JP2023125062A - Photosensitive flexographic printing original plate - Google Patents
Photosensitive flexographic printing original plate Download PDFInfo
- Publication number
- JP2023125062A JP2023125062A JP2022028979A JP2022028979A JP2023125062A JP 2023125062 A JP2023125062 A JP 2023125062A JP 2022028979 A JP2022028979 A JP 2022028979A JP 2022028979 A JP2022028979 A JP 2022028979A JP 2023125062 A JP2023125062 A JP 2023125062A
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive resin
- resin layer
- printing plate
- flexographic printing
- polyamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Landscapes
- Printing Plates And Materials Therefor (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
本発明は、感光性フレキソ印刷版原版に関する。 The present invention relates to a photosensitive flexographic printing plate precursor.
フレキソ印刷は、その柔軟性を活かして、紙器、ラベル、軟包装用途やエレクトロニクス用途などに広く使用されている。フレキソ印刷に用いられるフレキソ印刷版のレリーフを形成する方法として、フレキソ印刷版原版の感光層に、画像マスクや原画フィルムを介して紫外線を照射して画像部を選択的に光硬化させ、未硬化部分を現像液により除去する方法が、一般的に用いられている。 Due to its flexibility, flexographic printing is widely used for paper cartons, labels, flexible packaging, and electronics applications. As a method for forming reliefs on flexographic printing plates used in flexographic printing, the photosensitive layer of the flexographic printing plate precursor is irradiated with ultraviolet rays through an image mask or original film to selectively photocure the image areas, leaving the uncured areas A commonly used method is to remove the portion using a developer.
環境への配慮から、水系の現像液により現像可能なフレキソ印刷用の樹脂版原版として、例えば、イオン性を有する官能基を含む樹脂（Ａ）、光重合開始剤（Ｂ）、光重合性モノマー（Ｃ）、および樹脂（Ａ）と対イオンを形成しうるイオン性官能基を有するフッ素含有化合物（Ｄ）を含む感光性樹脂組成物を用いてなる感光性樹脂原版が提案されている（例えば、特許文献１参照）。フレキソ印刷用版材としてさらに低硬度化した樹脂原版として、ポリアミド系感光性樹脂組成物を用いた樹脂版原版の検討が進められているが、表面粘着により、塵、埃、紙粉などがレリーフ表面に付着し、印刷抜けが生じる課題があった。これに対して、例えば、少なくとも（ａ）ポリアミド及び／又はポリアミドブロック共重合体、（ｂ）１つ以上の不飽和基を有する架橋剤、（ｃ）光重合開始剤、及び（ｄ）脂肪酸エステルを含有する水現像可能なフレキソ印刷用感光性樹脂組成物から構成される感光性樹脂層、支持体、及びそれらを接着するための接着層を含むフレキソ印刷用感光性樹脂原版が提案されている（例えば、特許文献２参照）。 In consideration of the environment, resin plate precursors for flexographic printing that can be developed with an aqueous developer include, for example, a resin containing an ionic functional group (A), a photoinitiator (B), and a photopolymerizable monomer. (C) and a fluorine-containing compound (D) having an ionic functional group capable of forming a counter ion with the resin (A). , see Patent Document 1). As a resin original plate with lower hardness for use as a flexographic printing plate material, studies are underway on a resin plate original plate using a polyamide-based photosensitive resin composition. There was a problem that it adhered to the surface and caused printing defects. In contrast, for example, at least (a) a polyamide and/or a polyamide block copolymer, (b) a crosslinking agent having one or more unsaturated groups, (c) a photoinitiator, and (d) a fatty acid ester A photosensitive resin original plate for flexographic printing has been proposed, which includes a photosensitive resin layer composed of a water-developable photosensitive resin composition for flexographic printing, a support, and an adhesive layer for adhering them. (For example, see Patent Document 2).
特許文献２に記載の技術により、特定の脂肪酸エステルによって版面粘着が軽減されるものの、本発明者らの検討により、かかる脂肪酸エステルはＵＶインキのモノマー成分と親和性が高く、印刷中にインキに抽出され、ロングラン印刷時に版面粘着が増大することがわかった。ポリアミド系感光性樹脂組成物を用いた樹脂版による印刷方法のうち、印圧の高いレタープレス印刷とは異なり、キスタッチで印刷されるフレキソ印刷の場合、版面粘着によりレリーフ表面に異物が付着すると、異物周辺にインキが着肉せず、「す抜け」と呼ばれる印刷不良が生じやすく、版面粘着の影響が顕著となる。本発明は、上記課題に鑑み、ロングラン印刷時にもす抜けを抑制することができるフレキソ印刷版を得ることができる感光性フレキソ印刷版原版を提供することを目的とする。 Although the technique described in Patent Document 2 reduces plate surface adhesion with a specific fatty acid ester, the present inventors have found that such fatty acid ester has a high affinity with the monomer components of UV ink and does not absorb into the ink during printing. It was found that plate surface adhesion increases during long-run printing. Among printing methods using resin plates using polyamide-based photosensitive resin compositions, unlike letterpress printing, which requires high printing pressure, in the case of flexographic printing, which prints with a kiss touch, if foreign matter adheres to the relief surface due to plate adhesion, Ink does not adhere to the area around foreign objects, which tends to cause printing defects called "slip-through", and the effects of plate adhesion become noticeable. In view of the above problems, an object of the present invention is to provide a photosensitive flexographic printing plate precursor that can produce a flexographic printing plate that can suppress omission even during long-run printing.
本発明は、支持体上に、少なくとも、第１の感光性樹脂層および第２の感光性樹脂層をこの順に有する感光性フレキソ印刷版原版であって、
第１の感光性樹脂層が、少なくとも、（１ａ）親水性構造を有するポリアミド、（１ｂ）エチレン性二重結合を有する化合物および（１ｃ）光重合開始剤を含有し、無機微粒子を実質的に含有せず、
第２の感光性樹脂層が、少なくとも（２ａ）親水性構造を有するポリアミド、（２ｂ）エチレン性二重結合を有する化合物、（２ｃ）光重合開始剤および（２ｄ）無機微粒子を含有する感光性フレキソ印刷版原版親水性構造親水性構造である。
The present invention is a photosensitive flexographic printing plate precursor having at least a first photosensitive resin layer and a second photosensitive resin layer in this order on a support,
The first photosensitive resin layer contains at least (1a) a polyamide having a hydrophilic structure, (1b) a compound having an ethylenic double bond, and (1c) a photopolymerization initiator, and substantially contains inorganic fine particles. Contains no
The second photosensitive resin layer contains at least (2a) a polyamide having a hydrophilic structure, (2b) a compound having an ethylenic double bond, (2c) a photopolymerization initiator, and (2d) inorganic fine particles. Flexographic printing plate precursor has a hydrophilic structure.
本発明の感光性フレキソ印刷版原版によれば、ロングラン印刷時にもす抜けを抑制することができるフレキソ印刷版を得ることができる According to the photosensitive flexographic printing plate precursor of the present invention, it is possible to obtain a flexographic printing plate that can suppress omissions even during long-run printing.
本発明に係る感光性フレキソ印刷版原版（以下、「印刷版原版」と記載する場合がある）は、フレキソ印刷に用いられるフレキソ印刷版の前駆体であり、支持体上に、少なくとも、第１の感光性樹脂層および第２の感光性樹脂層をこの順に有する。支持体は、第１の感光性樹脂層および第２の感光性樹脂層を保持する機能を有する。第１の感光性樹脂層および第２の感光性樹脂層は、紫外線などの活性エネルギー線を照射することにより、硬化する層である。これらの感光性樹脂層は、例えば紫外線を画像様に照射することにより、所望のレリーフを形成することができる。本発明においては、感光性樹脂層として、主にフレキソ印刷に必要な柔軟性やインキ耐性などのレリーフ特性を付与する第１の感光性樹脂層と、印刷版表面に位置し、主に版面粘着を抑制する第２の感光性樹脂層を有する。支持体と感光性樹脂層の間に、両層を接着する接着層を有してもよいし、感光性樹脂層上に、カバーフィルムや、画像マスクを形成可能な感熱マスク層を有してもよい。 The photosensitive flexographic printing plate precursor (hereinafter sometimes referred to as "printing plate precursor") according to the present invention is a precursor of a flexographic printing plate used in flexographic printing, and is a precursor of a flexographic printing plate used for flexographic printing, and is a precursor of a flexographic printing plate used in flexographic printing. It has a photosensitive resin layer and a second photosensitive resin layer in this order. The support has a function of holding the first photosensitive resin layer and the second photosensitive resin layer. The first photosensitive resin layer and the second photosensitive resin layer are layers that are cured by irradiation with active energy rays such as ultraviolet rays. These photosensitive resin layers can be formed into a desired relief by, for example, being imagewise irradiated with ultraviolet rays. In the present invention, the photosensitive resin layer includes a first photosensitive resin layer that mainly provides relief characteristics such as flexibility and ink resistance required for flexographic printing, and a first photosensitive resin layer that is located on the surface of the printing plate and mainly provides plate surface adhesion. It has a second photosensitive resin layer that suppresses. An adhesive layer may be provided between the support and the photosensitive resin layer for adhering both layers, or a cover film or a heat-sensitive mask layer capable of forming an image mask may be provided on the photosensitive resin layer. Good too.
支持体は、可撓性を有し、寸法安定性に優れる材料から形成されることが好ましい。具体的には、ポリエステルなどのプラスチックシートや、スチール、ステンレス、アルミニウムなどの金属板などが挙げられる。これらを２種以上用いてもよい。 The support is preferably made of a material that is flexible and has excellent dimensional stability. Specific examples include plastic sheets such as polyester, metal plates such as steel, stainless steel, and aluminum. Two or more types of these may be used.
支持体の厚さは、取扱性および柔軟性の観点から、１００～３５０μｍの範囲が好ましい。 The thickness of the support is preferably in the range of 100 to 350 μm from the viewpoint of handleability and flexibility.
支持体と第１の感光性樹脂層との接着性を向上させる目的で、支持体は易接着処理されていてもよい。易接着処理としては、例えば、サンドブラストなどの機械的処理、コロナ放電などの物理的処理、コーティングなどによる化学的処理などが挙げられる。これらの中でも、接着性の観点から、コーティングにより易接着層を設けることが好ましい。 For the purpose of improving the adhesion between the support and the first photosensitive resin layer, the support may be subjected to adhesion-facilitating treatment. Examples of the adhesion-facilitating treatment include mechanical treatment such as sandblasting, physical treatment such as corona discharge, and chemical treatment such as coating. Among these, from the viewpoint of adhesion, it is preferable to provide an easily adhesive layer by coating.
第１の感光性樹脂層は、少なくとも、（１ａ）親水性構造を有するポリアミド、（１ｂ）エチレン性二重結合を有する化合物および（１ｃ）光重合開始剤を含有する。 The first photosensitive resin layer contains at least (1a) a polyamide having a hydrophilic structure, (1b) a compound having an ethylenic double bond, and (1c) a photopolymerization initiator.
（１ａ）親水性構造を有するポリアミドは、感光性樹脂層の形態を保持するための担体樹脂としての機能を有するとともに、感光性樹脂層へ水による現像性を付与する機能を有する。ここで、本発明における親水性構造とは、水分子の水素原子と水素結合しやすい化学構造のことを言う。親水性構造としては、例えば、水酸基、アミノ基、塩基性窒素、カルボキシル基、リン酸基、ポリエテールセグメントなどが挙げられる。これらの中でも、塩基性窒素とポリエーテルセグメントは、ポリアミドに導入しやすく、ポリアミドの紫外光に対する透過性を高めることができるため、好ましい。親水性構造を有するポリアミドとしては、塩基性窒素および／またはポリエーテルセグメントを主鎖に有するポリアミドが好ましい。 (1a) Polyamide having a hydrophilic structure has a function as a carrier resin for maintaining the shape of the photosensitive resin layer, and also has a function of imparting water developability to the photosensitive resin layer. Here, the hydrophilic structure in the present invention refers to a chemical structure that easily forms a hydrogen bond with a hydrogen atom of a water molecule. Examples of the hydrophilic structure include a hydroxyl group, an amino group, a basic nitrogen group, a carboxyl group, a phosphoric acid group, and a polyether segment. Among these, basic nitrogen and polyether segments are preferred because they are easy to introduce into polyamide and can increase the transparency of polyamide to ultraviolet light. As the polyamide having a hydrophilic structure, a polyamide having a basic nitrogen and/or a polyether segment in the main chain is preferable.
