WO2010074210A1 - Relief printing original plate for laser engraving and relief printing plate obtained therefrom - Google Patents
Relief printing original plate for laser engraving and relief printing plate obtained therefrom Download PDFInfo
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- WO2010074210A1 WO2010074210A1 PCT/JP2009/071554 JP2009071554W WO2010074210A1 WO 2010074210 A1 WO2010074210 A1 WO 2010074210A1 JP 2009071554 W JP2009071554 W JP 2009071554W WO 2010074210 A1 WO2010074210 A1 WO 2010074210A1
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- photosensitive resin
- laser engraving
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- original plate
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Abstract
Provided are a relief printing original plate for laser engraving capable of producing a printing plate which can prevent a printing failure at the time of high speed printing and is superior in resolution, a cured relief printing original plate for laser engraving, and a photosensitive resin relief printing plate.
The relief printing original plate for laser engraving is used for forming a printing plate by curing, with ultraviolet irradiation, a photosensitive resin composition layer obtained from a photosensitive resin composition comprising at least a soluble synthetic polymer, a photopolymerized unsaturated compound, and a photopolymerization initiator as main components, and thereafter, by forming an image by irradiating a laser beam, and is characterized by the fact that the photosensitive resin composition layer is formed by the photosensitive resin composition comprising polyether urea-urethane as a soluble synthetic polymer, an ethylene-based unsaturated monomer as a photopolymerized unsaturated compound, and a photopolymerization initiator, as essential components, and a content of a (meta) acryloyl group in the photosensitive resin composition is 2.2-3.7 mol inclusive in 1000 grams of mass of the photosensitive resin composition.
Description
本発明は、レーザー光照射により画像形成して印刷版を形成するレーザー彫刻用凸版印刷原版およびそれを用いて得られる凸版印刷版に関するものである。
The present invention relates to a letterpress printing original plate for laser engraving for forming a printing plate by forming an image by laser light irradiation, and a letterpress printing plate obtained using the same.
各種包装材やシール、ラベル印刷、他、多種の印刷に使用される凸版印刷版は、従来、感光性樹脂からなる印刷原版を像に従って露光して露光部の樹脂を架橋させ、次いで非露光部の未架橋樹脂を洗浄除去することにより製造されていたが、近年、印刷版製造の効率改善のため、レーザーを使って直接印刷原版上にレリーフ画像を形成するレーザー彫刻による印刷版が普及しつつある。レーザー彫刻による印刷版の製造工程では、レーザー光線を像に従って印刷原版に照射して照射部分の像形成材料を分解することにより版表面に凹凸が形成される。
A relief printing plate used for various packaging materials, seals, label printing, and other various types of printing is conventionally exposed to a printing original plate made of a photosensitive resin according to an image to crosslink the resin in the exposed portion, and then to the non-exposed portion. In recent years, printing plates by laser engraving that form a relief image directly on a printing original plate using a laser are becoming popular in order to improve the efficiency of printing plate production in recent years. is there. In the printing plate manufacturing process by laser engraving, unevenness is formed on the plate surface by irradiating the printing original plate with a laser beam according to the image to decompose the image forming material in the irradiated portion.
レーザー彫刻用の印刷原版としては、フレキソ版への技術応用が進んでおり、レーザー彫刻可能なフレキソ版原版、あるいはレーザー彫刻によって得られたフレキソ版が特許文献１及び２に開示されている。それらの文献には、バインダーとしてエラストマー性のゴムにモノマーを混合してフレキソ印刷原版を製造し、熱架橋又は光架橋により硬化させた後にレーザー彫刻を行い、フレキソ印刷版を得ている。しかし、これらは水性インキやエステルインキに適性のあるフレキソ印刷版であり、油性インキが主に用いられる樹脂凸版用途には適するものではない。一方、凸版印刷に用いるレーザー彫刻用印刷原版としては、ポリビニルアルコール又は変成ポリビニルアルコールやポリエーテルポリアミドなどの可溶性高分子に光重合性化合物及び光重合開始剤を配合した樹脂組成物からなるものが特許文献３～５に開示されている。
As a printing original plate for laser engraving, technical application to a flexographic plate is progressing, and a flexographic original plate capable of laser engraving or a flexographic plate obtained by laser engraving is disclosed in Patent Documents 1 and 2. In these documents, a flexographic printing plate precursor is produced by mixing a monomer with elastomeric rubber as a binder, and is cured by thermal crosslinking or photocrosslinking, followed by laser engraving to obtain a flexographic printing plate. However, these are flexographic printing plates suitable for water-based inks and ester inks, and are not suitable for resin letterpress applications in which oil-based inks are mainly used. On the other hand, as a printing original plate for laser engraving used for letterpress printing, there is a patent consisting of a resin composition in which a photopolymerizable compound and a photopolymerization initiator are blended with a soluble polymer such as polyvinyl alcohol or modified polyvinyl alcohol or polyether polyamide. Documents 3-5 disclose.
