含む正数を表す。また、このＹ鎖は−Ｏ−、−Ｓ−、−（ＮＲ１４）−、−（Ｏ−Ｃ＝Ｏ）−、−（Ｃ＝Ｏ−Ｏ）−、−（ＮＨ−ＣＯ）−、−（ＣＯ−ＮＨ）−の何れかで中断されていても良い。−Ｚ−は−Ｏ−、−Ｓ−、−（ＮＲ１５）−、−（ＣＲ１６Ｒ１７）−の何れかを表し、Ｒ１１’〜Ｒ１４’およびＲ１５〜Ｒ１７はそれぞれ独立に水素原子、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基を表す。」（３）「前記高分子材料は、鎖状構造部分を有する高分子材料であり、該高分子材料の主鎖はＡ−ｂ−［Ｂ−Ｃ］の繰り返し単位をもつブロック共重合体であり、該高分子主鎖の［Ｂ−Ｃ］部の何れか一方に秩序−無秩序状態を取り得る光吸収体がグラフトしたものであることを特徴とする前記（１）項又は前記（２）項に記載の光記録媒体。
但し、Ａ、Ｂ、Ｃは、繰り返しモノマー単位を表し、「−ｂ−」はＡと［Ｂ−Ｃ］とのジブロック共重合体（Ａ−ｂ−［Ｂ−Ｃ］）を表し、［Ｂ−Ｃ］はランダム共重合体を表す。」（４）「前記［Ｂ−Ｃ］部の何れか一方は、下記一般式（ＩＩＩ）で示される化合物を少なくとも１種類含有していることを特徴とする前記（１）項乃至前記（３）項何れか１に記載の光記録媒体；

In the general formula (II), R1 ′ to R5 ′ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted Alternatively, it represents an unsubstituted arylcarbonylamino group, a carbamoyl group, a substituted or unsubstituted alkylcarbamoyl group, or a substituted or unsubstituted arylcarbamoyl group. R1 ′ and R2 ′ and R4 ′ and R5 ′ may be linked to form a ring. A ′ represents a ring formed by linking N and B ′, B ′ represents any of O, S, N, NR7 ′, CR8 ′, CR9′R10 ′, and R7 ′ to R10 ′ are each independently Hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxy group, amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted Aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, carbamoyl group, substituted or unsubstituted An alkylcarbamoyl group and a substituted or unsubstituted arylcarbamoyl group are represented. -X- is -O-, -S-,-(NR11)-,-(CR12R13)-,-(C = O)-,-(O-C = O)-,-(C = O-O). -,-(NH-CO)-, or-(CO-NH)-. -Y- is _{- (CH 2) s -,} - (C 6 H 4) represents any t-, s and t represent a positive number including zero. The Y chain is -O-, -S-,-(NR14)-,-(O-C = O)-,-(C = O-O)-,-(NH-CO)-,-( CO-NH)-may be interrupted. -Z- represents any one of -O-, -S-,-(NR15)-,-(CR16R17)-, and R11 'to R14' and R15 to R17 are each independently a hydrogen atom, substituted or unsubstituted. An alkyl group or a substituted or unsubstituted aryl group is represented. (3) "The polymer material is a polymer material having a chain structure portion, and the main chain of the polymer material is a block copolymer having a repeating unit of Ab- [BC]. And (1) or (2) above, wherein a light absorber capable of taking an ordered-disordered state is grafted to any one of the [BC] part of the polymer main chain. The optical recording medium according to Item.
However, A, B, C represents a repeating monomer unit, “-b-” represents a diblock copolymer (Ab- [BC]) of A and [BC], [ BC] represents a random copolymer. "(4)" Any one of the [BC] parts contains at least one compound represented by the following general formula (III): (1) to (3) The optical recording medium according to any one of items 1);

上記一般式（ＩＩＩ）中、Ｒ１”〜Ｒ５”はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。また、Ｒ１”とＲ２”、Ｒ４”とＲ５”は、連結して環を形成していても良い。Ａ”はＮとＢ”が連結して成る環を表し、Ｂ”はＯ、Ｓ、Ｎ、ＮＲ７”、ＣＲ８”、ＣＲ９”Ｒ１０”の何れかを表し、Ｒ７”〜Ｒ１０”はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。−Ｘ’−は−Ｏ−、−Ｓ−、−（ＮＲ１１’）−、−（ＣＲ１２’Ｒ１３’）−、−（Ｃ＝Ｏ）−、−（Ｏ−Ｃ＝Ｏ）−、−（Ｃ＝Ｏ−Ｏ）−、−（ＮＨ−ＣＯ）−、−（ＣＯ−ＮＨ）−の何れかを表す。−Ｙ’−は−（ＣＨ_２）ｓ−、−（Ｃ_６Ｈ_４）ｔ−の何れかを表し、ｓ及びｔは０を含む正数を表す。また、このＹ’鎖は−Ｏ−、−Ｓ−、−（ＮＲ１４’）−、−（Ｏ−Ｃ＝Ｏ）−、−（Ｃ＝Ｏ−Ｏ）−、−（ＮＨ−ＣＯ）−、−（ＣＯ−ＮＨ）−の何れかで中断されていても良い。Ｒ１１’〜Ｒ１４’はそれぞれ独立に水素原子、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基を表す。」（５）「 前記記録層は、記録及び/又は再生光入射側界面（表面）が、前記光吸収体を含む第１のドメイン相と、前記光吸収体を含まない第２のドメイン相とに相分離していることを特徴とする前記（１）項乃至前記（４）項何れか１に記載の光記録媒体。」（６）「前記第２ドメイン相の熱伝導率が、前記第１のドメイン相の熱伝導率より小さいことを特徴とする前記（５）項に記載の光記録媒体。」（７）「前記第１のドメイン相のドメイン径が、記録及び/又は再生を行う光により記録層の入射側界面にできる最小スポット径よりも小さいことを特徴とする前記（５）項または前記（６）項に記載の光記録媒体。」（８）「 前記高分子材料全体の分子量に対する前記光吸収体の重量分率が、１０％以上５０％以下であることを特徴とする前記（１）項乃至前記（７）項何れか１に記載の光記録媒体。」により解決される。

In the general formula (III), R1 ″ to R5 ″ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted Alternatively, it represents an unsubstituted arylcarbonylamino group, a carbamoyl group, a substituted or unsubstituted alkylcarbamoyl group, or a substituted or unsubstituted arylcarbamoyl group. R1 ″ and R2 ″ and R4 ″ and R5 ″ may be linked to form a ring. A ″ represents a ring formed by linking N and B ″, B ″ represents any of O, S, N, NR7 ″, CR8 ″, CR9 ″ R10 ″, and R7 ″ to R10 ″ are each independently Hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxy group, amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted Aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, carbamoyl group, substituted or unsubstituted Represents an alkylcarbamoyl group, a substituted or unsubstituted arylcarbamoyl group, -X'- represents -O-, -S-,-( NR11 ′) —, — (CR12′R13 ′) —, — (C═O) —, — (O—C═O) —, — (C═O—O) —, — (NH—CO) —, - (CO-NH) - represents.-Y'- is either a _{- (CH 2) s -,} - (C 6 H 4) represents any t-, positive number s and t including 0 The Y ′ chain represents —O—, —S—, — (NR14 ′) —, — (O—C═O) —, — (C═O—O) —, — (NH—CO). )-Or-(CO-NH)-, R11 'to R14' each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. (5) "The recording layer has a recording and / or reproducing light incident side interface (surface) including a first domain phase including the light absorber and a second domain phase not including the light absorber. And to The optical recording medium according to any one of (1) to (4) above, wherein the thermal conductivity of the second domain phase is the first domain. The optical recording medium according to item (5), wherein the optical recording medium is smaller than the thermal conductivity of the phase. ”(7)“ The domain diameter of the first domain phase is recorded by light for recording and / or reproduction. The optical recording medium according to (5) or (6) above, wherein the optical recording medium is smaller than a minimum spot diameter that can be formed on the incident side interface of the layer. The optical recording medium according to any one of (1) to (7), wherein the weight fraction of the light absorber is 10% to 50%.

  According to the present invention, it is possible to provide an optical recording medium that prevents the recording material from exhibiting the deflection ability in an unrecorded state, exhibits the deflection ability after recording, has a large signal change amount, and can cope with high-speed writing. There is an effect.

