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

Abstract

An aqueous developer composition for a flexographic printing plate and a method for producing a flexographic printing plate. [Problem] To provide an aqueous developer composition for a flexographic printing plate, with which it is possible to 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. [Solution] An aqueous developer composition for a flexographic printing plate, which contains (a) a polyoxyalkylene alkyl ether compound having a branched chain structure having 3-11 carbon atoms and having an HLB value of less than 10.

Description

Technical Field

[0001] The present invention relates to an aqueous developer composition for a flexible printing plate and a method for manufacturing a flexible printing plate. Background Art

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

[0003] In recent years, from the viewpoints of improving the working environment and protecting the global environment, there has been a trend in various industries to reduce the use of organic solvents. In the developing process for removing the uncured photosensitive resin composition in the plate-making process of flexible printing plates, the use of photosensitive resin compositions capable of aqueous development has been increasing.

[0004] In addition, due to its high flexibility, flexible printing plates are also used in applications that require a high level of surface damage resistance, such as alkali-free glass plates for liquid crystals and semiconductor wafers. In particular, in printing plates for printing on alkali-free glass plates for liquid crystals, specifically flexible printing plates for alignment film printing, high thickness accuracy within the plate surface and high fineness of the surface pattern of the plate are required.

[0005] In the developing process for manufacturing the above-mentioned flexible printing plate for alignment film printing, it is required to provide high cleanability, a plate surface after cleaning that is preferable for printing, etc., so that the uncured photosensitive resin composition does not remain on the high-fineness plate surface pattern. In particular, a plate surface with less thickness unevenness of the printed alignment film is required. Conventionally, techniques for improving the cleanability of the above-mentioned plate surface have been proposed (for example, refer to Patent Documents 3 and 4).

[0006] For example, Patent Document 3 discloses "an aqueous developer composition for a photosensitive resin, which contains Component (A): a nonionic surfactant having an HLB of 10 or less, Component (B): a compound having at least one oxyalkylene unit and an HLB exceeding 10, and water".

[0007] In addition, 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)".

[0008] RO(AO) n R 1 (I)

[0009] In the above formula (I), R and R 1is an alkyl or alkenyl group having 2 to 6 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and n is a number from 1 to 5.

[0010] However, in recent years, in the development process of manufacturing a printing plate, there has been a demand for a technique to improve the cleanability of the plate surface and to obtain an improved printing quality effect using a developer.

[0011] Prior Art Documents

[0012] Patent Documents

[0013] Patent Document 1: Japanese Patent Laid-Open No. 11-92659

[0014] Patent Document 2: Japanese Patent Laid-Open No. 2004-148309

[0015] Patent Document 3: Japanese Patent Laid-Open No. 2021-43401

[0016] Patent Document 4: Japanese Patent Laid-Open No. 2018-116109 Summary of the Invention

[0017] Problems to be Solved by the Invention

[0018] The fragment recovery rate and the stability over time of the aqueous developer compositions disclosed in Patent Documents 3 and 4 are good, but there is still room for improvement in terms of printing unevenness during printing using a printing plate manufactured with the aqueous developer compositions disclosed therein. Furthermore, the aqueous developer compositions disclosed in Patent Documents 3 and 4 have a problem of insufficient cleanability for developing a fine concavo-convex shape. This is a particularly significant issue in liquid crystal printing applications.

[0019] Therefore, in the present invention, in view of the above problems of the prior art, an object is to provide an aqueous developer composition for a flexible printing plate that can achieve high removability of an uncured photosensitive resin composition, excellent reproducibility of a flexible printing plate, and less printing unevenness during printing.

[0020] Solutions to the Problems

[0021] The present inventors conducted in-depth research to solve the above problems of the prior art and found that by an aqueous developer composition containing a polyoxyalkylene alkyl ether compound having a specific structure and a specific HLB value, the above problems of the prior art can be solved, thereby completing the present invention.

[0022] That is, the present invention is as follows. [1]

[0024] An aqueous developer composition for a flexible printing plate, which contains (a) a polyoxyalkylene alkyl ether compound having a branched structure with 3 to 11 carbon atoms and an HLB value of less than 10. [2]

[0026] The aqueous developer composition for a flexible printing plate according to [1] above, wherein the aforementioned (a) polyoxyalkylene alkyl ether compound is a compound having a structure represented by the following formula (1).

[0027]

[0028] In formula (1), R is an alkyl group having 3 to 10 carbon atoms and having one or more tertiary carbons or quaternary carbons, A is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 8. [3]

[0030] The aqueous developer composition for a flexible printing plate according to [1] above, wherein the aforementioned (a) polyoxyalkylene alkyl ether compound has a structure represented by the following formula (2).

[0031]

[0032] 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]

[0034] The aqueous developer composition for a flexible printing plate according to any one of [1] to [3] above, which further contains (b) a polyoxyalkylene alkyl ether compound having a branched alkyl group with 6 to 20 carbon atoms and an HLB value of 10 or more.

[0035] [5] The aqueous developer composition for a flexible printing plate according to any one of [1] to [4] above, which further contains (c) a compound having a structure represented by the following formula (3).

[0036]

[0037] In formula (3), R is an alkyl group having 4 to 30 carbon atoms, and p is an integer of 0 to 2. [6]

[0039] The aqueous developer composition for a flexible printing plate according to any one of [1] to [5] above, wherein the content of the aforementioned (a) polyoxyalkylene alkyl ether compound is 0.01% by mass or more and 90% by mass or less. [7]

[0041] A method for manufacturing a flexible printing plate, which includes an exposure step, a development step, and a post-exposure step of a photosensitive resin composition.

[0042] In the aforementioned development step, the unexposed photosensitive resin composition is washed with the aqueous developer composition for a flexible printing plate described in any one of the aforementioned [1] to [6]. [8]

[0044] According to the method for manufacturing a flexible printing plate described in the aforementioned [7], the content of the (a) polyoxyalkylene alkyl ether-based compound in the aqueous developer composition for a flexible printing plate is 0.01% by mass or more and 55% by mass or less. [9]

[0046] According to the method for manufacturing a flexible printing plate described in the aforementioned [7] or [8], the aforementioned post-exposure step is performed in water.

[10]

[0048] According to the method for manufacturing a flexible printing plate described in any one of the aforementioned [7] to [9], the photosensitive resin composition before the aforementioned exposure step contains a (d) polymer having an acrylate group or a methacrylate group at at least one end.

[0049] The content of the aforementioned (d) polymer in the photosensitive resin composition is 50% by mass or more and 95% by mass or less.

[11]

[0051] According to the method for manufacturing a flexible printing plate described in the aforementioned

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

[0052] Effects of the Invention

[0053] According to the present invention, it is possible to provide an aqueous developer composition for a flexible printing plate that can achieve high removability of the uncured photosensitive resin composition, excellent reproducibility of the flexible printing plate, and less printing unevenness during printing. Detailed Description of the Invention

[0054] Hereinafter, a mode for implementing the present invention (hereinafter referred to as "the present embodiment") will be described in detail.

[0055] It should be noted that the following present embodiment is an example for explaining the present invention and is not intended to limit the present invention to the following content.

[0056] In addition, in the specification of the present application, the numerical range indicated by "~" means the range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

[0057] Furthermore, in this specification, each component can be used alone with one substance corresponding to each component, or two or more substances corresponding to each component can be used in combination. Here, when two or more substances are used in combination for each component, unless otherwise specified, the content of the component refers to the total content of the substances used in combination.

[0058] The present invention can be appropriately modified and implemented within the scope without departing from its gist.

[0059] [Aqueous Developing Solution Composition for Flexible Printing Plate]

[0060] The aqueous developing solution composition for a flexible printing plate of the present embodiment (hereinafter, sometimes referred to as the 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, sometimes referred to as compound (a)).

[0061] In addition, the aqueous developing solution composition of the present embodiment contains water.

[0062] The aqueous developing solution composition of the present embodiment includes either a form of a developing solution that can be directly used during the development of a printing plate or a form of a raw material composition (concentrate) for preparing a developing solution by further diluting with water or the like.