塩基性窒素を主鎖に有するポリアミドにおける塩基性窒素としては、例えば、ピペラジン基やアミノ基の窒素などが挙げられる。これらを２種以上用いてもよい。塩基性窒素を主鎖に有するポリアミドは、ピペラジン基や、Ｎ，Ｎ－ジアルキルアミノ基などのアミノ基を、主鎖に有することが好ましく、ピペラジン基を主鎖に有することが好ましい。これらの塩基性窒素を主鎖に有するポリアミドは、グリシジルメタクリレートなどの不飽和エポキシ化合物と、ポリアミド末端のアミノ基やカルボキシル基、アミド結合の活性水素などとの反応を促進することから、ポリアミド中に不飽和エポキシ化合物を用いてエチレン性二重結合を容易に導入することができる。ポリアミド中のエチレン性二重結合は、露光によりポリアミドやエチレン性二重結合を有する化合物中のエチレン性二重結合とラジカル重合することから、微細なレリーフを形成することができ、画像再現性を向上させることができる。 Examples of the basic nitrogen in the polyamide having basic nitrogen in its main chain include nitrogen of a piperazine group and an amino group. Two or more types of these may be used. The polyamide having basic nitrogen in the main chain preferably has an amino group such as a piperazine group or an N,N-dialkylamino group in the main chain, and preferably has a piperazine group in the main chain. Polyamides having these basic nitrogens in their main chains promote the reaction between unsaturated epoxy compounds such as glycidyl methacrylate, amino groups and carboxyl groups at the polyamide ends, and active hydrogen in amide bonds, so they are used in polyamides. Ethylenic double bonds can be easily introduced using unsaturated epoxy compounds. When exposed to light, the ethylenic double bonds in polyamide undergo radical polymerization with the ethylenic double bonds in polyamide and compounds containing ethylenic double bonds, which can form fine reliefs and improve image reproducibility. can be improved.
塩基性窒素を主鎖に有するポリアミドは、例えば、塩基性窒素を有する単量体を、必要に応じてそれ以外のジアミン、ジカルボン酸、ω－アミノ酸、ラクタムなどとともに、縮重合または重付加反応することにより得ることができる。塩基性窒素を有する単量体としては、ピペラジン基やＮ，Ｎ－ジアルキルアミノ基を有する単量体が好ましく、ピペラジン基を有する単量体がより好ましい。 Polyamides having basic nitrogen in the main chain can be produced by, for example, subjecting a monomer having basic nitrogen to a polycondensation or polyaddition reaction with other diamines, dicarboxylic acids, ω-amino acids, lactams, etc. as necessary. This can be obtained by As the monomer having basic nitrogen, a monomer having a piperazine group or an N,N-dialkylamino group is preferable, and a monomer having a piperazine group is more preferable.
塩基性窒素を有する単量体としては、例えば、Ｎ，Ｎ’－ビス（アミノメチル）－ピペラジン、Ｎ，Ｎ’－ビス（β－アミノエチル）－ピペラジン、Ｎ，Ｎ’－ビス（γ－アミノベンジル）－ピペラジン、Ｎ－（β－アミノエチル）ピペラジン、Ｎ－（β－アミノプロピル）ピペラジン、Ｎ－（ω－アミノヘキシル）ピペラジン、Ｎ－（β－アミノエチル）－２，５－ジメチルピペラジン、Ｎ，Ｎ－ビス（β－アミノエチル）－ベンジルアミン、Ｎ，Ｎ－ビス（γ－アミノプロピル）－ベンジルアミン、Ｎ，Ｎ’－ジメチル－Ｎ，Ｎ’－ビス（γ－アミノプロピル）－エチレンジアミン、Ｎ，Ｎ’－ジメチル－Ｎ，Ｎ’－ビス（γ－アミノプロピル）－テトラメチレンジアミンなどのジアミン類；Ｎ，Ｎ’－ビス（カルボキシメチル）－ピペラジン、Ｎ，Ｎ’－ビス（カルボキシメチル）－メチルピペラジン、Ｎ，Ｎ’－ビス（カルボキシメチル）－２，６－ジメチルピペラジン、Ｎ，Ｎ’－ビス（β－カルボキシエチル）－ピペラジン、Ｎ，Ｎ－ビス（カルボキシメチル）－メチルアミン、Ｎ，Ｎ－ビス（β－カルボキシエチル）－エチルアミン、Ｎ，Ｎ－ビス（β－カルボキシエチル）－メチルアミン、Ｎ，Ｎ－ジ（β－カルボキシエチル）－イソプロピルアミン、Ｎ，Ｎ’－ジメチル－Ｎ，Ｎ’－ビス－（カルボキシメチル）－エチレンジアミン、Ｎ，Ｎ’－ジメチル－Ｎ，Ｎ’－ビス－（β－カルボキシエチル）－エチレンジアミンなどのジカルボン酸類あるいはこれらの低級アルキルエステルや酸ハロゲン化物、Ｎ－（アミノメチル）－Ｎ’－（カルボキシメチル）－ピペラジン、Ｎ－（アミノメチル）－Ｎ’－（β－カルボキシエチル）－ピペラジン、Ｎ－（β－アミノエチル）－Ｎ’－（β－カルボキシエチル）－ピペラジン、Ｎ－カルボキシメチルピペラジン、Ｎ－（β－カルボキシエチル）ピペラジン、Ｎ－（γ－カルボキシヘキシル）ピペラジン、Ｎ－（ω－カルボキシヘキシル）ピペラジン、Ｎ－（アミノメチル）－Ｎ－（カルボキシメチル）－メチルアミン、Ｎ－（β－アミノエチル）－Ｎ－（β－カルボキシエチル）－メチルアミン、Ｎ－（アミノメチル）－Ｎ－（β－カルボキシエチル）－イソプロピルアミン、Ｎ，Ｎ’－ジメチル－Ｎ－（アミノメチル）－Ｎ’－（カルボキシメチル）－エチレンジアミンなどのω－アミノ酸などが挙げられる。 Examples of monomers having basic nitrogen include N,N'-bis(aminomethyl)-piperazine, N,N'-bis(β-aminoethyl)-piperazine, N,N'-bis(γ- aminobenzyl)-piperazine, N-(β-aminoethyl)piperazine, N-(β-aminopropyl)piperazine, N-(ω-aminohexyl)piperazine, N-(β-aminoethyl)-2,5-dimethyl Piperazine, N,N-bis(β-aminoethyl)-benzylamine, N,N-bis(γ-aminopropyl)-benzylamine, N,N'-dimethyl-N,N'-bis(γ-aminopropyl) )-Diamines such as ethylenediamine, N,N'-dimethyl-N,N'-bis(γ-aminopropyl)-tetramethylenediamine; N,N'-bis(carboxymethyl)-piperazine, N,N'- Bis(carboxymethyl)-methylpiperazine, N,N'-bis(carboxymethyl)-2,6-dimethylpiperazine, N,N'-bis(β-carboxyethyl)-piperazine, N,N-bis(carboxymethyl )-methylamine, N,N-bis(β-carboxyethyl)-ethylamine, N,N-bis(β-carboxyethyl)-methylamine, N,N-di(β-carboxyethyl)-isopropylamine, N , N'-dimethyl-N,N'-bis-(carboxymethyl)-ethylenediamine, N,N'-dimethyl-N,N'-bis-(β-carboxyethyl)-ethylenediamine, or lower versions thereof. Alkyl esters and acid halides, N-(aminomethyl)-N'-(carboxymethyl)-piperazine, N-(aminomethyl)-N'-(β-carboxyethyl)-piperazine, N-(β-aminoethyl )-N'-(β-carboxyethyl)-piperazine, N-carboxymethylpiperazine, N-(β-carboxyethyl)piperazine, N-(γ-carboxyhexyl)piperazine, N-(ω-carboxyhexyl)piperazine, N-(aminomethyl)-N-(carboxymethyl)-methylamine, N-(β-aminoethyl)-N-(β-carboxyethyl)-methylamine, N-(aminomethyl)-N-(β- Examples include ω-amino acids such as carboxyethyl)-isopropylamine, N,N'-dimethyl-N-(aminomethyl)-N'-(carboxymethyl)-ethylenediamine, and the like.
ポリエーテルセグメントを主鎖に有するポリアミドのポリエーテルセグメントとしては、例えば、ポリエチレンオキサイド、ポリプロピレンオキサイドなどが挙げられる。これらを２種以上用いてもよい。これらの中でも、ポリエチレンオキサイドが好ましく、ポリエチレンオキサイド部分の数平均分子量は、２００以上６，０００以下が好ましい。ポリエチレンオキサイド部分の数平均分子量を２００以上とすることにより、水を含む現像液に対する溶解性を向上させ、現像廃液の凝集を抑制することができる。一方、ポリエチレンオキサイド部分の数平均分子量を６，０００以下とすることにより、感光性樹脂層中の他の成分との相溶性を向上させることができる。これらのポリエーテルセグメントを主鎖に有するポリアミドは、感光性樹脂層を光硬化して得られるレリーフに柔軟性を付与し、各種印刷方式に好適な硬度に容易に調整することができる。 Examples of the polyether segment of the polyamide having a polyether segment in its main chain include polyethylene oxide, polypropylene oxide, and the like. Two or more types of these may be used. Among these, polyethylene oxide is preferred, and the number average molecular weight of the polyethylene oxide portion is preferably 200 or more and 6,000 or less. By setting the number average molecular weight of the polyethylene oxide portion to 200 or more, the solubility in a developer containing water can be improved and aggregation of developer waste can be suppressed. On the other hand, by setting the number average molecular weight of the polyethylene oxide portion to 6,000 or less, compatibility with other components in the photosensitive resin layer can be improved. A polyamide having these polyether segments in its main chain imparts flexibility to the relief obtained by photocuring the photosensitive resin layer, and can easily adjust the hardness to be suitable for various printing methods.
ポリエーテルセグメントを主鎖に有するポリアミドは、例えば、ポリエチレングルコールなどの両末端にアクリロニトリルを付加し、これを水素還元して得られるα，ω－ジアミノポリオキシエチレンや、ポリエチレングリコールの両末端に無水コハク酸などのジカルボン酸を付加させた化合物などのポリエーテルを有する単量体を、必要に応じてそれ以外のジアミン、ジカルボン酸、ω－アミノ酸、ラクタムなどとともに、縮重合または重付加反応することにより得ることができる。 Polyamides having polyether segments in their main chains are, for example, α,ω-diaminopolyoxyethylene obtained by adding acrylonitrile to both ends of polyethylene glycol and reducing this with hydrogen, or polyamides obtained by adding acrylonitrile to both ends of polyethylene glycol, etc. A polyether-containing monomer, such as a compound to which dicarboxylic acid such as succinic anhydride is added, is subjected to a polycondensation or polyaddition reaction with other diamines, dicarboxylic acids, ω-amino acids, lactams, etc., as necessary. This can be obtained by
ポリアミドは、ポリアミドを構成する全成分、すなわち、アミノカルボン酸単位（原料としてラクタムの場合を含む）、ジカルボン酸単位およびジアミン構造単位の総和中、親水性構造を有する単量体を合計２０～９０モル％用いることが好ましい。 Polyamide has a total of 20 to 90 monomers having a hydrophilic structure in the total of all components constituting the polyamide, that is, aminocarboxylic acid units (including lactam as a raw material), dicarboxylic acid units, and diamine structural units. Preferably, mole % is used.
