JP2009069211A - Method for producing photosensitive layer of electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a photosensitive layer of an electrophotographic photoreceptor with high accuracy. <P>SOLUTION: The method for producing a photosensitive layer of an electrophotographic photoreceptor includes: transferring an ink forming a photosensitive layer of an electrophotographic photoreceptor on a flexographic printing plate onto a substrate to be printed; and removing the solvent in the transferred ink by drying, or curing the transferred ink by irradiation with light to fix the ink forming a photosensitive layer of an electrophotographic photoreceptor on the substrate to be printed, wherein the ink forming a photosensitive layer of an electrophotographic photoreceptor is transferred onto the substrate to be printed by using the flexographic printing plate obtained by curing a resin composition containing a polymer produced from a polycarbonate diol comprising a repeating unit of a specific structure, having hydroxyl groups as both end groups, and having a number average molecular weight of 300-50,000. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a photosensitive layer of an electrophotographic photoreceptor using a flexographic printing plate.

  In electrophotography such as copying machines and printers, the entire photosensitive layer on the photosensitive drum is charged, and then a latent image such as a document is formed in the latent image forming unit, and then this latent image is charged with charged toner in the developing unit. After the visualization, the image is transferred to a recording medium such as plain paper at the transfer portion, and heat-welded at the fixing portion to obtain a hard copy. In this method, the photoreceptor is usually grounded via a conductive layer in order to improve the charge amount during charging, to provide a light attenuation effect during exposure, or to use as a bias electrode during development.

  Conventionally, photosensitive materials made of inorganic photoconductive materials such as selenium, selenium-tellurium alloys, cadmium sulfide, and zinc oxide have been widely used for the photosensitive layer of electrophotographic photoreceptors. In recent years, researches on organic photoconductive substances that are easy to synthesize and have characteristics such as exhibiting photoconductivity in an appropriate wavelength range have been advanced.

  For example, in Patent Document 1, an aluminum drum is used as the photosensitive drum, the charge transport layer coating solution is dip-coated, the charge transport layer is dip-coated, and the photosensitive layer is protected as a means for improving durability. An electrophotographic photoreceptor having a layer is disclosed.

  Patent Document 2 discloses an electrophotographic photoreceptor comprising a non-metallic flexible conductive support and a photosensitive layer comprising a plurality of thin films including a charge generation layer formed on the conductive support. is there. Thin film methods include vapor deposition, co-evaporation, spray coating, blade coating, casting, spinner coating, bead coating, wire bar coating, roller coating, curtain coating, and other coating methods. Has been.

  Further, in Patent Document 3, as a thin film forming method when the photoconductive composition is used for a photoreceptor such as an electrophotography, a spin coating method, a casting method, a dipping method, a bar coating method, a roll coating method, or the like is applied. The law is disclosed.

JP-A-6-123992 JP-A-8-190209 Japanese Patent No. 3146296

  However, the prior art does not disclose the production of a photosensitive layer of an electrophotographic photoreceptor by a printing method that is considered to be more advantageous in actual production. And in the methods disclosed in Patent Documents 1 to 3, in addition to the high-efficiency production by continuous process (roll-to-roll process), it is impossible to produce by patterning, It is not possible to produce a photosensitive layer of a highly accurate electrophotographic photoreceptor.

  An object of the present invention is to provide a method for producing a photosensitive layer of an electrophotographic photoreceptor with high accuracy.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors manufactured an electrophotographic photosensitive member photosensitive layer by transferring an ink for forming the photosensitive layer of the electrophotographic photosensitive member on a substrate to be printed. When using a flexographic printing plate obtained by curing a resin composition containing a polymer produced from a polycarbonate diol having a specific structure, a photosensitive layer of an electrophotographic photosensitive member can be produced with high accuracy. The headline and the present invention were completed.

(式中、Ｒ₁は、炭素数２〜５０の直鎖又は分岐した炭化水素基を表し、ｎは、２〜５０の整数を表す。）

（式中、Ｒ₂は、炭素数１０〜５０の直鎖又は分岐した炭化水素基を表す。）
［２］
前記樹脂組成物が、
前記ポリカーボネートジオールと、当該ポリカーボネートジオールの末端水酸基の当量未満のイソシアネート基当量の多官能イソシアネート化合物及び／又はポリイソシアネート化合物と、イソシアネートアルキルアクリレート及び／又はイソシアネートアルキルメタクリレートとを反応させることにより製造されるポリマー（ａ）、及び／又は
前記ポリカーボネートジオールの末端水酸基と、当該ポリカーボネートジオールの末端水酸基の当量を超えるイソシアネート基当量の多官能イソシアネート化合物及び／又はポリイソシアネート化合物と、ヒドロキシアルキルアクリレート及び／又はヒドロキシアルキルメタクリレートとを反応させることにより製造されるポリマー（ａ）を含有する、［１］に記載の電子写真感光体の感光層の製造方法。
［３］
前記樹脂組成物が、さらに、重合性不飽和基を有し、数平均分子量が５，０００未満である有機化合物（ｂ）を含有する、［１］又は［２］に記載の電子写真感光体の感光層の製造方法。
［４］
前記樹脂組成物が、さらに、無機系微粒子（ｃ）を含有する、［１］〜［３］のいずれに記載の電子写真感光体の感光層の製造方法。
［５］
前記樹脂組成物が感光性樹脂組成物である、［１］〜［４］のいずれかに記載の電子写真感光体の感光層の製造方法。
［６］
前記フレキソ印刷版が、フレキソ印刷原版表面に印刷パターンをレーザー彫刻することにより得られる、［１］〜［５］のいずれかに記載の電子写真感光体の感光層の製造方法。
［７］
前記フレキソ印刷版が、シート状又は円筒状に形成される、［１］〜［６］のいずれかに記載の電子写真感光体の感光層の製造方法。
［８］
前記フレキソ印刷版が、前記電子写真感光体の感光層を形成するインク中の前記溶剤に対する耐性を溶剤浸漬膨潤テストで評価した場合に、前記溶剤への浸漬前後で１０質量％以下の質量変化率を示す、［１］〜［７］のいずれかに記載の電子写真感光体の感光層の製造方法。 That is, the present invention provides the following method for producing a photosensitive layer of an electrophotographic photoreceptor.
[1]
The ink that forms the photosensitive layer of the electrophotographic photosensitive member on the flexographic printing plate is transferred onto the substrate to be printed, the solvent in the transferred ink is removed by drying, or the transferred ink is irradiated with light. Harden
A method for producing a photosensitive layer of an electrophotographic photosensitive member by fixing an ink for forming the photosensitive layer of the electrophotographic photosensitive member on a substrate to be printed,
A polymer (a) comprising a repeating unit represented by the following formula (1) and / or formula (2), wherein both terminal groups are hydroxyl groups, and the number average molecular weight is 300 to 50,000. The photosensitive layer of an electrophotographic photosensitive member is transferred onto a substrate to be printed using a flexographic printing plate obtained by curing a resin composition containing the above-mentioned resin composition.

(In the formula, R ₁ represents a linear or branched hydrocarbon group having 2 to 50 carbon atoms, and n represents an integer of 2 to 50.)

(In the formula, R ₂ represents a linear or branched hydrocarbon group having 10 to 50 carbon atoms.)
[2]
The resin composition is
Polymer produced by reacting the polycarbonate diol, a polyfunctional isocyanate compound and / or polyisocyanate compound having an isocyanate group equivalent less than the equivalent of the terminal hydroxyl group of the polycarbonate diol, and an isocyanate alkyl acrylate and / or an isocyanate alkyl methacrylate. (A) and / or a terminal hydroxyl group of the polycarbonate diol, an isocyanate group equivalent polyfunctional isocyanate compound and / or polyisocyanate compound exceeding the equivalent of the terminal hydroxyl group of the polycarbonate diol, and a hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate. The production of the photosensitive layer of the electrophotographic photosensitive member according to [1], comprising a polymer (a) produced by reacting Manufacturing method.
[3]
The electrophotographic photoreceptor according to [1] or [2], wherein the resin composition further contains an organic compound (b) having a polymerizable unsaturated group and a number average molecular weight of less than 5,000. A method for producing a photosensitive layer.
[4]
The method for producing a photosensitive layer of an electrophotographic photosensitive member according to any one of [1] to [3], wherein the resin composition further contains inorganic fine particles (c).
[5]
The method for producing a photosensitive layer of an electrophotographic photosensitive member according to any one of [1] to [4], wherein the resin composition is a photosensitive resin composition.
[6]
The method for producing a photosensitive layer of an electrophotographic photosensitive member according to any one of [1] to [5], wherein the flexographic printing plate is obtained by laser engraving a printing pattern on a surface of a flexographic printing original plate.
[7]
The method for producing a photosensitive layer of an electrophotographic photosensitive member according to any one of [1] to [6], wherein the flexographic printing plate is formed into a sheet shape or a cylindrical shape.
[8]
When the flexographic printing plate was evaluated for resistance to the solvent in the ink forming the photosensitive layer of the electrophotographic photosensitive member by a solvent immersion swelling test, the mass change rate was 10% by mass or less before and after immersion in the solvent. The manufacturing method of the photosensitive layer of the electrophotographic photoreceptor in any one of [1]-[7] which shows.