[0063] By containing the aforementioned compound (a), the aqueous developing solution composition of the present embodiment can achieve the following effects: (1) excellent removability of the photosensitive resin composition, (2) high reproducibility of the flexible printing plate, and (3) less printing unevenness during printing of the printing plate manufactured using the aqueous developing solution 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. In addition, the reproducibility of the flexible printing plate refers to the formation of fine patterns on the surface of the flexible printing plate. Furthermore, printing unevenness refers to the thickness deviation of the ink coated by printing on the same printed material.

[0064] 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 may be optionally contained hereinafter refers to Hydrophile Lipophile Balance, which is a value indicating the degree of affinity of each component for water and hydrophobic components.

[0065] The HLB values of compound (a) and compound (b) in this specification are values obtained by the Griffin method or a method calculated from the organic and inorganic values in "Emulsion Formulation Design Based on Organic Conceptual Diagram (NIHON EMULSION Co., Ltd. data)". Additionally, when multiple compound (a)'s and / or multiple compound (b)'s are mixed, the HLB value after mixing is calculated by weighted average. Which method to apply, either the Griffin method or the method calculated from the organic and inorganic values in "Emulsion Formulation Design Based on Organic Conceptual Diagram (NIHON EMULSION Co., Ltd. data)", can be appropriately selected according to the structure of the components.

[0066] For example, the HLB values of compound (a) and compound (b) are preferably values obtained by the Griffin method.

[0067] (Compound (a))

[0068] The aqueous developer composition of this embodiment contains a polyoxyalkylene alkyl ether compound (compound (a)) having a branched structure with 3 to 11 carbon atoms and an HLB value less than 10.

[0069] The branched structure refers to a structure having one or more groups selected from the group consisting of tertiary carbon, quaternary carbon, and secondary carbon bonded to the O of the ether, and also includes functional groups of cyclic structures.

[0070] In addition, the aforementioned "carbon number of the branched structure" refers to the total carbon number of the group bonded to the O of the ether in compound (a).

[0071] By including compound (a), the aqueous developer of this embodiment exhibits good developability, excellent flexographic plate reproducibility, and can improve printing unevenness.

[0072] The reason why the aqueous developer composition of this embodiment can exhibit the above effects can be speculated as follows.

[0073] First, by making the carbon number of the aforementioned branched structure 3 or more, micelles are formed, and the cleaning power for removing the uncured photosensitive resin composition can be exerted. Additionally, by making the carbon number of the branched structure 11 or less, the molecular weight does not become too large, and sufficient permeability to the uncured photosensitive resin composition can be obtained, and the cleanability becomes good.

[0074] The aforementioned compound (a) used in the aqueous developer composition of this embodiment has a branched structure. Thus, the following effects are obtained.

[0075] It is generally known that, when the number of carbon atoms in the lipophilic group is the same, the surfactant with a branched-chain lipophilic group has a higher penetrability to the photosensitive resin than the surfactant with a linear-chain lipophilic group. Since compound (a) has a branched-chain structure, the penetrability of compound (a) to the photosensitive resin composition becomes higher, and there is a tendency to exhibit sufficient detergency.

[0076] In addition, when compound (a) penetrates to 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 evenly on the plate surface, which has a tendency to contribute to the reduction of printing unevenness.

[0077] Therefore, since compound (a) has a branched-chain structure, compound (a) is captured in the crosslinked structure on the plate surface, and the modification of the plate surface is achieved.

[0078] By making the HLB value of compound (a) less than 10, the hydrophilicity does not become too high, sufficient penetration into the photosensitive resin composition is obtained, and there is a tendency to obtain excellent detergency.

[0079] In addition, since compound (a) is a polyoxyalkylene alkyl ether compound, excellent penetrability to the photosensitive resin composition can be obtained. For example, in 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 be penetrated is limited, and there is a tendency not to exhibit the above-mentioned effects. In addition, in the case of a compound having a charge such as a nonionic or anionic compound, the polarity is too high to penetrate into the photosensitive resin composition, and there is a tendency that sufficient detergency cannot be ensured.

[0080] From the viewpoint of improving the plate reproducibility and the ink acceptance of the surface of the printing plate when manufacturing a flexographic printing plate using the aqueous developer composition of the present embodiment, the number of carbon atoms in the branched-chain structure of compound (a) is 3 to 11, preferably 3 to 10, more preferably 6 to 9, and further preferably 7 to 8.

[0081] From the viewpoint of improving the detergency of the aqueous developer composition of the present embodiment, the HLB value of the aforementioned compound (a) used in the aqueous developer composition of the present embodiment is less than 10, preferably 4 to 9.5, more preferably 6 to 8.5.

[0082] Compound (a) can be used alone in one kind, or two or more kinds can be used in combination.

[0083] By adjusting the structure of the hydrophilic part and / or the hydrophobic part in compound (a), the HLB value of compound (a) can be controlled within a range less than 10. For example, in alkylene alkyl ether compounds, by adjusting the type of alkyl group (number of carbon atoms, etc.), the number of repeating units of the polyoxyalkylene unit, etc., the HLB value can be controlled to be less than 10. 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 become smaller. For example, if it is a compound having a polyoxyalkylene, with respect to the number of carbon atoms or molecular weight of the hydrophobic part in compound (a), reducing the number of repeating units of the polyoxyalkylene unit, whereby the HLB value is controlled to become smaller.

[0084] Examples of the aforementioned compound (a) include, but are not limited to, the following compounds.

[0085] Compounds having a cyclic structure such as 2-cyclobutoxyethanol, 2-(cyclopentyloxy)ethanol, 2-(cyclohexyloxy)ethanol, 2-(cycloheptyloxy)ethanol, 2-{[5-methyl-2-(propan-2-yl)cyclohexyl]oxy}ethanol, 2-(cyclooctylmethoxy)ethanol, 2-[(4-tert-butylcyclohexyl)methoxy]ethanol, etc.;

[0086] AO adducts for synthesizing secondary alcohols such as 2-(2-(octan-3-yloxy)ethoxy)ethanol; Compounds having a branched structure such as Finesurf D-35 (manufactured by Aoki Yushi Industry Co., Ltd.) and Nonion ID-203 (manufactured by NOF Corporation).

[0087] In addition, examples of the aforementioned compound (a) include the following compounds.

[0088] Examples include 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-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.

[0089] Furthermore, as the aforementioned compound (a), the following compounds can be cited.

[0090] Examples include 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.

[0091] Furthermore, as the aforementioned compound (a), the following compounds can be cited.

[0092] Examples include 3-(2-ethylbutoxy)propan-1-ol, 3-(3-(2-ethylbutoxy)propoxy)propan-1-ol, 3-((2-ethylpentyloxy)propan-1-ol, 3-(3-((2-ethylpentyloxy)propoxy)propan-1-ol, 3-((2-ethylhexyloxy)propan-1-ol, 3-(3-((2-ethylhexyloxy)propoxy)propan-1-ol, 3-((2-propylpentyloxy)propan-1-ol, 3-(3-((2-propylpentyloxy)propoxy)propan-1-ol, 3-((2-ethylheptyloxy)propan-1-ol, 3-((2-propylhexyloxy)propan-1-ol, 3-(3-((2-ethylheptyloxy)propoxy)propan-1-ol, 3-(3-((2-propylhexyloxy)propoxy)propan-1-ol, 3-((2-ethyloctyloxy)propan-1-ol, 3-(3-((2-ethyloctyloxy)propoxy)propan-1-ol, 3-((2-propylheptyloxy)propan-1-ol, 3-(3-((2-propylheptyloxy)propoxy)propan-1-ol, 3-((2-butylhexyloxy)propan-1-ol, 3-(3-((2-butylhexyloxy)propoxy)propan-1-ol, 3-((2-ethylnonyloxy)propan-1-ol, 3-(3-((2-ethylnonyloxy)propoxy)propan-1-ol, 3-((2-propyloctyloxy)propan-1-ol, 3-(3-((2-propyloctyloxy)propoxy)propan-1-ol, 3-((2-butylheptyloxy)propan-1-ol, 3-(3-((2-butylheptyloxy)propoxy)propan-1-ol).