親水性構造を有するポリアミドを構成するその他の単量体としては、例えば、ω－アミノカプロン酸、ω－アミノエナント酸、ω－アミノカプリル酸、ω－アミノベルゴン酸、ω－アミノカプリン酸、１１－アミノウンデカン酸、１２－アミノドデカン酸等のアミノカルボン酸；カプロラクタム、エナントラクタム、カプリルラクタム、ラウロラクタム等のラクタム；ヘキサメチレンジアミン、ドデカメチレンジアミンなどのジアミン、テレフタル酸、イソフタル酸、フタル酸、ナフタレン－２，６－ジカルボン酸、ナフタレン－２，７－ジカルボン酸、ジフェニル－４，４’－ジカルボン酸、ジフェノキシエタンジカルボン酸、５－スルホイソフタル酸ナトリウム等の芳香族ジカルボン酸；１，４－シクロヘキサンジカルボン酸、１，２－シクロヘキサンジカルボン酸、ジシクロヘキシル－４，４’－ジカルボン酸等の脂肪族ジカルボン酸；コハク酸、シュウ酸、アジピン酸、セバシン酸、デカンジカルボン酸等の脂肪族ジカルボン酸などが挙げられる。これらを２種以上用いてもよい。 Other monomers constituting the polyamide having a hydrophilic structure include, for example, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminocaprylic acid, Aminocarboxylic acids such as undecanoic acid and 12-aminododecanoic acid; Lactams such as caprolactam, enantholactam, capryllactam, and laurolactam; Diamines such as hexamethylene diamine and dodecamethylene diamine; terephthalic acid, isophthalic acid, phthalic acid, and naphthalene. Aromatic dicarboxylic acids such as 2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, sodium 5-sulfoisophthalate; 1,4-cyclohexane Aliphatic dicarboxylic acids such as dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid; aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, decanedicarboxylic acid, etc. Can be mentioned. Two or more types of these may be used.
親水性構造を有するポリアミドの重量平均分子量は、１０，０００以上２００，０００以下が好ましい。ここで、重量平均分子量は、ＧＰＣ測定により求めることができる。より具体的には、Ｗｙａｔｔ Ｔｅｃｈｎｏｌｏｇｙ製ゲル浸透クロマトグラフ－多角度光散乱光度計を用いて、カラム温度：４０℃、流速：０．７ｍＬ／分の条件で、重量平均分子量を測定することができる。標準サンプルとして、ポリメチルメタクリレートを用いる。 The weight average molecular weight of the polyamide having a hydrophilic structure is preferably 10,000 or more and 200,000 or less. Here, the weight average molecular weight can be determined by GPC measurement. More specifically, the weight average molecular weight can be measured using a gel permeation chromatograph-multi-angle light scattering photometer manufactured by Wyatt Technology under the conditions of column temperature: 40°C and flow rate: 0.7 mL/min. . Polymethyl methacrylate is used as a standard sample.
第１の感光性樹脂中における（１ａ）親水性構造を有するポリアミドの含有量は、第１の感光性樹脂層の耐久性や柔軟性をより向上させる観点から、２０重量％以上が好ましく、３０重量％以上がより好ましい。一方、第１の感光性樹脂中における（１ａ）親水性構造を有するポリアミドの含有量は、画像再現性を向上させる観点から、８０重量％以下が好ましく、７０重量％以下がより好ましい。 The content of (1a) polyamide having a hydrophilic structure in the first photosensitive resin is preferably 20% by weight or more, and 30% by weight or more from the viewpoint of further improving the durability and flexibility of the first photosensitive resin layer. More preferably, the amount is % by weight or more. On the other hand, the content of (1a) polyamide having a hydrophilic structure in the first photosensitive resin is preferably 80% by weight or less, more preferably 70% by weight or less, from the viewpoint of improving image reproducibility.
（１ｂ）エチレン性二重結合を有する化合物とは、エチレン性二重結合を有し、分子量が１０，０００未満であるものを指す。エチレン性二重結合を有する化合物の分子量は、２，０００以下が好ましい。エチレン性二重結合を有する化合物としては、（メタ）アクリル酸とアルコール化合物のエステル化物や（メタ）アクリル酸とグリシジル化合物の付加反応物である（メタ）アクリレート、（メタ）アクリル酸とアミン基含有化合物のアミド化物である（メタ）アクリルアミドなどが挙げられる。これらを２種以上含有してもよい。ここで、（メタ）アクリレートとは、アクリレートとメタクリレートの総称であり、（メタ）アクリル酸とは、アクリル酸とメタクリル酸の総称である。 (1b) A compound having an ethylenic double bond refers to a compound having an ethylenic double bond and a molecular weight of less than 10,000. The molecular weight of the compound having an ethylenic double bond is preferably 2,000 or less. Compounds with ethylenic double bonds include esterified products of (meth)acrylic acid and alcohol compounds, (meth)acrylates that are addition reaction products of (meth)acrylic acid and glycidyl compounds, and (meth)acrylic acid and amine groups. Examples include (meth)acrylamide, which is an amidated compound of the containing compound. Two or more types of these may be contained. Here, (meth)acrylate is a general term for acrylate and methacrylate, and (meth)acrylic acid is a general term for acrylic acid and methacrylic acid.
第１の感光性樹脂中における（１ｂ）エチレン性二重結合を有する化合物の含有量は、画像再現性や耐刷性を向上させる観点から、１０重量％以上が好ましく、１５重量％以上がより好ましい。一方、第１の感光性樹脂中における（１ｂ）エチレン性二重結合を有する化合物の含有量は、柔軟性をより向上させる観点から、５０重量％以下が好ましく、４０重量％以下がより好ましい。 The content of (1b) the compound having an ethylenic double bond in the first photosensitive resin is preferably 10% by weight or more, more preferably 15% by weight or more, from the viewpoint of improving image reproducibility and printing durability. preferable. On the other hand, the content of (1b) the compound having an ethylenic double bond in the first photosensitive resin is preferably 50% by weight or less, more preferably 40% by weight or less, from the viewpoint of further improving flexibility.
（１ｃ）光重合開始剤としては、光吸収によって、自己分解や水素引き抜きによってラジカルを生成する機能を有するものが好ましく用いられる。例えば、ベンゾインアルキルエーテル類、ベンゾフェノン類、アントラキノン類、ベンジル類、アセトフェノン類、ジアセチル類などが挙げられる。これらを２種以上含有してもよい。 (1c) As the photopolymerization initiator, one having the function of generating radicals by self-decomposition or hydrogen abstraction by light absorption is preferably used. Examples include benzoin alkyl ethers, benzophenones, anthraquinones, benzyls, acetophenones, and diacetyls. Two or more types of these may be contained.
第１の感光性樹脂中における（１ｃ）光重合開始剤の含有量は、０．５～１０重量％が好ましい。 The content of the photopolymerization initiator (1c) in the first photosensitive resin is preferably 0.5 to 10% by weight.
第１の感光性樹脂層には、必要に応じて、前述の親水性構造を有するポリアミド以外のバインダー樹脂、相溶助剤、撥インキ剤、重合禁止剤、染料、顔料、界面活性剤、消泡剤、紫外線吸収剤、香料などを含有してもよい。 The first photosensitive resin layer may optionally contain a binder resin other than the polyamide having a hydrophilic structure, a compatibility aid, an ink repellent, a polymerization inhibitor, a dye, a pigment, a surfactant, and an eraser. It may also contain foaming agents, ultraviolet absorbers, fragrances, etc.
第１の感光性樹脂層に相溶助剤を含有することにより、感光性樹脂層を構成する成分の相溶性を高め、低分子量成分のブリードアウトを抑制し、感光性樹脂層の柔軟性を向上させることができる。相溶助剤としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、グリセリン、トリメチロールプロパン、トリメチロールエタン、ペンタエリスリトールやこれらの誘導体などの多価アルコール類が挙げられる。第１の感光性樹脂層中における相溶助剤の含有量は、３０質量％以下が好ましい。 By containing a compatibility aid in the first photosensitive resin layer, the compatibility of the components constituting the photosensitive resin layer is increased, the bleed-out of low molecular weight components is suppressed, and the flexibility of the photosensitive resin layer is increased. can be improved. Examples of the compatibility aid include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, and derivatives thereof. The content of the compatible auxiliary agent in the first photosensitive resin layer is preferably 30% by mass or less.
第１の感光性樹脂層に重合禁止剤を含有することにより、熱安定性を向上させることができる。重合禁止剤としては、例えば、フェノール類、ハイドロキノン類、カテコール類、ヒドロキシアミン誘導体などが挙げられる。これらを１種以上含有してもよい。第１の感光性樹脂層中における重合禁止剤の含有量は、０．００１～５質量％が好ましい。 By containing a polymerization inhibitor in the first photosensitive resin layer, thermal stability can be improved. Examples of the polymerization inhibitor include phenols, hydroquinones, catechols, and hydroxyamine derivatives. One or more types of these may be contained. The content of the polymerization inhibitor in the first photosensitive resin layer is preferably 0.001 to 5% by mass.
第１の感光性樹脂層には、無機微粒子を実質的に含有しない。ここで、「実質含有しない」とは、第１の感光性樹脂層中における含有量が、０．５重量％未満であることを言う。第１の感光性樹脂層に無機微粒子を実質的に含有しないことにより、フィラー効果によるレリーフの高硬度化を抑制し、柔軟性を向上させることができる。 The first photosensitive resin layer does not substantially contain inorganic fine particles. Here, "not substantially containing" means that the content in the first photosensitive resin layer is less than 0.5% by weight. By not substantially containing inorganic fine particles in the first photosensitive resin layer, it is possible to suppress increase in hardness of the relief due to the filler effect and improve flexibility.
第２の感光性樹脂層は、少なくとも（２ａ）親水性構造を有するポリアミド、（２ｂ）エチレン性二重結合を有する化合物、（２ｃ）光重合開始剤および（２ｄ）無機微粒子を含有する。 The second photosensitive resin layer contains at least (2a) a polyamide having a hydrophilic structure, (2b) a compound having an ethylenic double bond, (2c) a photopolymerization initiator, and (2d) inorganic fine particles.
（２ａ）親水性構造を有するポリアミド、（２ｂ）エチレン性二重結合を有する化合物、（２ｃ）光重合開始剤としては、それぞれ第１の感光性樹脂層における（１ａ）親水性構造を有するポリアミド、（１ｂ）エチレン性二重結合を有する化合物、（１ｃ）光重合開始剤として例示したものが挙げられ、これらの好ましい態様として記載したものが好ましい。（１ａ）親水性構造を有するポリアミドと（２ａ）親水性構造を有するポリアミド、（１ｂ）エチレン性二重結合を有する化合物と（２ｂ）エチレン性二重結合を有する化合物、（１ｃ）光重合開始剤と（２ｃ）光重合開始剤は、それぞれ同じであっても異なってもよい。第１の感光性樹脂層と第２の感光性樹脂層との接着性を向上させる観点や、低分子量成分のマイグレーションによる影響を抑制する観点から、それぞれ同じ化合物を含有することが好ましく、（２ｄ）無機微粒子以外の組成が共通することがより好ましい。 (2a) polyamide having a hydrophilic structure, (2b) compound having an ethylenic double bond, and (2c) photopolymerization initiator used in the first photosensitive resin layer (1a) polyamide having a hydrophilic structure, respectively. , (1b) a compound having an ethylenic double bond, and (1c) a photopolymerization initiator, and the preferred embodiments of these are preferred. (1a) Polyamide with a hydrophilic structure, (2a) Polyamide with a hydrophilic structure, (1b) Compound with ethylenic double bond, (2b) Compound with ethylenic double bond, (1c) Photopolymerization initiation The agent and the photopolymerization initiator (2c) may be the same or different. From the viewpoint of improving the adhesion between the first photosensitive resin layer and the second photosensitive resin layer and suppressing the influence of migration of low molecular weight components, it is preferable that they each contain the same compound (2d ) It is more preferable that the compositions other than the inorganic fine particles are the same.
