Aqueous developer composition for flexographic printing plate and method for producing flexographic printing plate

Abstract

To provide an aqueous developer composition for flexographic printing plates, which exhibits high removal performance for uncured photosensitive resin composition, achieves superior reproducibility in flexographic printing plates, and yields flexographic printing plates with little printing unevenness during printing.SOLUTION: An aqueous developer composition for flexographic printing plates comprises (a) a polyoxyalkylene alkyl ether compound including a branched structure with 3 to 11 carbon atoms and having an HLB value of less than 10.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an aqueous developing solution composition for a flexographic printing plate and a method for manufacturing a flexographic printing plate.

Background Art

[0002] Flexographic printing using a flexographic printing plate made of a photosensitive resin composition exhibits excellent printing characteristics for paper with uneven surfaces, non-woven fabrics, and plastic films with high smoothness. Therefore, it has been widely used in various industries such as corrugated cardboard printing and food packaging printing (see, for example, Patent Documents 1 and 2).

[0003] In recent years, there has been a movement in various industries to reduce the use of organic solvents from the perspective of improving the working environment and conserving the global environment. Even in the developing process of removing the uncured photosensitive resin composition during the plate-making process of flexographic printing plates, the use of water-developable photosensitive resin compositions is increasing. In addition, since flexographic printing plates have high flexibility, they have also been developed for applications that require high scratch resistance on the surface, such as alkali-free glass plates for liquid crystals and semiconductor wafers. In particular, for printing plates used for printing on alkali-free glass plates for liquid crystals, specifically, flexographic printing plates used for alignment film printing, high thickness accuracy within the plate surface and high definition of the plate surface pattern are required.

[0004] In the developing process for manufacturing the above-described flexographic printing plate used for alignment film printing, high detergency is required so that the uncured photosensitive resin composition does not remain on the high-definition plate surface pattern, and a plate surface after cleaning that is favorable for printing is provided. In particular, a plate surface with less unevenness in the thickness of the printed alignment film is required. Conventionally, technologies for improving the detergency of such a plate surface have been proposed (see, for example, Patent Documents 3 and 4).

[0005] For example, Patent Document 3 discloses an aqueous developer composition for a photosensitive resin, which contains "(A) component: a nonionic surfactant having an HLB of 10 or less, (B) component: a compound having at least one oxyalkylene unit with an HLB exceeding 10, and water". Further, Patent Document 4 discloses an aqueous developer composition for a photosensitive polymer, which contains "an alkylene oxide adduct of a secondary alcohol having 8 to 20 carbon atoms and an HLB of 10 to 14, and a compound represented by the following formula (I)". RO(AO) n R 1 ···(I)

[0006] In the above formula (I), R and R 1 represent an alkyl group or alkenyl group having 2 to 6 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and n represents a number from 1 to 5.

[0007] However, in recent years, in the development process when manufacturing a printing plate, there has been a demand for a technology that can improve the cleaning property of the plate surface and obtain an effect of improving printing quality with the developer.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0009] The aqueous developer compositions disclosed in Patent Documents 3 and 4 have good debris recovery rates and stability over time. However, there is still room for improvement regarding printing unevenness when printing using a printing plate manufactured using these aqueous developer compositions. Furthermore, the aqueous developer compositions disclosed in Patent Documents 3 and 4 have the problem of insufficient detergency for developing a fine uneven shape, which is a particularly prominent issue in liquid crystal printing applications.

[0010] Therefore, in the present invention, in view of the problems of the above-described prior art, an object is to provide an aqueous developer composition for flexographic printing plates that has high removability of an uncured photosensitive resin composition, excellent reproducibility of flexographic printing plates, and little printing unevenness during printing.

Means for Solving the Problems

[0011] As a result of intensive research to solve the problems of the above-described prior art, the inventors of the present invention have found that an aqueous developer composition containing a polyoxyalkylene alkyl ether compound having a predetermined structure and a predetermined HLB value can solve the problems of the above-described prior art, and have thus completed the present invention. That is, the present invention is as follows.

[0012] 〔1〕 (a) A polyoxyalkylene alkyl ether compound having a branched structure with 3 to 11 carbon atoms and an HLB value of less than 10, An aqueous developer composition for flexographic printing plates, comprising the same. 〔2〕 The aqueous developer composition for flexographic printing plates according to the above 〔1〕, wherein the (a) polyoxyalkylene alkyl ether compound is a compound having a structure represented by the following formula (1).

[0013]

Chemical formula

[0014] In formula (1), R is an alkyl group having 3 to 10 carbon atoms and having one or more tertiary or quaternary carbon atoms. A is an alkylene group having 2 to 4 carbon atoms. n is an integer of 1 to 8.

[0015] 〔3〕 The aqueous developing solution composition for flexographic printing plates according to [1] above, wherein the (a) polyoxyalkylene alkyl ether compound has a structure represented by the following formula (2).

[0016]

Chemical formula

[0017] In formula (2), l, m, and n are integers satisfying l = 1 to 6, m = 1 to 6, and l + m ≤ 7. A is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 8.

[0018] 〔4〕 The aqueous developing solution composition for flexographic printing plates according to any one of [1] to [3] above, further comprising a polyoxyalkylene alkyl ether compound having a branched alkyl group having 6 to 20 carbon atoms and an HLB value of 10 or more. 〔5〕 The aqueous developing solution composition for flexographic printing plates according to any one of [1] to [4] above, further comprising a compound having a structure represented by the following formula (3).

[0019]

Chemical formula

[0020] In formula (3), R is an alkyl group having 4 to 30 carbon atoms. p is an integer of 0 to 2.

[0021] 〔6〕 The aqueous developing solution composition for flexographic printing plates according to any one of [1] to [5] above, wherein the content of the (a) polyoxyalkylene alkyl ether compound is 0.01% by mass or more and 90% by mass or less. 〔7〕 A method for manufacturing a flexographic printing plate having an exposure step, a development step, and a post-exposure step for a photosensitive resin composition, in the development step, using the aqueous developer composition for a flexographic printing plate according to any one of the above [1] to [6], washing the unexposed photosensitive resin composition, A method for manufacturing a flexographic printing plate. [8] The method for manufacturing a flexographic printing plate according to the above [7], wherein the content of the (a) polyoxyalkylene alkyl ether compound in the aqueous developer composition for a flexographic printing plate is 0.01% by mass or more and 55% by mass or less. [9] The method for manufacturing a flexographic printing plate according to the above [7] or [8], wherein the post-exposure step is performed in water.

[10] Before the exposure step, the photosensitive resin composition contains (d) a polymer having an acrylate group or a methacrylate group at at least one end, and the content of the (d) polymer in the photosensitive resin composition is 50% by mass or more and 95% by mass or less. The method for manufacturing a flexographic printing plate according to any one of the above [7] to [9].

[11] The method for manufacturing a flexographic printing plate according to the above

[10] , wherein the (d) polymer having an acrylate group or a methacrylate group at at least one end contains a polyurethane having a hydrogenated polybutadiene structure. [Advantages of the Invention]

[0022] According to the present invention, it is possible to provide an aqueous developer composition for a flexographic printing plate, which can obtain a flexographic printing plate having high removability of an uncured photosensitive resin composition, excellent reproducibility of the flexographic printing plate, and little printing unevenness during printing. [Embodiments for Carrying Out the Invention]

[0023] Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. Note that the following embodiments are examples for explaining the present invention and are not intended to limit the present invention to the following contents. In addition, in this specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. Furthermore, in this specification, each component may be used alone as one kind of substance corresponding to each component, or two or more kinds may be used in combination. Here, when two or more kinds of substances are used in combination for each component, the content of that component refers to the total content of the substances used in combination, unless otherwise specified. The present invention can be appropriately modified and implemented without departing from the gist thereof.

[0024] [Aqueous Developing Solution Composition for Flexographic Printing Plate] The aqueous developing solution composition for a flexographic printing plate of this embodiment (hereinafter, may be referred to as an aqueous developing solution composition) contains (a) a polyoxyethylene alkyl ether compound having a branched structure with 3 to 11 carbon atoms and an HLB value of less than 10 (hereinafter, may be referred to as compound (a)). In addition, the aqueous developing solution composition of this embodiment contains water.

[0025] The aqueous developing solution composition of this embodiment includes both an aspect as a developing solution that can be used as it is during the development of a printing plate, and an aspect as a raw material composition (concentrate) for preparing a developing solution by adding water or the like and diluting it.

[0026] The aqueous developer composition of the present embodiment contains the compound (a), and thus can achieve effects such as (1) excellent removability of the photosensitive resin composition, (2) high reproducibility of the flexographic printing plate, and (3) less printing unevenness during printing of the printing plate manufactured using the aqueous developer composition of the present embodiment. Here, the removability of the photosensitive resin composition refers to the removability of the uncured photosensitive resin composition from the photosensitive resin composition layer after pattern exposure. Also, the reproducibility of the flexographic printing plate refers to the quality of the fine pattern on the surface of the flexographic printing plate. Furthermore, printing unevenness refers to the thickness variation of the ink applied by printing on the same object to be printed.

[0027] In this specification, the HLB value of the polyoxyalkylene alkyl ether compound (a) and the polyoxyalkylene alkyl ether compound (b) (hereinafter sometimes referred to as compound (b)) that can be optionally contained described later refers to Hydrophile Lipophile Balance, and is a value representing the degree of affinity of each component for water and hydrophobic components. In this specification, the HLB in the compound (a) and the compound (b) is a value obtained by a method determined from the organic value and the inorganic value in the Griffin method or "Emulsion Formulation Design by Organic Concept Diagram (data of Nippon Emulsion Co., Ltd.)". Also, when mixing a plurality of the compound (a) and / or a plurality of the compound (b), the HLB value after mixing is determined by the weighted average. Which method of the Griffin method or the method determined from the organic value and the inorganic value in "Emulsion Formulation Design by Organic Concept Diagram (data of Nippon Emulsion Co., Ltd.)" to apply may be appropriately selected according to the structure of the components. For example, it is preferable that the HLB value of the compound (a) and the compound (b) is a value determined by the Griffin method.