[0093] Furthermore, as the aforementioned compound (a), the following compounds can be cited. For example, 4-(2-ethylbutoxy)butan-1-ol, 4-(4-(2-ethylbutoxy)butoxy)butan-1-ol, 4-((2-ethylpentyloxy)butan-1-ol, 4-(4-((2-ethylpentyloxy)butoxy)butan-1-ol, 4-((2-ethylhexyloxy)butan-1-ol, 4-(4-((2-ethylhexyloxy)butoxy)butan-1-ol, 4-((2-propylpentyloxy)butan-1-ol, 4-(4-((2-propylpentyloxy)butoxy)butan-1-ol, 4-((2-ethylheptyloxy)butan-1-ol, 4-(4-((2-ethylheptyloxy)butoxy)butan-1-ol, 4-((2-propylhexyloxy)butan-1-ol, 4-(4-((2-propylhexyloxy)butoxy)butan-1-ol, 4-((2-ethyloctyloxy)butan-1-ol, 4-(4-((2-ethyloctyloxy)butoxy)butan-1-ol, 4-((2-propylheptyloxy)butan-1-ol, 4-(4-((2-propylheptyloxy)butoxy)butan-1-ol, 4-((2-butylhexyloxy)butan-1-ol, 4-(4-((2-butylhexyloxy)butoxy)butan-1-ol, 4-((2-ethylnonyloxy)butan-1-ol, 4-(4-((2-ethylnonyloxy)butoxy)butan-1-ol, 4-((2-propyloctyloxy)butan-1-ol, 4-(4-((2-propyloctyloxy)butoxy)butan-1-ol, 4-((2-butylheptyloxy)butan-1-ol, 4-(4-((2-butylheptyloxy)butoxy)butan-1-ol, etc.

[0094] The aforementioned compound (a) is preferably a compound represented by the following formula (1).

[0095] That is, the aqueous developing solution composition of the present embodiment preferably contains a polyoxyethylene alkyl ether-based 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) in its structure. Although it is not clear in detail, the reason is that by having one or more secondary carbons between the oxygen atom in the hydrophilic part and the branched structure, the degree of freedom of rotation between the hydrophilic part and the branched structure increases, and in the manufacture of a printing plate, it is easy to adopt a conformation suitable for penetration into the surface of the photosensitive resin composition layer. As a result, there is a tendency to be able to form a printing plate surface that is preferable for reducing printing unevenness.

[0096]

[0097] In the aforementioned formula (1), R is an alkyl group having 3 to 10 carbon atoms and having one or more tertiary carbons or quaternary carbons.

[0098] R also includes a cyclic structure.

[0099] In addition, A is an alkylene group having 2 to 4 carbon atoms,

[0100] n is an integer from 1 to 8.

[0101] When there are a plurality of As, the plurality of As may be the same or different from each other.

[0102] Examples of the compound (a) having the structure of the aforementioned formula (1) include compounds having a cyclic structure such as 2-[(4-tert-butylcyclohexyl)methoxy]ethan-1-ol and 2-(cyclooctylmethoxy)ethan-1-ol; compounds having a branched chain such as Finesurf D-35 (manufactured by Aoki Yushi Kogyo Co., Ltd.) and Nonion ID-2030 (manufactured by NOF Corporation).

[0103] In addition, as the compound (a) having the structure of formula (1), examples 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)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, 3-(2-ethylbutoxy)propan-1-ol.

[0104] Furthermore, as the compound (a) having the structure of formula (1), examples 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.

[0105] Furthermore, as the compound (a) having the structure of formula (1), for example, 4-(2-ethylbutoxy)butan-1-ol, 4-(4-(2-ethylbutoxy)butoxy)butan-1-ol, 4-((2-ethylpentyloxy)butan-1-ol, 4-(4-((2-ethylpentyloxy)butoxy)butan-1-ol, 4-((2-ethylhexyloxy)butan-1-ol, 4-(4-((2-ethylhexyloxy)butoxy)butan-1-ol, 4-((2-propylpentyloxy)butan-1-ol, 4-(4-((2-propylpentyloxy)butoxy)butan-1-ol, 4-((2-ethylheptyloxy)butan-1-ol, 4-(4-((2-ethylheptyloxy)butoxy)butan-1-ol, 4-((2-propylhexyloxy)butan-1-ol, 4-(4-((2-propylhexyloxy)butoxy)butan-1-ol, 4-((2-ethyloctyloxy)butan-1-ol, 4-(4-((2-ethyloctyloxy)butoxy)butan-1-ol, 4-((2-propylheptyloxy)butan-1-ol, 4-(4-((2-propylheptyloxy)butoxy)butan-1-ol, 4-((2-butylhexyloxy)butan-1-ol, 4-(4-((2-butylhexyloxy)butoxy)butan-1-ol, 4-((2-ethylnonyloxy)butan-1-ol, 4-(4-((2-ethylnonyloxy)butoxy)butan-1-ol, 4-((2-propyloctyloxy)butan-1-ol, 4-(4-((2-propyloctyloxy)butoxy)butan-1-ol, 4-((2-butylheptyloxy)butan-1-ol, 4-(4-((2-butylheptyloxy)butoxy)butan-1-ol, etc. can be cited.

[0106] The aforementioned compound (a) is further preferably a compound represented by the following formula (2).

[0107] That is, it is preferably an organic compound containing a polyoxyethylene alkyl ether-based compound having a branched structure with 1 to 11 carbon atoms and an HLB value of less than 10, and further having a structure represented by the following formula (2).

[0108] By making the aqueous developer composition of the present embodiment contain the compound of the following formula (2), after penetrating into the plate surface, the compound (a) crosslinks and entangles and remains inside the plate, and there is a tendency to cause better surface modification. As a result, a plate surface preferable for reducing printing unevenness can be obtained.

[0109]

[0110] In the foregoing 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 As, the plurality of As may be the same or different from each other.

[0111] Examples of the compound (a) having the structure of the foregoing 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-ethylnonyloxy)ethan-1-ol, 2-(2-((2-ethylnonyloxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-ethylnonyloxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-propyloctyloxy)ethan-1-ol, 2-(2-((2-propyloctyloxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-propyloctyloxy)ethoxy)ethoxy)ethan-1-ol, 2-((2-butylheptyloxy)ethan-1-ol, 2-(2-((2-butylheptyloxy)ethoxy)ethan-1-ol, 2-(2-(2-((2-butylheptyloxy)ethoxy)ethoxy)ethan-1-ol, etc.

[0112] In addition, as the compound (a) having the structure of the aforementioned formula (2), examples 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, etc.

[0113] Furthermore, as the compound (a) having the structure of the aforementioned formula (2), examples 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.

[0114] From the viewpoint of appropriately maintaining the concentration of the active ingredient, the content of the aforementioned compound (a) in the aqueous developer composition of the present embodiment is preferably 0.01% by mass or more and preferably 90% by mass or less. 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, still further 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.

[0115] (Water)

[0116] The aqueous developer composition of the present embodiment contains water.

[0117] The water contained in the aqueous developer composition of the present embodiment is not particularly limited, and ultrapure water such as distilled water, purified water, ion-exchanged water, pure water, Milli-Q water, and tap water can be used.

[0118] It should be noted that the aforementioned Milli-Q water refers to ultrapure water obtained through a Milli-Q water manufacturing device, i.e., an ultrapure water manufacturing device of Merck & Co., Inc.

[0119] The aqueous developer composition of the present embodiment includes a form of a developer that can be directly used for development and a form of a raw material composition (concentrate) for preparing a developer by dilution with water or the like. Therefore, the water content in the aqueous developer composition of the present embodiment can be appropriately adjusted.

[0120] (Compound (b))

[0121] In addition to the aforementioned compound (a), the aqueous developer composition of the present embodiment further contains a polyoxyalkylene alkyl ether compound having a branched alkyl group with 6 to 10 carbon atoms and an HLB value of 10 or more (hereinafter sometimes referred to as compound (b)).

[0122] The aforementioned compound (b) functions as a nonionic surfactant.