（２ｄ）無機微粒子としては、金属微粒子、金属酸化物微粒子やシリカ微粒子などの無機酸化物粒子、無機塩微粒子、有機成分および無機成分を含む微粒子などが挙げられる。これらを２種以上含有してもよい。これらの中でも、第２の感光性樹脂層における光散乱を抑制する観点から、（２ａ）～（２ｃ）の成分との屈折率が近いものが好ましく、シリカ微粒子がより好ましい。安全性の観点から、非晶質シリカ微粒子がより好ましい。非晶質シリカ微粒子としては、例えば、（株）アドマテックスの“アドマフューズ”（商標登録）、デンカ（株）のデンカ溶融シリカＤＦシリーズなどが挙げられる。 (2d) Examples of the inorganic fine particles include metal fine particles, inorganic oxide particles such as metal oxide fine particles and silica fine particles, inorganic salt fine particles, and fine particles containing an organic component and an inorganic component. Two or more types of these may be contained. Among these, from the viewpoint of suppressing light scattering in the second photosensitive resin layer, those having a refractive index close to those of components (2a) to (2c) are preferable, and silica fine particles are more preferable. From the viewpoint of safety, amorphous silica fine particles are more preferred. Examples of the amorphous silica fine particles include "Adomafuse" (registered trademark) manufactured by Admatex Co., Ltd. and Denka Fused Silica DF series manufactured by Denka Corporation.
（２ｄ）無機微粒子の平均粒子径は、印刷版表面に凹凸を設けて版面粘着をより抑制し、す抜けをより抑制する観点から、０．５μｍ以上が好ましく、１．０μｍ以上がより好ましい。一方、（２ｄ）無機微粒子の平均粒子径は、印刷版表面の凹凸を適度に抑え、す抜けを効率的に抑制する観点から、５．０μｍ以下が好ましく、４．０μｍ以下がより好ましい。なお、本発明において、（２ｄ）無機微粒子の平均粒子径とは、レーザー回折散乱法により測定したメジアン径を言う。 (2d) The average particle diameter of the inorganic fine particles is preferably 0.5 μm or more, more preferably 1.0 μm or more, from the viewpoint of providing unevenness on the printing plate surface to further suppress plate adhesion and further suppressing through-through. On the other hand, the average particle diameter of the inorganic fine particles (2d) is preferably 5.0 μm or less, more preferably 4.0 μm or less, from the viewpoint of appropriately suppressing unevenness on the printing plate surface and efficiently suppressing through-through. In the present invention, the average particle diameter of the inorganic fine particles (2d) refers to the median diameter measured by a laser diffraction scattering method.
第２の感光性樹脂中における（２ｄ）無機微粒子の含有量は、版面粘着をより抑制し、す抜けをより抑制する観点から、３重量％以上が好ましく、５重量％以上がより好ましい。一方、第２の感光性樹脂中における（２ｄ）無機微粒子の含有量は、第２の感光性樹脂層の形成を容易にする観点から、７０重量％以下が好ましく、５０重量％以下がより好ましい。 The content of the inorganic fine particles (2d) in the second photosensitive resin is preferably 3% by weight or more, more preferably 5% by weight or more, from the viewpoint of further suppressing plate adhesion and further suppressing through-through. On the other hand, the content of (2d) inorganic fine particles in the second photosensitive resin is preferably 70% by weight or less, more preferably 50% by weight or less, from the viewpoint of facilitating the formation of the second photosensitive resin layer. .
第２の感光性樹脂層には、必要に応じて、前述の親水性構造を有するポリアミド以外のバインダー樹脂、相溶助剤、撥インキ剤、重合禁止剤、染料、顔料、界面活性剤、消泡剤、紫外線吸収剤、香料などを含有してもよい。相溶助剤や重合禁止剤としては、第１の感光性樹脂層において例示したものが挙げられる。 The second photosensitive resin layer may optionally contain a binder resin other than the polyamide having a hydrophilic structure, a compatibility aid, an ink repellent, a polymerization inhibitor, a dye, a pigment, a surfactant, and an eraser. It may also contain foaming agents, ultraviolet absorbers, fragrances, etc. Examples of the compatibility aid and polymerization inhibitor include those exemplified in the first photosensitive resin layer.
第２の感光性樹脂層中に撥インキ剤を含有することにより、印刷中にレリーフの凹部にインキが入り込むことを抑制し、再現性を向上させることができる。撥インキ剤としては、（２ｅ）フッ素原子および／または珪素原子を有する撥インキ剤が好ましい。フッ素原子を有する構造としては、例えば、フルオロアルキル基などが挙げられ、珪素原子を有する構造としては、例えば、ジメチルシロキサン構造などが挙げられる。 By containing an ink repellent in the second photosensitive resin layer, ink can be prevented from entering the recesses of the relief during printing, and reproducibility can be improved. As the ink repellent, (2e) an ink repellent having a fluorine atom and/or a silicon atom is preferable. Examples of the structure having a fluorine atom include a fluoroalkyl group, and examples of the structure having a silicon atom include a dimethylsiloxane structure.
第２の感光性樹脂層中における（２ｅ）フッ素原子および／または珪素原子を有する撥インキ剤の含有量は、再現性を向上させる観点から、０．１重量％以上が好ましく、０．３重量％以上がより好ましい。一方、第２の感光性樹脂層中における（２ｅ）フッ素原子および／または珪素原子を有する撥インキ剤の含有量は、印刷版表面のインキ着肉性を向上させる観点から、５．０重量％以下が好ましく、３．０重量％以下がより好ましい。 The content of (2e) the ink repellent having a fluorine atom and/or a silicon atom in the second photosensitive resin layer is preferably 0.1% by weight or more, and 0.3% by weight from the viewpoint of improving reproducibility. % or more is more preferable. On the other hand, the content of the ink repellent (2e) having a fluorine atom and/or a silicon atom in the second photosensitive resin layer is 5.0% by weight from the viewpoint of improving ink adhesion on the surface of the printing plate. The content is preferably 3.0% by weight or less, more preferably 3.0% by weight or less.
第１の感光性樹脂層の厚さＴ１に対する、第２の感光性樹脂層の厚さＴ２の比（Ｔ２／Ｔ１）は、０．０１～０．２５が好ましい。第２の感光性樹脂層は、インキを着肉する印刷版表面側に配置されており、（２ｄ）無機微粒子が、版面粘着を抑制してす抜けを抑制する効果を有する。Ｔ２／Ｔ１を０．０１以上とすることにより、版面粘着をより抑制し、す抜けをより抑制することができる。Ｔ２／Ｔ１は、０．０３以上がより好ましい。一方、Ｔ２／Ｔ１を０．２５以下とすることにより、（２ｄ）第１の感光性樹脂層が有するフレキソ版としての性能、例えば均一なベタ着肉性を向上させることができる。Ｔ２／Ｔ１は、０．２０以下がより好ましい。 The ratio (T2/T1) of the thickness T2 of the second photosensitive resin layer to the thickness T1 of the first photosensitive resin layer is preferably 0.01 to 0.25. The second photosensitive resin layer is disposed on the surface side of the printing plate to which ink is applied, and the inorganic fine particles (2d) have the effect of suppressing plate surface adhesion and suppressing through-through. By setting T2/T1 to 0.01 or more, plate surface adhesion can be further suppressed and through-through can be further suppressed. T2/T1 is more preferably 0.03 or more. On the other hand, by setting T2/T1 to 0.25 or less, (2d) the performance of the first photosensitive resin layer as a flexographic plate, for example, uniform solid ink receptivity can be improved. T2/T1 is more preferably 0.20 or less.
（Ｂ）第１の感光性樹脂層と（Ｃ）第２の感光性樹脂層の合計の厚さは、０．５ｍｍ～３ｍｍが好ましい。 The total thickness of (B) the first photosensitive resin layer and (C) the second photosensitive resin layer is preferably 0.5 mm to 3 mm.
（Ｂ）第１の感光性樹脂層と（Ｃ）第２の感光性樹脂層のそれぞれの厚さは、上記好ましい態様を満たす範囲で、任意に設定することが好ましい。 The thicknesses of the first photosensitive resin layer (B) and the second photosensitive resin layer (C) are preferably set arbitrarily within a range that satisfies the above preferred embodiments.
なお、第１の感光性樹脂層の厚さ、および第２の感光性樹脂層の厚さは、光学顕微鏡または走査電子顕微鏡（ＳＥＭ）により観測された印刷版原版の断面写真から測定することができる。具体的には、印刷版原版から、カバーフィルムがある場合はこれを剥離し、印刷版原版の断面を、全ての層が視野に入るような倍率で拡大観察する。印刷版原版の表面側において、無機微粒子が観測できる領域を第２の感光性樹脂層とし、無機微粒子が観測できない領域との界面までの距離を第２の感光性樹脂層の厚さとする。また、第２の感光性樹脂層のとの界面から、支持体、あるいは支持体上に易接着層などの他の層を有する場合は他の層との界面までの距離を、第１の感光性樹脂層の厚さとして求めることができる。なお、印刷版原版作製における各層の厚さが既知の場合には、その厚さからＴ２／Ｔ１を算出することもできる。 Note that the thickness of the first photosensitive resin layer and the thickness of the second photosensitive resin layer can be measured from a cross-sectional photograph of the printing plate precursor observed with an optical microscope or a scanning electron microscope (SEM). can. Specifically, if there is a cover film, it is peeled off from the printing plate precursor, and the cross section of the printing plate precursor is observed under magnification so that all layers can be seen. On the surface side of the printing plate precursor, the area where inorganic fine particles can be observed is defined as the second photosensitive resin layer, and the distance to the interface with the area where inorganic fine particles cannot be observed is defined as the thickness of the second photosensitive resin layer. In addition, the distance from the interface of the second photosensitive resin layer to the interface with the support or other layers such as an easily adhesive layer on the support is determined by the distance from the interface with the first photosensitive resin layer. It can be determined as the thickness of the resin layer. In addition, when the thickness of each layer in the printing plate precursor production is known, T2/T1 can also be calculated from the thickness.
本発明の印刷版原版は、第２の感光性樹脂層上に、カバーフィルムを有することが好ましく、印刷版原版表面を保護し、異物等の付着を抑制することができる。第２の感光性樹脂層はカバーフィルムと直接接していてもよいし、第２の感光性樹脂層とカバーフィルムの間に１層または複数の層を有していてもよい。第２の感光性樹脂層とカバーフィルムの間の層としては、例えば、感光性樹脂層表面の粘着を防止する粘着防止層などが挙げられる。 The printing plate precursor of the present invention preferably has a cover film on the second photosensitive resin layer, which can protect the surface of the printing plate precursor and suppress adhesion of foreign substances and the like. The second photosensitive resin layer may be in direct contact with the cover film, or may have one or more layers between the second photosensitive resin layer and the cover film. Examples of the layer between the second photosensitive resin layer and the cover film include an anti-adhesion layer that prevents the surface of the photosensitive resin layer from adhesion.
カバーフィルムとしては、例えば、ポリエステル、ポリエチレン、ポリプロピレンなどからなるプラスチックシートが挙げられる。カバーフィルムの厚さは、取扱性および柔軟性の観点から、１０～１５０μｍが好ましい。また、カバーフィルム表面は粗面化されていてもよく、原画フィルムとの密着性を向上させることができる。粗面化の方法としては、例えば、サンドブラスト、ケミカルエッチング、マット化粒子含有塗工剤のコーティングなどが挙げられる。 Examples of the cover film include plastic sheets made of polyester, polyethylene, polypropylene, and the like. The thickness of the cover film is preferably 10 to 150 μm from the viewpoint of handleability and flexibility. Further, the surface of the cover film may be roughened to improve adhesion to the original film. Examples of methods for roughening the surface include sandblasting, chemical etching, and coating with a coating agent containing matting particles.
また、本発明の印刷版原版が、デジタルデバイスで制御された画像データに基づいてレーザー照射を行い、マスク層要素から画像マスクをその場で形成し、露光・現像するいわゆるＣＴＰ製版方式に用いられる場合、印刷版原版は、さらに感熱マスク層を有していてもよい。感熱マスク層は、紫外光を事実上遮断し、描画時には赤外レーザー光を吸収し、その熱により瞬間的に一部または全部が昇華または融除するものが好ましい。これによりレーザーの照射部分と未照射部分の光学濃度に差が生じ、従来の原画フィルムと同様の機能を果たすことができる。印刷版原版が感熱マスク層を有する場合、感光性樹脂層と感熱マスク層との間に接着力調整層を有してもよく、感熱マスク層とカバーフィルムの間に剥離補助層を有してもよい。 Further, the printing plate precursor of the present invention can be used in a so-called CTP plate making method in which laser irradiation is performed based on image data controlled by a digital device, an image mask is formed on the spot from mask layer elements, and exposed and developed. In this case, the printing plate precursor may further include a heat-sensitive mask layer. The heat-sensitive mask layer is preferably one that substantially blocks ultraviolet light, absorbs infrared laser light during drawing, and momentarily sublimates or ablates part or all of it due to the heat. This creates a difference in optical density between the laser irradiated area and the non-irradiated area, allowing it to perform the same function as a conventional original film. When the printing plate precursor has a heat-sensitive mask layer, it may have an adhesion adjustment layer between the photosensitive resin layer and the heat-sensitive mask layer, and a peeling auxiliary layer between the heat-sensitive mask layer and the cover film. Good too.