しかしながら、凸版印刷に用いるレーザー彫刻用印刷原版としては、レーザー彫刻性と印刷性能との両者を満足できる印刷原版が得られていなかった。レーザー彫刻時の問題点としては、レーザー照射により生じた樹脂カスがレーザー照射中の吸引やレーザー照射後の洗浄でも除去されずに版に付着したまま残りやすいことが最大の課題であり、印刷版のレーザー非照射部分（凸部分）に付着した樹脂カスが印刷時にインクを受理して印刷不良を起こしやすくしていた。上記樹脂カス付着の課題に対しては、シリカ微粉末などの無色透明の充填剤を配合する方法（特許文献６参照）により印刷原版の機械的特性を向上させ、結果として粘着性や微細部の溶融を減少させる技術が提案されている。しかしながら、シリカ微粉末などの充填剤を配合する方法は、印刷原版の粘着性を十分に低下させるためには多量の充填剤が必要となり、印刷原版の成型性や版物性を著しく損なうという問題があった。
However, as a printing original plate for laser engraving used for letterpress printing, a printing original plate satisfying both laser engraving property and printing performance has not been obtained. The biggest problem with laser engraving is that the resin residue generated by laser irradiation tends to remain on the plate without being removed by suction during laser irradiation or cleaning after laser irradiation. The resin residue adhering to the non-irradiated part (convex part) of the ink received ink at the time of printing and easily caused printing defects. For the problem of adhesion of the resin residue, the mechanical properties of the printing original plate are improved by a method of blending a colorless and transparent filler such as silica fine powder (see Patent Document 6). Techniques have been proposed to reduce melting. However, the method of blending a filler such as silica fine powder requires a large amount of filler in order to sufficiently reduce the adhesiveness of the printing original plate, and there is a problem that the moldability and physical properties of the printing original plate are remarkably impaired. there were.
このように、従来技術の充填剤添加方法では印刷原版の成型性や版物性に悪影響を与えるので、充填剤を添加せずに印刷原版の粘着性を低減でき且つ微細部形成性を向上したレーザー彫刻用原版が待ち望まれていた。
As described above, the conventional filler addition method adversely affects the moldability and plate physical properties of the printing original plate. Therefore, it is possible to reduce the adhesiveness of the printing original plate without adding a filler and to improve the fine part forming property. A master for sculpture was awaited.
本発明は、かかる従来技術の現状に鑑み創案されたものであり、その目的は高速印刷時にも印刷不良を生じず、かつ解像度に優れた印刷版を製造できるレーザー彫刻用凸版印刷原版、レーザー彫刻用硬化済み凸版印刷原版および感光性樹脂凸版印刷版を提供することである。
The present invention was devised in view of the current state of the prior art, and the purpose thereof is a letterpress printing original plate for laser engraving, which can produce a printing plate that does not cause printing defects even during high-speed printing and has excellent resolution, and laser engraving. It is to provide a cured relief printing original plate and a photosensitive resin relief printing plate.