[0028] (Compound (a)) The aqueous developer composition of the present embodiment contains a polyoxyalkylene alkyl ether compound (compound (a)) having a branched structure with 3 to 11 carbon atoms and an HLB value of less than 10. The branched structure means a structure having one or more selected from the group consisting of a tertiary carbon, a quaternary carbon, and a secondary carbon bonded to O of an ether, and also includes a functional group of a cyclic structure. In addition, the "number of carbon atoms of the branched structure" refers to the total number of carbon atoms of the group bonded to O of the ether in the compound (a). By containing the compound (a), the aqueous developer of the present embodiment exhibits good developability, is excellent in flexographic printing plate reproducibility, and can improve printing unevenness. The reason why the aqueous developer composition of the present embodiment can exhibit the above-described effects can be speculated as follows.

[0029] First, when the number of carbon atoms of the branched structure is 3 or more, micelles are formed, and the detergency for removing the uncured photosensitive resin composition can be exhibited. In addition, when the number of carbon atoms of the branched structure is 11 or less, the molecular weight does not become too large and sufficient permeability to the uncured photosensitive resin composition is obtained, resulting in good detergency.

[0030] The compound (a) used in the aqueous developer composition of the present embodiment has a branched structure. As a result, the following effects can be obtained. Generally, when the number of carbon atoms of the lipophilic group is equal, it is known that a surfactant with a branched lipophilic group has a higher penetration power for a photosensitive resin than a surfactant with a linear lipophilic group. Since the compound (a) has a branched structure, the penetration power of the compound (a) for the photosensitive resin composition tends to be high, and sufficient detergency can be exhibited. In addition, when the compound (a) penetrates the plate surface, the plate surface changes, the compatibility with the ink for orientation film printing is improved, the ink acceptance amount during printing increases, and the ink spreads uniformly on the plate surface, which tends to contribute to the reduction of printing unevenness. Therefore, since the compound (a) has a branched structure, the compound (a) is trapped in the crosslinked structure of the plate surface, leading to the modification of the plate surface.

[0031] Since the HLB value of compound (a) is less than 10, the hydrophilicity does not become too high, sufficient penetration into the photosensitive resin composition is obtained, and excellent detergency tends to be obtained. In addition, since compound (a) is a polyoxyalkylene alkyl ether compound, excellent permeability into the photosensitive resin composition can be obtained. For example, in the case of a compound having an aromatic ring such as polyoxyethylene styrenated phenyl ether, due to the rigidity of the aromatic ring, the gap size of the crosslinking that can penetrate is limited, and the above-described effects tend not to be exhibited. Further, in the case of a compound having a charge such as nonion or anion, the polarity is too high, and it cannot penetrate into the photosensitive resin composition, and sufficient detergency tends not to be ensured.

[0032] From the viewpoint of enhancing the plate reproducibility when manufacturing a flexographic printing plate using the aqueous developer composition of the present embodiment and the ink receptivity of the surface of the printing plate, the number of carbon atoms in the branched structure of compound (a) is 3 to 11, preferably 3 to 10, more preferably 6 to 9, and still more preferably 7 to 8.

[0033] From the viewpoint of enhancing the detergency of the aqueous developer composition of the present embodiment, the compound (a) used in the aqueous developer composition of the present embodiment has an HLB value of less than 10, preferably 4 to 9.5, and more preferably 6 to 8.5. Compound (a) may be used alone or in combination of two or more. The HLB value of compound (a) can be controlled within a range of less than 10 by adjusting the structure of the hydrophilic part and / or hydrophobic part in compound (a). For example, in the case of alkylene alkyl ether compounds, the HLB value is controlled to be less than 10 by adjusting the type of alkyl group (number of carbon atoms, etc.), the number of repeating units of the polyoxyalkylene unit, etc. Specifically, according to the number of carbon atoms or molecular weight of the hydrophobic part in compound (a), by reducing the structure of the hydrophilic part, the HLB value can be controlled to decrease. For example, for a compound having polyoxyalkylene, by reducing the number of repeating units of the polyoxyalkylene unit with respect to the number of carbon atoms or molecular weight of the hydrophobic part in compound (a), the HLB value is controlled to decrease.

[0034] Examples of the compound (a) include, but are not limited to, the following compounds. Compounds having a cyclic structure such as 2-cyclobutoxyethan-1-ol, 2-(cyclopentyloxy)ethanol, 2-(cyclohexyloxy)ethan-1-ol, 2-(cycloheptyloxy)ethan-1-ol, 2-[[5-methyl-2-(propan-2-yl)cyclohexyl]oxy]ethan-1-ol, 2-(cyclooctylmethoxy)ethan-1-ol, 2-[(4-tert-butylcyclohexyl)methoxy]ethan-1-ol; AO adducts of synthetic secondary alcohols such as 2-(2-(octan-3-yloxy)ethoxy)ethan-1-ol; Compounds having iso-branching such as Fine Surf D-35 (manufactured by Aoki Yushi Industry Co., Ltd.) and Nonion ID-203 (manufactured by NOF Corporation) can be mentioned.

[0035] In addition, examples of the compound (a) include the following compounds. For example, ethylene glycol monoisopropyl ether, 2-(3-methylbutoxy)ethan-1-ol, 2-[2-(hexan-2-yloxy)ethoxy]ethan-1-ol, 2-(octan-3-yloxy)ethan-1-ol, 2-[2-(octan-2-yloxy)ethoxy]ethan-1-ol, 2-[(8-methylnonyl)oxy]ethan-1-ol, 2-(2-ethylbutoxy)ethan-1-ol, 2-[2-(2-ethylbutoxy)ethoxy]ethan-1-ol, 2-((2-ethylpentyl)oxy)ethan-1-ol, 2-(2-((2-ethylpentyl)oxy)ethoxy)ethan-1-ol, 2-((2-ethylhexyl)oxy)ethan-1-ol, 2-(2-((2-ethylhexyl)oxy)ethoxy)ethan-1-ol, 2-((2-propylpentyl)oxy)ethan-1-ol, 2-(2-((2-propylpentyl)oxy)ethoxy)ethan-1-ol, 2-((2-ethylheptyl)oxy)ethan-1-ol, 2-(2-((2-ethylheptyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-ethylheptyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-propylhexyl)oxy)ethan-1-ol, 2-(2-((2-propylhexyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-propylhexyl)oxy)ethoxy)ethoxy )ethan-1-ol, 2-((2-ethyloctyl)oxy)ethan-1-ol, 2-(2-((2-ethyloctyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-ethyloctyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-propylheptyl)oxy)ethan-1-ol, 2-(2-((2-propylheptyl)oxy)ethoxy)ethan-1-ol may be mentioned.

[0036] Furthermore, examples of the compound (a) include the following compounds. For example, 2-(2-(2-((2-propylheptyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-butylhexyl)oxy)ethan-1-ol, 2-(2-((2-butylhexyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-butylhexyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-ethylnonyl)oxy)ethan-1-ol, 2-(2-((2-ethylnonyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-ethylnonyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-propyloctyl)oxy)ethan-1-ol, 2-(2-((2-propyloctyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-propyloctyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-butylheptyl)oxy)ethan-1-ol, 2-(2-((2-butylheptyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-butylheptyl)oxy)ethoxy)ethoxy)ethan-1-ol may be mentioned.

[0037] Furthermore, examples of the compound (a) include the following compounds. For example, 3-(2-ethylbutoxy)propan-1-ol, 3-(3-(2-ethylbutoxy)propoxy)propan-1-ol, 3-((2-ethylpentyl)oxy)propan-1-ol, 3-(3-((2-ethylpentyl)oxy)propoxy)propan-1-ol, 3-((2-ethylhexyl)oxy)propan-1-ol, 3-(3-((2-ethylhexyl)oxy)propoxy)propan-1-ol, 3-((2-propylpentyl)oxy)propan-1-ol, 3-(3-((2-propylpentyl)oxy)propoxy)propan-1-ol, 3-((2-ethylheptyl)oxy)propan-1-ol, 3-((2-propylhexyl)oxy)propan-1-ol, 3-(3-((2-ethylheptyl)oxy)propoxy)propan-1-ol, 3-(3-((2-propylhexyl)oxy)propoxy)propan-1-ol, 3-((2-ethyloctyl)oxy)propan-1-ol, 3-(3-((2-ethyloctyl)oxy)propoxy)propan-1-ol, 3-((2-propylheptyl)oxy)propan-1-ol, 3-(3-((2-propylheptyl)oxy)propoxy)propan-1-ol, 3-((2-butylhexyl)oxy)propan-1-ol, 3-(3-((2-butylhexyl)oxy)propoxy)propan-1-ol, 3-((2-ethylnonyl)oxy)propan-1-ol, 3-(3-((2-ethylnonyl)oxy)propoxy)propan-1-ol, 3-((2-propyloctyl)oxy)propan-1-ol, 3-(3-((2-propyloctyl)oxy)propoxy)propan-1-ol, 3-((2-butylheptyl)oxy)propan-1-ol, 3-(3-((2-butylheptyl)oxy)propoxy)propan-1-ol may be mentioned.

[0038] Furthermore, examples of the compound (a) include the following compounds. For example, 4-(2-ethylbutoxy)butan-1-ol, 4-(4-(2-ethylbutoxy)butoxy)butan-1-ol, 4-((2-ethylpentyl)oxy)butan-1-ol, 4-(4-((2-ethylpentyl)oxy)butoxy)butan-1-ol, 4-((2-ethylhexyl)oxy)butan-1-ol, 4-(4-((2-ethylhexyl)oxy)butoxy)butan-1-ol, 4-((2-propylpentyl)oxy)butan-1-ol, 4-(4-((2-propylpentyl)oxy)butoxy)butan-1-ol, 4-((2-ethylheptyl)oxy)butan-1-ol, 4-(4-((2-ethylheptyl)oxy)butoxy)butan-1-ol, 4-((2-propylhexyl)oxy)butan-1-ol, 4-(4-((2-propylhexyl)oxy)butoxy)butan-1-ol, 4-((2-ethyloctyl)oxy)butan-1-ol, 4-(4-((2-ethyloctyl)oxy)butoxy)butan-1-ol, 4-((2-propylheptyl)oxy)butan-1-ol, 4-(4-((2-propylheptyl)oxy)butoxy)butan-1-ol, 4-((2-butylhexyl)oxy)butan-1-ol, 4-(4-((2-butylhexyl)oxy)butoxy)butan-1-ol, 4-((2-ethylnonyl)oxy)butan-1-ol, 4-(4-((2-ethylnonyl)oxy)butoxy)butan-1-ol, 4-((2-propyloctyl)oxy)butan-1-ol, 4-(4-((2-propyloctyl)oxy)butoxy)butan-1-ol, 4-((2-butylheptyl)oxy)butan-1-ol, 4-(4-((2-butylheptyl)oxy)butoxy)butan-1-ol, and the like.