感熱マスク層、接着力調整層、剥離補助層としては、例えば、国際公開第２０１７／０３８９７０号に記載されたものが挙げられる。 Examples of the heat-sensitive mask layer, adhesive force adjustment layer, and peeling auxiliary layer include those described in International Publication No. 2017/038970.
次に、本発明の印刷版原版の製造方法について、支持体上に、第１の感光性樹脂層、第２の感光性樹脂層およびカバーフィルムを有する場合を例に説明する。 Next, the method for producing a printing plate precursor of the present invention will be described using as an example a case in which a first photosensitive resin layer, a second photosensitive resin layer, and a cover film are provided on a support.
例えば、（１ａ）親水性構造を有するポリアミドを、溶媒に加熱溶解した後に、（１ｂ）エチレン性二重結合を有する化合物、（１ｃ）光重合開始剤および必要に応じてその他添加剤を添加し、撹拌混合することにより、第１の感光性樹脂層を形成する第１の感光性樹脂層組成物溶液を得ることが好ましい。溶媒としては、水や、水／アルコール混合溶媒などが挙げられる。 For example, (1a) a polyamide having a hydrophilic structure is heated and dissolved in a solvent, and then (1b) a compound having an ethylenic double bond, (1c) a photopolymerization initiator, and other additives as necessary are added. It is preferable to obtain a first photosensitive resin layer composition solution for forming the first photosensitive resin layer by stirring and mixing. Examples of the solvent include water and a water/alcohol mixed solvent.
また、（２ａ）親水性構造を有するポリアミドを、溶媒に加熱溶解した後に、（２ｂ）エチレン性二重結合を有する化合物、（２ｃ）光重合開始剤、および必要に応じて（２ｅ）フッ素原子および／または珪素原子を有する撥インキ剤やその他添加剤を添加し、撹拌混合する。次いで、（２ｄ）無機微粒子を添加し、混合・分散することにより、第２の感光性樹脂層を形成する第２の感光性樹脂組成物分散液を得ることが好ましい。（２ｄ）無機微粒子の混合・分散方法としては、例えば、機械撹拌法、超音波分散法、高圧分散法、メディア分散法などが挙げられる。これらの中でも（２ｄ）無機微粒子の分散性を向上させる観点から、メディア分散法が好ましい。溶媒としては、水や、水／アルコール混合溶媒などが挙げられる。 In addition, after heating and dissolving (2a) a polyamide having a hydrophilic structure in a solvent, (2b) a compound having an ethylenic double bond, (2c) a photopolymerization initiator, and optionally (2e) a fluorine atom. And/or an ink repellent agent containing silicon atoms and other additives are added and mixed by stirring. Next, (2d) inorganic fine particles are preferably added, mixed and dispersed to obtain a second photosensitive resin composition dispersion that forms the second photosensitive resin layer. (2d) Examples of methods for mixing and dispersing inorganic fine particles include mechanical stirring, ultrasonic dispersion, high pressure dispersion, and media dispersion. Among these, (2d) media dispersion method is preferred from the viewpoint of improving the dispersibility of inorganic fine particles. Examples of the solvent include water and a water/alcohol mixed solvent.
必要により易接着層を有する支持体上に、第１の感光性樹脂組成物溶液を流延し、乾燥することにより、第１の感光性樹脂層を形成することができる。その後、第２の感光性樹脂組成物分散液を、第１の感光性樹脂層上に流延し、乾燥することにより、第２の感光性樹脂層を形成することができる。次に、必要により粘着防止層を有するカバーフィルムを第２の感光性樹脂層上に密着させることにより、印刷版原版を得ることができる。また、乾燥製膜により第１の感光性樹脂シートと第２の感光性樹脂シートを作製し、必要により易接着層を有する支持体と必要により粘着防止層を有するカバーフィルムとの間に、第１の感光性樹脂シートと第２の感光性樹脂シートを挟み、ラミネートすることによっても、印刷版積層体を得ることができる。 The first photosensitive resin layer can be formed by casting the first photosensitive resin composition solution on a support having an easily adhesive layer, if necessary, and drying the solution. Thereafter, a second photosensitive resin layer can be formed by casting the second photosensitive resin composition dispersion onto the first photosensitive resin layer and drying it. Next, a printing plate precursor can be obtained by closely adhering a cover film having an anti-adhesive layer on the second photosensitive resin layer if necessary. In addition, a first photosensitive resin sheet and a second photosensitive resin sheet are produced by dry film forming, and a second photosensitive resin sheet is formed between the support having an easily adhesive layer if necessary and the cover film having an anti-adhesive layer if necessary. A printing plate laminate can also be obtained by sandwiching a first photosensitive resin sheet and a second photosensitive resin sheet and laminating them.
次に、本発明に係る印刷版原版を用いたフレキソ印刷版の製造方法について説明する。本発明におけるフレキソ印刷版は、本発明に係る印刷版原版の感光性樹脂層を部分的に光硬化させる露光工程、および、感光性樹脂層の未硬化部分を、水を含む現像液により除去する現像工程を有する方法により得ることができる。 Next, a method for manufacturing a flexographic printing plate using the printing plate precursor according to the present invention will be explained. The flexographic printing plate of the present invention includes an exposure step in which the photosensitive resin layer of the printing plate precursor according to the present invention is partially photocured, and an uncured portion of the photosensitive resin layer is removed using a developer containing water. It can be obtained by a method including a developing step.
まず、露光工程について説明する。印刷版原版が感熱マスク層を有するいわゆるＣＴＰ版の場合、カバーフィルムを有する場合にはこれを剥離し、レーザー描画機を用いて原画フィルムに相当する像の描画を実施した後、紫外線照射することによって、感光性樹脂層を光硬化させる。印刷版原版が感熱マスク層を有しない場合は、原画フィルムを介して紫外線照射することによって、感光性樹脂層を光硬化させる。紫外線としては、波長３００～４００ｎｍの光が好ましく、紫外線照射に用いるランプとしては、例えば、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、キセノン灯、カーボンアーク灯、ケミカル灯などが挙げられる。特に微細な細線、独立点の再現性が要求される場合は、カバーフィルムの剥離前に支持体側から短時間露光（裏露光）することも可能である。 First, the exposure process will be explained. In the case where the printing plate precursor is a so-called CTP plate having a heat-sensitive mask layer, if it has a cover film, this is peeled off, an image corresponding to the original film is drawn using a laser drawing machine, and then ultraviolet rays are irradiated. The photosensitive resin layer is photocured. When the printing plate precursor does not have a heat-sensitive mask layer, the photosensitive resin layer is photocured by irradiating ultraviolet rays through the original film. The ultraviolet light preferably has a wavelength of 300 to 400 nm, and examples of lamps used for ultraviolet irradiation include high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc lamps, and chemical lamps. In particular, when reproducibility of fine lines and independent points is required, it is also possible to perform short exposure from the support side (back exposure) before peeling off the cover film.
次に、現像工程について説明する。露光した印刷版原版を現像液に浸漬し、ブラシ式現像装置またはスプレー式現像装置を用いて、感光性樹脂層の未硬化部分を、現像液により除去することにより、基板上にレリーフ像を形成することができる。現像液は、中性水が好ましい。必要に応じて界面活性剤などの添加剤を含有してもよいが、その含有量は５重量％以下が好ましい。現像時の現像液温は１５～４０℃が好ましい。 Next, the developing process will be explained. A relief image is formed on the substrate by immersing the exposed printing plate precursor in a developer and removing the uncured portion of the photosensitive resin layer with the developer using a brush developing device or a spray developing device. can do. The developer is preferably neutral water. If necessary, additives such as surfactants may be contained, but the content thereof is preferably 5% by weight or less. The developer temperature during development is preferably 15 to 40°C.
現像後、５０～７０℃において１０分間程度乾燥することが好ましい。また、必要に応じてさらに大気中または真空中において、活性光線を照射する後露光を行ってもよい。 After development, it is preferable to dry at 50 to 70°C for about 10 minutes. Further, if necessary, post-exposure may be performed by irradiating actinic rays in the air or vacuum.
次に、フレキソ印刷版を用いた印刷物の製造方法について説明する。前述の方法により得られたフレキソ印刷版表面にインキを付着させる工程、および、前記インキを被印刷体に転写する工程を含むことが好ましい。フレキソ印刷機としては、例えば、インラインタイプ、センタードラムタイプ、スタックタイプなどが挙げられる。 Next, a method for producing printed matter using a flexographic printing plate will be described. It is preferable to include the steps of attaching ink to the surface of the flexographic printing plate obtained by the above-described method, and transferring the ink to a printing medium. Examples of flexo printing machines include inline type, center drum type, and stack type.
インキとしては、水性インキ、紫外線硬化型インキが好ましい。水性インキとしては、例えば、市販の“アクワ”（登録商標）ＥＬが挙げられる。紫外線硬化型インキとしては、例えば、顔料、アクリルオリゴマー等の樹脂、アクリレートモノマー、重合開始剤などを含有するものが好ましい。より具体的には、例えば、市販のＰＨＡ（（株）Ｔ＆Ｋ ＴＯＫＡ製）、“ＦＬＡＳＨ ＤＲＹ”（登録商標、東洋インキ（株）製）、“ＵＶＡＦＬＥＸ”（登録商標）Ｙ７７（Ｚｅｌｌｅｒ＋Ｇｍｅｌｉｎ社製）などのフレキソ印刷用インキが挙げられる。 As the ink, water-based ink and ultraviolet curable ink are preferred. Examples of water-based inks include commercially available "Aqua" (registered trademark) EL. As the ultraviolet curable ink, for example, one containing a pigment, a resin such as an acrylic oligomer, an acrylate monomer, a polymerization initiator, etc. is preferable. More specifically, for example, commercially available PHA (manufactured by T&K TOKA Co., Ltd.), “FLASH DRY” (registered trademark, manufactured by Toyo Ink Co., Ltd.), “UVAFLEX” (registered trademark) Y77 (manufactured by Zeller+Gmelin), etc. Examples include flexo printing inks.
各実施例および比較例における評価方法を以下に示す。 Evaluation methods for each example and comparative example are shown below.
［無機微粒子の平均粒子径］
各実施例および比較例に用いた無機微粒子について、（株）堀場製作所製ＬＡ－５００を用い、分散媒に水を用いて、屈折率を１．１に設定して、メジアン径を測定した。
[Average particle diameter of inorganic fine particles]
The median diameter of the inorganic fine particles used in each Example and Comparative Example was measured using LA-500 manufactured by Horiba, Ltd., using water as a dispersion medium, and setting the refractive index to 1.1.