  According to the production method of the present invention, a photosensitive layer of an electrophotographic photosensitive member can be produced with high accuracy, and an electrophotographic photosensitive member including the photosensitive layer can be provided.

  Hereinafter, the best mode for carrying out the present invention (hereinafter abbreviated as “the present embodiment”) will be described in detail. In addition, this invention is not restrict | limited to the following this Embodiment, A various deformation | transformation can be implemented within the range of the summary.

  The flexographic printing plate in the present embodiment is composed of repeating units represented by the following formula (1) and / or formula (2), both terminal groups are hydroxyl groups, and the number average molecular weight is 300 to 50,000. It is obtained by curing a resin composition containing the polymer (a) produced from a certain polycarbonate diol. Preferably, the flexographic printing plate includes a cured resin layer obtained by curing the resin composition layer including the resin composition. By including the resin composition in the flexographic printing plate in the present embodiment, it is possible to develop excellent solvent resistance against various solvents in the ink forming the photosensitive layer of the electrophotographic photosensitive member.

(式中、Ｒ₁は、炭素数２〜５０の直鎖又は分岐した炭化水素基を表し、ｎは、２〜５０の整数を表す。）

(In the formula, R ₁ represents a linear or branched hydrocarbon group having 2 to 50 carbon atoms, and n represents an integer of 2 to 50.)

（式中、Ｒ₂は、炭素数１０〜５０の直鎖又は分岐した炭化水素基を表す。）

(In the formula, R ₂ represents a linear or branched hydrocarbon group having 10 to 50 carbon atoms.)

The polycarbonate diol is, for example, HO— (R ₁ —O) _n —H, which is a diol compound corresponding to the formula (1) or the formula (2) with reference to Japanese Patent Publication No. 5-29648, etc. It can be produced from HO—R ₂ —OH by a known method.

  The number average molecular weight (Mn) means the molecular weight calculated from the end group concentration, and can be calculated from the OH value ([OHV]) of the polycarbonate diol according to the calculation formula described in the following examples.

As a C2-C50 linear or branched hydrocarbon group of said Formula (1), a C2-C50 linear alkylene group etc. are preferable, for example. From the viewpoints of availability and ease of handling, a linear alkylene group having 2 to 20 carbon atoms is preferred.
As a C10-50 linear or branched hydrocarbon group of the said Formula (2), a C10-C50 linear alkylene group etc. are preferable, for example. From the viewpoints of availability and ease of handling, a linear alkylene group having 12 to 40 carbon atoms is preferred.

  N in the formula (1) is preferably an integer of 2 to 30 from the viewpoints of availability and ease of handling.

  The branched hydrocarbon group preferably has a structure in which one or more hydrogen atoms in the main chain are substituted with an alkyl group.

  The polycarbonate diol has hydroxyl groups at both ends. The reason why both ends are hydroxyl groups is to bind polycarbonate diol and other functional molecules in the production of a resin composition suitable for producing a flexographic printing plate having high solvent resistance. The polycarbonate diol has a number average molecular weight of 300 to 50,000. The number average molecular weight is preferably 300 or more from the viewpoint of solvent resistance. Moreover, industrial manufacture of polycarbonate diol can be favorably performed by a number average molecular weight being 50,000 or less.

  As the polycarbonate diol, a compound having a number average molecular weight of 300 to 50,000 represented by the following formula (3) or (4) is preferable.

（式中、Ｒ₁は、炭素数２〜５０の直鎖又は分岐した炭化水素基を表し、ｎは、２〜５０の整数を表し、ａは、１以上の整数を表す。）

(In the formula, R ₁ represents a linear or branched hydrocarbon group having 2 to 50 carbon atoms, n represents an integer of 2 to 50, and a represents an integer of 1 or more.)

（式中、Ｒ₂は、炭素数１０〜５０の直鎖又は分岐した炭化水素基を表し、ｂは、１以上の整数を表す。）

(In the formula, R ₂ represents a linear or branched hydrocarbon group having 10 to 50 carbon atoms, and b represents an integer of 1 or more.)

  The polymer (a) is not particularly limited as long as it is produced from the polycarbonate diol, but is a polymer produced with formation of a chemical bond between the terminal hydroxyl group of the polycarbonate diol and another compound. And a polymer containing a polymerizable unsaturated group. Although the type of the chemical bond and the polymerizable unsaturated group is not limited, the chemical bond is preferably a urethane bond, and the polymerizable unsaturated group is preferably a double bond that can participate in radical polymerization or addition polymerization. . In producing a flexographic printing plate, since the polymer (a) can be linked to various molecules, the polymer (a) preferably has a polymerizable unsaturated group.

  As the polymer (a), a terminal hydroxyl group of a polycarbonate diol is a polymer produced with a chemical bond with a compound having an isocyanate group such as a polyfunctional isocyanate compound, a polyisocyanate compound, an isocyanate alkyl acrylate and an isocyanate alkyl methacrylate. It is preferably a polymer having a polymerizable unsaturated group such as an acryl group and a methacryl group.

  A preferred first example of the polymer (a) is that the terminal hydroxyl group of the polycarbonate diol is a polyfunctional isocyanate compound and / or polyisocyanate compound having an isocyanate group equivalent less than the equivalent of the terminal hydroxyl group of the polycarbonate diol, and an isocyanate alkyl acrylate and / or Or the polymer etc. which are manufactured by making it react with isocyanate alkyl methacrylate are mentioned.

  The polyfunctional isocyanate compound and / or polyisocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule. Examples of the diisocyanate compound include aromatic diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, etc .; aliphatic or alicyclic diisocyanate Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate and the like. Examples of the triisocyanate compound include triphenylmethane triisocyanate, tri (isocyanatephenyl) triphosphate, and the like. Furthermore, as polyfunctional polyisocyanate, polymeric (diphenylmethane diisocyanate) etc. are mentioned, for example. From the viewpoint of solvent resistance of the flexographic printing plate, a diisocyanate compound is preferable, an aromatic diisocyanate is more preferable, and tolylene diisocyanate is further preferable.

  The isocyanate group equivalent less than the equivalent of the terminal hydroxyl group of the polycarbonate diol means that the equivalent (mol) of the isocyanate group of the polyfunctional isocyanate compound and / or the polyisocyanate compound is less than the equivalent (mol) of the terminal hydroxyl group of the polycarbonate diol. means. The isocyanate group equivalent is not limited as long as it is less than the equivalent of the terminal hydroxyl group of the polycarbonate diol, but it is preferably 50 to 95% equivalent, preferably 60 to 90% equivalent of the equivalent of the terminal hydroxyl group of the polycarbonate diol. Is more preferable.

  As the isocyanate alkyl acrylate and / or isocyanate alkyl methacrylate, for example, a compound in which the alkyl portion in the acrylate compound is an alkylene group having 2 to 10 carbon atoms is preferable, and a compound having an alkylene group having 2 or 3 carbon atoms is preferable. More preferred. Specific examples of the isocyanate alkyl acrylate and / or isocyanate alkyl methacrylate include isocyanate ethyl (meth) acrylate and isocyanate propyl (meth) acrylate.

  Specific examples of the first preferred example of the polymer (a) include a polymer represented by the following formula (5) because it exhibits extremely excellent solvent resistance.

（式中、Ｒ_pは、前記式（１）及び／又は式（２）で表される繰り返し単位からなり、両末端基が水酸基であり、かつ数平均分子量が３００〜５０，０００であるポリカーボネートジオールから両末端水酸基を除いた残基を表し、Ｒ_qは、ジイソシアネート化合物からイソシアネート基を除いた残基を表し、Ｒ_rは、は、イソシアネートアルキルアクリレート及び／又はイソシアネートアルキルメタクリレートのアルキル部分を表し、Ｒ_S、Ｒ_Tは、各々独立して、メチル基又は水素原子を表し、Ｌは、１以上の整数を表す。）

(Wherein R _p is a polycarbonate having a repeating unit represented by the formula (1) and / or the formula (2), both terminal groups being hydroxyl groups, and a number average molecular weight of 300 to 50,000. Represents a residue obtained by removing hydroxyl groups at both terminals from a diol, R _q represents a residue obtained by removing an isocyanate group from a diisocyanate compound, and R _r represents an alkyl portion of isocyanate alkyl acrylate and / or isocyanate alkyl methacrylate. , R _S and R _T each independently represents a methyl group or a hydrogen atom, and L represents an integer of 1 or more.)