本発明者らは、かかる目的を達成するために好適な樹脂組成物の組成について鋭意検討した結果、本発明を完成するに至った。即ち、本発明は（１）少なくとも可溶性合成高分子化合物、光重合性不飽和化合物、光重合開始剤を基本成分とする感光性樹脂組成物から得られる感光性樹脂組成物層を紫外線照射によって硬化させた後にレーザー光照射により画像形成して印刷版を形成するレーザー彫刻用凸版印刷原版において、前記感光性樹脂層が可溶性合成高分子化合物としてポリエーテルウレアウレタン、光重合性不飽和化合物としてエチレン性不飽和モノマーおよび光重合開始剤を必須成分とする前記感光性樹脂組成物からなり、前記感光性樹脂組成物中の（メタ）アクリロイル基の含有量が前記感光性樹脂組成物１０００質量グラム当り２．２モル以上３．７モル以下含有すること特徴とするレーザー彫刻用凸版印刷原版、（２）前記エチレン性不飽和モノマーが少なくとも２個以上のアクリロイル基またはメタクリロイル基を有し、且つ、前記感光性樹脂組成物中に２０質量％～４５質量％含まれることを特徴とする（１）のレーザー彫刻用印刷原版、（３）前記エチレン性不飽和モノマーが、多価アルコールのポリグリシジルエーテルとメタクリル酸あるいはアクリル酸との開環付加反応生成物を含むことを特徴とする（１）又は（２）のレーザー彫刻用印刷原版、（４）ポリエーテルウレタンウレアが塩基性第３級窒素原子を含有し、ポリエーテルウレタンウレア１０００質量グラム中に塩基性第３級窒素原子を０．５０～２．００モル含有し、数平均分子量が４００～１５００のポリエチレングリコールをソフトセグメントとするブロック共重合体であることを特徴とする（１）～（３）に記載のレーザー彫刻用印刷原版、（５）ポリエーテルウレタンウレアがプロトン性四級化剤によって２５モル％以上を４級化された塩基性第３級窒素原子を含有することを特徴とする（４）のレーザー彫刻用印刷原版、（６）（１)～(５）のレーザー彫刻用印刷原版より得られることを特徴とする感光性樹脂凸版印刷版である。
As a result of intensive studies on the composition of a resin composition suitable for achieving the above object, the present inventors have completed the present invention. That is, the present invention (1) cures a photosensitive resin composition layer obtained from a photosensitive resin composition containing at least a soluble synthetic polymer compound, a photopolymerizable unsaturated compound, and a photopolymerization initiator as basic components by ultraviolet irradiation. In a letterpress printing original plate for laser engraving that forms a printing plate by forming an image by irradiating with a laser beam, the photosensitive resin layer is composed of polyether urea urethane as a soluble synthetic polymer compound and ethylenic as a photopolymerizable unsaturated compound It consists of the said photosensitive resin composition which has an unsaturated monomer and a photoinitiator as an essential component, and content of the (meth) acryloyl group in the said photosensitive resin composition is 2 per 1000 mass grams of the said photosensitive resin composition. 2. A letterpress printing original plate for laser engraving characterized by containing from 2 mol to 3.7 mol, (2) the ethylenically unsaturated monomer (1) a printing original plate for laser engraving according to (1), which has at least two acryloyl groups or methacryloyl groups, and is contained in the photosensitive resin composition in an amount of 20 to 45% by mass; The ethylenically unsaturated monomer contains a ring-opening addition reaction product of polyglycidyl ether of polyhydric alcohol and methacrylic acid or acrylic acid. (1) or (2) printing master for laser engraving (4) The polyether urethane urea contains a basic tertiary nitrogen atom, and 0.50 to 2.00 mol of the basic tertiary nitrogen atom in 1000 mass grams of the polyether urethane urea, the number average (1) to (3), which is a block copolymer having a soft segment of polyethylene glycol having a molecular weight of 400 to 1500 (5) The polyether urethane urea contains a basic tertiary nitrogen atom quaternized by 25 mol% or more with a protic quaternizing agent (4) A photosensitive resin relief printing plate obtained from the laser engraving printing original plate (6), (1) to (5).