［す抜けおよび版面粘着］
各実施例および比較例により得られた印刷版原版を１０ｃｍ×１０ｃｍに切り出し、高輝度ケミカル灯（Ｐｈｉｌｉｐｓ社製ＴＬ－Ｋ ４０Ｗ／１０Ｒ）を用いて、支持体側から積算光量が７００ｍＪ／ｃｍ２程度になるように裏露光した。カバーフィルムを剥離し、赤外線に発光領域を有するファイバーレーザーを備えた外面ドラム式プレートセッター（エスコ・グラフィックス（株）製ＣＤＩ ＳＰＡＲＫ ２５３０）に、支持体側がドラムに接するように装着し、テストパターン（１７５線１％～５０％網点、１０ｃｍ×１０ｃｍベタ部を有する）を出力２．４Ｊ／ｃｍ２のレーザーで描画し、感熱マスク層から画像マスクを形成した。その後、大気下において、裏露光と同じく高輝度ケミカル灯ＴＬ－Ｋ ４０Ｗ／１０Ｒを用いて、積算光量が１２，０００ｍＪ／ｃｍ２程度になるように、画像マスク側から主露光を行った。その後、バッチ式露光現像機（Ｉｎｇｌｅｓｅ， ｓ．ｒ．ｌ．製Ｉｎｇｌｅｓｅ Ｗ４３）を用いて、２５℃に温度調整した水道水により８０秒間現像し、温度６０℃のオーブンにより１０分間乾燥し、次いで高輝度ケミカル灯ＴＬ－Ｋ ４０Ｗ／１０Ｒを用いて、積算光量が１２，０００ｍＪ／ｃｍ２程度になるように後露光し、フレキソ印刷版を得た。
[Throughout and plate adhesion]
The printing plate precursors obtained in each example and comparative example were cut into 10 cm x 10 cm pieces, and using a high-intensity chemical lamp (TL-K 40W/10R manufactured by Philips), the cumulative light amount from the support side was about 700 mJ/cm 2 I back-exposed it so that it looked like this. The cover film was peeled off, and the plate setter (CDI SPARK 2530, manufactured by Esco Graphics Co., Ltd.) was equipped with an external drum type plate setter equipped with a fiber laser that emits light in the infrared region, so that the support side was in contact with the drum, and a test pattern was created. (175 lines, 1% to 50% halftone dots, 10 cm x 10 cm solid area) was drawn using a laser with an output of 2.4 J/cm 2 to form an image mask from the heat-sensitive mask layer. Thereafter, in the atmosphere, main exposure was performed from the image mask side using a high-intensity chemical lamp TL-K 40W/10R as in the back exposure so that the cumulative light amount was about 12,000 mJ/cm 2 . Thereafter, using a batch type exposure and development machine (Inglese W43 manufactured by Inglese, s.r.l.), it was developed for 80 seconds with tap water whose temperature was adjusted to 25°C, dried for 10 minutes in an oven at a temperature of 60°C, and then Post-exposure was performed using a high-intensity chemical lamp TL-K 40W/10R so that the cumulative light amount was about 12,000 mJ/cm 2 to obtain a flexographic printing plate.
得られたフレキソ印刷版と、インキとしてＵＶフレキソ紅ＰＨＡ－ＬＯ３（（株）Ｔ＆Ｋ ＴＯＫＡ製）を用い、１，０００線のアニロックスロールを具備したフレキソ印刷機を用いて、７０ｍ／分の印刷速度で、アート紙に印刷した。フレキソ印刷版を版胴に密着させるクッションテープとして、厚さ０．３８μｍの“Ｓｏｆｔｐｒｉｎｔ”（登録商標）５２０１７（ＴＥＳＡ社製）を用いた。印圧を徐々に印可しながら、ベタ部のかすれがなくなる印圧から６０μｍ押し込んだ条件で固定した。１０，０００ｍ印刷後に、印刷物のベタ部１０ｃｍ×１０ｃｍの部分をルーペで観察し、インキが着肉していない点状の白抜け部の個数を計数した。 Using the obtained flexographic printing plate and UV flexographic red PHA-LO3 (manufactured by T&K TOKA Co., Ltd.) as ink, a flexographic printing machine equipped with a 1,000-line anilox roll was used at a printing speed of 70 m/min. So I printed it on art paper. "Softprint" (registered trademark) 52017 (manufactured by TESA) having a thickness of 0.38 μm was used as a cushion tape for tightly adhering the flexographic printing plate to the plate cylinder. The printing pressure was gradually applied and fixed at a pressure of 60 μm from the printing pressure at which the solid area was no longer blurred. After printing for 10,000 m, a 10 cm x 10 cm solid portion of the printed matter was observed with a magnifying glass, and the number of dotted white areas to which ink had not been applied was counted.
また、印刷後のフレキソ印刷版のベタ部表面を目視観察し、紙粉や異物の付着を観察した。 In addition, the surface of the solid area of the flexographic printing plate after printing was visually observed to observe the adhesion of paper dust and foreign matter.
［ベタ着肉性］
各実施例において上記す抜けおよび版面粘着の評価方法により得られた、１０，０００ｍ印刷後の印刷物のベタ部から無作為に選択した３２点について、反射濃度計（Ｘ－ｒｉｔｅ社のｅＸａｃｔ Ｂａｓｉｃ）を用いて、紅の印刷濃度を測定し、最大と最小の濃度差を算出した。
[Solid flesh adhesion]
In each example, 32 points randomly selected from the solid area of the printed matter after 10,000 m of printing obtained by the above evaluation method of through-through and plate adhesion were measured using a reflection densitometer (eXact Basic from X-rite). was used to measure the print density of red, and calculate the difference between the maximum and minimum density.
［製造例１：易接着層を有する支持体の作製］
飽和ポリエステル樹脂のトルエン溶液（東洋紡（株）製“バイロン”（登録商標）３１ＳＳ）２６０重量部およびベンゾインエチルエーテル（和光純薬工業（株）製ＰＳ－８Ａ）２重量部の混合物を、７０℃で２時間加熱した後、３０℃に冷却し、エチレングリコールジグリシジルエーテルジメタクリレート７重量部を加えて、２時間混合した。さらに、多価イソシアネート樹脂の酢酸エチル溶液（東ソー（株）製“コロネート”（登録商標）３０１５Ｅ）２５重量部および工業用接着剤（住友スリーエム（株）製ＥＣ－１３６８）１４重量部を添加して混合し、易接着層組成物溶液１を得た。
[Production Example 1: Preparation of support having an easily adhesive layer]
A mixture of 260 parts by weight of a toluene solution of saturated polyester resin (“Vylon” (registered trademark) 31SS manufactured by Toyobo Co., Ltd.) and 2 parts by weight of benzoin ethyl ether (PS-8A manufactured by Wako Pure Chemical Industries, Ltd.) was heated at 70°C. After heating for 2 hours, the mixture was cooled to 30°C, 7 parts by weight of ethylene glycol diglycidyl ether dimethacrylate was added, and the mixture was mixed for 2 hours. Furthermore, 25 parts by weight of an ethyl acetate solution of polyvalent isocyanate resin ("Coronate" (registered trademark) 3015E manufactured by Tosoh Corporation) and 14 parts by weight of an industrial adhesive (EC-1368 manufactured by Sumitomo 3M Ltd.) were added. and mixed to obtain an easy-adhesion layer composition solution 1.
ケン化度７８．５～８１．５モル％のポリビニルアルコール（日本合成化学工業（株）製“ゴーセノール”（登録商標）ＫＨ－１７）５０重量部を、アルコール混合物（日本アルコール（株）製“ソルミックス”（登録商標）Ｈ－１１）２００重量部および水２００重量部の混合溶媒中、７０℃で２時間混合した後、グリシジルメタクリレート（日油（株）製“ブレンマー”（登録商標）Ｇ）１．５重量部を添加して１時間混合し、さらにジメチルアミノエチルメタクリレート／２－ヒドロキシエチルメタクリレート共重合体（共栄社化学（株）製、重量比２／１）３重量部、ベンジルメチルケタール（チバ・ガイギー社製“イルガキュア”（登録商標）６５１）５重量部、プロピレングリコールジグリシジルエーテルの２アクリル酸付加物（共栄社化学（株）製エポキシエステル７０ＰＡ）２１重量部およびエチレングリコールジグリシジルエーテルジメタクリレート２０重量部を添加して９０分間混合し、５０℃に冷却した後、“メガファック”（登録商標）Ｆ－５５６（ＤＩＣ（株）製）を０．１重量部添加して３０分間混合し、易接着層組成物溶液２を得た。 50 parts by weight of polyvinyl alcohol with a degree of saponification of 78.5 to 81.5 mol % ("GOHSENOL" (registered trademark) KH-17, manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.) was mixed with an alcohol mixture (" After mixing at 70°C for 2 hours in a mixed solvent of 200 parts by weight of "Solmix" (registered trademark) H-11) and 200 parts by weight of water, glycidyl methacrylate ("Blemmer" (registered trademark) G manufactured by NOF Corporation) ) and mixed for 1 hour, and further added 3 parts by weight of dimethylaminoethyl methacrylate/2-hydroxyethyl methacrylate copolymer (manufactured by Kyoeisha Chemical Co., Ltd., weight ratio 2/1) and benzyl methyl ketal. ("Irgacure" (registered trademark) 651 manufactured by Ciba Geigy) 5 parts by weight, 21 parts by weight of diacrylic acid adduct of propylene glycol diglycidyl ether (epoxy ester 70PA manufactured by Kyoeisha Chemical Co., Ltd.) and ethylene glycol diglycidyl ether After adding 20 parts by weight of dimethacrylate and mixing for 90 minutes and cooling to 50°C, 0.1 part by weight of "Megafac" (registered trademark) F-556 (manufactured by DIC Corporation) was added and mixed for 30 minutes. These were mixed to obtain an easy-adhesion layer composition solution 2.
厚さ１８８μｍの“ルミラー”（登録商標）Ｔ６０（ポリエステル（ＰＥＴ）フィルム、東レ（株）製）上に、バーコーターを用いて、易接着層組成物溶液１を、乾燥後の厚さが３０μｍになるように塗布し、１８０℃のオーブンで３分間加熱して溶媒を除去し、易接着層１を形成した。次に、易接着層１上に、バーコーターを用いて、易接着層組成物溶液２を、乾燥後の厚さが２０μｍになるように塗布し、１３０℃のオーブンで３分間加熱して溶媒を除去し、易接着層２を形成した。これにより、易接着層２／易接着層１／ＰＥＴフィルムの積層構造を有する、易接着層を有する支持体を得た。 Using a bar coater, easy adhesion layer composition solution 1 was applied onto Lumirror (registered trademark) T60 (polyester (PET) film, manufactured by Toray Industries, Inc.) with a thickness of 188 μm to a thickness of 30 μm after drying. The adhesive layer 1 was formed by applying the adhesive layer so as to have the following properties and heating it in an oven at 180° C. for 3 minutes to remove the solvent. Next, on the easy-adhesive layer 1, using a bar coater, apply the easy-adhesive layer composition solution 2 so that the thickness after drying becomes 20 μm, and heat it in an oven at 130° C. for 3 minutes to remove the solvent. was removed to form an easily adhesive layer 2. Thereby, a support having an easily adhesive layer having a laminated structure of easily adhesive layer 2/easily adhesive layer 1/PET film was obtained.
［製造例２：感熱マスク層を有するカバーフィルムの作製］
ケン化度９１～９４モル％のポリビニルアルコール（日本合成化学工業（株）製“ゴーセノール”（登録商標）ＡＬ－０５）１１重量部を、水５５重量部、メタノール１５重量部、ｎ－プロパノール２０重量部の混合溶媒に溶解させ、剥離補助層用塗工液を得た。
[Production Example 2: Production of cover film having a heat-sensitive mask layer]
11 parts by weight of polyvinyl alcohol ("Gohsenol" (registered trademark) AL-05 manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.) with a degree of saponification of 91 to 94 mol%, 55 parts by weight of water, 15 parts by weight of methanol, and 20 parts by weight of n-propanol. The mixture was dissolved in parts by weight of a mixed solvent to obtain a coating liquid for a peeling auxiliary layer.
カーボンブラック（三菱化学（株）製ＭＡ－１００）２３重量部、アルコール不溶性のアクリル樹脂（三菱レイヨン（株）製“ダイヤナール”（登録商標）ＢＲ－９５）１重量部、可塑剤としてアセチルクエン酸トリブチル（（株）ジェイプラス製“ＡＴＢＣ”）６重量部およびジエチレングリコールモノエチルエーテルモノアセテート３０重量部を混合した後に、３本ロールミルを用いて混練分散させ、カーボンブラック分散液を得た。 23 parts by weight of carbon black (MA-100 manufactured by Mitsubishi Chemical Corporation), 1 part by weight of alcohol-insoluble acrylic resin (“Dyanal” (registered trademark) BR-95 manufactured by Mitsubishi Rayon Co., Ltd.), acetyl quench as a plasticizer. After mixing 6 parts by weight of tributyl acid ("ATBC" manufactured by J-Plus Co., Ltd.) and 30 parts by weight of diethylene glycol monoethyl ether monoacetate, the mixture was kneaded and dispersed using a three-roll mill to obtain a carbon black dispersion.