[0123] Examples of the aforementioned compound (b) include polyoxyethylene ethylhexyl ethers such as Blaunon EH-4 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Blaunon EH-6 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Blaunon EH-11 (manufactured by Aoki Yushi Kogyo Co., Ltd.), and Blaunon EH-30 (manufactured by Aoki Yushi Kogyo Co., Ltd.); polyoxyethylene isodecyl ethers such as Finesurf D-60 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Finesurf D-65 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Finesurf D-85 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Finesurf ID-1033 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Finesurf ID-1055 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Finesurf ID-1061 (manufactured by Aoki Yushi Kogyo Co., Ltd.), Finesurf ID-1074 (manufactured by Aoki Yushi Kogyo Co., Ltd.), and Finesurf ID-1087 (manufactured by Aoki Yushi Kogyo Co., Ltd.); and polyoxyethylene isostearyl ethers such as Finesurf FO-80 (manufactured by Aoki Yushi Kogyo Co., Ltd.) and Finesurf FO-160 (manufactured by Aoki Yushi Kogyo Co., Ltd.).

[0124] In addition, as the aforementioned compound (b), examples thereof 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.), 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.), SOFTANOL 500 (manufactured by Nippon Shokubai Co., Ltd.); polyoxyethylene 2-hexyldecyl ethers such as ISOCETETH-10 (manufactured by NIHON EMULSION Co., Ltd.), ISOCETETH-15 (manufactured by NIHON EMULSION Co., Ltd.), ISOCETETH-20 (manufactured by NIHON EMULSION Co., Ltd.), ISOCETETH-25 (manufactured by NIHON EMULSION Co., Ltd.); polyoxyethylene isostearyl ethers such as ISOSTEARETH-10 (manufactured by NIHON EMULSION Co., Ltd.), ISOSTEARETH-15 (manufactured by NIHON EMULSION Co., Ltd.), ISOSTEARETH-20 (manufactured by NIHON EMULSION Co., Ltd.), ISOSTEARETH-25 (manufactured by NIHON EMULSION Co., Ltd.); polyoxyethylene octyldodecyl ethers such as OCTYLDODECETH-10 (manufactured by NIHON EMULSION Co., Ltd.), OCTYLDODECETH-15 (manufactured by NIHON EMULSION Co., Ltd.), OCTYLDODECETH-20 (manufactured by NIHON EMULSION Co., Ltd.), OCTYLDODECETH-25 (manufactured by NIHON EMULSION Co., Ltd.).

[0125] Further, examples of the aforementioned 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-pentaoxaeicosan-1-ol, 17-methyl-3,6,9,12,15-pentaoxaeicosan-1-ol, 18-methyl-3,6,9,12,15-pentaoxaeicosan-1-ol, 19-methyl-3,6,9,12,15-pentaoxaeicosan-1-ol, 16-ethyl-3,6,9,12,15-pentaoxaeicosan-1-ol, 16-ethyl-3,6,9,12,15-pentaoxaeicosan-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-3,6,9,12,15,18-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-pentaoxaheptadecan-1-ol, and the like.

[0126] In the aqueous developer composition of the present embodiment, by containing the nonionic compound (b) having an HLB value of 10 or more, there is a tendency to improve the stability of micelles and to be able to remove a wider variety of dirt, resulting in improved cleanability.

[0127] In addition, from the viewpoint of obtaining an appropriate HLB value by mixing the aforementioned compound (a) and compound (b) and being able to improve the cleanability, the content of 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, based on 100 parts by mass of compound (a).

[0128] In addition, compound (b) can be used alone as one kind, or two or more kinds can be used in combination. It is preferred that each compound (b) is within the aforementioned mass fraction range.

[0129] (Compound (c))

[0130] From the viewpoint of softening the uncured photosensitive resin composition to improve the cleanability, the aqueous developer composition of the present embodiment preferably contains a compound (c) having a structure represented by the following formula (3).

[0131]

[0132] In formula (3), R is an alkyl group having 4 to 30 carbon atoms. P is an integer of 0 to 2.

[0133] Examples of the compound having the structure represented by the aforementioned formula (3) include, but are not limited to, for example, 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-eicosylazetidin-2-one, 1-heneicosylazetidin-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-eicosyl-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-eicosyl-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.,

[0134] The compound represented by the foregoing formula (3) can be a surfactant.

[0135] From the viewpoints of ensuring the water dispersibility of the compound (c) having the structure represented by the foregoing formula (3), improving the cleaning property and reproducibility, the content of the foregoing 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 still more preferably 3 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the foregoing compound (a). In addition, the foregoing compound (c) can be used alone or in combination of two or more, and it is preferred that each compound (c) is within the foregoing mass fraction range.

[0136] (Other additives)

[0137] The aqueous developer composition of the present embodiment can contain other components within a range that does not impair the effects of the present invention. Examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, defoamers, fragrances, chelating agents, dyes, acids, and bases other than the foregoing compounds (a), (b), and (c).

[0138] [Method for manufacturing an aqueous developer composition for a flexible printing plate]

[0139] The aqueous developer composition of the present embodiment can be manufactured by a method of stirring and homogenizing the foregoing compound (a), water, and, as required, the compound (b), the compound (c), and other additives. The mixing order of each component is not particularly limited.

[0140] Each component can also be prepared separately and added separately during the preparation of the developer, thereby obtaining the aqueous developer composition. In addition, the aqueous developer composition can be made into a concentrated solution and diluted with water during the preparation of the developer.

[0141] Method for manufacturing a flexible printing plate

[0142] The method for manufacturing a flexible printing plate according to this embodiment includes an exposure step, a development step, and a post-exposure step of a photosensitive resin composition.

[0143] In the aforementioned development step, the unexposed photosensitive resin composition is washed with the aqueous developer composition of this embodiment.

[0144] More specifically, in the exposure step, a relief is formed on the photosensitive resin composition layer by exposure to obtain a printing original plate. In the development step, the uncured photosensitive resin composition of the aforementioned photosensitive resin composition layer, that is, the unexposed portion, is washed away with the aqueous developer composition of this embodiment for development, and the photosensitive resin composition layer after the aforementioned development is post-exposed.

[0145] (Printing original plate)

[0146] Before exposing the photosensitive resin composition layer, the printing original plate has a structure including at least a support (e) and a photosensitive resin composition layer (f) laminated on the support (e). In this specification, the above structure is sometimes referred to as a "photosensitive resin structure for printing plate".

[0147] That is, as described later, a relief is formed on the photosensitive resin structure for printing plate by pattern exposure to obtain a printing original plate. For this printing original plate, the unexposed portion is removed by a development step to obtain a flexible printing plate.

[0148] <Support (e)>

[0149] 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.

[0150] Among them, as the support (e), a polyester film is preferred.

[0151] The polyester used in the support (e) is not particularly limited, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.

[0152] The thickness of the support (e) is not particularly limited, and is preferably 50 to 300 μm.

[0153] In addition, in order to improve the adhesion between the support (e) and the photosensitive resin composition layer (f) described later, an adhesive layer may be provided on the support (e). There is no particular limitation on the adhesive layer, and examples thereof include the adhesive layers described in International Publication No. 2004 / 104701, Japanese Patent No. 3094647, and Japanese Patent No. 2634429.

[0154] <Photosensitive resin composition layer (f)>

[0155] The photosensitive resin structure for a printing plate has a photosensitive resin composition layer on a support.

[0156] The photosensitive resin composition layer may be directly laminated on the support or indirectly laminated on the support via a prescribed adhesive layer or the like.

[0157] There is no particular limitation on the photosensitive resin composition layer. For example, it contains the polymer (d) described later, and preferably further contains the ethylenically unsaturated compound (g) and the photopolymerization initiator (h) described later.

[0158] In addition, the photosensitive resin composition layer may further contain auxiliary additive components as needed.

[0159] Hereinafter, each component of the photosensitive resin composition layer will be described in detail.

[0160] [Polymer (d)]

[0161] The polymer (d) is an elastomer, and examples thereof include, but are not limited to, elastomers having structural units derived from conjugated dienes and / or vinyl aromatic compounds.