  A preferred second example of the polymer (a) is a polyhydric isocyanate compound and / or polyisocyanate compound having an isocyanate group equivalent exceeding the equivalent of the terminal hydroxyl group of the polycarbonate diol, hydroxyalkyl acrylate and / or Or the polymer etc. which are manufactured by making it react with a hydroxyalkyl methacrylate are mentioned.

  The polyfunctional isocyanate compound and / or polyisocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule. Examples of the diisocyanate compound include aromatic diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, etc .; aliphatic or alicyclic diisocyanate Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate and the like. Examples of the triisocyanate compound include triphenylmethane triisocyanate and tri (isocyanatephenyl) triphosphate. Furthermore, as polyfunctional polyisocyanate, polymeric (diphenylmethane diisocyanate) etc. are mentioned, for example. From the viewpoint of solvent resistance of the flexographic printing plate, a diisocyanate compound is preferable, an aromatic diisocyanate is more preferable, and tolylene diisocyanate is further preferable.

  The isocyanate group equivalent exceeding the equivalent of the terminal hydroxyl group of the polycarbonate diol means that the equivalent (mol) of the isocyanate group of the polyfunctional isocyanate compound and / or the polyisocyanate compound exceeds the equivalent (mol) of the terminal hydroxyl group of the polycarbonate diol. To do. The isocyanate group equivalent is not limited as long as it exceeds the equivalent of the terminal hydroxyl group of the polycarbonate diol, but it is preferably 105 to 150% equivalent of the equivalent of the terminal hydroxyl group of the polycarbonate diol, and preferably 110 to 140% equivalent. It is more preferable.

  As the hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate, for example, a compound in which the alkyl moiety in the acrylate compound is an alkylene group having 2 to 10 carbon atoms is preferable, and a compound having an alkylene group having 2 or 3 carbon atoms is preferable. More preferred. Specific examples of hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.

  As a specific example of the preferred second example of the polymer (a), a polymer represented by the following formula (6) is mentioned because it shows extremely excellent solvent resistance.

（式中、Ｒ_pは、前記式（１）及び／又は式（２）で表される繰り返し単位からなり、両末端基が水酸基であり、かつ数平均分子量が３００〜５０，０００であるポリカーボネートジオールから両末端水酸基を除いた残基を表し、Ｒ_qは、ジイソシアネート化合物からイソシアネート基を除いた残基を表し、Ｒ_uは、ヒドロキシアルキルアクリレート及び／又はヒドロキシアルキルメタクリレートのアルキル部分を表し、Ｒ_S、Ｒ_Tは、各々独立して、メチル基又は水素原子を表し、ｍは、１以上の整数を表す。）

(Wherein R _p is a polycarbonate having a repeating unit represented by the formula (1) and / or the formula (2), both terminal groups being hydroxyl groups, and a number average molecular weight of 300 to 50,000. R _q represents a residue obtained by removing both terminal hydroxyl groups from a diol, R _q represents a residue obtained by removing an isocyanate group from a diisocyanate compound, R _u represents an alkyl moiety of hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate, R _S and R _T each independently represents a methyl group or a hydrogen atom, and m represents an integer of 1 or more.)

In the formulas (5) and (6), R _p is preferably a residue obtained by removing both terminal hydroxyl groups from the compound represented by the following formula (3) and / or formula (4).

（式中、Ｒ₁は、炭素数２〜５０の直鎖又は分岐した炭化水素基を表し、ｎは、２〜５０の整数を表し、ａは、１以上の整数を表す。）

(In the formula, R ₁ represents a linear or branched hydrocarbon group having 2 to 50 carbon atoms, n represents an integer of 2 to 50, and a represents an integer of 1 or more.)

（式中、Ｒ₂は、炭素数１０〜５０の直鎖又は分岐した炭化水素基を表し、ｂは、１以上の整数を表す。）

(In the formula, R ₂ represents a linear or branched hydrocarbon group having 10 to 50 carbon atoms, and b represents an integer of 1 or more.)

In the above formulas (5) and (6), R _q is, for example, a fragrance such as diphenylmethane diisocyanate, tolylene diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate. Isocyanate groups are removed from aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, etc. Residue. Among these, a residue obtained by removing an isocyanate group from an aromatic diisocyanate compound is preferable, and a residue obtained by removing an isocyanate group from tolylene diisocyanate is more preferable.

In the formula (5) and formula (6), R _r and R _u are preferably an alkylene group having 2 to 10 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms.

The method for producing the polymer (a) is not particularly limited. For example, the polymer (a) can be produced by the following method. After reacting the polycarbonate diol with a polyfunctional isocyanate compound and / or polyisocyanate compound having an isocyanate group equivalent less than the terminal hydroxyl group equivalent of the polycarbonate diol at 50 to 90 ° C. for 1 to 5 hours, A polymer (a) can be manufactured by adding an isocyanate alkyl (meth) acrylate and a urethanization catalyst, and making it react at 50-90 degreeC for 1 to 5 hours.
Moreover, the polycarbonate diol, the polyfunctional isocyanate compound and / or polyisocyanate compound having an isocyanate group equivalent exceeding the equivalent of the terminal hydroxyl group of the polycarbonate diol, and the urethanization catalyst are reacted at 50 to 90 ° C. for 1 to 5 hours. Then, the polymer (a) can be produced by adding a hydroxyalkyl (meth) acrylate and a urethanization catalyst and reacting at 50 to 90 ° C. for 1 to 5 hours.

The resin composition in the present embodiment preferably further contains an organic compound (b) having a polymerizable unsaturated group and a number average molecular weight of 50 or more and less than 5,000.
The polymerizable unsaturated group in the present embodiment means an unsaturated group involved in radical polymerization or addition polymerization. As the polymerizable unsaturated group involved in the radical polymerization reaction, for example, an acryl group or a methacryl group is preferable, and as the polymerizable unsaturated group involved in the addition polymerization reaction, for example, an epoxy group, an oxetane group, a vinyl ether group, or the like. Is preferred.

Specific examples of the organic compound (b) include olefins such as ethylene, propylene, styrene and divinylbenzene; (meth) acrylic acid and derivatives thereof; unsaturated nitriles such as haloolefins and acrylonitrile; (meth) acrylamide And allyl compounds such as allyl alcohol and allyl isocyanate; unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and fumaric acid and derivatives thereof; vinyl acetates; N-vinylpyrrolidone; N-vinylcarbazole and the like. .
As the organic compound (b), one or more organic compounds can be used in combination depending on the purpose.

As the organic compound (b), for example, (meth) acrylic acid or a derivative thereof is preferable. Examples of the (meth) acrylic acid derivative include esters with the following compounds having an alcoholic hydroxyl group. Examples of the compound include compounds having an alicyclic skeleton such as cycloalkyl alcohol, bicycloalkyl alcohol, cycloalkenyl alcohol, and bicycloalkenyl alcohol; and having an aromatic skeleton such as benzyl alcohol, phenol, and fluorenyl alcohol. Compounds: alkyl alcohol, halogenated alkyl alcohol, alkoxyalkyl alcohol, phenoxyalkyl alcohol, hydroxyalkyl alcohol, aminoalkyl alcohol, tetrahydrofurfuryl alcohol, allyl alcohol and the like. Examples of (meth) acrylic acid derivatives include esters with glycidol, alkylene glycol, polyoxyalkylene glycol, (alkyl / allyloxy) polyalkylene glycol, and polyhydric alcohols such as trimethylolpropane. In addition, in the case where the derivative of (meth) acrylic acid is an ester with a compound having an aromatic skeleton, an organic compound such as an ester with a heteroaromatic compound containing nitrogen, sulfur or the like as a hetero atom Also mentioned.
Specific examples of the organic compound (b) include phenoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, diethylene glycol butyl ether (meth) acrylate, ethylene glycol phenyl ether (meth) acrylate, and trimethylolpropane (meth) acrylate. It is done.

  As the organic compound (b), a compound having an epoxy group that undergoes a ring-opening addition polymerization reaction is preferable. Examples of the compound having an epoxy group that undergoes a ring-opening addition reaction include compounds obtained by reacting polyols such as various diols and triols with epichlorohydrin, and epoxy compounds obtained by reacting peracid with an ethylene bond in the molecule. It is done.

Specifically, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerin diglycidyl ether,
Glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S propylene oxide diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A with ethylene oxide or propylene oxide Diglycidyl ether of added compound, polytetramethylene glycol diglycidyl ether, poly (propylene glycol adipate) diol diglycidyl ether, poly (ethylene glycol adipate) diol diglycidyl ether, poly (caprolactone) diol diglycidyl ether, 3, 4 -Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylca Boxylate, 1-methyl-3,4-epoxycyclohexylmethyl-1′-methyl-3 ′, 4′-epoxycyclohexylcarboxylate, bis [1-methyl-3,4-epoxycyclohexyl] ester adipate, vinylcyclohexenedi Examples thereof include polyepoxy compounds obtained by reacting peracetic acid with polydienes such as epoxide, polybutadiene and polyisoprene, and epoxidized soybean oil.