得られたカーボンブラック分散液に、エポキシ樹脂（旭チバ（株）製“アラルダイト”６０７１）２０重量部、メラミン樹脂（三井化学（株）製“ユーバン”（商標登録）６２）２７重量部、リン酸モノマー（共栄社化学（株）製“ライトエステル”Ｐ－１Ｍ）０．７重量部およびメチルイソブチルケトン１４０重量部を添加し、室温で３０分間撹拌した後、固形分濃度が３３質量％となるようにメチルイソブチルケトンをさらに添加し、感熱マスク層用塗工液を得た。 To the obtained carbon black dispersion, 20 parts by weight of epoxy resin (“Araldite” 6071 manufactured by Asahi Ciba Co., Ltd.), 27 parts by weight of melamine resin (“Yuban” (registered trademark) 62 manufactured by Mitsui Chemicals, Ltd.), and phosphorus were added. After adding 0.7 parts by weight of acid monomer ("Light Ester" P-1M manufactured by Kyoeisha Chemical Co., Ltd.) and 140 parts by weight of methyl isobutyl ketone and stirring at room temperature for 30 minutes, the solid content concentration becomes 33% by mass. Methyl isobutyl ketone was further added to obtain a coating solution for a heat-sensitive mask layer.
ケン化度７８～８２モル％のポリビニルアルコール（日本合成化学工業（株）製“ゴーセノール”（登録商標）ＫＬ－０５）１０重量部を水４０重量部、メタノール２０重量部、ｎ－プロパノール３０重量部に溶解させ、接着層用塗工液を得た。 10 parts by weight of polyvinyl alcohol with a degree of saponification of 78 to 82 mol% ("Gohsenol" (registered trademark) KL-05 manufactured by Nippon Gohsei Kagaku Kogyo Co., Ltd.) was mixed with 40 parts by weight of water, 20 parts by weight of methanol, and 30 parts by weight of n-propanol. A coating solution for an adhesive layer was obtained.
カバーフィルムとして、表面が粗面化処理されていない厚さ１００μｍのポリエステル（ＰＥＴ）フィルム（東レ（株）製“ルミラー”（登録商標）Ｓ１０）上に、バーコーターを用いて、上記剥離補助層用塗工液を、乾燥後の厚さが０．２５μｍになるように塗布し、１００℃で２５秒間乾燥し、剥離補助層を形成した。さらに、バーコーターを用いて、上記感熱マスク層用塗工液を、乾燥後の厚さが２．０μｍとなるように塗布し、１４０℃で３０秒間乾燥し、感熱マスク層を形成した。さらに、バーコーターを用いて、上記接着層用塗工液を、乾燥後の厚さが１．０μｍとなるように塗布し、１８０℃で３０秒間乾燥し、接着層／感熱マスク層／剥離補助層／カバーフィルムの積層構造を有する、感熱マスク層を有するカバーフィルムを得た。 As a cover film, the above peeling auxiliary layer was coated on a 100 μm thick polyester (PET) film (“Lumirror” (registered trademark) S10 manufactured by Toray Industries, Inc.) whose surface had not been roughened using a bar coater. The coating solution was applied so as to have a dry thickness of 0.25 μm, and dried at 100° C. for 25 seconds to form a peeling auxiliary layer. Furthermore, using a bar coater, the above coating liquid for a heat-sensitive mask layer was applied so that the thickness after drying was 2.0 μm, and dried at 140° C. for 30 seconds to form a heat-sensitive mask layer. Furthermore, using a bar coater, apply the above adhesive layer coating liquid so that the thickness after drying is 1.0 μm, dry at 180°C for 30 seconds, and apply the adhesive layer / thermal mask layer / peeling aid. A cover film with a heat-sensitive mask layer having a laminated structure of layer/cover film was obtained.
オルソクロマチックフィルターによる透過光を入射光とし、カバーフィルムをブランクとしてゼロ点補正して測定した接着層／感熱マスク層／剥離補助層の光学濃度は、３．６であった。 The optical density of the adhesive layer/thermal mask layer/peeling auxiliary layer was 3.6, which was measured using the transmitted light through the orthochromatic filter as incident light and zero point correction using the cover film as a blank.
［合成例１：親水性構造を有するポリアミドの合成］
数平均分子量６００のポリエチレングリコールの両末端にアクリロニトリルを付加し、これを水素還元して得たα，ω－ジアミノポリオキシエチレンとアジピン酸との等モル塩８０重量部、ε－カプロラクタム２０重量部を溶融重合し、主鎖エチレングリコール骨格を有するポリアミドを得た。
[Synthesis Example 1: Synthesis of polyamide with hydrophilic structure]
80 parts by weight of an equimolar salt of α,ω-diaminopolyoxyethylene and adipic acid obtained by adding acrylonitrile to both ends of polyethylene glycol having a number average molecular weight of 600 and reducing it with hydrogen, and 20 parts by weight of ε-caprolactam. was melt-polymerized to obtain a polyamide having a main chain ethylene glycol skeleton.
得られたポリアミド３．０ｇをヘキサフルオロイソプロパノール５ｍＬに溶解し、標準サンプルとして、単分散ポリメチルメタクリレート（昭和電工（株）製）を用い、Ｗｙａｔｔ Ｔｅｃｈｎｏｌｏｇｙ製ゲル浸透クロマトグラフ－多角度光散乱光度計を用いて、カラム温度：４０℃、流速：０．７ｍＬ／分の条件で重量平均分子量を測定した結果、１１．５万であった。 3.0 g of the obtained polyamide was dissolved in 5 mL of hexafluoroisopropanol, and monodisperse polymethyl methacrylate (manufactured by Showa Denko K.K.) was used as a standard sample, and a gel permeation chromatograph-multiangle light scattering photometer manufactured by Wyatt Technology was used. The weight average molecular weight was measured using a column temperature of 40° C. and a flow rate of 0.7 mL/min, and the result was 115,000.
（実施例１）
撹拌用ヘラおよび冷却管を取り付けた３つ口フラスコ中に、合成例１により得られた親水性構造を有するポリアミド ６５質量部、相溶化剤としてＰＥＧ－１０００（平均分子量１，０００のポリエチレングリコール、三洋化成工業（株）製） １０質量部、溶媒としてアルコール混合物（日本アルコール（株）製“ソルミックス”（登録商標）Ｈ－１１） １０質量部および蒸留水 ３０質量部を入れ、撹拌しながら７７℃で２時間加熱し、親水性構造を有するポリアミドを溶解させた後、グリシジメタクリレート ３質量部を添加し、３０分間撹拌し、親水性構造を有するポリアミドにグリシジルメタクリレートを付加させた。
(Example 1)
In a three-necked flask equipped with a stirring spatula and a cooling tube, 65 parts by mass of the polyamide having a hydrophilic structure obtained in Synthesis Example 1, PEG-1000 (polyethylene glycol with an average molecular weight of 1,000, Sanyo Chemical Industries, Ltd.)), 10 parts by mass of an alcohol mixture ("Solmix" (registered trademark) H-11, manufactured by Nippon Alcohol Co., Ltd.) as a solvent, and 30 parts by mass of distilled water were added, while stirring. After heating at 77°C for 2 hours to dissolve the polyamide having a hydrophilic structure, 3 parts by mass of glycidium methacrylate was added and stirred for 30 minutes to add glycidyl methacrylate to the polyamide having a hydrophilic structure.
次いで、７０℃に冷却した後に、（１ｂ）エチレン性二重結合を有する化合物としてポリエチレングリコールモノメタクリレート（日油（株）製“ブレンマー”（登録商標）ＡＥ４００） １０質量部およびトリプロピレングリコールのグリシジルアクリレートの１：２付加物（水酸基２官能、日油（株）製“エポキシエステル”（商標登録）２００ＰＡ） １０質量部、（１ｃ）光重合開始剤としてベンジルジメチルケタール １．３質量部、紫外線吸収剤として２－（２’－ヒドロキシ－３’－ｔ－ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール ０．０５質量部を添加して３０分間撹拌し、第１の感光性樹脂層組成物溶液を得た。 Then, after cooling to 70° C., (1b) 10 parts by mass of polyethylene glycol monomethacrylate (“Blenmar” (registered trademark) AE400 manufactured by NOF Corporation) as a compound having an ethylenic double bond and glycidyl tripropylene glycol were added. 1:2 adduct of acrylate (bifunctional hydroxyl group, "Epoxy Ester" (registered trademark) 200PA manufactured by NOF Corporation) 10 parts by mass, (1c) 1.3 parts by mass of benzyl dimethyl ketal as photopolymerization initiator, ultraviolet rays 0.05 parts by mass of 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole was added as an absorbent and stirred for 30 minutes to form the first photosensitive resin. A layer composition solution was obtained.
撹拌用ヘラおよび冷却管を取り付けた３つ口フラスコ中に、合成例１により得られた親水性構造を有するポリアミド ６５質量部、相溶化剤としてＰＥＧ－１０００（平均分子量１，０００のポリエチレングリコール、三洋化成工業（株）製） １０質量部、溶媒としてアルコール混合物（日本アルコール（株）製“ソルミックス”（登録商標）Ｈ－１１） ２０質量部および蒸留水 ６０質量部を入れ、撹拌しながら７７℃で２時間加熱し、親水性構造を有するポリアミド１を溶解させた後、グリシジメタクリレート ３質量部を添加し、３０分間撹拌し、親水性構造を有するポリアミドにグリシジルメタクリレートを付加させた。 In a three-necked flask equipped with a stirring spatula and a cooling tube, 65 parts by mass of the polyamide having a hydrophilic structure obtained in Synthesis Example 1, PEG-1000 (polyethylene glycol with an average molecular weight of 1,000, 10 parts by mass of Sanyo Chemical Industries, Ltd.), 20 parts by mass of an alcohol mixture ("Solmix" (registered trademark) H-11, manufactured by Nippon Alcohol Co., Ltd.) as a solvent, and 60 parts by mass of distilled water were added, and while stirring. After heating at 77°C for 2 hours to dissolve polyamide 1 having a hydrophilic structure, 3 parts by mass of glycidium methacrylate was added and stirred for 30 minutes to add glycidyl methacrylate to the polyamide having a hydrophilic structure.
次いで、７０℃に冷却した後に、（２ｂ）エチレン性二重結合を有する化合物としてポリエチレングリコールモノメタクリレート（日油（株）製“ブレンマー”（登録商標）ＡＥ４００） １０質量部およびトリプロピレングリコールのグリシジルアクリレートの１：２付加物（水酸基２官能、日油（株）製“エポキシエステル”（商標登録）２００ＰＡ） １０質量部、（２ｃ）光重合開始剤としてベンジルジメチルケタール １．３質量部、（２ｄ）無機微粒子として非晶質シリカ微粒子（（株）アドマテックス製ＳＣ－２５００ＳＱ、平均粒子径：０．５μｍ） ３０質量部、（２ｅ）撥インキ剤としてフルオロアルキル基を有するフッ素含有４級アンモニウム塩化合物（（株）ネオス製“フタージェント”（登録商標）３２０）０．６質量部、紫外線吸収剤として２－（２’－ヒドロキシ－３’－ｔ－ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール ０．０５質量部を添加して６０分間撹拌した。続いて、２５℃まで冷却した後、連続型メディア分散機（浅田鉄工（株）製ＮＡＮＯ ＧＲＡＩＮ ＭＩＬＬ）を用いて分散し、第２の感光性樹脂層組成物分散液を得た。 Then, after cooling to 70° C., (2b) 10 parts by mass of polyethylene glycol monomethacrylate (“Blemmer” (registered trademark) AE400 manufactured by NOF Corporation) as a compound having an ethylenic double bond and glycidyl tripropylene glycol. 10 parts by mass of a 1:2 adduct of acrylate (bifunctional hydroxyl group, "Epoxy Ester" (registered trademark) 200PA manufactured by NOF Corporation), (2c) 1.3 parts by mass of benzyl dimethyl ketal as a photopolymerization initiator, ( 2d) 30 parts by mass of amorphous silica fine particles (SC-2500SQ manufactured by Admatex Co., Ltd., average particle diameter: 0.5 μm) as inorganic fine particles, (2e) fluorine-containing quaternary ammonium having a fluoroalkyl group as an ink repellent 0.6 parts by mass of a salt compound (“Ftergent” (registered trademark) 320 manufactured by Neos Co., Ltd.), 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)- as an ultraviolet absorber 0.05 parts by mass of 5-chlorobenzotriazole was added and stirred for 60 minutes. Subsequently, after cooling to 25° C., the mixture was dispersed using a continuous media dispersion machine (NANO GRAIN MILL manufactured by Asada Tekko Co., Ltd.) to obtain a second photosensitive resin layer composition dispersion.