At least one of the materials constituting the recording layer has a portion that cannot take an order-disorder state by light and a light absorber that can take an order-disorder state, and the light absorber is represented by the following general formula (I). An optical recording medium characterized in that it is a polymer material containing at least one kind of compound.

上記一般式（Ｉ）中、Ｒ１〜Ｒ５はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。また、Ｒ１とＲ２、Ｒ２とＲ３、Ｒ３とＲ４、Ｒ４とＲ５は、連結して環を形成していても良い。Ｒ１〜Ｒ５の何れか１つは高分子主鎖と連結している。ＡはＮとＢが連結して成る環を表し、ＢはＯ、Ｓ、Ｎ、ＮＲ７、ＣＲ８、ＣＲ９Ｒ１０の何れかを表し、Ｒ７〜Ｒ１０はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。

In the general formula (I), R1 to R5 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group. Substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted A substituted arylcarbonylamino group, a carbamoyl group, a substituted or unsubstituted alkylcarbamoyl group, and a substituted or unsubstituted arylcarbamoyl group are represented. R1 and R2, R2 and R3, R3 and R4, and R4 and R5 may be linked to form a ring. Any one of R1 to R5 is linked to the polymer main chain. A represents a ring formed by linking N and B, B represents any of O, S, N, NR7, CR8, CR9R10, and R7 to R10 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano Group, hydroxyl group, carboxy group, amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkyl Amino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, carbamoyl group, substituted or unsubstituted alkylcarbamoyl group, substituted or unsubstituted aryl Represents a rucarbamoyl group.

The present inventors have dispersively ordered-disordered state (a state in which molecules grafted to a main chain polymer are arranged and assembled by intermolecular force, electrostatic action, etc., and exhibit crystal and / or deflection ability. The disordered state refers to a state in which an array and an assembly are not performed, and an amorphous and / or non-deflecting ability is taken.) It was found that applying low energy to a polymer thin film can impart polarizing ability at high speed to the heat collecting point of the polymer thin film that does not exhibit polarization ability.

  This is achieved, for example, by using a polymer material bonded (grafted) with a light absorber capable of taking an order-disorder state. As shown in FIG. 6, this polymer material does not exhibit polarization ability in the initial state (unrecorded state), but the light absorber in the polymer material absorbs the recording light, and the light absorber is melt-oriented. Therefore, it is an optical recording medium using a polymer material capable of high-speed recording and exhibiting deflection ability after recording, and liquid crystal is used as a polymer material in which the main chain of the conventional polymer material moves and rearranges. This is fundamentally different from storage media using polymer liquid crystal materials including those obtained by introducing a compound.

  As shown in the AMF photograph of FIG. 8, the recording layer of the optical recording medium of the present invention is a polymer material since the domain of 20 to 100 nm of microphase separation is not destroyed and the phase separation shape does not change by heating. It is presumed that the main chain itself does not move, it can cope with high-speed writing, and the presence or absence of deflection ability changes before and after heating as shown in FIG.

  Further, FIG. 7 shows the change in reflectance with respect to the reproduction wavelength immediately after application and after heating of the polymer material example 6 shown later. This polymer material example 6 changes the reflectance immediately after coating and after heating even in the vicinity of a wavelength of 430 nm, and can be used for short-wavelength recording light useful for high-density recording.

The recording mechanism of the present invention is considered as follows. At the recording light focus irradiated to the recording layer, sufficient heat is generated to soften the polymer material, so that the polymer main chain is softened. At this time, the restraint of the grafted material is released, and light absorbers that can take an order-disorder state existing in the vicinity gather to form a crystalline state or an orientation state equivalent thereto.
When a polarizer is placed in the optical system in the recording system, that is, the light path from the light source to the light receiving unit, and the reproduction light is irradiated onto the optical recording medium, in addition to the change in light transmittance and reflectance, the deflected light Therefore, it is possible to obtain a larger signal change than a recording layer phase-separated using a general recording dye.
In contrast, general recording dyes are designed to have high solubility in coating solvents in order to obtain a homogeneous coating film and to inhibit dye association in order to eliminate coating defects. It is considered that an ordered state cannot be created.

In addition, by using a phase separation structure smaller than the spot diameter of the recording / reproducing light as the recording material in the polymer main chain, the propagation of heat generated in the recording layer is sufficiently suppressed, the edge of the recording mark is sharpened, and the low jitter It was found that a recording medium can be provided. It has also been found that it is effective for increasing the writing laser output accompanying the achievement of high-speed writing.

The difficulty in developing a recording material capable of high-speed writing is due to the following.
DVD-based recording marks have a width of about 0.4 μm and vary in length according to each signal. On the other hand, the spot diameter of the recording / reproducing light for reading and writing is as large as about 1.1 μm. The track pitch of the medium is about 0.8 μm or less, and recording / reproducing light always hits the adjacent information recording area. Under such circumstances, in order to write a recording mark of about 0.4 μm, an extremely complicated strategy is being solved to solve the assembly problem.
After all, the purpose of this strategy development is to control the heat generated by the recording material absorbing the laser and aim at low jitter by sharpening the edge of the recording mark.

  However, the heat generated in the recording layer spreads beyond the spot diameter of the recording / reproducing light beyond the diameter of the laser beam having the intensity capable of writing the recording mark. Will increase. In order to sharpen the edge shape, it is only necessary to prevent the heat generated in the recording layer from spreading to the peripheral portion and prevent the recording mark from being formed beyond the diameter of the laser beam having a strength capable of writing the recording mark.

In an optical recording medium that employs the mark edge recording / reproducing method and performs recording in the heat mode, it is essential to sharpen the edge shape. Sharpening the edge shape can be achieved by preventing the heat of the recording layer (on the recording mark) from being diffused.
FIG. 1 shows a schematic diagram of a recording mark shape having a conventional uniform recording layer. The recording layer (A) represents a known recording layer in which a recording material (dye) is uniformly formed. In the figure, concentric circles of different sizes are drawn. The area from the edge of the largest circle to the center point (1), the area from the edge of the smallest circle to the center point (2), the area from the edge of the middle circle to the edge of the smallest circle Is region (3). Region (1) represents a range in which the recording light strikes the recording layer surface (interface). Region (2) represents a range in which the recording light generates thermal energy that can change the recording layer. Region (3) represents a range in which the heat can propagate to region (2) and the recording layer can change.

The recording layer (A) of the conventional optical recording medium is made of a uniform organic dye. If the thermal conductivity of the recording material (dye) of the recording layer (A) is sufficiently small, the region (3) that changes due to the conduction heat will not be wider than the region (2).
However, as is generally known, since the thermal conductivity of the recording layer composed of the organic dye is large, a region (3) outside the region (2) is greatly generated.

  FIG. 2 is a schematic diagram of a recording mark shape when a recording layer in which the surface (interface) is phase-separated and the recording material is present in an island shape in the sea of the non-recording material is used. In the recording layer (B), the recording material presence portion (5) represents a domain that absorbs recording light well, and the recording material non-existence portion (6) represents a domain that hardly absorbs recording light. Region (1), region (2) and region (3) have the same meaning as in FIG.

  As shown in FIG. 2, the area (3) of the recording layer (B) is smaller than the area (3) of the recording layer (A) in FIG. The place where heat is generated is limited to the recording material existence portion (5) where the recording dye material (substance that absorbs light) is present in the region (2), so the region (3) is reduced.

However, this optical recording medium has a problem that the amount of change in signal is correspondingly smaller because the density of the recording material is smaller than that of a normal recording medium having a recording layer formed only of a recording dye material. .
Further, in this optical recording medium, colonies due to the dye materials are generated, but this causes a wide range of areas where no recording material exists, which is inconvenient for a system that records and reproduces with a mark length of 0.4 μm or less. .