[0039] The compound (a) is preferably a compound represented by the following formula (1). That is, the aqueous developer composition of the present embodiment preferably contains a polyoxyethylene alkyl ether compound having a branched structure with 1 to 11 carbon atoms and an HLB value of less than 10, and further a compound represented by the following formula (1). Although not clear in detail, having one or more secondary carbons between the oxygen atom of the hydrophilic part and the branched structure increases the degree of freedom of rotation between the hydrophilic part and the branched structure, and when manufacturing a printing plate, it easily takes a conformation suitable for penetrating the surface of the photosensitive resin composition layer. As a result, it tends to be possible to form a printing plate surface favorable for reducing printing unevenness.

[0040]

Chemical formula

[0041] In the formula (1), R is an alkyl group having 3 to 10 carbon atoms and having one or more tertiary carbons or quaternary carbons. R also includes a cyclic structure. Further, A is an alkylene group having 2 to 4 carbon atoms. n is an integer of 1 to 8. When there are a plurality of A, the plurality of A may be the same or different from each other.

[0042] Examples of the compound (a) having the structure of the formula (1) include compounds having a cyclic structure such as 2-[(4-tert-butylcyclohexyl)methoxy]ethan-1-ol and 2-(cyclooctylmethoxy)ethan-1-ol; and compounds having an isobranch such as Finesurf D-35 (manufactured by Aoki Yushi Industry Co., Ltd.) and Nonion ID-2030 (manufactured by NOF Corporation).

[0043] Examples of the compound (a) having the structure of formula (1) include 2-(3-methylbutoxy)ethan-1-ol, 2-[(8-methylnonyl)oxy]ethan-1-ol, 2-(2-ethylbutoxy)ethan-1-ol, 2-[2-(2-ethylbutoxy)ethoxy]ethan-1-ol, 2-((2-ethylpentyl)oxy)ethan-1-ol, 2-(2-((2-ethylpentyl)oxy)ethoxy)ethan-1-ol, 2-((2-ethylhexyl)oxy)ethan-1-ol, 2-(2-((2-ethylhexyl)oxy)ethoxy)ethan-1-ol, 2-((2-propylpentyl)oxy)ethan-1-ol, 2-(2-((2-propylpentyl)oxy)ethoxy)ethan-1-ol, 2-((2-ethylheptyl)oxy)ethan-1-ol, 2-(2-((2-ethylheptyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-ethylheptyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-propylhexyl)oxy)ethan-1-ol, 2-(2-((2-propylhexyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-propylhexyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-ethyloctyl)oxy)ethan-1-ol, 2-(2-((2-ethyloctyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-ethyloctyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-propylheptyl)oxy)ethan-1-ol, 2-(2-((2-propylheptyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-propylheptyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-butylhexyl)oxy)ethan-1-ol, 2-(2-((2-butylhexyl)2-(2-(2-((2-Butylhexyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-Ethylnonyl)oxy)ethoxy)ethan-1-ol, 2-((2-Ethylnonyl)oxy)ethan-1-ol, 2-(2-((2-Ethylnonyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-Ethylnonyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-Propyloctyl)oxy)ethan-1-ol, 2-(2-((2-Propyloctyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-Propyloctyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-Butylheptyl)oxy)ethan-1-ol, 2-(2-((2-Butylheptyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-Butylheptyl)oxy)ethoxy)ethoxy)ethan-1-ol, 3-(2-Ethylbutoxy)propan-1-ol are mentioned.

[0044] Furthermore, examples of the compound (a) having the structure of formula (1) include 3-(3-(2-ethylbutoxy)propoxy)propan-1-ol, 3-((2-ethylpentyl)oxy)propan-1-ol, 3-(3-((2-ethylpentyl)oxy)propoxy)propan-1-ol, 3-((2-ethylhexyl)oxy)propan-1-ol, 3-(3-((2-ethylhexyl)oxy)propoxy)propan-1-ol, 3-((2-propylpentyl)oxy)propan-1-ol, 3-(3-((2-propylpentyl)oxy)propoxy)propan-1-ol, 3-((2-ethylheptyl)oxy)propan-1-ol, 3-((2-propylhexyl)oxy)propan-1-ol, 3-(3-((2-ethylheptyl)oxy)propoxy)propan-1-ol, 3-(3-((2-propylhexyl)oxy)propoxy)propan-1-ol, 3-((2-ethyloctyl)oxy)propan-1-ol, 3-(3-((2-ethyloctyl)oxy)propoxy)propan-1-ol, 3-((2-propylheptyl)oxy)propan-1-ol, 3-(3-((2-propylheptyl)oxy)propoxy)propan-1-ol, 3-((2-butylhexyl)oxy)propan-1-ol, 3-(3-((2-butylhexyl)oxy)propoxy)propan-1-ol, 3-((2-ethylnonyl)oxy)propan-1-ol, 3-(3-((2-ethylnonyl)oxy)propoxy)propan-1-ol, 3-((2-propyloctyl)oxy)propan-1-ol, 3-(3-((2-propyloctyl)oxy)propoxy)propan-1-ol, 3-((2-butylheptyl)oxy)propan-1-ol, 3-(3-((2-butylheptyl)oxy)propoxy)propan-1-ol.

[0045] Furthermore, examples of the compound (a) having the structure of formula (1) include 4-(2-ethylbutoxy)butan-1-ol, 4-(4-(2-ethylbutoxy)butoxy)butan-1-ol, 4-((2-ethylpentyl)oxy)butan-1-ol, 4-(4-((2-ethylpentyl)oxy)butoxy)butan-1-ol, 4-((2-ethylhexyl)oxy)butan-1-ol, 4-(4-((2-ethylhexyl)oxy)butoxy)butan-1-ol, 4-((2-propylpentyl)oxy)butan-1-ol, 4-(4-((2-propylpentyl)oxy)butoxy)butan-1-ol, 4-((2-ethylheptyl)oxy)butan-1-ol, 4-(4-((2-ethylheptyl)oxy)butoxy)butan-1-ol, 4-((2-propylhexyl)oxy)butan-1-ol, 4-(4-((2-propylhexyl)oxy)butoxy)butan-1-ol, 4-((2-ethyloctyl)oxy)butan-1-ol, 4-(4-((2-ethyloctyl)oxy)butoxy)butan-1-ol, 4-((2-propylheptyl)oxy)butan-1-ol, 4-(4-((2-propylheptyl)oxy)butoxy)butan-1-ol, 4-((2-butylhexyl)oxy)butan-1-ol, 4-(4-((2-butylhexyl)oxy)butoxy)butan-1-ol, 4-((2-ethylnonyl)oxy)butan-1-ol, 4-(4-((2-ethylnonyl)oxy)butoxy)butan-1-ol, 4-((2-propyloctyl)oxy)butan-1-ol, 4-(4-((2-propyloctyl)oxy)butoxy)butan-1-ol, 4-((2-butylheptyl)oxy)butan-1-ol, 4-(4-((2-butylheptyl)oxy)butoxy)butan-1-ol, and the like.

[0046] It is more preferable that the compound (a) is a compound represented by the following formula (2). That is, it preferably contains a polyoxyethylene alkyl ether compound having a branched structure with 1 to 11 carbon atoms and an HLB value of less than 10, and further an organic compound whose structure is represented by the following formula (2). When the aqueous developer composition of the present embodiment contains the compound of the following formula (2), after permeating into the plate surface, the compound (a) gets entangled in the crosslinking and remains inside the plate, tending to cause better surface modification. As a result, a plate surface favorable for reducing printing unevenness is obtained.

[0047]

Chemical formula

[0048] In the formula (2), l, m, and n are integers satisfying l = 1 to 6, m = 1 to 6, and l + m ≤ 7. A is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 8. When there are a plurality of A's, the plurality of A's may be the same as or different from each other.

[0049] Examples of the compound (a) having the structure of the formula (2) include 2-(2-ethylbutoxy)ethan-1-ol, 2-[2-(2-ethylbutoxy)ethoxy]ethan-1-ol, 2-((2-ethylpentyloxy)ethan-1-ol, 2-(2-((2-ethylpentyloxy)ethoxy)ethan-1-ol, 2-((2-ethylhexyloxy)ethan-1-ol, 2-(2-((2-ethylhexyloxy)ethoxy)ethan-1-ol, 2-((2-propylpentyloxy)ethan-1-ol, 2-(2-((2-propylpentyloxy)ethoxy)ethan-1-ol, 2-((2-ethylheptyloxy)ethan-1-ol, 2-(2-((2-ethylheptyloxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-ethylheptyloxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-propylhexyloxy)ethan-1-ol, 2-(2-((2-propylhexyloxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-propylhexyloxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-ethyloctyloxy)ethan-1-ol, 2-(2-((2-ethyloctyloxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-ethyloctyloxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-propylheptyloxy)ethan-1-ol, 2-(2-((2-propylheptyloxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-propylheptyloxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-butylhexyloxy)ethan-1-ol, 2-(2-((2-butylhexyloxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-butylhexyloxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-ethylnonyl)oxy)ethan-1-ol, 2-(2-((2-ethylnonyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-ethylnonyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-propyloctyloxy)ethan-1-ol, 2-(2-((2-propyloctyloxy)ethoxy)ethan-1-ol,2-(2-(2-((2-propyl octyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-butyl heptyl)oxy)ethan-1-ol, 2-(2-((2-butyl heptyl)oxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-butyl heptyl)oxy)ethoxy)ethoxy)ethan-1-ol, etc. can be mentioned.