[0162] From the viewpoints of improving cleanability and reproducibility, the polymer (d) is preferably polyurethane. Since polyurethane has a hydrophilic molecular backbone, it is easy for the compound (a) to penetrate into the uncured resin, thereby improving cleanability. In addition, since it is polyurethane, the mechanical strength of the cured plate is improved by having urethane bonds, thereby improving reproducibility. In addition, from the viewpoint of the above mechanism, when the total amount of the photosensitive resin composition layer (f) is 100% by mass, the content of the polyurethane is preferably 50% by mass or more and 95% by mass or less, more preferably 60 to 90% by mass, and further preferably 70 to 85% by mass.

[0163] In addition, 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.

[0164] As a method for identifying polyurethane, examples include, but are not limited to, a method in which polymer components are separated by liquid chromatography (LC) and then identified by nuclear magnetic resonance (NMR) and mass spectrometry (MS); a method in which identification is carried out by gas chromatography - mass spectrometry (GC / MS), etc.

[0165] The polymer (d) is not particularly limited. As an unsaturated carbon bond, it may have an acrylate group or a methacrylate group (hereinafter sometimes referred to as (meth)acryloyl group) at at least one terminal.

[0166] As a method for producing a polyurethane having a (meth)acryloyl group at the terminal group, for example, the following method can be cited: reacting a diol having a repeating unit in the molecule with a diisocyanate to form a polyurethane having an isocyanate group at the terminal with an arbitrary molecular weight, and then reacting this polyurethane with a compound containing an active hydrogen and a (meth)acryloyl group in one molecule.

[0167] In addition, as another method, the following method can also be cited: reacting a diol having a repeating unit in the molecule with a diisocyanate to first form a polyurethane having a hydroxyl group at the terminal with an arbitrary molecular weight, and then reacting this polyurethane with a compound containing an isocyanate group and a (meth)acryloyl group in one molecule. By having acrylate groups or methacrylate groups at both terminals, the strength after curing of the photosensitive resin composition layer becomes higher, and there is a tendency for the formability to be improved.

[0168] The polyurethane structure obtained by the above - mentioned production method is a structure formed by reacting a diol having a repeating unit in the molecule with a diisocyanate.

[0169] In this specification, the "polyurethane having a (meth)acryloyl group at the terminal group" synthesized by the above method is sometimes referred to as an "unsaturated prepolymer".

[0170] Examples of the "diol having a repeating unit in the molecule" used in the production of the aforementioned unsaturated prepolymer include, but are not limited to, polyester diols containing dicarboxylic acids and diols; polyether diols; polyether - polyester copolymer diols; 1,2 - polybutadiene compounds having terminal hydroxyl groups and their hydrogenated compounds, etc.

[0171] The aforementioned diol having a repeating unit in the molecule can be used alone or in combination of two or more.

[0172] Examples of the dicarboxylic acid constituting the aforementioned polyester diol include, but are not limited to, 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.

[0173] Examples of the diol constituting the aforementioned polyester diol include, but are not limited to, 1,4-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, and diethylene glycol (dioxydiethylene glycol), etc.

[0174] Examples of the aforementioned polyether diol include, but are not limited to, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxy-1,2-butylene glycol, polyoxyethylene / polyoxypropylene random copolymer diol, polyoxyethylene / polyoxypropylene block copolymer diol, polyoxyethylene / polyoxytetramethylene random copolymer diol, and polyoxyethylene / polyoxytetramethylene block copolymer diol, etc.

[0175] Examples of the aforementioned polyether polyester copolymer polyol include, but are not limited to, copolymers having a structure in which the repeating units forming the molecular chain of the aforementioned polyether polyol and the repeating units forming the molecular chain of the aforementioned polyester polyol are block or randomly linked.

[0176] From the viewpoint of improving the cleanability due to the structural similarity with the compound (a) having a branched structure, and from the viewpoint that the surfactant penetrating into the plate surface is easily replenished into the plate interior due to steric hindrance, which is advantageous for modifying the plate surface, the aforementioned polymer (d) preferably contains a polyurethane having a hydrogenated polybutadiene structure. Examples of the raw materials for the polyurethane satisfying such conditions include the hydride of poly-1-butene having a terminal hydroxyl group, the hydride of 1,2-polybutadiene having a terminal hydroxyl group, etc.

[0177] Examples of the aforementioned diisocyanate include, but are not limited to, toluene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and norbornene diisocyanate, etc.

[0178] The diisocyanate can be used alone in one kind, or two or more kinds can be used in combination.

[0179] [Ethylenically unsaturated compound (g)]

[0180] As described above, the photosensitive resin composition layer preferably contains an ethylenically unsaturated compound (g).

[0181] The ethylenically unsaturated compound (g) refers to a compound having an unsaturated double bond capable of radical polymerization.

[0182] Examples of such ethylenically unsaturated compounds (g) include, but are not limited to, for example, olefins such as ethylene, propylene, vinyltoluene, styrene, divinylbenzene; acetylenes; (meth)acrylic acid and / or its derivatives; halogenated olefins; 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.

[0183] Examples of the aforementioned various derivatives include, but are not limited to, for example, 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 glycols, polyoxyalkylene glycols, polyalkylene glycols, trimethylolpropane; compounds having a polysiloxane structure such as polydimethylsiloxane and polydiethylsiloxane, etc.

[0184] In addition, the ethylenically unsaturated compound (g) can be a heteroaromatic compound containing elements such as nitrogen and sulfur.

[0185] Examples of the aforementioned (meth)acrylic acid and / or its derivatives include, but are not limited to, for example, 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 butanediol; trimethylolpropane tri(meth)acrylate; dimethyloltricyclodecane di(meth)acrylate; isobornyl (meth)acrylate; phenoxypolyethylene glycol (meth)acrylate; pentaerythritol tetra(meth)acrylate, etc.

[0186] The aforementioned ethylenically unsaturated compound (g) can be used alone as only 1 type, or 2 or more types can be used in combination.

[0187] From the viewpoint of improving the strength of the printing original plate and preventing damage to the relief surface caused by the load when peeling the protective film after exposure, as the ethylenically unsaturated compound (g), it is preferable to use at least 1 type or more of (meth)acrylate, and more preferably to use at least 1 type or more of bifunctional (meth)acrylate.

[0188] 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) as 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 still more preferably 10% by mass or more and 40% by mass or less.

[0189] [Photoinitiator (h)]

[0190] The photosensitive resin composition layer preferably contains a photoinitiator (h).

[0191] The photoinitiator (h) refers to a compound that generates free radicals by absorbing light energy, and examples thereof include cleavage-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 cleavage-type photoinitiator within the same molecule.

[0192] Examples of such photoinitiators (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 tert-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, benzil dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 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-trimethylbenzoyl diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; methyl benzoylformate; 1,7-bisacridylheptane; 9-phenylacridine; azo compounds such as azobisisobutyronitrile, diazonium compounds, and tetraazene compounds.

[0193] They can be used alone or in combination of two or more.

[0194] From the viewpoint of ensuring the strength to suppress the breakage of independent points caused by spraying during development and the friction of the brush, when the total amount of the photosensitive resin composition layer (f) is set to 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 further preferably 0.3 to 5% by mass.

[0195] [Auxiliary additives]

[0196] Examples of the auxiliary additives include, but are not limited to, plasticizers, thermal polymerization inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, dyes / pigments, etc.

[0197] Examples of the plasticizers include, but are not limited to, liquid polybutadiene, liquid polyisoprene, modified products of liquid polybutadiene, modified products of liquid polyisoprene, liquid acrylonitrile-butadiene copolymers, liquid styrene-butadiene copolymers and other liquid dienes; naphthenic oil, paraffin oil and other hydrocarbon oils; conjugated diene rubbers mainly composed of liquid dienes such as liquid acrylonitrile-butadiene copolymers, liquid styrene-butadiene copolymers; polystyrene with a number average molecular weight of 2000 or less; ester plasticizers such as sebacate and phthalate.

[0198] These plasticizers may have hydroxyl groups or carboxyl groups. In addition, photopolymerizable reactive groups such as (meth)acryloyl groups may be imparted to these plasticizers. The aforementioned plasticizers may be used alone or in combination of two or more.

[0199] It should be noted that "liquid" in this specification refers to a property of being easily flowable and deformable and capable of being solidified into the deformed shape by cooling.