また、本発明は、（７）（１）～（５）のいずれかに記載のレーザー彫刻用印刷原版に紫外線を照射し、感光性樹脂組成物層中の（メタ）アクリロイル基含有量を紫外線照射前の３０モル％未満としたレーザー彫刻用硬化済み凸版印刷原版、（８）（１）～（５）のいずれかに記載のレーザー彫刻用印刷原版に紫外線を照射し、感光性樹脂組成物層中の（メタ）アクリロイル基含有量を、前記感光性樹脂組成物１０００質量グラム中に１モル未満としたレーザー彫刻用硬化済み凸版印刷原版、（９）少なくとも可溶性合成高分子化合物、光重合性不飽和化合物、光重合開始剤を基本成分とする感光性樹脂組成物から得られる感光性樹脂組成物層を紫外線照射によって硬化させたレーザー彫刻用硬化済み印刷原版であって、
紫外線照射後の感光性樹脂組成物層が可溶性合成高分子化合物としてポリエーテルウレアウレタン、光重合性不飽和化合物としてエチレン性不飽和モノマー、および前記エチレン性不飽和モノマーのラジカル重合反応生成物を含有し、紫外線照射後の感光性樹脂組成物層中の（メタ）アクリロイル基の含有量が前記感光性樹脂組成物１０００質量グラム中に１モル未満であることを特徴とするレーザー彫刻用硬化済み凸版印刷原版、（１０）（７）～（９）のいずれかに記載のレーザー彫刻用硬化済み凸版印刷原版より得られることを特徴とする感光性樹脂凸版印刷版、である。 In the present invention, the laser engraving printing original plate described in any one of (7) (1) to (5) is irradiated with ultraviolet rays, and the (meth) acryloyl group content in the photosensitive resin composition layer is reduced to ultraviolet rays. A cured letterpress printing original plate for laser engraving that is less than 30 mol% before irradiation, and a laser engraving printing original plate according to any one of (8) (1) to (5), which is irradiated with ultraviolet rays, and a photosensitive resin composition Cured letterpress printing original plate for laser engraving wherein the (meth) acryloyl group content in the layer is less than 1 mol in 1000 mass grams of the photosensitive resin composition, (9) at least a soluble synthetic polymer compound, photopolymerizable A cured printing original plate for laser engraving in which a photosensitive resin composition layer obtained from a photosensitive resin composition containing an unsaturated compound and a photopolymerization initiator as a basic component is cured by ultraviolet irradiation,
The photosensitive resin composition layer after ultraviolet irradiation contains polyether urea urethane as a soluble synthetic polymer compound, an ethylenically unsaturated monomer as a photopolymerizable unsaturated compound, and a radical polymerization reaction product of the ethylenically unsaturated monomer. And a cured letterpress for laser engraving, wherein the content of (meth) acryloyl groups in the photosensitive resin composition layer after ultraviolet irradiation is less than 1 mol in 1000 mass grams of the photosensitive resin composition. A photosensitive resin letterpress printing plate obtained from the cured letterpress printing original plate for laser engraving according to any one of (10), (7) to (9).
紫外線照射後の感光性樹脂組成物層が可溶性合成高分子化合物としてポリエーテルウレアウレタン、光重合性不飽和化合物としてエチレン性不飽和モノマー、および前記エチレン性不飽和モノマーのラジカル重合反応生成物を含有し、紫外線照射後の感光性樹脂組成物層中の（メタ）アクリロイル基の含有量が前記感光性樹脂組成物１０００質量グラム中に１モル未満であることを特徴とするレーザー彫刻用硬化済み凸版印刷原版、（１０）（７）～（９）のいずれかに記載のレーザー彫刻用硬化済み凸版印刷原版より得られることを特徴とする感光性樹脂凸版印刷版、である。 In the present invention, the laser engraving printing original plate described in any one of (7) (1) to (5) is irradiated with ultraviolet rays, and the (meth) acryloyl group content in the photosensitive resin composition layer is reduced to ultraviolet rays. A cured letterpress printing original plate for laser engraving that is less than 30 mol% before irradiation, and a laser engraving printing original plate according to any one of (8) (1) to (5), which is irradiated with ultraviolet rays, and a photosensitive resin composition Cured letterpress printing original plate for laser engraving wherein the (meth) acryloyl group content in the layer is less than 1 mol in 1000 mass grams of the photosensitive resin composition, (9) at least a soluble synthetic polymer compound, photopolymerizable A cured printing original plate for laser engraving in which a photosensitive resin composition layer obtained from a photosensitive resin composition containing an unsaturated compound and a photopolymerization initiator as a basic component is cured by ultraviolet irradiation,
The photosensitive resin composition layer after ultraviolet irradiation contains polyether urea urethane as a soluble synthetic polymer compound, an ethylenically unsaturated monomer as a photopolymerizable unsaturated compound, and a radical polymerization reaction product of the ethylenically unsaturated monomer. And a cured letterpress for laser engraving, wherein the content of (meth) acryloyl groups in the photosensitive resin composition layer after ultraviolet irradiation is less than 1 mol in 1000 mass grams of the photosensitive resin composition. A photosensitive resin letterpress printing plate obtained from the cured letterpress printing original plate for laser engraving according to any one of (10), (7) to (9).