  When the resin composition in the present embodiment is a flexographic printing plate, in addition to excellent solvent resistance to various solvents, it is excellent in laser engraving property, which is an important characteristic in a method of directly forming a relief image with a laser. It has both characteristics. In order to further improve the laser engraving property, the resin composition preferably further contains inorganic fine particles (c). The material and form of the inorganic fine particles (c) are not limited, but those having fine pores or fine voids in the particles are more preferable. Since the inorganic fine particles (c) have a function of effectively absorbing and removing the liquid gas generated when the flexographic printing plate is decomposed by a laser, the inorganic fine particles (c) are contained in the resin composition. In addition to improving the accuracy of the relief image by laser engraving, the cleaning operation after laser engraving becomes extremely simple.

Although the size of the inorganic fine particles (c) is not limited, the average particle size is preferably 0.01 to 100 μm, more preferably 0.1 to 20 μm, and still more preferably 1 to 10 μm. Although there is no restriction | limiting in the average pore diameter of inorganic type microparticles | fine-particles (c), it is 1-1000 nm, More preferably, it is 2-200 nm, More preferably, it is 2-50 nm. Although there is no restriction | limiting in the pore volume of inorganic type microparticles | fine-particles (c), 0.01-10 ml / g is preferable, More preferably, it is 0.1-5 ml / g. Although there is no restriction | limiting in the specific surface area of inorganic type microparticles | fine-particles (c), 1-1,500m < ² > / g is preferable, More preferably, it is 10-800m < ² > / g.

  The shape of the inorganic fine particles (c) is not limited, but spherical, flat, needle-shaped, amorphous, or particles having protrusions on the surface can be used. In addition, particles in which the inside of the particles are hollow, spherical granules having a uniform pore diameter such as silica sponge, and the like can also be used. As the inorganic fine particles, both porous inorganic fine particles and nonporous inorganic fine particles can be used. For example, porous silica, mesoporous silica, silica-zirconia porous gel, mesoporous molecular sieve, porous alumina, porous Glass, alumina, silica, zirconium oxide, barium titanate, strontium titanate, titanium oxide, silicon nitride, boron nitride, silicon carbide, chromium oxide, vanadium oxide, tin oxide, bismuth oxide, germanium oxide, aluminum borate, nickel oxide Molybdenum oxide, tungsten oxide, iron oxide, cerium oxide, or the like can be used. Moreover, what has a space | gap of several nm-100 nm between layers like a layered clay compound can also be used as inorganic type fine particles.

  The resin composition in the present embodiment preferably further contains a photopolymerization initiator. The photopolymerization initiator may be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, and anion illustrated in “Polymer Data Handbook-Fundamentals” edited by the Society of Polymer Science (1986, published by Baifukan) A polymerization initiator such as polymerization can be used.

  Crosslinking the resin composition by photopolymerization using a photopolymerization initiator is useful as a method for producing a flexographic printing plate precursor with high productivity while maintaining storage stability.

  Known polymerization initiators that can be used as the photopolymerization initiator include benzoin alkyl ethers such as benzoin and benzoin ethyl ether; 2-hydroxy-2-methylpropiophenone, 4′-isopropyl-2-hydroxy- Acetophenones such as 2-methylpropiophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone; 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2- Photoradical polymerization initiators such as morpholino-propan-1-one, methyl phenylglyoxylate, benzophenone, benzyl, diacetyl, diphenyl sulfide, eosin, thionine, anthraquinones; aromatic diazonium that generates acid by absorbing light , Aromatic iodonium salts, cationic photopolymerization initiators such as aromatic sulfonium salts; and the like can be exemplified anionic photopolymerization initiator which absorbs light and generates a base.

  Although the composition of the resin composition is not limited, from the viewpoint of solvent resistance of the flexographic printing plate, an organic compound having a polymerizable unsaturated group is used with respect to 100 parts by mass of the polymer (a) produced from the polycarbonate diol. The compound (b) is preferably 5 to 200 parts by mass, and the inorganic fine particles (c) are preferably 1 to 100 parts by mass. Further, from the viewpoint of solvent resistance of the flexographic printing plate, the organic compound (b) having a polymerizable unsaturated group is 10 to 180 parts by mass with respect to 100 parts by mass of the polymer (a) produced from the polycarbonate diol. More preferably, the amount of the inorganic fine particles (c) is 1 to 80 parts by mass. Furthermore, from the viewpoint of the efficiency of flexographic printing plate production, it is preferable to contain 1 to 100 parts by mass of a photopolymerization initiator, and from the viewpoint of solvent resistance of the flexographic printing plate, 1 to 80 parts by mass of a photopolymerization initiator is included. Is more preferable.

  A polymerization inhibitor, an ultraviolet absorber, a dye, a lubricant, a surfactant, a plasticizer, a fragrance, and the like can be added to the resin composition depending on applications and purposes. The total addition amount is preferably in the range of 10 parts by mass or less with respect to 100 parts by mass of the resin composition.

  Although there is no limitation on the method of molding the resin composition into a sheet or a cylindrical shape, an existing molding method of the resin composition can be used. For example, a method of extruding a resin composition from a nozzle or a die with a machine such as a pump or an extruder and adjusting the thickness with a blade (casting method); a method of adjusting the thickness by calendaring with a roll can be exemplified. It is also possible to perform molding while heating within a range that does not degrade the performance of the resin composition. Moreover, you may perform a rolling process, a grinding process, etc. as needed. Usually, the resin composition is formed on an underlay called a back film made of a material such as PET (polyethylene terephthalate) or nickel, but it can also be formed directly on a cylinder of a printing press. In that case, a seamless seamless sleeve can be formed. Also, a sleeve molding and engraving device (a laser light source for laser engraving is installed in a device in which a liquid photosensitive resin composition is applied onto a cylindrical support and irradiated with light to crosslink the liquid photosensitive resin composition. The flexographic printing plate can be formed using the incorporated one). When such an apparatus is used, a flexographic printing plate can be formed by laser engraving immediately after forming the sleeve, so it is impossible to think of a conventional rubber sleeve that required several weeks for the forming process. Short-time machining can be realized.

  The conductive support used for the electrophotographic photosensitive member in the present embodiment may be any conductive support known in the art, such as a metal plate and a metal drum such as aluminum and aluminum alloy, tin oxide, and oxidation. A plate made of a metal oxide such as indium, or various plastic films, paper, or the like obtained by attaching these metals and metal oxides by vacuum deposition, sputtering, laminating, coating, or the like.

  Examples of the photosensitive layer of the electrophotographic photoreceptor include a laminated type photosensitive layer composed of a charge transport layer and a charge generation layer, and a photosensitive layer obtained by mixing the charge transport layer and the charge generation layer instead of laminating them. It is done. Specific examples of the laminated photosensitive layer include the photosensitive layers disclosed in Patent Documents 1 and 2, and specific examples of the mixed photosensitive layer include, for example, the photosensitive layer disclosed in Patent Document 3. Is mentioned.

  An electrophotographic photosensitive member having a multilayer type photosensitive layer formed by laminating a charge transport layer made of an electron donating substance and a charge generation layer made of an electron accepting substance will be described in detail.

  Examples of the electron donating substance used for the charge transport layer forming the photosensitive layer include compounds having an electron donating group such as an alkyl group, an alkoxy group, an amino group, and an imide group, and polycyclic aromatic compounds such as anthracene, pyrene, and phenanthrene. And derivatives containing them, heterocyclic compounds such as indole, oxazole, oxadiazole, carbazole, thiazole, pyrazoline, imidazole, triazole and derivatives thereof, polyphenylene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polysilane and derivatives thereof, Examples thereof include polyalkylthiophene and derivatives thereof. An electron donating substance is dissolved or dispersed in an appropriate solvent, and printed and dried using the flexographic printing plate in this embodiment to form a charge transport layer. It is preferable that a binder resin or the like is mixed in the charge transport layer of the photosensitive layer formed of the electron donating substance. However, when the electron donating substance is a polymer compound, the charge transport layer alone is not mixed with the binder resin. May be formed.

  Examples of the electron accepting material used for the charge generation layer forming the photosensitive layer include various pigments or dyes such as phthalocyanine, azo, squarylium, cyanine, and perylene, poly (fluorene) derivatives, and fullerene derivatives such as C60. And carbon nanotubes. The ink for forming the photosensitive layer of the electrophotographic photoreceptor prepared by dissolving or dispersing the electron-accepting substance in an appropriate solvent is printed and dried using the flexographic printing plate in this embodiment to form a charge generation layer. May be. In the charge generation layer forming the photosensitive layer of the electrophotographic photoreceptor, it is preferable to use a mixture of an electron accepting substance and a binder resin.

  Binder resins include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, poly Vinylidene chloride, polyacrylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin And thermoplastic or thermosetting resins such as phenol resins and alkyd resins.