[0200] As the thermal polymerization inhibitor and antioxidant, those commonly used in the field of resin materials or rubber materials can be used, and examples include phenolic materials.

[0201] Examples of the phenolic materials include, but are not limited to, vitamin E, tetra-(methylene-3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl)propionate)methane, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-p-cresol, 3,9-bis-{1,1-dimethyl-2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-methyl phenyl acrylate, etc.

[0202] Other examples of the thermal polymerization inhibitor and antioxidant include phosphine-based materials such as triphenyl phosphite.

[0203] The heat polymerization inhibitor and antioxidant can be used alone, or two or more of them can be used in combination.

[0204] Examples of the light stabilizer and ultraviolet absorber include, but are not limited to, known benzophenone compounds, salicylic acid ester compounds, acrylonitrile compounds, metal complex salt compounds, and hindered amine compounds.

[0205] In addition, the following dyes / pigments can also be used as ultraviolet absorbers.

[0206] Examples of such light stabilizers and ultraviolet absorbers include, but are not limited to, 2-ethoxy-2'-ethyl oxalic acid bisaniline, 2,2'-dihydroxy-4-methoxybenzophenone, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,2,3-benzotriazole, etc.

[0207] Dyes / pigments are effective as coloring means for improving visual recognition.

[0208] Examples of the dyes include, but are not limited to, water-soluble basic dyes, acid dyes, direct dyes, etc., and water-insoluble sulfur dyes, oil-soluble dyes, disperse dyes, etc. Anthraquinone dyes, indigo dyes, and azo dyes are particularly preferred.

[0209] Examples of the pigments include, but are not limited to, natural pigments, synthetic inorganic pigments, synthetic organic pigments, etc. Examples of the synthetic organic pigments include azo pigments, triphenylmethane pigments, quinoline pigments, anthraquinone pigments, and phthalocyanine pigments.

[0210] (Exposure process)

[0211] In the method for manufacturing a flexible printing plate according to the present embodiment, the photosensitive resin structure for a printing plate is subjected to pattern exposure to form a relief, thereby obtaining a printing original plate. The unexposed portion of the printing original plate is removed by a developing process described later, thereby obtaining a printing plate.

[0212] In the aforementioned pattern exposure, for example, light containing a wavelength of 360 nm is irradiated to photocure the aforementioned photosensitive resin composition. Then, a developing process for removing the unexposed portion and a post-exposure process are performed.

[0213] In the exposure process, for example, a negative film is placed on a glass plate, covered with a thin protective film thereon, and a photosensitive resin composition is laminated thereon. In a state where a base film serving as a support is adhered, the glass plate is adhered to the base film such that the thickness of the photosensitive resin composition layer becomes a preset constant value. Then, back exposure is performed for a short time using 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 formation exposure is performed by irradiating light having a wavelength of 360 nm using a lower active light source.

[0214] It should be noted that, from the viewpoint of imparting peelability, the surface of the flexographic printing plate may be brought into contact with a liquid containing a silicone compound and / or a fluorine compound.

[0215] Examples of the active light source used for exposure in the manufacturing process of the flexographic printing plate include, for example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp, etc. In addition, as the transparent image carrier for forming the relief image, a negative or positive film for photoengraving based on a silver salt image is mainly used.

[0216] It should be noted that when the photosensitive resin composition is in a liquid state at room temperature, in the above-described embodiment, a prescribed forming process is usually included so that the photosensitive resin composition becomes a state of being formed into a film of a certain thickness on the support inside a dedicated device (plate-making machine).

[0217] As described above, when using a photosensitive resin composition that is in a liquid state at room temperature, the exposure process is preferably performed, for example, by the following steps (A1) to (A3).

[0218] (A1):

[0219] Step (A1) is a photosensitive resin composition layer forming step. A negative film is placed on an ultraviolet-transmissive glass plate (lower glass plate), a protective film is disposed thereon, and further, a photosensitive resin composition is caused to flow thereon. A base film serving as a support is adhered by means of a spacer such that it becomes a certain plate thickness, and further, it is pressed from above with an ultraviolet-transmissive glass plate (upper glass plate) to form a photosensitive resin composition layer.

[0220] After placing the protective film on the lower glass plate, in order to reliably fix the protective film and remove the oxygen hindrance factor, evacuation of the film is preferably performed. The evacuation mechanism is not particularly limited. For example, there is a method of evacuating using a pump through a groove provided around the lower glass.

[0221] In the case of manufacturing a flexographic printing plate (with a thickness of 4 mm or more) for corrugated cardboard printing, in order to fill the strength of the relief with respect to the printing pressure during printing, it is preferable to form a base layer on the part of the photosensitive resin composition layer on the upper glass plate side. In this case, before the relief exposure, a special negative film (masking film) is clamped between the upper glass plate and the base film to form the photosensitive resin composition layer.

[0222] (A2):

[0223] Process (A2) is a back exposure process. After the forming process of the photosensitive resin composition layer, active light rays (for example, light rays having a wavelength distribution of 300 nm or more) from the upper glass plate side are irradiated through the base film using an ultraviolet fluorescent lamp or the like as the active light source, thereby precipitating a uniform thin cured resin layer (i.e., the bottom forming layer (back precipitation layer)) on the entire surface of the base film side of the plate.

[0224] In the case where a masking film is provided in the photosensitive resin composition layer forming process, a base layer is formed by the same exposure. At this time, it is called a masking exposure process.

[0225] Both the back precipitation layer and the base 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 body side. When the entire photosensitive resin composition layer on the support body side is cured, it becomes the back precipitation layer, and when the photosensitive resin composition layer is partially cured according to the position of the relief forming layer, it becomes the base layer.

[0226] (A3):

[0227] Process (A3) is a relief forming exposure process. After the back exposure process or the masking exposure process, the photosensitive resin composition layer is irradiated with the same active light rays as above from the lower glass side through the negative film to precipitate the image forming layer (relief forming layer).

[0228] It should be noted that when the base layer is formed by the masking exposure process, it is also one of the preferable methods to remove the masking film after the relief forming exposure process and then go through the back exposure process, thereby forming the back precipitation layer on the entire surface of the base film.

[0229] (Developing process)

[0230] In the manufacturing method of the flexographic printing plate of the present embodiment, the unexposed part is removed using the aqueous developer composition of the present embodiment in the developing process.

[0231] The developing method using the aqueous developer composition can be carried out in the same manner as the conventionally known developing method using an aqueous developer. For example, the following methods can be cited: bringing the aqueous developer composition into contact with the unexposed portion of the printing plate original, and applying physical actions such as water pressure, a brush, and ultrasonic waves, whereby the photosensitive resin composition constituting the unexposed portion is dispersed or dissolved in the aqueous developer and removed from the cured plate surface.

[0232] At this time, the aqueous developer composition can immerse the unexposed portion, or can be continuously supplied and brought into contact therewith when the physical action is applied. Further, from the viewpoint of improving the cleaning power, the liquid temperature during the development of the aqueous developer composition is preferably 20 to 60°C, more preferably 30 to 50°C.

[0233] In addition, as a commonly used physical force, spraying is used, and the water pressure, nozzle diameter, nozzle configuration, etc. are appropriately selected.

[0234] It should be noted that, as a pre-treatment before removal, a doctor blade or a roller can be used to remove the unexposed portion in advance.

[0235] In addition, the aqueous developer composition of the present embodiment can be made into a concentrated solution, and water is added for dilution when preparing the aqueous developer composition used in the developing step.

[0236] From the viewpoint of appropriately maintaining the concentration of the active ingredient, the concentration of the aforementioned compound (a) in the aqueous developer composition, including the case of being a concentrated solution or the case of being prepared by dilution, is preferably 0.01% by mass or more and preferably 90% by mass or less. More preferably, it is 0.01% by mass or more and 55% by mass or less, further preferably 0.1% by mass or more and 20% by mass or less, still further 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.