本発明の凸版印刷に用いるレーザー彫刻用印刷原版およびレーザー彫刻用硬化済み印刷原版を用いることにより、レーザー彫刻性能が向上することで、印刷性能が大幅に向上したレーザー彫刻用印刷版を提供することが可能となるので産業界に寄与すること大である。
To provide a printing plate for laser engraving with greatly improved printing performance by improving the laser engraving performance by using the laser engraving printing original plate used for the relief printing of the present invention and the cured printing original plate for laser engraving. It is important to contribute to the industry.
本発明のレーザー彫刻用印刷原版は、可溶性合成高分子化合物がハードセグメントとソフトセグメントとからなるブロック共重合体であるポリエーテルウレアウレタンを用いること、さらに好ましくは感光性樹脂組成物中の（メタ）アクリロイル基の含有量が感光性樹脂組成物１０００質量グラム当り２．２モル以上３．７モル以下含有することで、本発明を達成したものである。本発明は、前記可溶性高分子化合物を用いることで優れたレーザー彫刻性能が得られ、高速印刷性能の面から特に優れた印刷特性が得られる。
The printing original plate for laser engraving of the present invention uses polyether urea urethane, which is a block copolymer in which a soluble synthetic polymer compound is composed of a hard segment and a soft segment, more preferably (meta ) The content of the acryloyl group is 2.2 mol or more and 3.7 mol or less per 1000 mass grams of the photosensitive resin composition, thereby achieving the present invention. In the present invention, excellent laser engraving performance can be obtained by using the soluble polymer compound, and particularly excellent printing characteristics can be obtained in terms of high-speed printing performance.
また、本発明のレーザー彫刻用硬化済み印刷原版は、前記レーザー彫刻用印刷原版を紫外線露光し硬化させることによって得ることができ、優れたレーザー彫刻性能が得られ、高速印刷性能の面から特に優れた印刷特性が得られる。
Further, the cured printing original plate for laser engraving of the present invention can be obtained by exposing the printing original plate for laser engraving to ultraviolet rays and curing it, whereby excellent laser engraving performance is obtained, and particularly excellent in terms of high-speed printing performance. Printing characteristics can be obtained.
本発明における可溶性高分子化合物としてのポリエーテルウレタンウレアは、塩基性第３級窒素原子を含有することが好ましく、ポリエーテルウレタンウレア１０００質量グラム中に塩基性第３級窒素原子を０．５０～２．００モル含有することが好ましく、数平均分子量が４００～１５００のポリエチレングリコールをソフトセグメントとするブロック共重合体であることが好ましく、プロトン性４級化剤によって２５モル％以上を４級化させた塩基第３級窒素原子を含有することが好ましい。塩基性第３級窒素原子を含有させることで、もしレーザー彫刻時に樹脂カスが付着したとしても、水を溶剤としてブラシ洗浄等により容易に樹脂カスを除去することができる。また、塩基性第３級窒素原子をプロトン性４級化剤により４級化することで、更に容易にレーザー彫刻時の樹脂カスを除去することが可能となる。ポリエーテルウレタンウレア中の第３級窒素原子含有量がポリエーテルウレタンウレア１０００グラム中に０．５０モル未満だと、樹脂カス除去性が不十分であり、又、２．００モルを超えると樹脂カス除去中に画像がダメージを受けやすくなるために好ましくない。本発明において、塩基性第３級窒素原子含有量を可溶性合成高分子化合物１０００グラム中に０．５０～２．００モルに含有させる方法としては、ハードセグメント中の塩基性第３級窒素原子含有原料の配合比率によって設定する事も可能である。本発明において、４級化率とは可溶性合成高分子化合物中に含有する塩基性第３級窒素原子のモル数に対して、４級化した塩基性第３級窒素原子モル数の割合であり、モル％で表される。
The polyether urethane urea as the soluble polymer compound in the present invention preferably contains a basic tertiary nitrogen atom, and the basic tertiary nitrogen atom is added in an amount of 0.50 to 1,000 mass grams in the polyether urethane urea. It is preferable to contain 2.00 mol, and it is preferable to be a block copolymer having polyethylene glycol having a number average molecular weight of 400 to 1500 as a soft segment, and quaternization of 25 mol% or more by a protic quaternizing agent It is preferable to contain the made base tertiary nitrogen atom. By containing a basic tertiary nitrogen atom, even if a resin residue adheres during laser engraving, the resin residue can be easily removed by brush cleaning using water as a solvent. Further, by quaternizing a basic tertiary nitrogen atom with a protic quaternizing agent, it becomes possible to easily remove the resin residue during laser engraving. If the tertiary nitrogen atom content in the polyether urethane urea is less than 0.50 mol in 1000 grams of the polyether urethane urea, the resin residue removal is