The film thickness of the charge transport layer is preferably 5 μm to 100 μm, more preferably 5 μm to 50 μm.
The thickness of the charge generation layer is preferably 0.05 μm to 2 μm, more preferably 0.1 μm to 1 μm.

The electrophotographic photosensitive member having a mixed photosensitive layer formed by mixing an electron donating substance and an electron accepting substance will be described in detail.
When an electrophotographic photosensitive member is produced using an ink for forming a photosensitive layer prepared by mixing an electron-donating substance and an electron-accepting substance and dissolving them in a solvent that dissolves both, the photosensitive layer is formed. The ink is printed and dried using the flexographic printing plate in the present embodiment to form a photosensitive layer. Further, in order to improve the mechanical characteristics of the mixed photosensitive layer, a polymer compound may be mixed with a solution to form a film. As the polymer compound to be mixed, those that do not extremely inhibit carrier transport are preferable, and those that do not strongly absorb visible light are preferably used. Examples thereof include poly (p-phenylene vinylene) and derivatives thereof, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  The film thickness of the photosensitive layer must be at least such that no pinholes are generated, and the film thickness is 5 nm to 300 μm, preferably 10 nm to 100 μm, and more preferably 50 nm to 50 μm.

  The ink solvent for forming the photosensitive layer of the electrophotographic photosensitive member is not particularly limited, but hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene, and ketone solvents such as methyl ethyl ketone and cyclohexanone. , Carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, halogenated unsaturated hydrocarbon solvents such as chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, ether solvents such as tetrahydrofuran, etc. Is mentioned.

  When the ink for forming the photosensitive layer of the electrophotographic photosensitive member is cured by irradiation with light, a photopolymerizable monomer may be contained in the ink. Examples of the photopolymerizable monomer include urethane acrylate and epoxy acrylate.

  The solvent resistance to the solvent contained in the ink forming the photosensitive layer of the electrophotographic photosensitive member in the present embodiment can be evaluated by a solvent immersion swelling test. The mass change rate of the flexographic printing plate before and after immersion in the solvent is preferably 10% by mass or less, and more preferably 5% by mass or less.

  The solvent immersion swelling test is performed by immersing a test sample in a solvent at room temperature for 24 hours. If the mass change rate is 10% by mass or less, the dimensional change of the laser engraving printing plate is small, and not only flexographic printing of fine patterns and uniform application of the photosensitive layer of the electrophotographic photosensitive member is possible, but also the flexographic printing plate. Dimensional stability can be ensured, the durability of the flexographic printing plate can be improved, and it can withstand repeated printing processes.

  When forming a printing pattern on the surface of a flexographic printing original plate by laser engraving, the depth of the formed printing pattern is preferably 1 μm or more and 1,000 μm or less. More preferably, they are 5 micrometers or more and 700 micrometers or less, More preferably, they are 20 micrometers or more and 500 micrometers or less. If the depth of the printed pattern is 1 μm or more, the electron-accepting organic material layer ink and the electron-donating organic material layer ink transferred from the flexographic printing plate can be retained. If it is 000 micrometers or less, since a printing pattern does not deform | transform or destroy during a printing process, it is preferable.

In the method for producing a photosensitive layer of an electrophotographic photosensitive member according to the present embodiment, an ink for forming a photosensitive layer of an electrophotographic photosensitive member on a flexographic printing plate is transferred onto a substrate to be printed, and a solvent in the transferred ink is used. Are removed by drying, or the transferred ink is irradiated with light and cured,
A method for producing a photosensitive layer of an electrophotographic photosensitive member by fixing an ink for forming the photosensitive layer of the electrophotographic photosensitive member on a substrate to be printed,
A polymer (a) comprising a repeating unit represented by the formula (1) and / or the formula (2), wherein both terminal groups are hydroxyl groups, and the number average molecular weight is 300 to 50,000. The ink for forming the photosensitive layer of the electrophotographic photosensitive member is transferred onto a substrate to be printed using a flexographic printing plate obtained by curing a resin composition containing (A).

  In the production method of the present embodiment, the method for transferring the ink for forming the photosensitive layer of the electrophotographic photosensitive member on the flexographic printing plate onto the substrate to be printed is not particularly limited. A method in which the ink is supplied to the surface of the convex portion with an ink supply roll or the like, then the flexographic printing plate is brought into contact with the substrate to be printed, and the ink on the surface of the convex portion is transferred to the substrate to be printed. Can be mentioned.

In the manufacturing method of the present embodiment, as a first aspect of the method for fixing the ink for forming the photosensitive layer of the electrophotographic photosensitive member on the substrate to be printed, the solvent in the ink transferred by the method is used. In this method, the ink that forms the photosensitive layer of the electrophotographic photosensitive member on the substrate to be printed is fixed by drying.
Examples of the method for fixing the ink by drying and removing the solvent in the ink include a method in which the solvent is vaporized and dried by heat treatment in the presence of an inert gas such as nitrogen gas. Can be mentioned.

In the manufacturing method of the present embodiment, as a second aspect of the method for fixing the ink for forming the photosensitive layer of the electrophotographic photosensitive member on the substrate to be printed, light is applied to the ink transferred by the method. This is a method of fixing the ink that is cured to form the photosensitive layer of the electrophotographic photosensitive member on the substrate to be printed.
Examples of the method of fixing the ink by irradiating with light include a method of curing a photopolymerizable monomer such as a (meth) acrylic acid derivative blended in the ink with light.

  In order to describe the present embodiment in more detail, examples and comparative examples are shown below, but these examples specifically illustrate the description of the present embodiment and the effects obtained thereby. Thus, the scope of the present embodiment is not limited at all. Various characteristics in the following examples and comparative examples were measured according to the following methods.

<Measurement method>
1. OH value of polycarbonate diol 12.5 g of acetic anhydride was diluted with 50 ml of pyridine to prepare an acetylating reagent. 1.0 g of the sample was precisely weighed into a 100 ml eggplant flask. After adding 2 ml of acetylating reagent and 4 ml of toluene with a whole pipette, a condenser tube was attached, and the mixture was stirred and heated at 100 ° C. for 1 hour. 1 ml of distilled water was added with a whole pipette, and the mixture was further heated and stirred for 10 minutes.
After cooling for 2 to 3 minutes, 5 ml of ethanol was added, and 2 to 3 drops of 1% phenolphthalein / ethanol solution was added as an indicator, followed by titration with 0.5 mol / l ethanolic potassium hydroxide.
As a blank test, 2 ml of an acetylating reagent, 4 ml of toluene, and 1 ml of distilled water were placed in a 100 ml eggplant flask and stirred for 10 minutes, and then titrated in the same manner. Based on this result, the OH value was calculated using the following calculation formula (i).

[Equation 1]
OH value (mg-KOH / g) = {(ba) × 28.05 × f} / e (i)
a: Titration volume of sample (ml)
b: titration of blank test (ml)
e: Sample mass (g)
f: Factor of titrant

2. Several molecular weight of polycarbonate diol The terminal of the polycarbonate diol in an Example and a comparative example was substantially all the hydroxyl groups by the measurement of < ¹³ > C-NMR (270 MHz). Moreover, when the acid value in polycarbonate diol was measured by titration with KOH, the acid value was 0.01 or less in all of the Examples and Comparative Examples.
Therefore, the number average molecular weight of the obtained polymer was determined by the following calculation formula (ii).

[Equation 2]
Number average molecular weight Mn = 2 / (OH value × 10 ⁻³ /56.11) (ii)

3. Mass change rate of flexographic printing original plate Regarding the mass change rate of the flexographic printing original plate with respect to the solvent, the flexographic printing original plate is cut into 1 cm × 2 cm, immersed in each solvent at room temperature for 24 hours, and swollen using the following calculation formula (iii) The rate was determined.

[Equation 3]
Mass change rate (%) = {(mass after immersion−mass before immersion) / mass before immersion} × 100
(Iii)

4). Laser engraving of the flexographic printing original plate Laser engraving of the flexographic printing original plate was performed using a carbon dioxide laser engraving machine (output: 12 watt, trademark Laser Pro Venus, manufactured by GCC). The engraving was performed by creating a pattern including a line drawing with a convex line having a width of 200 μm. The engraving depth was 400 μm. The presence or absence of viscous liquid residue generated by laser engraving and the sharpness of the line drawing were visually determined.