[0050] Examples of the compound (a) having the structure of the formula (2) include 3-(2-ethylbutoxy)propan-1-ol, 3-(3-(2-ethylbutoxy)propoxy)propan-1-ol, 3-((2-ethylpentyl)oxy)propan-1-ol, 3-(3-((2-ethylpentyl)oxy)propoxy)propan-1-ol, 3-((2-ethylhexyl)oxy)propan-1-ol, 3-(3-((2-ethylhexyl)oxy)propoxy)propan-1-ol, 3-((2-propylpentyl)oxy)propan-1-ol, 3-(3-((2-propylpentyl)oxy)propoxy)propan-1-ol, 3-((2-ethylheptyl)oxy)propan-1-ol, 3-((2-propylhexyl)oxy)propan-1-ol, 3-(3-((2-ethylheptyl)oxy)propoxy)propan-1-ol, 3-(3-((2-propylhexyl)oxy)propoxy)propan-1-ol, 3-((2-ethyloctyl)oxy)propan-1-ol, 3-(3-((2-ethyloctyl)oxy)propoxy)propan-1-ol, 3-((2-propylheptyl)oxy)propan-1-ol, 3-(3-((2-propylheptyl)oxy)propoxy)propan-1-ol, 3-((2-butylhexyl)oxy)propan-1-ol, 3-(3-((2-butylhexyl)oxy)propoxy)propan-1-ol, 3-((2-ethylnonyl)oxy)propan-1-ol, 3-(3-((2-ethylnonyl)oxy)propoxy)propan-1-ol, 3-((2-propyloctyl)oxy)propan-1-ol, 3-(3-((2-propyloctyl)oxy)propoxy)propan-1-ol, 3-((2-butylheptyl)oxy)propan-1-ol, 3-(3-((2-butylheptyl)oxy)propoxy)propan-1-ol, and the like.

[0051] Furthermore, examples of the compound (a) having the structure of the formula (2) include 4-(2-ethylbutoxy)butan-1-ol, 4-(4-(2-ethylbutoxy)butoxy)butan-1-ol, 4-((2-ethylpentyl)oxy)butan-1-ol, 4-(4-((2-ethylpentyl)oxy)butoxy)butan-1-ol, 4-((2-ethylhexyl)oxy)butan-1-ol, 4-(4-((2-ethylhexyl)oxy)butoxy)butan-1-ol, 4-((2-propylpentyl)oxy)butan-1-ol, 4-(4-((2-propylpentyl)oxy)butoxy)butan-1-ol, 4-((2-ethylheptyl)oxy)butan-1-ol, 4-(4-((2-ethylheptyl)oxy)butoxy)butan-1-ol, 4-((2-propylhexyl)oxy)butan-1-ol, 4-(4-((2-propylhexyl)oxy)butoxy)butan-1-ol, 4-((2-ethyloctyl)oxy)butan-1-ol, 4-(4-((2-ethyloctyl)oxy)butoxy)butan-1-ol, 4-((2-propylheptyl)oxy)butan-1-ol, 4-(4-((2-propylheptyl)oxy)butoxy)butan-1-ol, 4-((2-butylhexyl)oxy)butan-1-ol, 4-(4-((2-butylhexyl)oxy)butoxy)butan-1-ol, 4-((2-ethylnonyl)oxy)butan-1-ol, 4-(4-((2-ethylnonyl)oxy)butoxy)butan-1-ol, 4-((2-propyloctyl)oxy)butan-1-ol, 4-(4-((2-propyloctyl)oxy)butoxy)butan-1-ol, 4-((2-butylheptyl)oxy)butan-1-ol, 4-(4-((2-butylheptyl)oxy)butoxy)butan-1-ol, and the like.

[0052] In the aqueous developer composition of the present embodiment, the content of the compound (a) is preferably 0.01% by mass or more and preferably 90% by mass or less from the viewpoint of appropriately maintaining the concentration of the active ingredient. More preferably, it is 0.01% by mass or more and 55% by mass or less, still more preferably 0.1% by mass or more and 20% by mass or less, even more preferably 0.2% by mass or more and 10% by mass or less, and even more preferably 0.5% by mass or more and 5% by mass or less.

[0053] (Water) The aqueous developer composition of the present embodiment contains water. The water contained in the aqueous developer composition of the present embodiment is not particularly limited, and any of distilled water, purified water, ion-exchanged water, pure water, ultrapure water such as Milli-Q water, and tap water can be used. Note that the Milli-Q water refers to ultrapure water obtained by a Milli-Q water production apparatus, which is an ultrapure water production apparatus of Merck & Co., Ltd. The aqueous developer composition of the present embodiment includes an aspect of a developer that can be used as it is for development and an aspect of a raw material composition (concentrate) for preparing a developer by adding water or the like and diluting it. Therefore, the water content in the aqueous developer composition of the present embodiment can be adjusted as appropriate.

[0054] (Compound (b)) In addition to the compound (a) described above, the aqueous developer composition of the present embodiment preferably contains a polyoxyalkylene alkyl ether compound having a branched alkyl group having 6 to 10 carbon atoms and an HLB value of 10 or more (hereinafter sometimes referred to as compound (b)). The compound (b) has a function as a nonionic surfactant.

[0055] Examples of the compound (b) include polyoxyethylene ethylhexyl ethers such as Braunon EH-4 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Braunon EH-6 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Braunon EH-11 (manufactured by Aoki Yushi Kogyo Co., Ltd.), and Braunon EH-30 (manufactured by Aoki Yushi Kogyo Co., Ltd.); polyoxyethylene isodecyl ethers such as Fine Surf D-60 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Fine Surf D-65 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Fine Surf D-85 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Fine Surf ID-1033 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Fine Surf ID-1055 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Fine Surf ID-1061 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Fine Surf ID-1074 (manufactured by Aoki Yushi Kogyo Co., Ltd.), and Fine Surf ID-1087 (manufactured by Aoki Yushi Kogyo Co., Ltd.); and polyoxyethylene isostearyl ethers such as Fine Surf FO-80 (manufactured by Aoki Yushi Kogyo Co., Ltd.) and Fine Surf FO-160 (manufactured by Aoki Yushi Kogyo Co., Ltd.).

[0056] Examples of the compound (b) include polyoxyethylene secondary alcohol ethers such as Newcol NT-5 (manufactured by Nippon Emulsifier Co., Ltd.), Newcol NT-7 (manufactured by Nippon Emulsifier Co., Ltd.), Newcol NT-12 (manufactured by Nippon Emulsifier Co., Ltd.), Newcol NT-15 (manufactured by Nippon Emulsifier Co., Ltd.), Newcol NT-20 (manufactured by Nippon Emulsifier Co., Ltd.), Newcol NT-30 (manufactured by Nippon Emulsifier Co., Ltd.), Newcol NT-40 (manufactured by Nippon Emulsifier Co., Ltd.), and Newcol NT-50 (manufactured by Nippon Emulsifier Co., Ltd.); polyoxyethylene secondary alcohol ethers such as Softanol 50 (manufactured by Nippon Shokubai Co., Ltd.), Softanol 70 (manufactured by Nippon Shokubai Co., Ltd.), Softanol 120 (manufactured by Nippon Shokubai Co., Ltd.), Softanol 150 (manufactured by Nippon Shokubai Co., Ltd.), Softanol 200 (manufactured by Nippon Shokubai Co., Ltd.), Softanol 300 (manufactured by Nippon Shokubai Co., Ltd.), Softanol 400 (manufactured by Nippon Shokubai Co., Ltd.), and Softanol 500 (manufactured by Nippon Shokubai Co., Ltd.); polyoxyethylene 2-hexyldecyl ethers such as Isocetes-10 (manufactured by Nippon Emulsion Co., Ltd.), Isocetes-15 (manufactured by Nippon Emulsion Co., Ltd.), Isocetes-20 (manufactured by Nippon Emulsion Co., Ltd.), and Isocetes-25 (manufactured by Nippon Emulsion Co., Ltd.); polyoxyethylene isostearyl ethers such as Isostares-10 (manufactured by Nippon Emulsion Co., Ltd.), Isostares-15 (manufactured by Nippon Emulsion Co., Ltd.), Isostares-20 (manufactured by Nippon Emulsion Co., Ltd.), and Isostares-25 (manufactured by Nippon Emulsion Co., Ltd.); and polyoxyethylene octyldodecyl ethers such as Octyldeces-10 (manufactured by Nippon Emulsion Co., Ltd.), Octyldeces-15 (manufactured by Nippon Emulsion Co., Ltd.), Octyldeces-20 (manufactured by Nippon Emulsion Co., Ltd.), and Octyldeces-25 (manufactured by Nippon Emulsion Co., Ltd.).

[0057] Furthermore, examples of the compound (b) include 2-(2-(2-(hexan-2-yloxy)ethoxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-methylpentyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-(2-(2-(((3-methylpentyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-(2-(2-((4-methylpentyl)oxy)ethoxy)ethoxy)ethan-1-ol, 2-(2-(2-(hexan-3-yloxy)ethoxy)ethoxy)ethan-1-ol, 2-(2-(2-(2-ethylbutoxy)ethoxy)ethoxy)ethan-1-ol, 2-(2-(2-(cyclohexyloxy)ethoxy)ethoxy)ethan-1-ol, 13-methyl-3,6,9,12-tetraoxaheptadecan-1-ol, 14-methyl-3,6,9,12-tetraoxaheptadecan-1-ol, 15-methyl-3,6,9,12-tetraoxaheptadecan-1-ol, 16-methyl-3,6,9,12-tetraoxaheptadecan-1-ol, 13-ethyl-3,6,9,12-tetraoxahexadecan-1-ol, 14-ethyl-3,6,9,12-tetraoxahexadecan-1-ol, 2-(2-(2-(2-(cyclohexyloxy)ethoxy)ethoxy)ethoxy)ethan-1-ol, 16-methyl-3,6,9,12,15-pentaoxicosan-1-ol, 17-methyl-3,6,9,12,15-pentaoxicosan-1-ol, 18-methyl-3,6,9,12,15-pentaoxicosan-1-ol, 19-methyl-3,6,9,12,15-pentaoxicosan-1-ol, 16-ethyl-3,6,9,12,15-pentaoxicosan-1-ol, 16-ethyl-3,6,9,12,15-pentaoxicosan-1-ol, 14-(cyclohexyloxy)-3,6,9,12-pentaoxaheptadecan-1-ol, 19-methyl-3,6,9,12,15,18-hexaoxatricosane-1-ol, 20-methyl-3,6,9,12,15,18-hexaoxatricosane-1-ol, 21-methyl-3,6,9,12,15,18-hexaoxatricosane-1-ol, 22-methyl-3,6,9,12,15,Examples include 18 - hexaoxatricosane - 1 - ol, 19 - ethyl - 3,6,9,12,18 - hexaoxatricosane - 1 - ol, 19 - ethyl - 3,6,9,12,15,18 - hexaoxatricosane - 1 - ol, 17 - (cyclohexyloxy) - 3,6,9,12,15 - pentaoxaheptadecane - 1 - ol, etc.