  Further, in order to sharpen the recording mark edge, in order to reduce the region (3) changed by conduction heat, as shown in FIG. 4, the size of one island of the recording material existence portion (5) is set as shown in FIG. It is necessary to make it sufficiently smaller than the non-existing part (6). As shown in FIG. 3, when the island of the recording material existence portion (5) is larger than the recording material non-existence portion (6), the recording material existence portion (in the range over the region (2) and the region (3) ( 5) is present in large quantities and conducts heat, so that the effect of reducing the area of the region (3) and sharpening the edge does not appear. Therefore, in the recording layer, the light incident side interface is phase-separated into a first domain phase including a light absorber capable of taking an order-disorder state and a second domain phase not including the light absorber. Preferably it is. The domain diameter of the first domain phase is preferably smaller than the minimum spot diameter that can be formed on the incident side interface of the recording layer by recording / reproducing light, and specifically, it is preferably 20 to 100 nm.

A recording medium in which the recording layer surface (interface) is in a phase-separated state is obtained by adding a material incompatible with the polymer material or a polymer having repeating units in which the polymer main chains are incompatible with each other It can be easily created by using a material.
In particular, repeating units having different solubility parameters are easily phase separated. The solubility parameter is described in a polymer handbook or the like. For example, if a polystyrene (SP value 18) and polyvinyl pyridine (SP value 22) are mixed, a target phase separator can be easily obtained.
The difference in solubility parameter is preferably 1.3 or more, and more preferably 3.0 or more.
The solubility parameter can be calculated by calculation. The use of either the calculated SP value or the measured SP value had no effect on the presence or absence of the appearance of the phase separation state.

In addition, the sea-island phase separation can be roughly obtained by mixing one or more repeating units having different properties to 30 parts or less and the other to 70 parts or more. Further, the size of the island can be controlled by selecting a repeating unit having an appropriate molecular weight.

The best method for obtaining a sea-island-like phase separator as shown in FIG. 4 is a polymer which is a block copolymer in which repeating units having different compatibility (different solubility parameter values) are chemically bonded to each other. The material is to be used. The block copolymer phase separation state is known as “microphase separation”.
For example, an AB block copolymer in which block A and block B are chemically bonded and the difference in solubility parameter between A and B is 1.3 or more is the degree of polymerization of A and B. By adjusting the length of B, it is possible to easily obtain a very well-organized phase separation structure.
As shown in FIG. 5, when A and B have the same length, a lamellar shape is obtained. Since A and B are connected, a structure that exceeds twice the length of AB cannot be made. Next, when the length of A is shortened, A gathers together to form a sea island with A as the island and B as the sea. By adjusting the length of A and the length of B, the diameter of the island and the distance between the island and the island can be arbitrarily made.
In the present invention, A sphere / B is expressed as a sea island, A bar / B as a string, sea island or amorphous, and an AB alternating phase as a string, and a domain formed by a simple blend of polymer materials or a random copolymer. Amorphous phase separation with nonuniform diameters is expressed as a blend.

In order to form a disordered state having no deflection ability in the recording layer in the initial state, for example, the recording layer may be formed by a wet process from a solution in which a polymer material is dissolved in a solvent.
Since this is a polymer material, it is arranged randomly.

In the present invention, the [BC] part of the block copolymer having a repeating unit of Ab- [BC] is used as a material that does not have the deflection ability when not recorded and exhibits the deflection ability after recording. Either one is grafted with a light absorber capable of taking an order-disorder state. B and C are preferably compatible with each other.
For example, when the light absorber is grafted on B of the random copolymer portion [BC] of the block copolymer having a repeating unit of Ab- [BC], C is the density of the light absorber. Therefore, the ordered arrangement of the light absorber is disturbed at the initial coating stage, and no polarized light is emitted.
Also, the anti-aggregation action of C present in the polymer main chain also causes a sufficiently long light absorber to easily aggregate and generate polarized light when heat exceeding the softening point is applied.
Thus, the polymer material of the present invention is preferably an ab- [BC] block copolymer, but is not limited to this, and even when a polymer material having another configuration is used, the polymer material is wet. By appropriately adjusting the solvent in the process, it is possible to prevent polarized light from being applied at the initial stage of coating.

It is preferable that the weight fraction with respect to the molecular weight of the whole polymer material of the light absorber capable of taking the ordered-disordered state is 50% or less. This is because if it exceeds 50%, the density of the light absorber is high, and the deflection ability may be manifested in the initial stage of coating. However, it is possible to suppress the expression of deflection ability (array of light absorbers) at the initial stage of coating by adjusting the dissolution conditions of the polymer material.
The weight fraction is preferably 10% or more from the recording characteristics (signal change amount). This is because if it is less than 10%, the generation of polarized light may not be sufficient even after recording light irradiation.
It is also possible to heat and melt the polymer material to form a recording layer, but if the temperature is not strictly controlled, a light absorber that can take an order-disorder state in an unrecorded state is arranged. Care must be taken because it has polarization ability.

In addition to the polymer material, in order to increase the amount of signal change, other additives can be included.
The additional additive may be either one that can take an order-disorder state or one that cannot take an order-disorder state. For example, a non-polymerizable low molecular compound or a high molecular compound can be included, and Although depending on the additive, it is preferable that the content is 15% by weight or less with respect to the polymer material because the light absorber can exhibit a deflection ability as it forms an ordered state.

  In the present invention, the light absorber capable of taking the order-disorder state of the polymer material preferably forms an island portion when a sea-island structure is formed.

In addition, it is preferable to directly bond the light absorber to the polymer main chain because the bias due to colony formation between the coloring agents can be inhibited.
The light absorbing material to be grafted may be any material that absorbs the recording / reproducing light, and can be arbitrarily selected according to the wavelength of the recording light.
For example, azo, phthalocyanine, naphthalocyanine, porphyrin, porphyrazine, dipyrromethene, cyanine, styryl, triphenylmethane, phthalide, xanthene, acridine, oxazine, rhodamine, indoaniline, indophenol, benzoquinone, naphthoquinone, anthraquinone, indigo, thioindigo, It can be selected from coumarin, quinophthalone, spiropyran, fulgide, diarylethene, squarylium, croconium and the like.

By using azobenzene as a light absorber capable of taking the order-disorder state of the polymer material of the present invention, azobenzene is arranged in the alignment direction of laser light used as a recording and / or reproducing light source. The amount of signal change can be increased.
As azobenzene, the following are particularly preferable.

上記一般式（Ｉ）中、Ｒ１〜Ｒ５はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。また、Ｒ１とＲ２、Ｒ２とＲ３、Ｒ３とＲ４、Ｒ４とＲ５は、連結して環を形成していても良い。Ｒ１〜Ｒ５の何れか１つは高分子主鎖と連結している。ＡはＮとＢが連結して成る環を表し、ＢはＯ、Ｓ、Ｎ、ＮＲ７、ＣＲ８、ＣＲ９Ｒ１０の何れかを表し、Ｒ７〜Ｒ１０はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。

In the general formula (I), R1 to R5 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group. Substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted A substituted arylcarbonylamino group, a carbamoyl group, a substituted or unsubstituted alkylcarbamoyl group, and a substituted or unsubstituted arylcarbamoyl group are represented. R1 and R2, R2 and R3, R3 and R4, and R4 and R5 may be linked to form a ring. Any one of R1 to R5 is linked to the polymer main chain. A represents a ring formed by linking N and B, B represents any of O, S, N, NR7, CR8, CR9R10, and R7 to R10 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano Group, hydroxyl group, carboxy group, amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkyl Amino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, carbamoyl group, substituted or unsubstituted alkylcarbamoyl group, substituted or unsubstituted aryl Represents a rucarbamoyl group.

As a light absorber capable of taking the order-disorder used in the present invention, good results have been obtained with a structure in which an azobenzene compound is bonded to a polymer main chain via a spacer. The synthesis of azobenzene can be easily performed by a conventional method (Synthesis Examples 1 to 5).
Moreover, the azo compound grafted to the polymer main chain can select the structure of the A ring of the general formula (I) according to the wavelength of recording and / or reproducing light, and can correspond to various light sources.

  Further, when R3 has a spacer molecule residue portion, the coupling reaction can be easily performed, so that an inexpensive recording medium can be provided.