[0237] (Post-exposure step)

[0238] In the method for manufacturing a flexible printing plate of the present embodiment, it is preferable to have a post-exposure step of further irradiating the entire plate with actinic light (post-exposure) in water or in air after the above-mentioned developing step to make the curing more complete. From the viewpoint of fixing the aqueous developer composition infiltrated into the plate surface in a state with an appropriate orientation on the plate surface and improving printing unevenness, the post-exposure step is preferably carried out in water. In addition, from the viewpoints of water being a liquid and the safety of workability, the liquid temperature during post-exposure is preferably 0°C to 60°C.

[0239] After the post-exposure step, a drying treatment is carried out to obtain a flexible printing plate.

[0240] (Recovery and reuse of the photosensitive resin composition in the unexposed portion)

[0241] In the method for manufacturing a flexible printing plate according to the present embodiment, a recovery step can be implemented in which the photosensitive resin composition in the unexposed portion that is previously removed by a doctor blade or a roller in the above-described developing step is recovered as the photosensitive resin composition in the manufacture of a new flexible printing plate. The recovered photosensitive resin composition can be reused as the photosensitive resin composition in the manufacture of a new flexible printing plate.

[0242] The recovered photosensitive resin composition can be put into an exposure machine when manufacturing a new flexible printing plate. When the photosensitive resin composition is processed and formed before exposure, the recovered photosensitive resin composition can be used in the processing and forming step as described above.

[0243] The exposure machine into which the recovered photosensitive resin composition is put refers to an exposure machine having a unit for laminating a support and a photosensitive resin composition in a layer. When filling the photosensitive resin composition in the unit, the recovered photosensitive resin composition can be used.

[0244] By using the recovered photosensitive resin composition, waste can be reduced and the material cost can also be lowered.

[0245] [Printing method]

[0246] The printing method according to the present embodiment includes: a step of manufacturing a flexible printing plate by using the method for manufacturing a flexible printing plate as described above; an ink application step of applying ink to the convex portions of the flexible printing plate; and a transfer step of transferring the ink.

[0247] In particular, it is a preferred mode to manufacture a flexible printing plate by the method for manufacturing a printing plate according to the present embodiment and perform flexographic printing.

[0248] [Examples]

[0249] Hereinafter, specific examples and comparative examples are listed to more specifically explain the present embodiment, but the present invention is not limited by any of the following examples.

[0250] [Physical properties and characteristics of the photosensitive resin composition]

[0251] [GPC measurement]

[0252] GPC measurement was performed under the following conditions to determine the number average molecular weight in terms of polystyrene of the high molecular weight component in the polymer (unsaturated prepolymer compositions 1 and 2 described later) contained in the photosensitive resin composition.

[0253] Equipment: "HLC-8220GPC" manufactured by Tosoh Corporation

[0254] Chromatographic column: "TSLgel GMHXL" manufactured by Tosoh Corporation

[0255] Solvent: Tetrahydrofuran

[0256] Flow rate: 1 mL / min

[0257] Injection volume: 100 μL

[0258] Detector: RI detector

[0259] Standard curve standard: Polystyrene (molecular weight 500 - 1,260,000)

[0260] Sample: 0.3 mass% tetrahydrofuran solution

[0261] Regarding the molecular weight of other liquid components, the number average molecular weight is obtained by calculating from the structural formula through the molecular weight.

[0262] <Relief depth>

[0263] The thickness (relief depth) of the relief formation layer is measured as follows.

[0264] Using an ABS digital display indicator ID-C112 (manufactured by Mitutoyo Corporation) measuring instrument, measure the thicknesses of the relief formation layer, the shelf layer, and the back precipitation layer, and calculate the relief depth using the following calculation formula.

[0265] The relief formation layer refers to the layer formed in (A3) of the <Forming / Exposure Process> described below.

[0266] The shelf layer refers to the layer formed in (A2) of the <Forming / Exposure Process> described below.

[0267] The back precipitation layer refers to the layer formed in (A2) of the <Forming / Exposure Process> described below.

[0268] 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)

[0269] (Manufacture of Unsaturated Prepolymer Compositions 1 and 2)

[0270] The unsaturated prepolymer compositions 1 and 2 used in the photosensitive resin composition are manufactured as follows.

[0271] As the diol, polyoxyethylene (EO)-oxypropylene (PO) block copolymer diol (manufactured by Sanyo Chemical Industries, Ltd., "SANNIX PL2100", hereinafter simply referred to as "PL2100") or hydrogenated polybutadiene diol (manufactured by Nippon Soda Co., Ltd., "GI-2000") in the amounts shown in the following [Table 9] and 0.03 g of dibutyltin dilaurate were added, and the mixture was stirred at 40 °C until homogeneous to obtain a mixture.

[0272] Toluene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., "CORONATE T80", hereinafter simply referred to as "TDI") in the amounts shown in the following [Table 9] was added to the obtained mixture, and the mixture was further stirred to obtain a mixture.

[0273] After the mixture became homogeneous, the temperature was raised to 80 °C, and the mixture was allowed to react for 4 to 5 hours to prepare a prepolymer precursor having isocyanate groups at both ends.

[0274] Poly(oxypropylene) glycol monomethacrylate (manufactured by NOF Corporation, "BLEMMER PP", hereinafter simply referred to as "PPM") in the amounts shown in the following [Table 9] as a (meth)acrylation agent was added to the obtained prepolymer precursor, and the mixture was allowed to react for 2 hours.

[0275] A part of the obtained reaction product was taken out and subjected to IR spectroscopic measurement, and the disappearance of the isocyanate groups was confirmed.

[0276] Unsaturated prepolymer compositions 1 and 2 were obtained as described above.

[0277] The unsaturated prepolymer compositions were subjected to GPC measurement. The number average molecular weight Mn of the high molecular weight bodies derived from the unsaturated prepolymer components in the unsaturated prepolymer compositions is shown in the following [Table 9].

[0278] [Manufacture of flexographic printing plate]

[0279] (Preparation of photosensitive resin composition)

[0280] The liquid components shown in the following Table 10, a photopolymerization initiator and a polymerization inhibitor as auxiliary agents were added to the unsaturated prepolymer compositions manufactured as described above, and the mixture was stirred and mixed under a heating condition of 60 °C to obtain photosensitive resin compositions 1 to 6.

[0281] Regarding the abbreviations of the compounds described in the following Table 10, they are as follows. LM: lauryl methacrylate: vinyl monomer

[0282] 9G: polyethylene glycol #400 dimethacrylate: vinyl monomer

[0283] DMPAP: 2,2-dimethoxy-2-phenylacetophenone: photopolymerization initiator

[0284] BHT: 2,6 - Di - tert - butyl - 4 - methylphenol: Polymerization inhibitor

[0285] (Forming / Exposure Process)

[0286] Using the "ALF - 213E Plate - making Machine" manufactured by Asahi Kasei Corporation, forming and exposure are carried out through the following (A1) to (A3).

[0287] (A1):

[0288] Place a negative film on a glass plate (lower glass plate) with ultraviolet light permeability, cover the negative film with a thin protective film, then flow a photosensitive resin composition thereon, and laminate a base film serving as a support by means of spacers so that it becomes a certain plate thickness. Further, press it from above with a glass plate (upper glass plate) with ultraviolet light permeability to form a photosensitive resin composition layer. In order to fill the strength of the relief with respect to the printing pressure, a shelf layer serving as a base is formed in a part of the photosensitive resin composition layer on the upper glass plate side. Before relief exposure, a special negative film (masking film) is clamped between the upper glass plate and the base film to form the photosensitive resin composition layer.

[0289] (A2):

[0290] After the formation of the photosensitive resin composition layer, active light rays (rays having a wavelength distribution of 300 nm or more) using an ultraviolet fluorescent lamp or the like as an active light source are irradiated from the upper glass plate side through the base film.

[0291] In order to set a masking film in the photosensitive resin composition layer formation process, a shelf layer is formed by the same exposure.

[0292] (A3):

[0293] After the masking exposure process, the photosensitive resin composition layer is irradiated with the same active light rays as above from the lower glass side through the negative film, and an image - forming relief formation exposure process is carried out.

[0294] As described in (A1) above, a photosensitive resin composition layer having a negative film for the shelf layer is formed.