insufficient, and if it exceeds 2.00 mol, the resin This is not preferable because the image is easily damaged during the removal of debris. In the present invention, the basic tertiary nitrogen atom content in 1000 grams of the soluble synthetic polymer compound is contained in 0.50 to 2.00 mol in the hard synthetic segment. It is also possible to set according to the blending ratio of raw materials. In the present invention, the quaternization rate is the ratio of the number of moles of basic tertiary nitrogen atoms quaternized to the number of moles of basic tertiary nitrogen atoms contained in the soluble synthetic polymer compound. , Expressed in mole percent.
まず、本発明の可溶性合成高分子化合物について説明する。本発明に用いる可溶性合成高分子化合物は、ソフトセグメントを含有するブロック共重合体であり、ハードセグメント中に水素結合を形成可能なアミド結合、ウレア結合又はウレタン結合を分子内に含有することで高い結晶性を有する。そのために感光性樹脂組成物としても３０％以上の高い反発弾性率を有し、さらに感光性樹脂組成物中の（メタ）アクリロイル基の含有量が感光性樹脂組成物１０００質量グラム当り２．２モル以上３．７モル以下含有することで十分に光架橋され、レーザー彫刻時に発生した熱によって発生する熱変形を小さくすることが可能となる。その結果、本発明を用いたレーザー彫刻用印刷原版は従来の高反発弾性を有する印刷原版では得られなかった優れたレーザー彫刻性能を達成し、且つ早い印刷速度においても優れた印刷性を満足するものである。
First, the soluble synthetic polymer compound of the present invention will be described. The soluble synthetic polymer compound used in the present invention is a block copolymer containing a soft segment, and is high by containing an amide bond, urea bond or urethane bond capable of forming a hydrogen bond in the hard segment in the molecule. It has crystallinity. Therefore, the photosensitive resin composition also has a high impact resilience of 30% or more, and the content of (meth) acryloyl groups in the photosensitive resin composition is 2.2 per 1000 mass grams of the photosensitive resin composition. When it is contained in a molar amount of 3.7 mol or less, it is sufficiently photocrosslinked, and it becomes possible to reduce thermal deformation caused by heat generated during laser engraving. As a result, the printing original plate for laser engraving using the present invention achieves excellent laser engraving performance that could not be obtained with conventional printing original plates having high rebound resilience, and satisfies excellent printability even at high printing speeds. Is.
次に、本発明に用いるハードセグメント中の塩基性第３級窒素原子を４級化するプロトン性４級化剤について説明する。本発明に用いる４級化剤はプロトン性４級化剤であり、紫外線によって重合する光重合性基を含有する化合物であっても光重合性基を含有しない化合物であっても良い。プロトン性４級化剤としては公知一般の化合物を用いることができる。光重合性基を含有する化合物の具体的な例としてはマレイン酸、イタコン酸、アクリル酸、メタクリル酸、桂皮酸などが挙げられるが、樹脂カス除去性の面より好ましいものとしてはアクリル酸やメタクリル酸である。一方、光重合性基を含有しない化合物の具体的な例としては、脂肪族の４級化剤としてグリコール酸、コハク酸、アジピン酸、芳香族の４級化剤としては安息香酸など挙げられるが、樹脂カス除去性の面よりこれらの中でもアジピン酸や安息香酸が好ましい。
Next, the protic quaternizing agent for quaternizing the basic tertiary nitrogen atom in the hard segment used in the present invention will be described. The quaternizing agent used in the present invention is a protic quaternizing agent, and may be a compound containing a photopolymerizable group that is polymerized by ultraviolet rays or a compound not containing a photopolymerizable group. A known general compound can be used as the protic quaternizing agent. Specific examples of the compound containing a photopolymerizable group include maleic acid, itaconic acid, acrylic acid, methacrylic acid, cinnamic acid, and the like, and acrylic acid and methacrylic acid are preferable from the viewpoint of resin residue removal. It is an acid. On the other hand, specific examples of the compound not containing a photopolymerizable group include glycolic acid, succinic acid, adipic acid as an aliphatic quaternizing agent, and benzoic acid as an aromatic quaternizing agent. Of these, adipic acid and benzoic acid are preferable in terms of resin residue removal.