上記一般式（ＩＩ）中、Ｒ１’〜Ｒ５’はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。また、Ｒ１’とＲ２’、Ｒ４’とＲ５’は、連結して環を形成していても良い。Ａ’はＮとＢ’が連結して成る環を表し、Ｂ’はＯ、Ｓ、Ｎ、ＮＲ７’、ＣＲ８’、ＣＲ９’Ｒ１０’の何れかを表し、Ｒ７’〜Ｒ１０ ’はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。−Ｘ−は−Ｏ−、−Ｓ−、−（ＮＲ１１）−、−（ＣＲ１２Ｒ１３）−、−（Ｃ＝Ｏ）−、−（Ｏ−Ｃ＝Ｏ）−、−（Ｃ＝Ｏ−Ｏ）−、−（ＮＨ−ＣＯ）−、−（ＣＯ−ＮＨ）−の何れかを表す。−Ｙ−は−（ＣＨ_２）ｓ−、−（Ｃ_６Ｈ_４）ｔ−の何れかを表し、ｓ及びｔは０を含む正数を表す。また、このＹ鎖は−Ｏ−、−Ｓ−、−（ＮＲ１４）−、−（Ｏ−Ｃ＝Ｏ）−、−（Ｃ＝Ｏ−Ｏ）−、−（ＮＨ−ＣＯ）−、−（ＣＯ−ＮＨ）−の何れかで中断されていても良い。−Ｚ−は−Ｏ−、−Ｓ−、−（ＮＲ１５）−、−（ＣＲ１６Ｒ１７）−の何れかを表し、Ｒ１１’〜Ｒ１４’およびＲ１５〜Ｒ１７はそれぞれ独立に水素原子、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基を表す。

In the general formula (II), R1 ′ to R5 ′ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted Alternatively, it represents an unsubstituted arylcarbonylamino group, a carbamoyl group, a substituted or unsubstituted alkylcarbamoyl group, or a substituted or unsubstituted arylcarbamoyl group. R1 ′ and R2 ′ and R4 ′ and R5 ′ may be linked to form a ring. A ′ represents a ring formed by linking N and B ′, B ′ represents any of O, S, N, NR7 ′, CR8 ′, CR9′R10 ′, and R7 ′ to R10 ′ are each independently Hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxy group, amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted Aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, carbamoyl group, substituted or unsubstituted An alkylcarbamoyl group and a substituted or unsubstituted arylcarbamoyl group are represented. -X- is -O-, -S-,-(NR11)-,-(CR12R13)-,-(C = O)-,-(O-C = O)-,-(C = O-O). -,-(NH-CO)-, or-(CO-NH)-. -Y- is _{- (CH 2) s -,} - (C 6 H 4) represents any t-, s and t represent a positive number including zero. The Y chain is -O-, -S-,-(NR14)-,-(O-C = O)-,-(C = O-O)-,-(NH-CO)-,-( CO-NH)-may be interrupted. -Z- represents any one of -O-, -S-,-(NR15)-,-(CR16R17)-, and R11 'to R14' and R15 to R17 are each independently a hydrogen atom, substituted or unsubstituted. An alkyl group or a substituted or unsubstituted aryl group is represented.

  The portions of general formula (I) and general formula (II) can be relatively easily introduced into the previously synthesized polymer material by appropriately modifying the spacer portion. However, it cannot be introduced into any position of the polymer chain, for example.

  In order to solve this problem, monomerization represented by general formula (III) is effective as a chemical modification of general formula (I) and general formula (II).

上記一般式（ＩＩＩ）中、Ｒ１”〜Ｒ５”はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。また、Ｒ１”とＲ２”、Ｒ４”とＲ５”は、連結して環を形成していても良い。Ａ”はＮとＢ”が連結して成る環を表し、Ｂ”はＯ、Ｓ、Ｎ、ＮＲ７”、ＣＲ８”、ＣＲ９”Ｒ１０”の何れかを表し、Ｒ７”〜Ｒ１０”はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシ基、アミノ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアルキルオキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基、置換もしくは未置換のアルキルカルボニルアミノ基、置換もしくは未置換のアリールカルボニルアミノ基、カルバモイル基、置換もしくは未置換のアルキルカルバモイル基、置換もしくは未置換のアリールカルバモイル基を表す。−Ｘ−は−Ｏ−、−Ｓ−、−（ＮＲ１１’）−、−（ＣＲ１２’Ｒ１３’）−、−（Ｃ＝Ｏ）−、−（Ｏ−Ｃ＝Ｏ）−、−（Ｃ＝Ｏ−Ｏ）−、−（ＮＨ−ＣＯ）−、−（ＣＯ−ＮＨ）−の何れかを表す。−Ｙ’−は−（ＣＨ_２）ｓ−、−（Ｃ_６Ｈ_４）ｔ−の何れかを表し、ｓ及びｔは０を含む正数を表す。また、このＹ’鎖は−Ｏ−、−Ｓ−、−（ＮＲ１４’）−、−（Ｏ−Ｃ＝Ｏ）−、−（Ｃ＝Ｏ−Ｏ）−、−（ＮＨ−ＣＯ）−、−（ＣＯ−ＮＨ）−の何れかで中断されていても良い。Ｒ１１’〜Ｒ１４’はそれぞれ独立に水素原子、置換もしくは未置換のアルキル基、置換もしくは未置換のアリール基を表す。

In the general formula (III), R1 ″ to R5 ″ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted Alternatively, it represents an unsubstituted arylcarbonylamino group, a carbamoyl group, a substituted or unsubstituted alkylcarbamoyl group, or a substituted or unsubstituted arylcarbamoyl group. R1 ″ and R2 ″ and R4 ″ and R5 ″ may be linked to form a ring. A ″ represents a ring formed by linking N and B ″, B ″ represents any of O, S, N, NR7 ″, CR8 ″, CR9 ″ R10 ″, and R7 ″ to R10 ″ are each independently Hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxy group, amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted Aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, carbamoyl group, substituted or unsubstituted An alkylcarbamoyl group, a substituted or unsubstituted arylcarbamoyl group, -X- represents -O-, -S-,-( R11 ′) —, — (CR12′R13 ′) —, — (C═O) —, — (O—C═O) —, — (C═O—O) —, — (NH—CO) —, - (CO-NH) - represents.-Y'- is either a _{- (CH 2) s -,} - (C 6 H 4) represents any t-, positive number s and t including 0 The Y ′ chain represents —O—, —S—, — (NR14 ′) —, — (O—C═O) —, — (C═O—O) —, — (NH—CO). )-Or-(CO-NH)-, R11 'to R14' each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. .

Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Specific examples of the alkyl group are methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n -Primary alkyl group such as decyl group, isobutyl group, isoamyl group, 2-methylbutyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2-ethylbutyl group, 2-methylhexyl group, 3 -Methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, 3-ethylpentyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methyl Heptyl group, 2-ethylhexyl group, 3-ethylhexyl group, isopropyl group, sec-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1,2-dimethylpropyl group, 1-methylheptyl group, 1 Ethylbutyl group, 1,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1-methylhexyl group, 1-ethylheptyl group, 1-propylbutyl group, 1-isopropyl -2-methylpropyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-propyl-2-methylpropyl group, 1-methylheptyl group, 1-ethylhexyl group, 1-propylpentyl Group, 1-isopropylpentyl group, 1-isopropyl-2-methylbutyl group, 1-isopropyl-3-methylbutyl group, 1-methyloctyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-isobutyl-3- Secondary alkyl group such as methylbutyl group, tertiary alkyl group such as neopentyl group, tert-butyl group, tert-hexyl group, tert-amyl group, tert-octyl group, cyclohexyl And cycloalkyl groups such as syl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-tert-butylcyclohexyl group, 4- (2-ethylhexyl) cyclohexyl group, bornyl group, isobornyl group (adamantane group), etc. It is done. Furthermore, these primary and secondary alkyl groups may be substituted with a hydroxyl group, a halogen atom, a nitro group, a carboxy group, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic residue, and the like. In addition, the alkyl group may be substituted with an atom such as oxygen, sulfur or nitrogen. Examples of the alkyl group substituted through oxygen include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, a butoxyethyl group, an ethoxyethoxyethyl group, a phenoxyethyl group, a methoxypropyl group, an ethoxypropyl group, As an alkyl group in which a piperidino group, a morpholino group, or the like is substituted through sulfur, a methylthioethyl group, an ethylthioethyl group, an ethylthiopropyl group, a phenylthioethyl group, or the like is substituted through nitrogen Examples of the alkyl group include a dimethylaminoethyl group, a diethylaminoethyl group, and a diethylaminopropyl group. Specific examples of the heterocyclic residue include indolyl group, furyl group, thienyl group, pyridyl group, piperidyl group, quinolyl group, isoquinolyl group, piperidino group, morpholino group, pyrrolyl group and the like.