[Synthesis Example 1]
Regular packing Helipak packing No. 3 was charged in a 500 ml four-necked flask equipped with a distillation tower having a packing height of 300 mm and an inner diameter of 30 mm, and a fractionation head, and diethylene glycol 214 g (2.01 mol) and ethylene carbonate 186 g (2.12 mol) were charged at 70 ° C. Then, the system was purged with nitrogen, and 0.177 g of tetrabutoxy titanium was added as a catalyst. This flask was heated in an oil bath while extracting a part of the reflux liquid from the fractionation head so that the internal temperature of the flask was 145 to 150 ° C. and the pressure was 2.5 to 3.5 kPa, and the reaction was continued for 22 hours. did. Thereafter, the packed distillation column is removed and replaced with a simple distillation apparatus, the internal temperature of the flask is raised to 170 ° C., the pressure is lowered to 0.2 kPa, and the diethylene glycol and ethylene carbonate remaining in the flask are distilled over 1 hour. Left. Thereafter, the reaction was further continued for 5 hours at an internal temperature of the flask of 170 ° C. and a pressure of 0.1 kPa. By this reaction, 174 g of a liquid polycarbonate diol that was viscous at room temperature was obtained. The obtained polycarbonate diol had an OH value of 60.9 (number average molecular weight Mn = 1,843).
A 300 ml separable flask equipped with a stirrer was charged with 65.0 g of this polycarbonate diol and 0.05 g of monobutyl phosphate, and stirred at 80 ° C. for 3 hours to deactivate tetrabutoxytitanium. Thereafter, 4.63 g of tolylene diisocyanate, 0.07 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of adipic acid, and 0.001 g of di-n-butyltin dilaurate were added under a dry air atmosphere. , And stirred at 80 ° C. for 3 hours. Thereafter, 2.77 g of 2-methacryloyloxyethyl isocyanate and 0.001 g of di-n-butyltin dilaurate were added, and the mixture was stirred at 80 ° C. for 2 hours in a dry air atmosphere. At this stage, it was confirmed by infrared spectroscopic analysis that a terminal hydroxyl group of polycarbonate diol was linked by a urethane bond and a polymer having a double bond was obtained.
Thereafter, 10.74 g of ethylene glycol phenyl ether methacrylate, 5.96 g of trimethylolpropane trimethacrylate, 5.55 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), 1.21 g of silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) 2,2-dimethoxy-2-phenylacetophenone 0.72 g, benzophenone 1.21 g, 2,6-di-tert-butyl-4-methylphenol 0.72 g, triphenyl phosphate 2.17 g, Sanol LS-785 (Sankyo Co., Ltd.) While adding 1.21 g and stirring at 80 ° C., the pressure was reduced to 13 kPa and defoamed to obtain a viscous liquid resin composition at room temperature.

[Synthesis Example 2]
A 300 ml separable flask equipped with a stirrer was charged with 65.0 g of the polycarbonate diol of Synthesis Example 1 and 0.05 g of monobutyl phosphate, and stirred at 80 ° C. for 3 hours to deactivate tetrabutoxytitanium. Thereafter, 8.16 g of tolylene diisocyanate, 0.08 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of adipic acid, and 0.001 g of di-n-butyltin dilaurate were added, and in a dry air atmosphere. , And stirred at 80 ° C. for 3 hours. Thereafter, 6.66 g of 2-hydroxypropyl methacrylate and 0.001 g of di-n-butyltin dilaurate were added, and the mixture was stirred at 80 ° C. for 2 hours in a dry air atmosphere. At this stage, it was confirmed by infrared spectroscopic analysis that a terminal hydroxyl group of the polycarbonate diol was connected by a urethane bond and a polymer having a double bond was obtained.
Thereafter, 10.74 g of ethylene glycol phenyl ether methacrylate, 5.96 g of trimethylolpropane trimethacrylate, 5.55 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), 1.21 g of silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) 2,2-dimethoxy-2-phenylacetophenone 0.72 g, benzophenone 1.21 g, 2,6-di-tert-butyl-4-methylphenol 0.72 g, triphenyl phosphate 2.17 g, Sanol LS-785 (Sankyo Co., Ltd.) While adding 1.21 g and stirring at 80 ° C., the pressure was reduced to 13 kPa and defoamed to obtain a viscous liquid resin composition at room temperature.

[Synthesis Example 3]
Regular packing Helipak packing No. 3 in a 500 ml four-necked flask equipped with a distillation tower having a packing height of 300 mm and an inner diameter of 30 mm, and a fractionation head, 254.8 g (1.57 mol) of dibutylene glycol and 145.2 g (1.65 mol) of ethylene carbonate. ) And stirred and dissolved at 80 ° C., and the inside of the system was purged with nitrogen. Then, 0.16 g of tetrabutoxy titanium was added as a catalyst. The flask was heated in an oil bath while extracting a part of the reflux liquid from the fractionation head so that the internal temperature of the flask was 150 to 155 ° C. and the pressure was 2 to 3 kPa, and reacted for 20 hours. Then, remove the packed distillation column, replace it with a simple distillation apparatus, set the internal temperature of the flask to 155 ° C. and the pressure to 1.0 kPa, and distill out the dibutylene glycol and ethylene carbonate remaining in the flask over 1 hour. did. Thereafter, the reaction was further continued for 7 hours at an internal temperature of the flask of 155 to 175 ° C. and a pressure of 0.1 to 0.2 kPa. By this reaction, 164 g of polycarbonate diol that was solid at room temperature was obtained. The polycarbonate diol thus obtained had an OH value of 55.8 (number average molecular weight Mn = 2,011).
A 300 ml separable flask equipped with a stirrer was charged with 65.0 g of this polycarbonate diol and 0.04 g of monobutyl phosphate and stirred at 95 ° C. for 3 hours to deactivate tetrabutoxytitanium. Thereafter, 4.13 g of tolylene diisocyanate, 0.07 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of adipic acid, and 0.001 g of di-n-butyltin dilaurate were added, and the atmosphere was in a dry air atmosphere. The mixture was stirred at 40 ° C. for 30 minutes and further at 80 ° C. for 4 hours. Thereafter, 2.75 g of 2-methacryloyloxyethyl isocyanate and 0.001 g of di-n-butyltin dilaurate were added, and the mixture was stirred at 80 ° C. for 2 hours in a dry air atmosphere.
Thereafter, ethylene glycol phenyl ether methacrylate 24.14 g, diethylene glycol butyl ether methacrylate 7.26 g, trimethylolpropane trimethacrylate 0.13 g, silica gel C-1504 (Fuji Silysia Chemical Ltd.) 5.55 g, silicone oil KF-410 (Shin-Etsu Chemical) 1.20 g, 0.72 g of 2,2-dimethoxy-2-phenylacetophenone, 1.19 g of benzophenone, 0.72 g of 2,6-di-tert-butyl-4-methylphenol, triphenyl phosphate 2 .16 g, Sanol LS-785 (Sankyo Co., Ltd.) 1.19 g, Pigment Green AG (Nippon Kayaku Co., Ltd.) 0.007 g and stirring at 80 ° C., degassing by depressurizing to 13 kPa, solid at room temperature Resin composition It was.

[Synthesis Example 4]
A 300 ml four-necked flask equipped with a fractionation head was charged with 100 g (0.32 mol) of 1,20-eicosanediol and 30 g (0.34 mol) of ethylene carbonate, dissolved by stirring at 70 ° C., and the system was purged with nitrogen. Thereafter, 0.062 g of tetrabutoxy titanium was added as a catalyst. This flask was heated in an oil bath while extracting a part of the reflux liquid from the fractionation head so that the internal temperature of the flask was 150 to 155 ° C. and the pressure was 7 to 8 kPa, and reacted for 11 hours. Thereafter, 30 g (0.34 mol) of ethylene carbonate was added, and after reacting at an internal temperature of the flask of 155 ° C. and a pressure of 6 to 7 kPa for 7 hours, the pressure was reduced to 0.2 kPa, and the ethylene carbonate remaining in the flask was retained. Left. Thereafter, 30 g (0.34 mol) of ethylene carbonate was further added, and after similarly reacting at an internal temperature of the flask of 155 ° C. and a pressure of 5 to 6 kPa for 5 hours, the pressure was reduced to 0.2 kPa and remained in the flask. Ethylene carbonate was distilled off. This reaction yielded 102 g of polycarbonate diol that was solid at room temperature. The obtained polycarbonate diol had an OH value of 45.3 (number average molecular weight Mn = 2,476).
A 300 ml separable flask equipped with a stirrer was charged with 65.1 g of this polycarbonate diol and 0.03 g of monobutyl phosphate, and stirred at 80 ° C. for 3 hours to deactivate tetrabutoxytitanium. Thereafter, 3.18 g of tolylene diisocyanate, 0.08 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of adipic acid, and 0.002 g of di-n-butyltin dilaurate were added, and the atmosphere was in a dry air atmosphere. , And stirred at 80 ° C. for 3 hours. Thereafter, 2.77 g of 2-methacryloyloxyethyl isocyanate and 0.001 g of di-n-butyltin dilaurate were added, and the mixture was stirred at 80 ° C. for 2 hours in a dry air atmosphere. At this stage, it was confirmed by infrared spectroscopic analysis that a terminal hydroxyl group of polycarbonate diol was linked by a urethane bond and a polymer having a double bond was obtained.
Thereafter, 23.61 g of ethylene glycol phenyl ether methacrylate, 7.08 g of diethylene glycol butyl ether methacrylate, 0.12 g of trimethylolpropane trimethacrylate, 5.43 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), silicone oil KF-410 (Shin-Etsu Chemical) Industrial Co., Ltd.) 1.12 g, 2,1-dimethoxy-2-phenylacetophenone 0.71 g, benzophenone 1.19 g, 2,6-di-tert-butyl-4-methylphenol 0.71 g, triphenyl phosphate 2 .13 g and 1.20 g of Sanol LS-785 (Sankyo Co., Ltd.) were added and the mixture was degassed by reducing the pressure to 13 kPa while stirring at 80 ° C. to obtain a solid resin composition at room temperature.