[0295] Here, a negative film with a design in which linear unexposed portions (hereinafter referred to as "hollows" or "hollow lines") with a width of 500 μm are formed within a shelf layer of 300 mm × 500 mm and a solid image of 200 mm × 250 mm, and circular exposed portions (hereinafter referred to as "independent points") with diameters differing by 5 μm each in the range of 20 μm to 200 μm is used as the negative film.

[0296] Next, as shown in the aforementioned (A2) and (A3), the photosensitive resin composition layer is exposed to obtain a flexible printing original plate with a plate thickness of 3 mm and a relief depth as shown in Tables 2 to 8 below.

[0297] To adjust the relief depth, the masking exposure amount is appropriately adjusted.

[0298] The relief exposure is carried out under the exposure conditions of 200 mJ / cm 2 .

[0299] (Development process)

[0300] The protective film is peeled off from the flexible printing original plate, and a rubber squeegee is used to recover and remove the unexposed photosensitive resin composition from the flexible printing original plate.

[0301] Then, in the "AL-400W type developing machine" manufactured by Asahi Kasei Corporation (drum rotation spray type, drum rotation speed: 20 revolutions per minute, spray pressure: 0.18 Pa), an aqueous developing solution composition shown in Tables 2 to 8 below and an aqueous solution containing 0.3% by mass of "Defoamer SH-4" (silicone mixture) manufactured by Asahi Kasei Corporation are prepared as the developing solution, and development is carried out under the conditions of a liquid temperature of 45°C and a development time of 30 minutes.

[0302] After development, it is washed with tap water until the bubbles generated by the developing solution fall.

[0303] (Examples 1 to 23, Comparative Examples 1 to 5)

[0304] Using the following raw materials, an aqueous developing solution composition is prepared.

[0305] Compound A: The compound or product shown in Table 1 below

[0306] Compound B: SOFTANOL 50 (trade name of Nippon Shokubai Co., Ltd.)

[0307] Compound C: NOP (abbreviation of 1-n-octyl-2-pyrrolidone, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0308] The aforementioned Compound A corresponds to the aforementioned Compound (a).

[0309] The aforementioned Compound B corresponds to the aforementioned Compound (b).

[0310] The aforementioned Compound C corresponds to the aforementioned Compound (c).

[0311] (Post-exposure process)

[0312] Using the "AL-200UP type post-exposure machine" manufactured by Asahi Kasei Corporation, which is equipped with both an ultraviolet fluorescent lamp and a germicidal lamp, post-exposure is carried out by the water immersion exposure method. For Example 45, post-exposure is carried out by the atmospheric exposure method.

[0313] At the exposure time when the exposure amount irradiated from each light source is ultraviolet fluorescent lamp: 1000 mJ / cm 2 and germicidal lamp: 2000 mJ / cm 2 , the surface of the photosensitive resin composition is exposed.

[0314] (Drying process)

[0315] Using the "ALF-DRYER" manufactured by Asahi Kasei Corporation, the post-exposed plate is dried for about 30 minutes to obtain a flexographic printing plate.

[0316] [Evaluation of flexographic printing plate]

[0317] [Evaluation of hollow depth (residue)]

[0318] Using the μDEPTH&HEIGHT MEASURING SCOPE KY-90 (manufactured by Nissho Seimitsu Kogaku Co., Ltd.), the groove shape of a 500-μm line width hollow line is observed and the depth of the groove is measured.

[0319] The evaluation criteria for the measurement results are as follows.

[0320] In the following evaluation criteria, if it is A to E, it is evaluated that it can be used without practical problems.

[0321] (Evaluation criteria)

[0322] A: Depth 151 μm or more

[0323] B: Depth 131 μm or more and less than 151 μm

[0324] C: Depth 111 μm or more and less than 131 μm

[0325] D: Depth 91 μm or more and less than 111 μm

[0326] E: Depth 71 μm or more and less than 91 μm

[0327] F: Depth less than 71 μm

[0328] [Evaluation of independent point formation]

[0329] Using a NIKON SMZ1500 microscope (manufactured by Nikon Corporation), observe the shapes of independent points with diameters ranging from 20 μm to 200 μm, each differing by 5 μm, and measure the diameter of the smallest independent point formed.

[0330] The evaluation criteria for the measurement results are as follows.

[0331] In the following evaluation criteria, if it is A - D, it is evaluated that it can be used without practical problems.

[0332] (Evaluation criteria)

[0333] A: Diameter less than 60 μm

[0334] B: Diameter 60 μm or more and less than 80 μm

[0335] C: Diameter 80 μm or more and less than 100 μm

[0336] D: Diameter 100 μm or more and less than 120 μm

[0337] E: Diameter 120 μm or more

[0338] (Evaluation of thickness non-uniformity)

[0339] Each flexible printing plate impregnated in N-methyl-2-pyrrolidone (NMP) for 24 hours is used for printing.

[0340] Using SUNEVER SE7492 (manufactured by Nissan Chemical Industries, Ltd.) as ink, print on the ITO side of a glass substrate with ITO vapor-deposited on one side.

[0341] After printing, let it stand for 2 minutes and dry on a heating plate at 60 °C for 90 seconds.

[0342] Then, evaluate the film thickness non-uniformity from the film thickness of the coating film by the following method.

[0343] Using a nano 3D optical interferometer measurement system VS1800 (manufactured by Hitachi High-Technologies Corporation), measure the film thickness of the alignment film after printing. The thickness non-uniformity of the alignment film is evaluated by the standard deviation of the film thickness, and the standard deviation is calculated from the film thicknesses of 20 points measured on the same alignment film.

[0344] The evaluation criteria for the measurement results are as follows.

[0345] In the following evaluation criteria, if it is A - D, it is evaluated that it can be used without practical problems.

[0346] (Evaluation criteria)

[0347] A: The standard deviation is less than

[0348] B: The standard deviation or more and less than

[0349] C: The standard deviation or more and less than

[0350] D: The standard deviation or more and less than

[0351] E: The standard deviation is or more

[0352] (Printing conditions)

[0353] Printing machine: KOMURA-TECH CO.,LTD.SmartLabo-III

[0354] Substrate: ITO (Indium Tin Oxide) sputtered glass substrate

[0355] Coating area: 20mm×20mm [Table 1]

[0356]

[0357] [Table 2]

[0358]

[0359] [Table 3]

[0360]

[0361] [Table 4]

[0362]

[0363] [Table 5]

[0364]

[0365] [Table 6]

[0366]

[0367] [Table 7]

[0368]

[0369] [Table 8]

[0370]

[0371] [Table 9]

[0372]

[0373] [Table 10]

[0374]

[0375] Industrial Applicability

[0376] The method for manufacturing the flexible printing plate of the present invention has wide industrial applicability in the field of general commercial printing.

Claims

1. An aqueous developer composition for a flexographic printing plate, comprising (a) 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 (a) polyoxyalkylene alkyl ether compound is a compound having a structure represented by the following formula (1): 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, and n is an integer of 1 to 8.

3. The aqueous developer composition for a flexographic printing plate according to claim 1, wherein The (a) polyoxyalkylene alkyl ether compound has a structure represented by the following formula (2): In formula (2), l, m, and n are integers satisfying l=1-6, m=1-6, and l+m≤7; A is an alkylene group having 2 to 4 carbon atoms; and n is an integer of 1-8. 4 . The aqueous developer composition for a flexographic printing plate according to claim 1 , further comprising (b) a polyoxyalkylene alkyl ether compound having a branched alkyl group with a carbon number of 6 to 20 and an HLB value of 10 or more.

5. The aqueous developer composition for a flexographic printing plate according to claim 1, further comprising (c) a compound having a structure represented by the following formula (3): In the formula (3), R is an alkyl group having 4 to 30 carbon atoms, and 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 (a) polyoxyalkylene alkyl ether compound is 0.01% by mass or more and 90% by mass or less.

7. A method for producing a flexographic printing plate, comprising: exposing a photosensitive resin composition to light, developing the photosensitive resin composition, and post-exposure. In the development step, the 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 producing a flexographic printing plate according to claim 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 producing a flexographic printing plate according to claim 7, wherein: The post-exposure process is performed in water.

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

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

Images