  Specific examples of the aryl group include a phenyl group, a pentarenyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group, a phenalenyl group, a phenanthrenyl group, an anthracenyl group, a triphenylenyl group, and a pyrenyl group.

  Specific examples of the alkyloxy group are not particularly limited as long as a directly substituted or unsubstituted alkyl group is bonded to an oxygen atom, and specific examples of the alkyl group include the above-described specific examples.

  Specific examples of the aryloxy group may be those in which a substituted or unsubstituted aryl group is bonded directly to an oxygen atom, and specific examples of the aryl group may include the above-described specific examples.

  Specific examples of the alkylamino group are not particularly limited as long as a directly substituted or unsubstituted alkyl group is bonded to the nitrogen atom, and specific examples of the alkyl group include the above-described specific examples.

  Specific examples of the arylamino group are not particularly limited as long as a directly substituted or unsubstituted aryl group is bonded to a nitrogen atom, and specific examples of the aryl group include the above-described specific examples.

  Specific examples of the alkylcarbonylamino group may be those in which a directly substituted or unsubstituted alkyl group is bonded to a carbon atom of the carbonylamino group, and specific examples of the alkyl group include the specific examples described above. Can do.

  Specific examples of the arylcarbonylamino group may be those in which a directly or unsubstituted aryl group is bonded to a carbon atom of the carbonylamino group, and specific examples of the aryl group include the specific examples described above. Can do.

  Specific examples of the alkylcarbamoyl group are not particularly limited as long as one or two substituted or unsubstituted alkyl groups are directly and independently bonded to the nitrogen atom of the carbamoyl group. Can include the specific examples described above.

  Specific examples of the arylcarbamoyl group are not particularly limited as long as one or two substituted or unsubstituted aryl groups are directly and independently bonded to the nitrogen atom of the carbamoyl group. Can include the specific examples described above.

Further, if there is a difference in thermal conductivity between the recording material existence part (5) and the recording material non-existence part (6), an increase in the area (3) can be further prevented. The heat generated in the recording material presence portion (5) diffuses to the surrounding recording material non-existence portion (6). Here, if the thermal conductivity of the recording material non-existing portion (6) is smaller than that of the recording material existing portion (5), it is not sufficiently transmitted to the next recording material existing portion (5). Thereby, the increase in the area (3) can be prevented.
Therefore, it is preferable that the recording material non-existing portion (6) material has sufficiently lower thermal conductivity than the recording dye material of the recording material existing portion (5).

As the material having a small thermal conductivity, a material that hardly absorbs recording light can be used. For example, polyacrylates, polymethacrylates, polysiloxanes, polyureas, polyurethanes, polyamides, polyesters, Examples include polystyrenes.
When a polymer material obtained by grafting a light absorber on the repeating unit having a small thermal conductivity was used, there was an effect of reducing the region (3) that was changed by the conduction heat.

Next, a specific configuration aspect of the optical recording medium of the present invention having the recording layer 20 as shown in FIG. 4 will be described with reference to the drawings.
9 to 12 are schematic cross-sectional views of the write-once type optical recording medium. As shown in FIG. 9, the optical recording medium has a recording layer 20 formed on a substrate 101, and a base layer 102 is interposed between the substrate 101 and the recording layer 20 as shown in FIG. Also good. Further, as shown in FIG. 11, an arbitrary protective layer 103 may be formed on the outermost surface, and as shown in FIG. 12, a hard coat layer 104 is formed on the main surface opposite to the recording layer forming surface. It may be.

13 to 15 are schematic configuration diagrams of conventionally known optical recording media for CD-R.
As shown in FIG. 13, the optical recording medium in this example has a configuration in which a recording layer 20, a metal reflective layer 106, and a protective layer 103 are sequentially stacked on a substrate 101. Further, as shown in FIG. 14, a base layer 102 may be interposed between the substrate 101 and the recording layer 20, and a hard coat is formed on the main surface opposite to the recording layer forming surface as shown in FIG. A layer 104 may be formed.

16 to 18 are schematic configuration diagrams of conventionally known optical recording media for DVD-R.
As shown in FIG. 16, the optical recording medium in this example basically has a configuration in which a protective layer 20, a metal reflective layer 106, and a protective layer 103 are laminated on a substrate 101, and an adhesive layer as shown in FIG. A protective substrate 107 may be provided via 108, and a hard coat layer 104 may be formed on the main surface opposite to the recording layer forming surface as shown in FIG.

Examples are shown below, but the present invention is not limited to these examples.
(Synthesis Example 1)
2-Amino-4,5-dicyanoimidazole (13.3 g) was added to water (65 ml) and acidified with 35% concentrated hydrochloric acid (35 ml). After cooling to 0 ° C., 5N aqueous sodium nitrite solution (22 ml) was added dropwise to diazotize. After completion of the reaction, amidosulfuric acid was added until the iodine starch paper was no longer colored, and the excess nitrous acid was removed to obtain a diazo solution. Next, phenol (9.4 g) was added to water (150 ml) and sodium hydroxide was added until the solution was alkaline. The diazo liquid was added to this solution, and a coupling reaction was performed while maintaining pH> 9. Next, the precipitate and sodium hydrogen carbonate (16 g) were added to water (50 ml), and dimethyl sulfate (20 g) was allowed to act. After completion of the reaction, the reaction mixture was neutralized with ethanolamine (5 ml) to obtain Compound 1 (20.4 g).

Compound 1 (15.1 g) was added to DMSO (50 ml), and potassium carbonate (10.4 g) was added. 6-Chloro-1-hexanol (9.8 g) was added to this solution, and the temperature was raised to 110 ° C. to carry out the reaction. After completion of the reaction, the reaction solution was discharged into water, and the target product was extracted with toluene. The extract was dried over anhydrous magnesium sulfate and concentrated, and purified with a silica gel column to give compound 2 (16.5 g).
Compound 2 (10.6 g) and triethylamine (4.0 g) were added to dry THF (100 ml), and then methacryloyl chloride (3.8 g) was added dropwise for reaction. After completion of the reaction, the target product was extracted with chloroform. The extract was dried over anhydrous magnesium sulfate and concentrated, and purified with a silica gel column to give compound 3 (11.5 g).

(Synthesis Example 2)
3-Methoxy-2-naphthoic acid (10.1 g) was suspended in toluene (15 ml), and thionyl chloride (10 ml) was added dropwise. After completion of the reaction, unnecessary thionyl chloride was removed by concentration under reduced pressure with toluene. This was dissolved again in toluene and added dropwise to a toluene solution of 3-aminophenyl acrylate (8.2 g) to obtain Compound 4 (16.2 g).
Next, 2-amino-5,6-dimethoxybenzothiazole (8.4 g) was added to acetic acid (100 ml) and heated to dissolve. After rapidly cooling this solution, 5N sodium nitrite aqueous solution (9 ml) was added dropwise while maintaining -10 ° C to diazotize. After completion of the reaction, amidosulfuric acid was added, and the diazo liquid was obtained by removing excess nitrous acid until the iodine starch paper was no longer colored. Compound 4 (13.9 g) was then added to water and sodium hydroxide was added until the solution was alkaline. The diazo liquid was added to this solution to carry out a coupling reaction. The precipitate was filtered and washed with water to give dry compound 5 (19.1 g).

(Synthesis Example 3)
2-Amino-5-ethyl-4-phenyloxazole (1.9 g) was added to phosphoric acid (20 ml), and concentrated sulfuric acid (1 ml) was added thereto and dissolved by heating. This was rapidly cooled with a stirrer to obtain a suspension in which fine crystals were precipitated, and a 5N sodium nitrite aqueous solution (2 ml) was added dropwise while maintaining -20 ° C. to prepare a diazo solution. This was put into a methanol solution of compound 6 (2.3 g), and a coupling reaction was performed to obtain compound 7 (3.1 g).
Compound 7 (3.1 g) and triethylamine (1.1 g) were added to dry THF (20 ml), and then methacryloyl chloride (0.8 g) was added dropwise for reaction. After completion of the reaction, the target product was extracted with chloroform. The extract was dried over anhydrous magnesium sulfate and concentrated, and purified with a silica gel column to give compound 8 (3.3 g).