[Comparative Synthesis Example 1]
Regular packing Helipak packing No. 3 in a 500 ml four-necked flask equipped with a distillation column having a packing height of 300 mm and an inner diameter of 30 mm, and a fractionation head, 197.4 g (2.19 mol) of 1,4-butanediol and 202.6 g of ethylene carbonate ( 2.30 mol) was charged and dissolved by stirring at 80 ° C., and the inside of the system was purged with nitrogen, and 0.033 g of tetrabutoxy titanium was added as a catalyst. The flask was heated in an oil bath while extracting a part of the reflux liquid from the fractionation head so that the internal temperature of the flask was 139 to 145 ° C. and the pressure was 2 to 3 kPa, and reacted for a total of 23 hours. Then, the packed distillation column is removed and replaced with a simple distillation apparatus. The flask is set to an internal temperature of 145 ° C. and a pressure of 1.5 kPa, and 1,4-butanediol and ethylene carbonate remaining in the flask are spent for 1 hour. Distilled off. Thereafter, the reaction was further performed for 7.5 hours at an internal temperature of the flask of 145 to 185 ° C. and a pressure of 0.08 to 0.3 kPa. By this reaction, 128 g of a polycarbonate diol that was solid at room temperature was obtained. The polycarbonate diol thus obtained had an OH value of 45.0 (number average molecular weight Mn = 2,493).
Into a 300 ml separable flask equipped with a stirrer, 50.2 g of this polycarbonate diol and 0.009 g of monobutyl phosphate were added and stirred at 80 ° C. for 3 hours to inactivate tetrabutoxytitanium. Thereafter, 2.36 g of tolylene diisocyanate, 0.05 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of adipic acid, and 0.001 g of di-n-butyltin dilaurate were added under a dry air atmosphere. , And stirred at 80 ° C. for 3 hours. Thereafter, 2.09 g of 2-methacryloyloxyethyl isocyanate and 0.001 g of di-n-butyltin dilaurate were added, and the mixture was stirred at 80 ° C. for 2 hours in a dry air atmosphere.
Thereafter, 18.22 g of ethylene glycol phenyl ether methacrylate, 5.47 g of diethylene glycol butyl ether methacrylate, 0.09 g of trimethylolpropane trimethacrylate, 4.19 g of silica gel C-1504 (Fuji Silysia Chemical Ltd.), silicone oil KF-410 (Shin-Etsu Chemical) Kogyo Co., Ltd.) 0.91 g, 2,2-dimethoxy-2-phenylacetophenone 0.55 g, benzophenone 0.91 g, 2,6-di-tert-butyl-4-methylphenol 0.55 g, triphenyl phosphate 1 .64 g, Sanol LS-785 (Sankyo Co., Ltd.) 0.91 g, Pigment Green AG (Nippon Kayaku Co., Ltd.) 0.006 g and stirring at 80 ° C., degassing by reducing pressure to 13 kPa, solid at room temperature Resin composition It was.

[Comparative Synthesis Example 2]
In a 300 ml separable flask equipped with a stirrer, polycarbonate diol “T6002” (OH number = 56, number average molecular weight Mn = 2,004 Asahi Kasei Chemicals) 61.67 g, tolylene diisocyanate 3.93 g, 2,6- Di-tert-butyl-4-methylphenol 0.07 g, adipic acid 0.01 g, and di-n-butyltin dilaurate 0.001 g were added, and the mixture was stirred at 80 ° C. for 3 hours in a dry air atmosphere. Thereafter, 2.61 g of 2-methacryloyloxyethyl isocyanate and 0.001 g of di-n-butyltin dilaurate were added, and the mixture was stirred at 80 ° C. for 2 hours in a dry air atmosphere.
Thereafter, 22.74 g of ethylene glycol phenyl ether methacrylate, 6.82 g of diethylene glycol butyl ether methacrylate, 0.11 g of trimethylolpropane trimethacrylate, 5.23 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), silicone oil KF-410 (Shin-Etsu Chemical) Kogyo Co., Ltd.) 1.14 g, 2,2-dimethoxy-2-phenylacetophenone 0.68 g, benzophenone 1.14 g, 2,6-di-tert-butyl-4-methylphenol 0.68 g, triphenyl phosphate 2 .05 g, Sanol LS-785 (Sankyo Co., Ltd.) 1.14 g, Pigment Green AG (Nippon Kayaku Co., Ltd.) 0.007 g was added, and the mixture was stirred at 80 ° C., depressurized to 13 kPa, defoamed, and solid at room temperature Resin composition It was.

(Preparation of flexographic printing plate)
Using each of the resin compositions obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2, flexographic printing original plates were produced by the following method.
After thinly applying diethylene glycol to a 12 × 11 × 0.3 cm glass plate, a PET film was placed thereon and rubbed closely with a spatula. A square frame with a side of 10 cm made of a sponge frame fixed by double-sided sealing on the film and an aluminum spacer with a thickness of 3 mm were placed at the four corners outside the frame. The prepared jig was placed on a hot plate at about 90 ° C.
After pouring each resin composition into the frame of the jig, a glass plate coated with diethylene glycol and placed with a PET film was covered so that the PET film surface was in contact with the resin composition. Thereafter, the upper and lower glass plates were clamped and fixed.
About this jig, after exposing it to 500 mJ / cm ² (illuminance 33.7 mW / cm ² , time 14.8 seconds) using a high-pressure mercury lamp (HC-98, Sen Engineering Co., Ltd.), the jig surface was reversed, Further, exposure was performed at 500 mJ / cm ² . This was performed once again on both sides, and a total of 2,000 mJ / cm ^{2 was} exposed to prepare a flexographic printing original plate. Table 1 shows the laser engraving properties of the obtained flexographic printing original plate.

[Example 1]
(Printing evaluation of photosensitive layer of electrophotographic photoreceptor)
A mixture of poly (2,5-dioctyloxy-p-phenylene vinylene) and fullerene C60 was dispersed in dehydrated xylene at a concentration of 0.5 wt% to prepare a photosensitive layer forming ink. The mixing ratio of fullerene C60 to the repeating unit of substituted poly (p-phenylene vinylene) was 5 mol%.
Printing evaluation of the ink was carried out using the flexographic printing plate 1 in which a printing pattern was drawn by laser engraving on the flexographic printing plate 1 obtained from the resin composition of Synthesis Example 1. For flexographic printing, a desktop proofing machine (trademark “Flexiproof 100” manufactured by KR, UK) was used, and the flexographic printing plate 1 was attached to the plate cylinder using a double-sided tape. As a substrate to be printed, an ITO film having a thickness of 0.1 μm is formed on the surface of a 0.7 mm thick glass substrate (soda lime glass) by a vacuum vapor deposition method, and then UV-ozone cleaning is performed to attach an organic substance or the like. What removed the kimono was used. The photosensitive layer forming ink was printed on a glass plate having the ITO thin film electrode, and then dried at 120 ° C. for 10 minutes in a nitrogen atmosphere to produce a photosensitive layer of an electrophotographic photosensitive member. The results are shown in Table 1.

(Measurement of mass change rate)
A test sample prepared from the flexographic printing original plate 1 was immersed in xylene at 20 ° C. for 24 hours, and then the droplets adhering to the surface were wiped off, and the mass increase rate was measured to determine the mass change rate. The results are shown in Table 1.

[Example 2]
(Printing evaluation of photosensitive layer of electrophotographic photoreceptor)
A mixture of poly (2,5-dioctyloxy-p-phenylene vinylene) and fullerene C60 was dispersed in dehydrated xylene at a concentration of 0.5 wt% to prepare a photosensitive layer forming ink. The mixing ratio of fullerene C60 to the repeating unit of substituted poly (p-phenylene vinylene) was 5 mol%.
Printing evaluation of the ink was performed using the flexographic printing plate 2 in which a printing pattern was drawn by laser engraving on the flexographic printing plate 2 obtained from the resin composition of Synthesis Example 2. For flexographic printing, a desktop proofing machine (trade name “Flexiproof 100” manufactured by KR, UK) was used, and the flexographic printing plate 2 was attached to the plate cylinder using a double-sided tape. As a substrate to be printed, an ITO film having a thickness of 0.1 μm is formed on the surface of a 0.7 mm thick glass substrate (soda lime glass) by a vacuum vapor deposition method, and then UV-ozone cleaning is performed to attach an organic substance or the like. What removed the kimono was used. The photosensitive layer forming ink was printed on a glass plate having the ITO thin film electrode, and then dried at 120 ° C. for 10 minutes in a nitrogen atmosphere to produce a photosensitive layer of an electrophotographic photosensitive member. The results are shown in Table 1.