[0058] Since the aqueous developer composition of this embodiment contains the compound (b) which is a non - ionic with an HLB value of 10 or more, the stability of the micelles is improved, and more diverse stains can be removed, and the detergency tends to be improved. Also, from the viewpoint of obtaining a suitable HLB value and improving the detergency by mixing the compound (a) and the compound (b), the content of the compound (b) is preferably 0.1 part by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 70 parts by mass or less, and still more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the compound (a). Also, the compound (b) may be used alone or in combination of two or more, and each compound (b) is preferably within the above - mentioned part - by - mass range.

[0059] (Compound (c)) From the viewpoint of softening the uncured photosensitive resin composition and improving the detergency, the aqueous developer composition of this embodiment preferably contains a compound (c) having a structure represented by the following formula (3).

[0060]

Chemical formula

[0061] In formula (3), R is an alkyl group having 4 to 30 carbon atoms. P is an integer of 0 to 2.

[0062] Examples of the compound having the structure represented by the formula (3) include, but are not limited to, 1-butylazetidin-2-one, 1-pentylazetidin-2-one, 1-hexylazetidin-2-one, 1-heptylazetidin-2-one, 1-octylazetidin-2-one, 1-nonylazetidin-2-one, 1-decylazetidin-2-one, 1-undecylazetidin-2-one, 1-tridecylazetidin-2-one, 1-tetradecylazetidin-2-one, 1-pentadecylazetidin-2-one, 1-hexadecylazetidin-2-one, 1-heptadecylazetidin-2-one, 1-octadecylazetidin-2-one, 1-nonadecylazetidin-2-one, 1-icosylazetidin-2-one, 1-henicosylazetidin-2-one, 1-docosylazetidin-2-one, 1-tricosylazetidin-2-one, 1-tetracosylazetidin-2-one, 1-pentacosylazetidin-2-one, 1-octacosylazetidin-2-one, 1-nonacosylazetidin-2-one, 1-triacontylazetidin-2-one, 1-cyclohexylazetidin-2-one, 1-N-butyl-2-pyrrolidone,1-N-pentyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, 1-N-octyl-2-pyrrolidone, 1-N-nonyl-2-pyrrolidone, 1-N-decyl-2-pyrrolidone, 1-N-undecyl-2-pyrrolidone, 1-N-dodecyl-2-pyrrolidone, 1-N-tridecyl-2-pyrrolidone, 1-N-tetradecyl-2-pyrrolidone, 1-N-pentadecyl-2-pyrrolidone, 1-N-hexadecyl-2-pyrrolidone, 1-N-heptadecyl-2-pyrrolidone, 1-N-octadecyl-2-pyrrolidone, 1-N-nonadecyl-2-pyrrolidone, 1-N-icosyl-2-pyrrolidone, 1-N-heneicosyl-2-pyrrolidone, 1-N-docosyl-2-pyrrolidone, 1-N-tricosyl-2-pyrrolidone, 1-N-tetracosyl-2-pyrrolidone, 1-N-pentacosyl-2-pyrrolidone, 1-N-hexacosyl-2-pyrrolidone, 1-N-heptacosyl-2-pyrrolidone, 1-N-octacosyl-2-pyrrolidone, 1-N-nonacosyl-2-pyrrolidone, 1-N-triacontyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 1-N-butyl-2-piperidone, 1-N-pentyl-2-piperidone, N-hexyl-2-piperidone, N-heptyl-2-piperidone, 1-N-octyl-2-piperidone, 1-N-nonyl-2-piperidone, 1-N-decyl-2-piperidone, 1-N-undecyl-2-piperidone, 1-N-dodecyl-2-piperidone, 1-N-tridecyl-2-piperidone, 1-N-tetradecyl-2-piperidone, 1-N-pentadecyl-2-piperidone, 1-N-hexadecyl-2-piperidone, 1-N-heptadecyl-2-piperidone, 1-N-octadecyl-2-piperidone, 1-N-nonadecyl-2-piperidone, 1-N-icosyl-2-piperidone, 1-N-heneicosyl-2-piperidone, 1-N-docosyl-2-piperidone, 1-N-tricosyl-2-piperidone, 1-N-tetracosyl-2-piperidone, 1-N-pentacosyl-2-piperidone, 1-N-hexacosyl-2-piperidone, 1-N-heptacosyl-2-piperidone, 1-N-octacosyl-2-piperidone, 1-N-nonacosyl-2-piperidone, 1-N-triacontyl-2-piperidone, N-cyclohexyl-2-piperidone are included., The compound represented by the formula (3) may be a surfactant.

[0063] From the viewpoint of ensuring the water dispersibility of the compound (c) having the structure represented by the formula (3) and improving the detergency and reproducibility, the content of the compound (c) is preferably 0.1 part by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 70 parts by mass or less, and even more preferably 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the compound (a). Further, the compound (c) may be used alone or in combination of two or more, and each compound (c) is preferably within the above-mentioned range of parts by mass.

[0064] (Other additives) The aqueous developer composition of the present embodiment may contain other components as long as the effects of the present invention are not impaired. For example, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, antifoaming agents, fragrances, chelating agents, dyes, acids, and alkalis other than the compounds (a), (b), and (c) are included.

[0065] [Method for producing an aqueous developer composition for flexographic printing plate] The aqueous developer composition of the present embodiment can be produced by a method of stirring and homogenizing the compound (a), water, and, if necessary, the compound (b), the compound (c), and other additives. The order of blending the respective components is not particularly limited. The respective components may be prepared separately and added separately at the time of preparing the developer to obtain an aqueous developer composition. Further, the aqueous developer composition may be used as a concentrated solution and diluted by adding water at the time of preparing the developer.

[0066] [Method for producing a flexographic printing plate] The method for producing a flexographic printing plate of the present embodiment includes an exposure step, a development step, and a post-exposure step for the photosensitive resin composition. In the development step, the unexposed photosensitive resin composition is washed using the aqueous developer composition of the present embodiment. More specifically, in the exposure step, a relief is formed by exposing the photosensitive resin composition layer to obtain a printing original plate. In the development step, the unexposed portion, which is the uncured photosensitive resin composition of the photosensitive resin composition layer, is washed away with the aqueous developer composition of the present embodiment for development, and the photosensitive resin composition layer after the development is post-exposed.

[0067] (Printing original plate) Before exposure to the photosensitive resin composition layer, the printing original plate has a configuration including at least a support (e) and a photosensitive resin composition layer (f) laminated on the support (e). In this specification, such a configuration may be described as a "photosensitive resin structure for printing plate". That is, as described later, by performing relief formation on the photosensitive resin structure for printing plate by pattern exposure, a printing original plate is obtained. By removing the unexposed portion from the printing original plate in the development step, a flexographic printing plate is obtained.

[0068] <Support (e)> The support (e) is not particularly limited, and examples thereof include a polyester film, a polyamide film, a polyacrylonitrile film, and a polyvinyl chloride film. Among these, a polyester film is preferable as the support (e). The polyester used for the support (e) is not particularly limited, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. The thickness of the support (e) is not particularly limited, but is preferably 50 to 300 μm. Also, for the purpose of enhancing the adhesive force between the support (e) and the photosensitive resin composition layer (f) described later, an adhesive layer may be provided on the support (e). The adhesive layer is not particularly limited, and examples thereof include the adhesive layers described in International Publication No. 2004 / 104701, Japanese Patent No. 3094647, and Japanese Patent No. 2634429.

[0069] <Photosensitive resin composition layer (f)> The photosensitive resin composition for printing plates has a photosensitive resin composition layer on a support. The photosensitive resin composition layer may be directly laminated on the support, or may be indirectly laminated via a predetermined adhesive layer or the like. The photosensitive resin composition layer is not particularly limited, but for example, it preferably contains a polymer (d) described later, and further contains an ethylenically unsaturated compound (g) and a photopolymerization initiator (h) described later. In addition, the photosensitive resin composition layer may further contain auxiliary additive components as necessary. Hereinafter, each component of the photosensitive resin composition layer will be described in detail.

[0070] [Polymer (d)] The polymer (d) is an elastomer, and examples thereof include elastomers having structural units derived from conjugated dienes and / or vinyl aromatic compounds, although not limited thereto. The polymer (d) is preferably a polyurethane from the viewpoint of improving cleanability and reproducibility. Since polyurethane has a hydrophilic molecular skeleton, it is likely to penetrate into the uncured resin of the compound (a), leading to an improvement in cleanability. In addition, being a polyurethane, having a urethane bond improves the mechanical strength of the cured plate, leading to an improvement in reproducibility. In addition, from the viewpoint of the above mechanism, the content of the polyurethane is preferably 50% by mass or more and 95% by mass or less, more preferably 60 - 90% by mass, and even more preferably 70 - 85% by mass when the total amount of the photosensitive resin composition layer (f) is 100% by mass. The polymer (d) may be a linear, branched or dendritic polymer, and may be a homopolymer or a copolymer. The copolymer may be a random copolymer, an alternating copolymer or a block copolymer.

[0071] The methods for identifying polyurethane include, but are not limited to, the method of separating polymer components by liquid chromatography (LC) and then identifying them by nuclear magnetic resonance (NMR) or mass spectrometry (MS), or the method of identifying them by gas chromatography - mass spectrometry (GC / MS), etc.

[0072] The polymer (d) is not particularly limited, but as an unsaturated carbon bond, it may have an acrylate group or a methacrylate group (hereinafter sometimes referred to as a (meth)acrylic group) at at least one end. As a method for producing a polyurethane having a (meth)acrylic group at the terminal group, for example, a diol having a repeating unit in the molecule is reacted with a diisocyanate to form a polyurethane having an isocyanate group at the terminal at an arbitrary molecular weight, and then the polyurethane is reacted with a compound containing an active hydrogen and a (meth)acrylic group in one molecule. As another method, a diol having a repeating unit in the molecule is reacted with a diisocyanate to first form a polyurethane having a hydroxyl group at the terminal at an arbitrary molecular weight, and then the polyurethane is reacted with a compound containing an isocyanate group and a (meth)acrylic group in one molecule. By having acrylate groups or methacrylate groups at both ends, the strength after curing of the photosensitive resin composition layer tends to increase and the formability tends to improve.

[0073] The polyurethane structure obtained by the above - described production method is a structure formed by the reaction of a diol having a repeating unit in the molecule and a diisocyanate. In this specification, the "polyurethane having a (meth)acrylic group at the terminal group" synthesized by the above method may sometimes be referred to as an "unsaturated prepolymer".