(Synthesis Example 4)
Cyanuric chloride (9.2 g) was dissolved in acetone (100 ml), and then an aqueous solution containing thiol (12.1 g) and an equivalent amount of sodium hydroxide was added thereto to phenothioxylate. Subsequently, the compound 9 (11.1 g) was obtained by reacting with hydrazine monohydrate (2 g) in ethanol in the presence of potassium acetate (15 g).
The previous compound 6 (6.8 g) and compound 9 (9.8 g) were added to an ethanol-acetic acid aqueous solution (1: 1, 200 ml), and a very small amount of iodine was added, followed by 30% aqueous hydrogen peroxide (5 ml). Was further reacted with methacryloyl chloride in the same manner as in Synthesis Example 3 to obtain Compound 10 (5.6 g).

(Synthesis Example 5)
6-Aminonicotinonitrile (11.9 g) was added to THF (100 ml), and then 60% sodium amide (7.8 g) was added. To this, isoamyl nitrite (14.1 g) was added dropwise to obtain Compound 11 (14.5 g).
Compound 11 (11.9 g) and compound 12 (21.0 g) were suspended in ethanol, and carbon dioxide gas was passed through the suspension for 1 week to obtain compound 13 (10.5 g).
Compound 13 (8.6 g) and 4-methylchlorostyrene (3.1 g) were added to dry THF (100 ml), 60% sodium hydride (0.8 g) was added, and the mixture was stirred at room temperature. After completion of the reaction, the reaction solution was discharged into water, and the target product was extracted with toluene. The extract was dried over anhydrous magnesium sulfate and concentrated, and purified with a silica gel column to give compound 14 (6.5 g).

(Synthesis Example 6)
Compound 14 (0.00280 g), Compound 15 (1.0 g), Compound 16 (0.00201 g), Cuprous chloride (0.00092 g), Methyl methacrylate (2.0 g) and Anisole (7 ml) in a reaction vessel Was added, and dissolved oxygen was sufficiently removed, and then argon gas was vented. Under an argon stream, the temperature was raised to 110 ° C. and polymerization was carried out for 4 hours. After completion of the reaction, the reaction mixture was sufficiently cooled in an ice bath and then discharged into methanol to obtain Compound 17 (2.3 g, m1 = 131, n1 = 48, Mw / Mn = 1.29).

(Synthesis Example 7)
A reaction vessel was charged with methyl methacrylate (3.0 g), compound 14 (0.01205 g), compound 16 (0.00865 g), cuprous chloride (0.00396 g) and 2-butanone (4.5 ml). Argon gas was bubbled after sufficiently removing dissolved oxygen. Under an argon stream, the temperature was raised to 50 ° C. and polymerization was carried out for 6 hours. After completion of the reaction, the reaction mixture was sufficiently cooled in an ice bath and then discharged into methanol to obtain a MMA polymer (2.1 g, m2 = 562, Mn / Mw = 1.37).
This polymer (2.1 g), compound 16 (0.00795 g), compound 18 (1.5 g) and cuprous chloride (0.00363 g) were dissolved in anisole (10 ml) and dissolved oxygen by vacuum degassing. Then, argon gas was vented. Under an argon stream, the temperature was raised to 120 ° C. and polymerization was carried out for 7 hours. After completion of the reaction, the reaction mixture was sufficiently cooled in an ice bath and then discharged into methanol to obtain Compound 19 (2.5 g, m2 = 562, n2 = 70, Mw / Mn = 1.35).

(Chemical Formula 14)

Specific examples of the polymer material synthesized as described above are shown below.
In the following chemical formula, the polymer delimited by “-b-” represents a diblock copolymer (Ab- [BC]) of A and [BC].
[B-C] represents a random copolymer composed of B and C.
Further, the number of repetitions m, n, q... In the polymer formula is an integer value calculated from the number average molecular weight (Mn), and does not define the number of repetitions. The number average molecular weight (Mn). Can be determined by GPC.
Moreover, although the residue etc. derived from an initiator are couple | bonded with the terminal of following Chemical formula, respectively, it abbreviate | omits.

高分子材料例 １： Ｍｗ／Ｍｎ＝１．３０、ｍ１＝１０５０、ｎ１＝３８０
２： Ｍｗ／Ｍｎ＝１．２８、ｍ１＝１０５０、ｎ１＝１８０
３： Ｍｗ／Ｍｎ＝１．２７、ｍ１＝１０５０、ｎ１＝ ９０

Example of polymer material 1: Mw / Mn = 1.30, m1 = 1050, n1 = 380
2: Mw / Mn = 1.28, m1 = 1050, n1 = 180
3: Mw / Mn = 1.27, m1 = 1050, n1 = 90

高分子材料例 ４： Ｍｗ／Ｍｎ＝１．３７、ｍ２＝１２４０、ｎ２＝１４０
５： Ｍｗ／Ｍｎ＝１．３４、ｍ２＝１２４０、ｎ２＝ ８０
６： Ｍｗ／Ｍｎ＝１．３２、ｍ３＝１２４０、ｎ２＝ ４０

Polymer material example 4: Mw / Mn = 1.37, m2 = 1240, n2 = 140
5: Mw / Mn = 1.34, m2 = 1240, n2 = 80
6: Mw / Mn = 1.32, m3 = 1240, n2 = 40

高分子材料例 ７： Ｍｗ／Ｍｎ＝１．３６、ｍ３＝１１６０、ｎ３＝２６０、ｑ３＝ １８０
８： Ｍｗ／Ｍｎ＝１．３６、ｍ３＝１１６０、ｎ３＝１１０、ｑ３＝３３０
９： Ｍｗ／Ｍｎ＝１．３６、ｍ３＝１１６０、ｎ３＝３０、ｑ３＝４１０

Polymer material example 7: Mw / Mn = 1.36, m3 = 1160, n3 = 260, q3 = 180
8: Mw / Mn = 1.36, m3 = 1160, n3 = 110, q3 = 330
9: Mw / Mn = 1.36, m3 = 1160, n3 = 30, q3 = 410

高分子材料例１０： Ｍｗ／Ｍｎ＝１．２９、ｍ４＝１４００、ｎ４＝２４０、ｑ４＝ ９０
１１： Ｍｗ／Ｍｎ＝１．２８、ｍ４＝１４００、ｎ４＝７０、ｑ４＝２６０
１２： Ｍｗ／Ｍｎ＝１．３１、ｍ４＝１４００、ｎ４＝２０、ｑ４＝３１０

Polymer material example 10: Mw / Mn = 1.29, m4 = 1400, n4 = 240, q4 = 90
11: Mw / Mn = 1.28, m4 = 1400, n4 = 70, q4 = 260
12: Mw / Mn = 1.31, m4 = 1400, n4 = 20, q4 = 310

高分子材料例１３： Ｍｗ／Ｍｎ＝１．４２、ｎ５＝１３０
１４： Ｍｗ／Ｍｎ＝１．４０、ｎ５＝ ６０

Polymer material example 13: Mw / Mn = 1.42, n5 = 130
14: Mw / Mn = 1.40, n5 = 60

高分子材料例１５： Ｍｗ／Ｍｎ＝１．４５、ｎ６＝１１０
１６： Ｍｗ／Ｍｎ＝１．４１、ｎ６＝ ５０

Polymer material example 15: Mw / Mn = 1.45, n6 = 110
16: Mw / Mn = 1.41, n6 = 50

高分子材料例１７： Ｍｗ／Ｍｎ＝１．２６、ｍ７＝１２４０、ｎ７＝３３０、ｑ７＝ ６０
１８： Ｍｗ／Ｍｎ＝１．２６、ｍ７＝１２４０、ｎ７＝１７０、ｑ７＝２２０

Polymer material example 17: Mw / Mn = 1.26, m7 = 1240, n7 = 330, q7 = 60
18: Mw / Mn = 1.26, m7 = 1240, n7 = 170, q7 = 220