製造例１により得られた易接着層を有する支持体上に、前述の方法により得られた第１の感光性樹脂層組成物溶液を流延し、６５℃で３．５時間乾燥し、厚さ８７０μｍの第１の感光性樹脂層を形成した。第１の感光性樹脂層の厚みは、易接着層を有する支持体上に所定の厚みのスペーサーを置き、はみ出している部分の第１の感光性樹脂層組成物溶液を、水平な金尺で掻き出すことによって調整した。 The first photosensitive resin layer composition solution obtained by the above-mentioned method was cast onto the support having the easy-adhesive layer obtained in Production Example 1, and dried at 65°C for 3.5 hours. A first photosensitive resin layer having a thickness of 870 μm was formed. The thickness of the first photosensitive resin layer can be determined by placing a spacer of a predetermined thickness on a support having an easily adhesive layer, and using a horizontal metal ruler to measure the protruding portion of the first photosensitive resin layer composition solution. It was adjusted by scraping it out.
次に、第１の感光性樹脂層上に、前述の方法により得られた第２の感光性樹脂組成物分散液を流延し、６０℃で２時間乾燥し、厚さ５０μｍの第２の感光性樹脂層を形成した。第２の感光性樹脂層の厚みは、第２の感光性樹脂層上に所定の厚みのスペーサーを置き、はみ出している部分の第２の感光性樹脂層組成物分散液を、水平な金尺で掻き出すことによって調整した。 Next, the second photosensitive resin composition dispersion obtained by the method described above was cast onto the first photosensitive resin layer, dried at 60°C for 2 hours, and a second photosensitive resin composition having a thickness of 50 μm was cast. A photosensitive resin layer was formed. The thickness of the second photosensitive resin layer can be determined by placing a spacer with a predetermined thickness on the second photosensitive resin layer, and dispersing the second photosensitive resin layer composition dispersion in the protruding portion on a horizontal metal scale. It was adjusted by scraping it out.
その後、第２の感光性樹脂層上に、水５０質量部／エタノール５０質量部の混合溶媒を塗布し、製造例２により得られた感熱マスク層を有するカバーフィルムを、接着層が第２の感光性樹脂層側となるように圧着し、印刷版原版１を得た。 Thereafter, a mixed solvent of 50 parts by mass of water/50 parts by mass of ethanol was applied onto the second photosensitive resin layer, and the cover film having the heat-sensitive mask layer obtained in Production Example 2 was applied to the second photosensitive resin layer. The printing plate precursor 1 was obtained by pressure-bonding the photosensitive resin layer side.
得られた印刷版原版１を用いて前述の方法により評価したところ、白抜け個数は５個です抜けが抑制されており、印刷後のフレキソ印刷版のベタ部表面に、紙粉や異物の付着は認められず、版面粘着が抑制されていた。ベタ部の印刷濃度差は０．０２であり、ベタ着肉性は均一であった。 When the obtained printing plate precursor 1 was evaluated using the method described above, the number of white spots was 5. The number of blank spots was suppressed, and there was no adhesion of paper powder or foreign matter on the solid surface of the flexo printing plate after printing. was not observed, and plate adhesion was suppressed. The printing density difference in the solid area was 0.02, and the solid ink adhesion was uniform.
（比較例１）
第１の感光性樹脂層の厚さを９２０μｍに変更し、第２の感光性樹脂層を設けなかったこと以外は実施例１と同様にして印刷版原版２を得た。得られた印刷版原版２を用いて前述の方法により評価したところ、白抜け個数は１００個以上であり、印刷後のフレキソ印刷版のベタ部表面には、無数の紙粉や異物が付着していた。
(Comparative example 1)
A printing plate precursor 2 was obtained in the same manner as in Example 1 except that the thickness of the first photosensitive resin layer was changed to 920 μm and the second photosensitive resin layer was not provided. When the obtained printing plate precursor 2 was evaluated by the method described above, the number of white spots was 100 or more, and countless paper dust and foreign substances were attached to the solid surface of the flexo printing plate after printing. was.
（実施例２）
第２の感光性樹脂層中の（２ｄ）無機微粒子を、非晶質シリカ微粒子（デンカ（株）製、ＦＢ－５ＤＭ、平均粒子径：３．０μｍ）に変更したこと以外は実施例１と同様にして、印刷版原版３を得た。得られた印刷版原版３を用いて前述の方法により評価したところ、白抜け個数は３個です抜けが抑制されており、印刷後のフレキソ印刷版のベタ部表面に、紙粉や異物は認められず、版面粘着が抑制されていた。ベタ部の印刷濃度差は０．０２であり、ベタ着肉性は均一であった。
(Example 2)
Same as Example 1 except that (2d) inorganic fine particles in the second photosensitive resin layer were changed to amorphous silica fine particles (manufactured by Denka Corporation, FB-5DM, average particle diameter: 3.0 μm). A printing plate precursor 3 was obtained in the same manner. When the obtained printing plate precursor 3 was evaluated using the method described above, the number of white spots was 3, indicating that voids were suppressed, and no paper powder or foreign matter was observed on the solid surface of the flexo printing plate after printing. The plate surface adhesion was suppressed. The printing density difference in the solid area was 0.02, and the solid ink adhesion was uniform.
（実施例３）
第２の感光性樹脂層中の（２ｄ）無機微粒子を、非晶質シリカ微粒子（（株）アドマテックス製、ＦＥ９２０Ｇ－ｓＱ、平均粒子径：５．０μｍ）に変更したこと以外は実施例１と同様にして、印刷版原版４を得た。得られた印刷版原版４を用いて前述の方法により評価したところ、白抜け個数は１０個です抜けが抑制されており、印刷後のフレキソ印刷版のベタ部表面に、紙粉や異物は認められず、版面粘着が抑制されていた。ベタ部の印刷濃度差は０．０２であり、ベタ着肉性は均一であった。
(Example 3)
Example 1 except that (2d) inorganic fine particles in the second photosensitive resin layer were changed to amorphous silica fine particles (manufactured by Admatex Co., Ltd., FE920G-sQ, average particle diameter: 5.0 μm). In the same manner as above, a printing plate precursor 4 was obtained. When the obtained printing plate precursor 4 was evaluated according to the method described above, the number of white spots was 10.The number of blank spots was suppressed, and no paper dust or foreign matter was observed on the surface of the solid area of the flexo printing plate after printing. The plate surface adhesion was suppressed. The printing density difference in the solid area was 0.02, and the solid ink adhesion was uniform.
（実施例４）
第１の感光性樹脂層の厚さ（Ｔ１）を８７０μｍから９１５μｍに、第２の感光性樹脂層の厚さ（Ｔ２）を５０μｍから５μｍに変更した以外は実施例２と同様にして、印刷版原版５を得た。得られた印刷版原版５を用いて前述の方法により評価したところ、白抜け個数は２０個です抜けが抑制されており、印刷後のフレキソ印刷版のベタ部表面に、少し紙粉や異物が確認された。ベタ部の印刷濃度差は０．０２であり、ベタ着肉性は均一であった。
(Example 4)
Printing was carried out in the same manner as in Example 2, except that the thickness (T1) of the first photosensitive resin layer was changed from 870 μm to 915 μm, and the thickness (T2) of the second photosensitive resin layer was changed from 50 μm to 5 μm. Original version 5 was obtained. When the obtained printing plate precursor 5 was evaluated using the method described above, the number of white spots was 20.The number of blank spots was suppressed, and there were no paper dust or foreign matter on the solid surface of the flexo printing plate after printing. confirmed. The printing density difference in the solid area was 0.02, and the solid ink adhesion was uniform.
（実施例５）
第１の感光性樹脂層の厚さ（Ｔ１）を８７０μｍから９０５μｍに、第２の感光性樹脂層の厚さ（Ｔ２）を５０μｍから１５μｍに変更した以外は実施例２と同様にして、印刷版原版６を得た。得られた印刷版原版６を用いて前述の方法により評価したところ、白抜け個数は８個です抜けが抑制されており、印刷後のフレキソ印刷版のベタ部表面に、紙粉や異物は認められず、版面粘着が抑制されていた。ベタ部の印刷濃度差は０．０２であり、ベタ着肉性は均一であった。
(Example 5)
Printing was carried out in the same manner as in Example 2, except that the thickness (T1) of the first photosensitive resin layer was changed from 870 μm to 905 μm, and the thickness (T2) of the second photosensitive resin layer was changed from 50 μm to 15 μm. I got the original version 6. When the obtained printing plate precursor 6 was evaluated using the method described above, the number of white spots was 8, indicating that voids were suppressed, and no paper dust or foreign matter was observed on the surface of the solid area of the flexographic printing plate after printing. The plate surface adhesion was suppressed. The printing density difference in the solid area was 0.02, and the solid ink adhesion was uniform.
（実施例６）
第１の感光性樹脂層の厚さ（Ｔ１）を８７０μｍから７２０μｍに、第２の感光性樹脂層の厚さ（Ｔ２）を５０μｍから２００μｍに変更した以外は実施例２と同様にして、印刷版原版７を得た。得られた印刷版原版６を用いて前述の方法により評価したところ、白抜け個数は３個です抜けが抑制されており、印刷後のフレキソ印刷版のベタ部表面に、紙粉や異物は認められず、版面粘着が抑制されていた。ベタ部の印刷濃度差は０．０８であり、わずかに濃度ムラが認められた。
(Example 6)
Printing was carried out in the same manner as in Example 2, except that the thickness (T1) of the first photosensitive resin layer was changed from 870 μm to 720 μm, and the thickness (T2) of the second photosensitive resin layer was changed from 50 μm to 200 μm. I got the original version 7. When the obtained printing plate precursor 6 was evaluated according to the method described above, the number of white spots was 3, indicating that voids were suppressed, and no paper dust or foreign matter was observed on the solid surface of the flexo printing plate after printing. The plate surface adhesion was suppressed. The printing density difference in the solid area was 0.08, and slight density unevenness was observed.
Claims (6)
第１の感光性樹脂層が、少なくとも、（１ａ）親水性構造を有するポリアミド、（１ｂ）エチレン性二重結合を有する化合物および（１ｃ）光重合開始剤を含有し、無機微粒子を実質的に含有せず、
第２の感光性樹脂層が、少なくとも（２ａ）親水性構造を有するポリアミド、（２ｂ）エチレン性二重結合を有する化合物、（２ｃ）光重合開始剤および（２ｄ）無機微粒子を含有する感光性フレキソ印刷版原版。 A photosensitive flexographic printing plate precursor having at least a first photosensitive resin layer and a second photosensitive resin layer in this order on a support,
The first photosensitive resin layer contains at least (1a) a polyamide having a hydrophilic structure, (1b) a compound having an ethylenic double bond, and (1c) a photopolymerization initiator, and substantially contains inorganic fine particles. Contains no
The second photosensitive resin layer contains at least (2a) a polyamide having a hydrophilic structure, (2b) a compound having an ethylenic double bond, (2c) a photopolymerization initiator, and (2d) inorganic fine particles. Flexo printing plate original plate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022028979A JP2023125062A (en) | 2022-02-28 | 2022-02-28 | Photosensitive flexographic printing original plate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022028979A JP2023125062A (en) | 2022-02-28 | 2022-02-28 | Photosensitive flexographic printing original plate |
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| Publication Number | Publication Date |
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| JP2023125062A true JP2023125062A (en) | 2023-09-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022028979A Pending JP2023125062A (en) | 2022-02-28 | 2022-02-28 | Photosensitive flexographic printing original plate |
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| JP (1) | JP2023125062A (en) |
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