[0074] The "diol having repeating units in the molecule" used in the production of the unsaturated prepolymer is not limited to the following, and examples include, for example, polyester diols composed of dicarboxylic acids and diols; polyether diols; polyether-polyester copolymer diols; 1,2-polybutadiene compounds having terminal hydroxyl groups and hydrogenated compounds thereof, etc. The diol having repeating units in the molecule may be used alone or in combination of two or more.

[0075] Examples of the dicarboxylic acid constituting the polyester diol include, but are not limited to, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, terephthalic acid, isophthalic acid, and 1,5-naphthalenedicarboxylic acid, etc. Examples of the diol constituting the polyester diol include, but are not limited to, for example, 1,4-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl diol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, and diethylene glycol (dioxydiethylene glycol), etc. Examples of the polyether diol include, but are not limited to, for example, polyoxyethylene diol, polyoxypropylene diol, polyoxytetramethylene diol, polyoxy-1,2-butylene diol, polyoxyethylene / polyoxypropylene random copolymer diol, polyoxyethylene / polyoxypropylene block copolymer diol, polyoxyethylene / polyoxytetramethylene random copolymer diol, and polyoxyethylene / polyoxytetramethylene block copolymer diol, etc.

[0076] Examples of the polyether polyester copolymer polyol include, but are not limited to, a copolymer having a structure in which the repeating unit forming the molecular chain of the polyether polyol described above and the repeating unit forming the molecular chain of the polyester polyol described above are linked in blocks or randomly.

[0077] From the viewpoint of improving detergency due to the structural similarity with the compound (a) having a branched structure, and from the viewpoint that the surfactant penetrated into the plate surface is easily trapped inside the plate due to steric hindrance and is advantageous for plate surface modification, the polymer (d) preferably contains a polyurethane having a hydrogenated polybutadiene structure. Examples of raw materials for such a polyurethane that satisfy such conditions include hydrides of poly-1-butene having terminal hydroxyl groups, hydrides of 1,2-polybutadiene having terminal hydroxyl groups, and the like.

[0078] Examples of the diisocyanate include, but are not limited to, tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and norbornene diisocyanate. The diisocyanate may be used alone or in combination of two or more.

[0079] [Ethylenically unsaturated compound (g)] As described above, the photosensitive resin composition layer preferably contains an ethylenically unsaturated compound (g). The ethylenically unsaturated compound (g) is a compound having an unsaturated double bond capable of radical polymerization. Examples of such ethylenically unsaturated compounds (g) include, but are not limited to, olefins such as ethylene, propylene, vinyltoluene, styrene, and divinylbenzene; acetylenes; (meth)acrylic acid and / or its derivatives; haloolefins; unsaturated nitriles such as acrylonitrile; unsaturated amides such as acrylamide and methacrylamide and their derivatives; unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, and fumaric acid and their derivatives; vinyl acetates; N-vinylpyrrolidone; N-vinylcarbazole; N-substituted maleimide compounds, etc.

[0080] Examples of said derivatives include, but are not limited to, alicyclic compounds having a cycloalkyl group, bicycloalkyl group, cycloalkenyl group, bicycloalkenyl group, etc.; aromatic compounds having a benzyl group, phenyl group, phenoxy group, or naphthalene skeleton, anthracene skeleton, biphenyl skeleton, phenanthrene skeleton, fluorene skeleton, etc.; compounds having an alkyl group, halogenated alkyl group, alkoxyalkyl group, hydroxyalkyl group, aminoalkyl group, glycidyl group, etc.; ester compounds with polyhydric alcohols such as alkylene glycol, polyoxyalkylene glycol, polyalkylene glycol, and trimethylolpropane; compounds having a polysiloxane structure such as polydimethylsiloxane and polydiethylsiloxane, etc.

[0081] Also, the ethylenically unsaturated compound (g) may be a heteroaromatic compound containing elements such as nitrogen and sulfur.

[0082] Examples of the (meth)acrylic acid and / or its derivatives include, but are not limited to, diacrylates and dimethacrylates of alkanediols such as hexanediol and nonanediol; diacrylates and dimethacrylates of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, and butylene glycol; trimethylolpropane tri(meth)acrylate; dimethyloltricyclodecane di(meth)acrylate; isobornyl (meth)acrylate; phenoxypolyethylene glycol (meth)acrylate; pentaerythritol tetra(meth)acrylate, and the like.

[0083] The ethylenically unsaturated compound (g) may be used alone or in combination of two or more.

[0084] From the viewpoint of improving the strength of the printing original plate and preventing damage to the relief surface due to the load during peeling of the protective film after exposure, it is preferable to use at least one type of (meth)acrylate as the ethylenically unsaturated compound (g), and more preferably to use at least one type of bifunctional (meth)acrylate.

[0085] From the viewpoint of removability during development, when the total amount of the photosensitive resin composition layer (f) is 100% by mass, the content of the ethylenically unsaturated compound (g) which is a liquid component in the photosensitive resin composition layer (f) is preferably 2% by mass or more and less than 60% by mass, more preferably 5% by mass or more and 50% by mass or less, and even more preferably 10% by mass or more and 40% by mass or less.

[0086] [Photoinitiator (h)] The photosensitive resin composition layer preferably contains a photoinitiator (h). The photoinitiator (h) is a compound that absorbs the energy of light and generates radicals, and examples thereof include decomposition-type photoinitiators, hydrogen abstraction-type photoinitiators, and compounds having a site that functions as a hydrogen abstraction-type photoinitiator and a site that functions as a decomposition-type photoinitiator in the same molecule.

[0087] Examples of such a photopolymerization initiator (h) include, but are not limited to, benzophenones such as benzophenone, 4,4-bis(diethylamino)benzophenone, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-tetramethoxybenzophenone; anthraquinones such as t-butylanthraquinone, 2-ethylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; Michler's ketone; acetophenones such as diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, trichloroacetophenone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; methyl benzoylformate; 1,7-bisacridinylheptane; 9-phenylacridine; azo compounds such as azobisisobutyronitrile, diazonium compounds, tetrazene compounds. These may be used alone or in combination of two or more.

[0088] From the viewpoint of ensuring the strength to suppress the breakage of independent points due to spray atomization or brush friction during development, when the total amount of the photosensitive resin composition layer (f) is 100% by mass, the content of the photoinitiator (h) in the photosensitive resin composition layer (f) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 5% by mass.

[0089] [Auxiliary additive components] Examples of the auxiliary additive components include, but are not limited to, plasticizers, thermal polymerization inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, and the like. Examples of the plasticizer include, but are not limited to, liquid dienes such as liquid polybutadiene, liquid polyisoprene, modified products of liquid polybutadiene, modified products of liquid polyisoprene, liquid acrylonitrile-butadiene copolymers, and liquid styrene-butadiene copolymers; hydrocarbon oils such as naphthene oil and paraffin oil; conjugated diene rubbers mainly composed of liquid dienes such as liquid acrylonitrile-butadiene copolymers and liquid styrene-butadiene copolymers; polystyrene having a number average molecular weight of 2000 or less; and ester plasticizers such as sebacic acid esters and phthalic acid esters. These plasticizers may have a hydroxyl group or a carboxyl group. Further, these plasticizers may be provided with a photopolymerizable reactive group such as a (meth)acryloyl group. The plasticizer may be used alone or in combination of two or more. In addition, the term "liquid" in this specification means a property that can be easily deformed by flowing and can be solidified into a deformed shape by cooling.

[0090] As the thermal polymerization inhibitor and the antioxidant, those commonly used in the field of resin materials or rubber materials can be used, and examples thereof include phenolic materials. Examples of phenolic materials include, but are not limited to, vitamin E, tetrakis-(methylene-3-(3’,5’-di-t-butyl-4’-hydroxyphenyl)propionate)methane, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 3,9-bis-{1,1-dimethyl-2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, and the like. Other examples of heat polymerization inhibitors and antioxidants include phosphine-based materials such as triphenyl phosphite. The heat polymerization inhibitor and antioxidant may be used alone or in combination of two or more.

[0091] Examples of light stabilizers and ultraviolet absorbers include, but are not limited to, known benzophenone-based compounds, salicylate-based compounds, acrylonitrile-based compounds, metal complex-based compounds, and hindered amine-based compounds. Also, the dyes and pigments shown below may be used as ultraviolet absorbers. Examples of such light stabilizers and ultraviolet absorbers include, but are not limited to, 2-ethoxy-2’-ethyloxalic acid bisanilide, 2,2’-dihydroxy-4-methoxybenzophenone, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-decandioate, 1,2,3-benzotriazole, and the like. Dyes and pigments are effective as coloring means for improving visibility. Examples of dyes include, but are not limited to, water-soluble basic dyes, acidic dyes, direct dyes, etc., and water-insoluble sulfur dyes, oil-soluble dyes, disperse dyes, etc. Anthraquinone-based dyes, indigoid-based dyes, and azo-based dyes are particularly preferred. Examples of the pigment include, but are not limited to, natural pigments, synthetic inorganic pigments, synthetic organic pigments, etc. Examples of the synthetic organic pigment include azo pigments, triphenylmethane pigments, quinoline pigments, anthraquinone pigments, and phthalocyanine pigments.

[0092] (Exposure step) In the method for manufacturing a flexographic printing plate of the present embodiment, a printing original plate is obtained by forming a relief by pattern exposure on a photosensitive resin composition for a printing plate, and the unexposed portion of the printing original plate is removed in a developing step described later to obtain a printing plate. In the pattern exposure, for example, light including a wavelength of 360 nm is irradiated to photocure the photosensitive resin composition. Then, a developing step of removing the unexposed portion and a post-exposure step are performed.

[0093] In the exposure step, for example, a negative film is placed on a glass plate and covered with a thin protective film thereon, and a photosensitive resin composition is laminated thereon. With a base film serving as a support bonded thereto, a glass plate is applied onto the base film so that the thickness of the photosensitive resin composition layer becomes a preset constant value. Next, back exposure for a short time is performed by an upper active light source to form a uniform thin resin layer, i.e., a back exposure layer, over the entire surface of the support. Then, image-forming exposure is performed by irradiating light including a wavelength of 360 nm with a lower active light source. From the viewpoint of imparting releasability, the surface of the flexographic printing plate may be brought into contact with a liquid containing a silicone compound and / or a fluorine compound. Examples of the active light source used for exposure in the manufacturing process of the flexographic printing plate include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp, etc. Further, as the transparent image carrier used for forming a relief image, a negative or positive film for photomechanical printing by a silver salt image is mainly used.