高分子材料例１９： Ｍｗ／Ｍｎ＝１．２９、ｍ８＝１５７０、ｎ８＝１６０、ｑ８＝ ２８０
２０： Ｍｗ／Ｍｎ＝１．２９、ｍ８＝１５７０、ｎ８＝６０、ｑ８＝３８０

Polymer material example 19: Mw / Mn = 1.29, m8 = 1570, n8 = 160, q8 = 280
20: Mw / Mn = 1.29, m8 = 1570, n8 = 60, q8 = 380

高分子材料例２１： Ｍｗ／Ｍｎ＝１．３５、ｍ９＝２５１０、ｎ９＝２９０、ｑ９＝ ４０
２２： Ｍｗ／Ｍｎ＝１．３５、ｍ９＝２５１０、ｎ９＝６０、ｑ９＝２７０

Polymer material example 21: Mw / Mn = 1.35, m9 = 2510, n9 = 290, q9 = 40
22: Mw / Mn = 1.35, m9 = 2510, n9 = 60, q9 = 270

高分子材料例２３： Ｍｗ／Ｍｎ＝１．３８、ｍ１０＝２９７０、ｎ１０＝２３０、ｑ１０＝ ４０
２４： Ｍｗ／Ｍｎ＝１．３８、ｍ１０＝２９７０、ｎ１０＝５０、ｑ１０＝２２０

Polymer material example 23: Mw / Mn = 1.38, m10 = 2970, n10 = 230, q10 = 40
24: Mw / Mn = 1.38, m10 = 2970, n10 = 50, q10 = 220

高分子材料例２５： Ｍｗ／Ｍｎ＝１．３５、ｍ１１＝１７００、ｎ１１＝２８０、ｑ１１＝ ７０
２６： Ｍｗ／Ｍｎ＝１．３５、ｍ１１＝１７００、ｎ１１＝６０、ｑ１１＝２９０

Polymer material example 25: Mw / Mn = 1.35, m11 = 1700, n11 = 280, q11 = 70
26: Mw / Mn = 1.35, m11 = 1700, n11 = 60, q11 = 290

高分子材料例２７： Ｍｗ／Ｍｎ＝１．４１、ｍ１２＝９７０、ｎ１２＝２００、ｑ１２＝３０
２８： Ｍｗ／Ｍｎ＝１．４１、ｍ１２＝９７０、ｎ１２＝６０、ｑ１２＝１７０

Polymer material example 27: Mw / Mn = 1.41, m12 = 970, n12 = 200, q12 = 30
28: Mw / Mn = 1.41, m12 = 970, n12 = 60, q12 = 170

高分子材料例２９： Ｍｗ／Ｍｎ＝１．３６、ｍ１３＝１２００、ｎ１３＝１３０

Polymer material example 29: Mw / Mn = 1.36, m13 = 1200, n13 = 130

高分子材料例３０： Ｍｗ／Ｍｎ＝１．３２、ｍ１４＝１０００、ｎ１４＝１２０

Polymer material example 30: Mw / Mn = 1.32, m14 = 1000, n14 = 120

高分子材料例３１： Ｍｗ／Ｍｎ＝１．３４、ｍ１５＝１９５０、ｎ１５＝３１０、ｑ４＝４０

Polymer material example 31: Mw / Mn = 1.34, m15 = 1950, n15 = 310, q4 = 40

高分子材料例３２： Ｍｗ／Ｍｎ＝１．２９、ｍ１６＝２５６０、ｎ１６＝２９０、ｑ１６＝１１０

Polymer material example 32: Mw / Mn = 1.29, m16 = 2560, n16 = 290, q16 = 110

高分子材料例３３： Ｍｗ／Ｍｎ＝１．４０、ｍ１７＝１２２０、ｎ１７＝３４０、ｑ４＝８０

Polymer material example 33: Mw / Mn = 1.40, m17 = 1220, n17 = 340, q4 = 80

高分子材料例３４： Ｍｗ／Ｍｎ＝１．３５、ｍ１８＝１９９０、ｎ１８＝３１０、ｑ１８＝８０

Polymer material example 34: Mw / Mn = 1.35, m18 = 1990, n18 = 310, q18 = 80

高分子材料例３５： Ｍｗ／Ｍｎ＝１．３６、ｍ１９＝１９４０、ｎ１９＝１４０、ｑ１９＝１５０

Polymer material example 35: Mw / Mn = 1.36, m19 = 1940, n19 = 140, q19 = 150

高分子材料例３６： Ｍｗ／Ｍｎ＝１．４２、ｍ２０＝１６２０、ｎ２０＝９０、ｑ２０＝６０

Polymer material example 36: Mw / Mn = 1.42, m20 = 1620, n20 = 90, q20 = 60

高分子材料例３７： Ｍｗ／Ｍｎ＝１．４４、ｍ２１＝１５２０、ｎ２１＝４５０、ｑ２１＝８０

Polymer material example 37: Mw / Mn = 1.44, m21 = 1520, n21 = 450, q21 = 80

  Table 1 shows polymer material examples 38 to 45 represented by the following general formula (IV).

＊Ｒに於いて、指定無き場合はＨを表す。

* In R, H is indicated if not specified.

  Table 2 shows polymer material examples 46 to 51 represented by the following general formula (V).

Examples 1 to 9 and Comparative Examples 1 to 4
Polymer material examples 2 to 6, 8 to 11, and 13 to 16 were dissolved in toluene, respectively. Spinner coating on a polycarbonate substrate (0.6 mm thick injection-molded plate, 200 nm deep, half width 0.25 μm, track pitch 0.74 μm guide groove formed) with this solution protected by photopolymer Then, a recording layer having a thickness of 300 nm was formed.
Using the unrecorded state of this optical recording medium and semiconductor laser light having an oscillation wavelength of 657 nm, the surface shape and the presence / absence of deflection after recording the EFM signal were measured while tracking.

  The presence or absence of deflection is determined by using a single optical microscope in which light from the light source is transmitted or reflected in the order of the light source-sample-lens barrel, and a fixed polarizer between the light source and sample and a movable polarization between the sample and lens barrel. When the polarizer rotation angle is 90 °, adjust the polarization direction of the fixed polarizer so that the polarization direction of the movable polarizer is orthogonal, and the polarizer rotation angle is 45 ° from 0 ° to 180 °. The presence or absence of deflection was measured by the presence or absence of the change in brightness. The case where the polarization before recording was “none” and the polarization after recording was “present” was evaluated as “OK”, and the others were evaluated as “NG”.

  The surface shape was observed with an AFM (atomic force microscope) and the domain diameter was measured.

Examples 10 to 19 and Comparative Examples 5 to 8
Polymer material examples 13 to 16, 18 to 23, and 25 to 28 were dissolved in toluene, respectively. Spinner coating on a polycarbonate substrate (0.6 mm thick injection-molded plate, 200 nm deep, half width 0.25 μm, track pitch 0.74 μm guide groove formed) with this solution protected by photopolymer Then, a 300 nm recording layer was formed. Thereafter, a gold 1200 mm reflective layer is formed by a sputtering method, and a protective layer is further formed thereon with a photopolymer, and then an injection molded polycarbonate planar substrate having a thickness of 0.6 mm is adhered with the photopolymer, did.
[Recording / playback conditions]
Using a semiconductor laser beam with an oscillation wavelength of 657 nm, an EFM signal was recorded while tracking, reproduced with continuous light from a semiconductor laser with an oscillation wavelength of 657 nm, and C / N was measured.

Examples 20-38, Comparative Examples 9-12
Polymer material examples 29 to 32, 34 to 36, 38 to 40, 42 to 44, and 46 to 51 were dissolved in toluene, respectively. Spinner coating on a polycarbonate substrate (0.6 mm thick injection-molded plate, 200 nm deep, half width 0.25 μm, track pitch 0.74 μm guide groove formed) with this solution protected by photopolymer Then, a 300 nm recording layer was formed. A semiconductor laser beam having an oscillation wavelength of 405 nm was recorded on this recording layer, and an EFM signal was recorded while tracking. The surface shape was observed and photographed by AFM, and the average value of domain diameters contained in 5 μm ² was measured.