本発明に用いる可溶性合成高分子化合物は、印刷版として優れた高速印刷性を満足するために高反発弾性率を有することが重用である。好ましい反発弾性率としては、３０%以上、さらに好ましい反発弾性率は４０％以上である。反発弾性率が３０％未満では１００ｍ／分以上の高速印刷時においてベタ部インキ乗りが悪いために好ましくない。３０％以上の高反発弾性率を有する可溶性合成高分子化合物を得る方法としては、ソフトセグメントとして数平均分子量が４００～１５００のポリエチレングリコールを用いることが好ましく、より好ましい数平均分子量は４００～１０００であり、特に好ましい数平均分子量は４００～６００である。さらに可溶性合成高分子化合物中に含有するポリエチレングリコールの含有率も重要であり、好ましい含有率は４０質量％～７５質量％であり、さらに好ましい含有率は４０質量％～６０質量％である。ソフトセグメント含有比率が４０質量％未満ではソフトセグメントの役割を果たさず、又７５質量％を超えるとハードセグメントの機能が発揮されずに十分な樹脂硬度が得られなので、好ましくない。
It is important that the soluble synthetic polymer compound used in the present invention has a high rebound resilience in order to satisfy excellent high-speed printability as a printing plate. The rebound resilience is preferably 30% or more, and more preferably 40% or more. A rebound resilience of less than 30% is not preferable because the solid ink is poor when printing at 100 m / min or higher. As a method for obtaining a soluble synthetic polymer compound having a high rebound resilience of 30% or more, it is preferable to use polyethylene glycol having a number average molecular weight of 400 to 1500 as a soft segment, and a more preferable number average molecular weight is 400 to 1000. The number average molecular weight is particularly preferably 400 to 600. Further, the content of polyethylene glycol contained in the soluble synthetic polymer compound is also important, and the preferable content is 40% by mass to 75% by mass, and the more preferable content is 40% by mass to 60% by mass. If the soft segment content is less than 40% by mass, it does not play the role of a soft segment, and if it exceeds 75% by mass, the function of the hard segment is not exhibited and sufficient resin hardness is obtained, which is not preferable.
次に、本発明の感光性樹脂組成物の可溶性合成高分子化合物として用いる具体的なポリエーテルウレアウレタンについて説明する。本発明に用いるポリエーテルウレアウレタンは、ジアミンとポリエチレングリコールを含有する末端ジイソシアネート化合物とを溶剤中で付加重合させることで得られる。本発明に用いるポリエーテルウレタンを製造する方法としては、加熱重合法や溶液重合法などの公知の付加重合方法が使用可能である。
Next, a specific polyether urea urethane used as the soluble synthetic polymer compound of the photosensitive resin composition of the present invention will be described. The polyether urea urethane used in the present invention can be obtained by addition polymerization of a diamine and a terminal diisocyanate compound containing polyethylene glycol in a solvent. As a method for producing the polyether urethane used in the present invention, known addition polymerization methods such as a heat polymerization method and a solution polymerization method can be used.
ジアミン成分は、レーザー彫刻性能と印刷性能の両者を満足するためには第３級窒素原子を含有しないジアミンと第３級窒素原子を含有するジアミンとを併用することが好ましい。
In order to satisfy both the laser engraving performance and the printing performance, the diamine component is preferably used in combination with a diamine containing no tertiary nitrogen atom and a diamine containing a tertiary nitrogen atom.