[0094] In addition, when the photosensitive resin composition is liquid at room temperature, in the above-described embodiments, usually, a predetermined forming step is included so that the photosensitive resin composition is formed into a film having a certain thickness on a support inside a dedicated apparatus (plate-making machine). As described above, when using a photosensitive resin composition that is liquid at room temperature, in the exposure step, it is preferable to perform, for example, each of the following steps (A1) to (A3). (A1): Step (A1) is a step of forming a photosensitive resin composition layer in which a negative film is placed on an ultraviolet-transmissive glass plate (lower glass plate), a protective film is disposed thereon, a photosensitive resin composition is further flowed thereon, and a base film serving as a support is bonded via a spacer so that it has a certain plate thickness, and further pressed from above with an ultraviolet-transmissive glass plate (upper glass plate) to form a photosensitive resin composition layer. After placing the protective film on the lower glass plate, it is preferable to securely fix the protective film and perform film evacuation for the purpose of removing oxygen inhibition factors. The evacuation mechanism is not particularly limited. For example, there is a method of evacuating with a pump through a groove provided around the lower glass. When producing a flexographic printing plate (thickness of 4 mm or more) for use in corrugated printing, in order to compensate for the strength of the relief against the printing pressure during printing, it is preferable to form a shelf layer serving as a base in the portion of the photosensitive resin composition layer on the upper glass plate side. In this case, before relief exposure, a dedicated negative film (masking film) is sandwiched between the upper glass plate and the base film to form the photosensitive resin composition layer. (A2): Step (A2) is a back exposure step in which, after the forming step of the photosensitive resin composition layer, an active ray using an ultraviolet fluorescent lamp or the like as an active light source (for example, a ray having a wavelength distribution of 300 nm or more) is irradiated from the upper glass plate side through the base film, thereby depositing a uniform thin cured resin layer (that is, a floor portion forming layer (back deposition layer)) on the entire surface on the base film side of the plate. When a masking film is provided in the photosensitive resin composition layer forming step, a shelf layer is formed by the same exposure. In this case, it is called a masking exposure step. Both the back deposition layer and the shelf layer are formed by curing the photosensitive resin composition layer on the side opposite to the relief forming layer side of the photosensitive resin composition layer, that is, the support side. When the entire photosensitive resin composition layer on the support side is cured, it becomes the back deposition layer, and when the photosensitive resin composition layer is partially cured according to the position of the relief forming layer, it becomes the shelf layer. (A3): Step (A3) is a relief forming exposure step in which, after the back exposure step or the masking exposure step, the photosensitive resin composition layer is irradiated with the same actinic rays as the upper part through a negative film from the lower glass side to deposit an image forming layer (relief forming layer). When a shelf layer is formed by the masking exposure step, it is also a preferred embodiment to remove the masking film after the relief forming exposure step and further pass through the back exposure step to form a back deposition layer on the entire surface of the base film.

[0095] (Development step) In the method for manufacturing a flexographic printing plate of the present embodiment, the aqueous developer composition of the present embodiment is used to remove the unexposed portion in the development step. The development method using the aqueous developer composition can apply the same method as the development method using a conventionally known aqueous developer. For example, the aqueous developer composition is brought into contact with the unexposed portion of the printing plate original, and physical actions such as water pressure, brush, and ultrasonic waves are applied to disperse or dissolve the photosensitive resin composition constituting the unexposed portion in the aqueous developer and remove it from the cured plate surface. At this time, the aqueous developer composition may immerse the unexposed portion, or may be continuously supplied and brought into contact when the physical action reaches. Further, from the viewpoint of improving the detergency, the liquid temperature during development is preferably 20 to 60 ° C, and more preferably 30 to 50 ° C for the aqueous developer composition. In addition, as the physical force that is usually used, a spray is used, and the water pressure, nozzle diameter, nozzle arrangement, etc. are appropriately selected. As a pre-removal process, the unexposed portion may be removed in advance using a spatula or a roll.

[0096] Further, the aqueous developer composition of the present embodiment may be used as a concentrated solution, and water may be added and diluted when preparing the aqueous developer composition used in the developing step. The concentration of the compound (a) in the aqueous developer composition is preferably 0.01% by mass or more and preferably 90% by mass or less, including the case where it is a concentrated solution or the case where it is prepared by dilution, from the viewpoint of appropriately maintaining the concentration of the active ingredient. More preferably, it is 0.01% by mass or more and 55% by mass or less, still more preferably 0.1% by mass or more and 20% by mass or less, even more preferably 0.2% by mass or more and 10% by mass or less, and even more preferably 0.5% by mass or more and 5% by mass or less.

[0097] (Post-exposure step) In the method for manufacturing a flexographic printing plate of the present embodiment, after the above-described developing step, it is preferable to have a post-exposure step of irradiating the entire plate with actinic rays (post-exposure) in water or in air to make the curing more complete. The post-exposure step is preferably performed in water from the viewpoint of fixing the aqueous developer composition that has penetrated the plate surface in an appropriate orientation on the plate surface and improving printing unevenness. Further, from the viewpoints that water is a liquid and the workability and safety, the liquid temperature during post-exposure is preferably 0°C to 60°C. After the post-exposure step, a drying treatment is performed to obtain a flexographic printing plate.

[0098] (Recovery and reuse of the photosensitive resin composition in the unexposed portion) In the method for manufacturing a flexographic printing plate of the present embodiment, a recovery step can be implemented in which the photosensitive resin composition in the unexposed portion that has been removed in advance with a spatula or a roll in the above-described developing step is recovered as the photosensitive resin composition in the manufacture of a new flexographic printing plate. The recovered photosensitive resin composition can be reused as the photosensitive resin composition in the manufacture of a new flexographic printing plate. The recovered photosensitive resin composition may be put into an exposure machine when manufacturing a new flexographic printing plate. When the photosensitive resin composition is processed and molded before exposure, the photosensitive resin composition recovered as described above may be used in the processing and molding step. The exposure machine into which the recovered photosensitive resin composition is put refers to an exposure machine equipped with a unit for laminating a support and the photosensitive resin composition in layers. When filling the unit with the photosensitive resin composition, the recovered photosensitive resin composition can be used. By using the recovered photosensitive resin composition, waste is reduced and the material cost can also be reduced.

[0099] 〔Printing method〕 The printing method of this embodiment includes a step of manufacturing a flexographic printing plate by the manufacturing method of the flexographic printing plate described above, an ink adhesion step of attaching ink to the convex portions of the flexographic printing plate, and a transfer step of transferring the ink. In particular, it is a preferred embodiment to manufacture a flexographic printing plate by the manufacturing method of the printing plate of this embodiment and perform flexographic printing.

Examples

[0100] Hereinafter, the present embodiment will be described in more detail with specific examples and comparative examples, but the present invention is not limited to the following examples at all.

[0101] 〔Physical properties and characteristics of the photosensitive resin composition〕 <GPC measurement> GPC measurement was performed under the following conditions, and the number average molecular weight in terms of polystyrene of the high molecular weight polymer in the polymer (unsaturated prepolymer compositions 1 and 2 described later) contained in the photosensitive resin composition was determined. Equipment: "HLC-8220GPC" manufactured by Tosoh Corporation Column: "TSLgel GMHXL" manufactured by Tosoh Corporation Solvent: Tetrahydrofuran Flow rate: 1 milliliter / minute Injection volume: 100 microliters Detector: RI detector Calibration curve standard: Polystyrene (molecular weight 500 - 12,600,000) Sample: 0.3 mass% tetrahydrofuran solution Regarding the molecular weights of other liquid components, the number average molecular weight was determined by molecular weight calculation from the structural formula.

[0102] <Relief depth> The thickness of the relief formation layer (relief depth) was measured as follows. Using an ABS digital indicator ID-C112 (manufactured by Mitutoyo Corporation), the thicknesses of the relief formation layer, the shelf layer, and the back precipitation layer were measured, and the relief depth was calculated using the following formula. The relief formation layer is the layer formed in (A3) of the <Molding and Exposure Process> described later. The shelf layer is the layer formed in (A2) of the <Molding and Exposure Process> described later. The back precipitation layer is the layer formed in (A2) of the <Molding and Exposure Process> described later. Relief depth (mm) = Thickness of the entire printing plate (mm) - (Thickness of the back precipitation layer and / or shelf layer + Thickness of the support) (mm)

[0103] (Production of Unsaturated Prepolymer Compositions 1 and 2) The unsaturated prepolymer compositions 1 and 2 used in the photosensitive resin composition were produced as follows. As the diol, polyoxyethylene (EO)-oxypropylene (PO) block copolymer diol (manufactured by Sanyo Chemical Industries, Ltd., "Sunnex PL2100", hereinafter abbreviated as "PL2100") in the amounts shown in the following [Table 9], or hydrogenated polybutadiene diol (manufactured by Nippon Soda Co., Ltd., "GI-2000") was added, and 0.03 g of dibutyltin dilaurate was added, followed by stirring at 40°C until uniform to obtain a mixture. To the obtained mixture, tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., "Coronate T80", hereinafter abbreviated as "TDI") in the amounts shown in the following [Table 9] was added and further stirred to obtain a mixture. After the mixture became uniform, its temperature was raised to 80 °C, and then it was reacted for 4 to 5 hours to prepare a prepolymer precursor having isocyanate groups at both ends. To the obtained prepolymer precursor, as a (meth)acrylation agent, poly(oxypropylene) glycol monomethacrylate in the amount shown in the following [Table 9] (manufactured by NOF Corporation, "Blemmer PP", hereinafter abbreviated as "PPM") was added and reacted for 2 hours. A part of the obtained reaction product was taken out and subjected to IR spectroscopic measurement to confirm the disappearance of isocyanate groups. Unsaturated prepolymer compositions 1 and 2 were obtained as described above. GPC measurement was performed on the unsaturated prepolymer composition. The number average molecular weight Mn of the high molecular weight substance derived from the unsaturated prepolymer component in the unsaturated prepolymer composition was described in the following [Table 9].