＊ドメイン系は、記録材Ａ若しくはＢが結合している高分子鎖から成るドメインの直径を表す。尚、相分離形状がラメラ状及び網目状の場合、ドメイン系は幅長さを表す。
＊比較例
・比較例 ９：高分子材料例１３を３５部と市販のポリスチレン６５部の混合物
・比較例１０：高分子材料例１３を１５部と市販のポリスチレン８５部の混合物
・比較例１１：高分子材料例１４を４０部と市販のポリスチレン６０部の混合物
・比較例１２：高分子材料例１４を２０部と市販のポリスチレン８０部の混合物

* The domain system represents the diameter of a domain composed of a polymer chain to which the recording material A or B is bonded. When the phase separation shape is lamellar or mesh-like, the domain system represents the width length.
Comparative Example / Comparative Example 9: Mixture of 35 parts of Polymer Material Example 13 and 65 parts of commercially available polystyrene / Comparative Example 10: Mixture of 15 parts of Polymer Material Example 13 and 85 parts of commercially available polystyrene / Comparative Example 11: A mixture of 40 parts of polymeric material example 14 and 60 parts of commercially available polystyrene. Comparative Example 12: A mixture of 20 parts of polymeric material example 14 and 80 parts of commercially available polystyrene.

FIG. 4 is a diagram showing a recording state of a conventional recording medium. FIG. 4 is a diagram showing a recording state of a recording medium in which the recording layer surface (interface) is phase-separated. FIG. 4 is a diagram showing a situation that is not suitable as a phase-separated recording layer. FIG. 4 is a diagram showing a desirable situation as a phase-separated recording layer. These are the figures showing the basic phase separation of the block (A and B couple | bonded) copolymer. These are the tables | surfaces which showed the change of the observation image accompanying rotation of a polarizer when the thin film of the polymeric material example 4 formed into a film on the silicon wafer was observed with the reflective polarizing microscope. FIG. 5 is a spectrum diagram in which the reflectance was measured with a spectrophotometer in which a thin film of polymer material example 6 formed on a quartz plate was disposed with a polarizer disposed in the light irradiating unit and the light receiving unit so that the polarization direction was perpendicular. . These are the surface shape images which observed the thin film of the polymer material example 6 formed into a film on the silicon wafer by AFM. FIG. 2 is a diagram showing a normal write-once type optical recording medium. FIG. 5 is another diagram showing a normal write-once type optical recording medium. FIG. 5 is another diagram showing a normal write-once type optical recording medium. FIG. 5 is another diagram showing a normal write-once type optical recording medium. FIG. 3 is a diagram illustrating a configuration of a medium for CD-R. FIG. 5 is another diagram showing the configuration of a medium for CD-R. FIG. 5 is another diagram showing the configuration of a medium for CD-R. FIG. 3 is a diagram illustrating a configuration of a DVD-R medium. FIG. 5 is another diagram showing the configuration of a medium for DVD-R. FIG. 5 is another diagram showing the configuration of a medium for DVD-R.

Explanation of symbols

1 Range that does not change even when recording light is received (area 1)
2 Range changed by recording light (area 2)
3 Range changed by evangelistic heat (region 3)
5 Recording material (dye) existing range (region 5)
6 Range without recording material (dye) (area 6)
20 recording layer 101 substrate 102 base layer 103 protective layer 104 hard coat layer 106 metal reflective layer 107 protective substrate 108 adhesive layer

Claims (8)

At least one of the materials constituting the recording layer has a portion that cannot take an order-disorder state by light and a light absorber that can take an order-disorder state, and the light absorber is represented by the following general formula (I). An optical recording medium, which is a polymer material containing at least one kind of compound.

In the general formula (I), R1 to R5 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group. Substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted A substituted arylcarbonylamino group, a carbamoyl group, a substituted or unsubstituted alkylcarbamoyl group, and a substituted or unsubstituted arylcarbamoyl group are represented. R1 and R2, R2 and R3, R3 and R4, and R4 and R5 may be linked to form a ring. Any one of R1 to R5 is linked to the polymer main chain. A represents a ring formed by linking N and B, B represents any of O, S, N, NR7, CR8, CR9R10, and R7 to R10 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano Group, hydroxyl group, carboxy group, amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkyl Amino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, carbamoyl group, substituted or unsubstituted alkylcarbamoyl group, substituted or unsubstituted aryl Represents a rucarbamoyl group. 2. The optical recording medium according to claim 1, wherein the light absorber contains at least one compound represented by the following general formula (I).

In the general formula (II), R1 ′ to R5 ′ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted Alternatively, it represents an unsubstituted arylcarbonylamino group, a carbamoyl group, a substituted or unsubstituted alkylcarbamoyl group, or a substituted or unsubstituted arylcarbamoyl group. R1 ′ and R2 ′ and R4 ′ and R5 ′ may be linked to form a ring. A ′ represents a ring formed by linking N and B ′, B ′ represents any of O, S, N, NR7 ′, CR8 ′, CR9′R10 ′, and R7 ′ to R10 ′ are each independently Hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxy group, amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted Aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, carbamoyl group, substituted or unsubstituted An alkylcarbamoyl group and a substituted or unsubstituted arylcarbamoyl group are represented. -X- is -O-, -S-,-(NR11)-,-(CR12R13)-,-(C = O)-,-(O-C = O)-,-(C = O-O). -,-(NH-CO)-, or-(CO-NH)-. -Y- is _{- (CH 2) s -,} - (C 6 H 4) represents any t-, s and t represent a positive number including zero. The Y chain is -O-, -S-,-(NR14)-,-(O-C = O)-,-(C = O-O)-,-(NH-CO)-,-( CO-NH)-may be interrupted. -Z- represents any one of -O-, -S-,-(NR15)-,-(CR16R17)-, and R11 'to R14' and R15 to R17 are each independently a hydrogen atom, substituted or unsubstituted. An alkyl group or a substituted or unsubstituted aryl group is represented. The polymer material is a polymer material having a chain structure portion, and the main chain of the polymer material is a block copolymer having a repeating unit of Ab- [BC], and the polymer The optical recording medium according to claim 1 or 2, wherein a light absorber capable of taking an ordered-disordered state is grafted on any one of the [BC] portions of the main chain.
However, A, B, C represents a repeating monomer unit, “-b-” represents a diblock copolymer (Ab- [BC]) of A and [BC], [ BC] represents a random copolymer. The optical recording medium according to any one of claims 1 to 3, wherein any one of the [BC] parts contains at least one compound represented by the following general formula (III). .

In the general formula (III), R1 ″ to R5 ″ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted Alternatively, it represents an unsubstituted arylcarbonylamino group, a carbamoyl group, a substituted or unsubstituted alkylcarbamoyl group, or a substituted or unsubstituted arylcarbamoyl group. R1 ″ and R2 ″ and R4 ″ and R5 ″ may be linked to form a ring. A ″ represents a ring formed by linking N and B ″, B ″ represents any of O, S, N, NR7 ″, CR8 ″, CR9 ″ R10 ″, and R7 ″ to R10 ″ are each independently Hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxy group, amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted Aryloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, carbamoyl group, substituted or unsubstituted Represents an alkylcarbamoyl group, a substituted or unsubstituted arylcarbamoyl group, -X'- represents -O-, -S-,-( NR11 ′) —, — (CR12′R13 ′) —, — (C═O) —, — (O—C═O) —, — (C═O—O) —, — (NH—CO) —, - (CO-NH) - represents.-Y'- is either a _{- (CH 2) s -,} - (C 6 H 4) represents any t-, positive number s and t including 0 The Y ′ chain represents —O—, —S—, — (NR14 ′) —, — (O—C═O) —, — (C═O—O) —, — (NH—CO). )-Or-(CO-NH)-, R11 'to R14' each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. .   In the recording layer, the recording and / or reproducing light incident side interface (surface) is phase-separated into a first domain phase including the light absorber and a second domain phase not including the light absorber. The optical recording medium according to claim 1, wherein the optical recording medium is a recording medium. 6. The optical recording medium according to claim 5, wherein the thermal conductivity of the second domain phase is smaller than the thermal conductivity of the first domain phase.   7. The optical recording medium according to claim 5, wherein a domain diameter of the first domain phase is smaller than a minimum spot diameter that can be formed on an incident side interface of a recording layer by light for recording and / or reproduction. .     The optical recording medium according to any one of claims 1 to 7, wherein a weight fraction of the light absorber with respect to a molecular weight of the entire polymer material is 10% or more and 50% or less.

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