(Measurement of mass change rate)
A test sample prepared from the flexographic printing original plate 2 was immersed in xylene at 20 ° C. for 24 hours, and then the droplets adhering to the surface were wiped off, and the mass increase rate was measured to determine the mass change rate. The results are shown in Table 1.

Example 3
(Printing evaluation of photosensitive layer of electrophotographic photoreceptor)
A mixture of poly (2,5-dioctyloxy-p-phenylene vinylene) and fullerene C60 was dispersed in dehydrated xylene at a concentration of 0.5 wt% to prepare a photosensitive layer forming ink. The mixing ratio of fullerene C60 to the repeating unit of substituted poly (p-phenylene vinylene) was 5 mol%.
Printing evaluation of the ink was performed using the flexographic printing plate 3 in which a printing pattern was drawn by laser engraving on the flexographic printing original plate 3 obtained from the resin composition of Synthesis Example 3. For flexographic printing, a desktop proofing machine (trade name “Flexiprofer100” manufactured by KR, UK) was used, and the flexographic printing plate 3 was attached to the plate cylinder using a double-sided tape. As a substrate to be printed, an ITO film having a thickness of 0.1 μm is formed on the surface of a 0.7 mm thick glass substrate (soda lime glass) by a vacuum vapor deposition method, and then UV-ozone cleaning is performed to attach an organic substance or the like. What removed the kimono was used. The photosensitive layer forming ink was printed on a glass plate having the ITO thin film electrode, and then dried at 120 ° C. for 10 minutes in a nitrogen atmosphere to produce a photosensitive layer of an electrophotographic photosensitive member. The results are shown in Table 1.

(Measurement of mass change rate)
The test sample produced from the flexographic printing original plate 3 was immersed in xylene at 20 ° C. for 24 hours, and then the droplets adhering to the surface were wiped off, and the mass increase rate was measured to determine the mass change rate. The results are shown in Table 1.

Example 4
(Printing evaluation of photosensitive layer of electrophotographic photoreceptor)
A mixture of poly (2,5-dioctyloxy-p-phenylene vinylene) and fullerene C60 was dispersed in dehydrated methyl ethyl ketone at a concentration of 0.5 wt% to prepare a photosensitive layer forming ink. The mixing ratio of fullerene C60 to the repeating unit of substituted poly (p-phenylene vinylene) was 5 mol%.
Printing evaluation of the ink was carried out using the flexographic printing plate 4 obtained by drawing a printing pattern by laser engraving on the flexographic printing plate 4 obtained from the resin composition of Synthesis Example 4. For flexographic printing, a desktop proofing machine (trade name “Flexiproof 100” manufactured by KR, UK) was used, and the flexographic printing plate 4 was stuck on the plate cylinder using a double-sided tape. As a substrate to be printed, an ITO film having a thickness of 0.1 μm is formed on the surface of a 0.7 mm thick glass substrate (soda lime glass) by a vacuum vapor deposition method, and then UV-ozone cleaning is performed to attach an organic substance or the like. What removed the kimono was used. The photosensitive layer forming ink was printed on a glass plate having the ITO thin film electrode, and then dried at 120 ° C. for 10 minutes in a nitrogen atmosphere to produce a photosensitive layer of an electrophotographic photosensitive member. The results are shown in Table 1.

(Measurement of mass change rate)
The test sample prepared from the flexographic printing original plate 4 was immersed in methyl ethyl ketone at 20 ° C. for 24 hours, and then the droplets adhering to the surface were wiped off, and the mass increase rate was measured to determine the mass change rate. The results are shown in Table 1.

[Comparative Example 1]
(Print evaluation)
As a result of printing and drying in the same manner as in Example 1 using the printing plate (a) on which the printing pattern was drawn by laser engraving on the printing original plate (a) obtained from the resin composition of Comparative Synthesis Example 1, Although the film thickness of the photosensitive layer of the electrophotographic photosensitive member after drying was about 50 nm, it was non-uniform and uneven.

(Measurement of mass change rate)
A test sample prepared from the printing original plate (a) was immersed in xylene and methyl ethyl ketone at 20 ° C. for 24 hours, and then the droplets adhering to the surface were wiped off, and the mass increase rate was measured to determine the mass change rate. . The results are shown in Table 1.

[Comparative Example 2]
(Print evaluation)
As a result of printing and drying in the same manner as in Example 1 using the printing plate (a) on which the printing pattern was drawn by laser engraving on the printing original plate (a) obtained from the resin composition of Comparative Synthesis Example 2, Although the film thickness of the photosensitive layer of the electrophotographic photosensitive member after drying was about 50 nm, it was non-uniform and uneven.

(Measurement of mass change rate)
The test sample prepared from the printing original plate (I) was immersed in xylene and methyl ethyl ketone at 20 ° C. for 24 hours, and then the droplet adhering to the surface was wiped off, and the mass increase rate was measured to determine the mass change rate. . The results are shown in Table 1.

  When the flexographic printing plate in the present embodiment is used, the thickness variation of the flexographic printing plate due to solvent swelling can be reduced, so that the thickness variation of the photosensitive layer of the electrophotographic photosensitive member, which is the printed material, can be reduced. According to the present embodiment, it is possible to control the thickness of the photosensitive layer of the electrophotographic photosensitive member directly connected to the performance of the electrophotographic photosensitive member with high accuracy.

  By the method for producing a photosensitive layer of an electrophotographic photoreceptor of the present invention, it is possible to produce a photosensitive layer of an electrophotographic photoreceptor with high accuracy. It is also possible to provide an electrophotographic photoreceptor including the photosensitive layer.

Claims (8)

The ink that forms the photosensitive layer of the electrophotographic photosensitive member on the flexographic printing plate is transferred onto the substrate to be printed, the solvent in the transferred ink is removed by drying, or the transferred ink is irradiated with light. Harden
A method for producing a photosensitive layer of an electrophotographic photosensitive member by fixing an ink for forming the photosensitive layer of the electrophotographic photosensitive member on a substrate to be printed,
A polymer (a) comprising a repeating unit represented by the following formula (1) and / or formula (2), wherein both terminal groups are hydroxyl groups, and the number average molecular weight is 300 to 50,000. The photosensitive layer of an electrophotographic photosensitive member is transferred onto a substrate to be printed using a flexographic printing plate obtained by curing a resin composition containing the above-mentioned resin composition.

(In the formula, R ₁ represents a linear or branched hydrocarbon group having 2 to 50 carbon atoms, and n represents an integer of 2 to 50.)

(In the formula, R ₂ represents a linear or branched hydrocarbon group having 10 to 50 carbon atoms.) The resin composition is
Polymer produced by reacting the polycarbonate diol, a polyfunctional isocyanate compound and / or polyisocyanate compound having an isocyanate group equivalent less than the terminal hydroxyl group equivalent of the polycarbonate diol, and an isocyanate alkyl acrylate and / or an isocyanate alkyl methacrylate. (A) and / or a terminal hydroxyl group of the polycarbonate diol, an isocyanate group equivalent polyfunctional isocyanate compound and / or polyisocyanate compound exceeding the equivalent of the terminal hydroxyl group of the polycarbonate diol, and a hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate. The photosensitive layer of the electrophotographic photosensitive member according to claim 1, comprising a polymer (a) produced by reacting Production method.   3. The electrophotographic photosensitive member according to claim 1, wherein the resin composition further contains an organic compound (b) having a polymerizable unsaturated group and a number average molecular weight of less than 5,000. Layer manufacturing method.   The method for producing a photosensitive layer of an electrophotographic photosensitive member according to claim 1, wherein the resin composition further contains inorganic fine particles (c).   The manufacturing method of the photosensitive layer of the electrophotographic photosensitive member as described in any one of Claims 1-4 whose said resin composition is a photosensitive resin composition.   The method for producing a photosensitive layer of an electrophotographic photosensitive member according to any one of claims 1 to 5, wherein the flexographic printing plate is obtained by laser engraving a printing pattern on the surface of a flexographic printing original plate.   The method for producing a photosensitive layer of an electrophotographic photosensitive member according to claim 1, wherein the flexographic printing plate is formed in a sheet shape or a cylindrical shape.   When the flexographic printing plate was evaluated for resistance to the solvent in the ink forming the photosensitive layer of the electrophotographic photosensitive member by a solvent immersion swelling test, the mass change rate was 10% by mass or less before and after immersion in the solvent. The manufacturing method of the photosensitive layer of the electrophotographic photoreceptor as described in any one of Claims 1-7 which shows these.