[0104] [Manufacture of flexographic printing plate] (Preparation of photosensitive resin composition) To the unsaturated prepolymer composition manufactured as described above, a liquid component shown in the following Table 10, a photopolymerization initiator and a polymerization inhibitor as auxiliary agents were added, and they were stirred and mixed in a heated state at 60 °C to obtain photosensitive resin compositions 1 to 6. Regarding the abbreviations of the compounds described in the following Table 10, they are shown below. LM: lauryl methacrylate: ethylenic monomer 9G: polyethylene glycol #400 dimethacrylate: ethylenic monomer DMPAP: 2,2-dimethoxy-2-phenylacetophenone: photopolymerization initiator BHT: 2,6-di-t-butyl-4-methylphenol: polymerization inhibitor

[0105] (Molding and exposure process) Using the "ALF-213E type plate making machine" manufactured by Asahi Kasei Corporation, molding and exposure were performed according to the following (A1) to (A3). (A1): A negative film was placed on a glass plate (lower glass plate) with ultraviolet light transmittance, and after covering the negative film with a thin protective film, a photosensitive resin composition was poured thereon, and a base film serving as a support was bonded through a spacer so that the composition became a certain plate thickness. Further, the photosensitive resin composition layer was formed by pressing it from above with a glass plate (upper glass plate) having ultraviolet light transmittance. In order to compensate for the strength of the relief against the printing pressure during printing, a shelf layer serving as a base was formed in the portion of the photosensitive resin composition layer on the upper glass plate side. Before relief exposure, a dedicated negative film (masking film) was sandwiched between the upper glass plate and the base film to form the photosensitive resin composition layer. (A2): After forming the photosensitive resin composition layer, actinic light (light having a wavelength distribution of 300 nm or more) using an ultraviolet fluorescent lamp or the like as an actinic light source was irradiated from the upper glass plate side through the base film. Since a masking film was provided in the formation step of the photosensitive resin composition layer, a shelf layer was formed by the same exposure. (A3): After the masking exposure step, the photosensitive resin composition layer was irradiated with the same actinic light as the upper part from the lower glass side through the negative film, and a relief formation exposure step for image formation was performed.

[0106] As in the above (A1), a photosensitive resin composition layer provided with a negative film for the shelf layer was formed. Here, the negative film was designed with a 300 mm × 500 mm shelf layer and a 500 μm-wide linear unexposed portion (hereinafter referred to as "white out" or "white out line") and circular exposed portions with diameters different by 5 μm each from 20 μm to 200 μm (hereinafter referred to as "independent points") within a 200 mm × 250 mm solid image. Next, as in the above (A2) and (A3), the photosensitive resin composition layer was exposed to obtain a flexographic printing original plate with a plate thickness of 3 mm and a relief depth as shown in Tables 2 to 8 below. In order to adjust the relief depth, the masking exposure amount was appropriately adjusted. The relief exposure amount was 200 mJ / cm2 It was carried out under the exposure conditions of

[0107] (Development process) The protective film was peeled off from the flexographic printing original plate, and the unexposed photosensitive resin composition was recovered and removed from the flexographic printing original plate using a rubber spatula. Thereafter, an aqueous solution containing the aqueous developer composition shown in Tables 2 to 8 below and 0.3% by mass of "Defoamer SH-4" (silicone mixture) manufactured by Asahi Kasei Corporation was prepared as a developer using an "AL-400W type developing machine" manufactured by Asahi Kasei Corporation (drum rotation spray type, drum rotation speed: 20 rotations / minute, spray pressure: 0.18 Pa), and development was carried out under the conditions of a liquid temperature of 45°C and a development time of 30 minutes. After development, it was washed with tap water until the bubbles caused by the developer disappeared. <Examples 1 to 23>, <Comparative Examples 1 to 5> An aqueous developer composition was prepared using the following raw materials. Compound A: The compound or product shown in Table 1 below Compound B: Softanol 50 (trade name, manufactured by Nippon Shokubai Co., Ltd.) Compound C: NOP (abbreviation of 1-n-octyl-2-pyrrolidone, manufactured by Tokyo Chemical Industry Co., Ltd.) Said Compound A corresponds to said Compound (a). Said Compound B corresponds to said Compound (b). Said Compound C corresponds to said Compound (c).

[0108] (Post-exposure process) Using an "AL-200UP type post-exposure machine" manufactured by Asahi Kasei Corporation equipped with both an ultraviolet fluorescent lamp and a germicidal lamp, post-exposure was carried out by the underwater exposure method. For Example 45, post-exposure was carried out by the atmospheric exposure method. The exposure amount irradiated from each light source was 1000 mJ / cm on the surface of the photosensitive resin composition for the ultraviolet fluorescent lamp 2 , and 2000 mJ / cm for the germicidal lamp 2 Exposure was carried out for the exposure time that would result in this.

[0109] (Drying process) Using the "ALF-DRYER" manufactured by Asahi Kasei Corporation, the plate after post-exposure was dried for about 30 minutes to obtain a flexographic printing plate.

[0110] 〔Evaluation of Flexographic Printing Plate〕 <Evaluation of White Depth (Residue)> Using μDEPTH&HEIGHT MEASURING SCOPE KY-90 (manufactured by Nissho Seimitsu Kogaku Co., Ltd.), the groove shape of the white line with a line width of 500 μm was observed, and the depth of the groove was measured. The evaluation criteria for the measurement results are shown below. In the following evaluation criteria, those rated A to E were evaluated as being usable without practical problems. (Evaluation Criteria) A: Depth of 151 μm or more B: Depth less than 131 - 151 μm C: Depth less than 111 - 131 μm D: Depth less than 91 - 111 μm E: Depth less than 71 - 91 μm F: Depth less than 71 μm

[0111] <Evaluation of Independent Point Formation> Using a NIKON SMZ1500 microscope (manufactured by Nikon Corporation), the shapes of independent points with diameters varying by 5 μm from 20 μm to 200 μm were observed, and the diameter of the smallest formed independent point was measured. The evaluation criteria for the measurement results are shown below. In the following evaluation criteria, those rated A to D were evaluated as being usable without practical problems. (Evaluation Criteria) A: Diameter less than 60 μm B: Diameter less than 60 - 80 μm C: Diameter less than 80 - 100 μm D: Diameter less than 100 - 120 μm E: Diameter of 120 μm or more

[0112] <Evaluation of Thickness Non-uniformity> Each flexographic printing plate immersed in N-methyl-2-pyrrolidone (NMP) for 24 hours was used for printing. Sun Ever SE7492 (manufactured by Nissan Chemical Industries, Ltd.) was used as the ink and printed on the ITO side of a glass substrate with ITO vapor-deposited on one side. After printing, it was left standing for 2 minutes and then dried on a hot plate at 60°C for 90 seconds. Thereafter, the film thickness unevenness was evaluated from the film thickness of the coating film by the following method. Using a nano 3D optical interferometry system VS1800 (manufactured by Hitachi High-Tech Corporation), the film thickness of the alignment film after printing was measured. The film thickness unevenness of the alignment film was evaluated by the standard deviation of the film thickness, and the standard deviation was calculated from the film thicknesses of 20 points measured on the same alignment film. The evaluation criteria for the measurement results are shown below. In the following evaluation criteria, those rated A to D were evaluated as being usable without practical problems. (Evaluation Criteria) A: Standard deviation less than 21 Å B: Standard deviation of 21 Å to less than 31 Å C: Standard deviation of 31 Å to less than 41 Å D: Standard deviation of 41 Å to less than 51 Å E: Standard deviation of 51 Å or more (Printing Conditions) Printer: Komrattec SmartLabo-III Substrate: ITO (indium tin oxide) vapor-deposited glass substrate Coating area: 20 mm × 20 mm

[0113]

Table 1

[0114]

Table 2

[0115]

Table 3

[0116]

Table 4

[0117]

Table 5

[0118]

Table 6

[0119]

Table 7

[0120]

Table 8

[0121]

Table 9

[0122]

Table 10

Industrial Applicability

[0123] The method for manufacturing a flexographic printing plate of the present invention has industrial applicability in the broad field of general commercial printing.

Claims

1. An aqueous developer composition for a flexographic printing plate, comprising: a polyoxyalkylene alkyl ether compound having a branched structure with 3 to 11 carbon atoms and an HLB value of less than 10.

2. The aqueous developer composition for a flexographic printing plate according to Claim 1, wherein the polyoxyalkylene alkyl ether compound (a) has a structure represented by the following formula (1). (In formula (1), R is an alkyl group having 3 to 10 carbon atoms and having at least one tertiary carbon or quaternary carbon. A is an alkylene group having 2 to 4 carbon atoms. n is an integer of 1 to 8.)

3. 【Chemical 1】 The aqueous developer composition for a flexographic printing plate according to Claim 1, wherein the polyoxyalkylene alkyl ether compound (a) has a structure represented by the following formula (2). (In formula (2), l, m, and n are integers satisfying l = 1 to 6, m = 1 to 6, and l + m ≤ 7. A is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 8.)

4. The aqueous developer composition for a flexographic printing plate according to Claim 1, further comprising: 【Chemical 2】 a polyoxyalkylene alkyl ether compound having a branched alkyl group with 6 to 20 carbon atoms and an HLB value of 10 or more.

5. The aqueous developer composition for a flexographic printing plate according to Claim 1, further comprising: a compound having a structure represented by the following formula (3). (In formula (3), R is an alkyl group having 4 to 30 carbon atoms. p is an integer of 0 to 2.)

6. The aqueous developer composition for a flexographic printing plate according to Claim 1, wherein the content of the polyoxyalkylene alkyl ether compound (a) is 0.01% by mass or more and 90% by mass or less. 【Chemical Formula 3】

7. A method for manufacturing a flexographic printing plate having an exposure step, a development step, and a post-exposure step for a photosensitive resin composition, wherein: in the development step, an unexposed photosensitive resin composition is washed using the aqueous developer composition for a flexographic printing plate according to any one of Claims 1 to 6.

8. The method for manufacturing a flexographic printing plate according to Claim 7, wherein the content of the polyoxyalkylene alkyl ether compound (a) in the aqueous developer composition for a flexographic printing plate is 0.01% by mass or more and 55% by mass or less.

9. The method for manufacturing a flexographic printing plate according to Claim 7, wherein the post-exposure step is performed in water.

10. Before the exposure step, the photosensitive resin composition is... ​ ​ ​ ​ ​ ​ ​ (d) a polymer having an acrylate group or a methacrylate group at at least one terminal, and the content of the polymer (d) in the photosensitive resin composition is 50% by mass or more and 95% by mass or less, The method for producing a flexographic printing plate according to claim 7.

11. the polymer (d) having an acrylate group or a methacrylate group at at least one terminal contains a polyurethane having a hydrogenated polybutadiene structure, The method for producing a flexographic printing plate according to claim 10.

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