第３級窒素原子を含有しないジアミンとしては、トリメチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、２－メチルペンタメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、２,２,４ 或は２,４,４ －トリメチルヘキサメチレンジアミン、１,３ －或は１,４ －ビス（アミノメチル）シクロヘキサン、１,３ －或は１,４ －アミノシクロヘキサンなどが挙げられるが、好ましくは２－メチルペンタメチレンジアミン、２,２,４ 或は２,４,４ －トリメチルヘキサメチレンジアミン、１,３－ビス（アミノメチル）シクロヘキサンである。
Examples of diamines that do not contain a tertiary nitrogen atom include trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4, or 2,4. 1,4 -trimethylhexamethylenediamine, 1,3-or 1,4 -bis (aminomethyl) cyclohexane, 1,3-or 1,4 -aminocyclohexane, and the like, preferably 2-methylpentamethylene Diamine, 2,2,4 or 2,4,4 -trimethylhexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane.
一方、第３級窒素原子を含有するジアミンの具体的例としては、主鎖又は側鎖に塩基性第３級窒素原子を有するジアミンである。具体的なジアミンとしてはピペラジン環を有するジアミン及びそれ以外のジアミンが挙げられる。具体的なピペラジン環を有するジアミンの例としては、Ｎ，Ｎ’－ビス（アミノメチル）ピペラジン、Ｎ，Ｎ’－ビス（２－アミノエチル）ピペラジン、Ｎ，Ｎ’－ビス（３－アミノプロピル）ピペラジン、Ｎ，Ｎ’－ビス（２－アミノエチル）メチルピペラジン、Ｎ－（アミノメチル）－Ｎ’－（２－アミノエチル）ピペラジン、Ｎ，Ｎ’－ビス（３－アミノペンチル）ピペラジン、Ｎ－（２－アミノエチル）ピペラジン、Ｎ－（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－（３－アミノシクロヘキシル）ピペラジン、Ｎ－（２－アミノエチル）－３－メチルピペラジン、Ｎ－（２－アミノエチル）－２，５－ジメチルピペラジン、Ｎ－（２－アミノプロピル）－３－メチルピペラジン、Ｎ－（３－アミノプロピル）－２,５ －ジメチルピペラジンなどのピペラジン環を有するジアミンが挙げられる。上記ジアミンの中でも、Ｎ，Ｎ’－ビス（アミノエチル）－ピペラジン、Ｎ，Ｎ’－ビス（３－アミノプロピル）ピペラジン、Ｎ－（２－アミノエチル）ピペラジン等のピペラジン環を有するジアミンが重合性及び物性面より優れるために好ましい。
On the other hand, a specific example of a diamine containing a tertiary nitrogen atom is a diamine having a basic tertiary nitrogen atom in the main chain or side chain. Specific examples of the diamine include a diamine having a piperazine ring and other diamines. Specific examples of diamines having a piperazine ring include N, N′-bis (aminomethyl) piperazine, N, N′-bis (2-aminoethyl) piperazine, and N, N′-bis (3-aminopropyl). ) Piperazine, N, N′-bis (2-aminoethyl) methylpiperazine, N- (aminomethyl) -N ′-(2-aminoethyl) piperazine, N, N′-bis (3-aminopentyl) piperazine, N- (2-aminoethyl) piperazine, N- (aminopropyl) piperazine, N- (ω-aminohexyl) piperazine, N- (3-aminocyclohexyl) piperazine, N- (2-aminoethyl) -3-methyl Piperazine, N- (2-aminoethyl) -2,5-dimethylpiperazine, N- (2-aminopropyl) -3-methylpiperazine, N- (3-amino Propyl) -2,5 - diamine having a piperazine ring such as dimethyl piperazine. Among the above diamines, diamines having a piperazine ring such as N, N′-bis (aminoethyl) -piperazine, N, N′-bis (3-aminopropyl) piperazine, and N- (2-aminoethyl) piperazine are polymerized. It is preferable because it is superior in terms of properties and physical properties.
ポリエーテルウレアウレタンに用いるもう一方の原料である上記ジイソシアネート化合物は公知の脂肪族、脂環族、芳香族のジイソシアネートと等モル以下のポリオキシエチレングリコールとを反応させて得られる、実質的に両末端にイソシアネート基を有するジイソシアネート化合物である。該ジイソシアネート化合物の製造方法は従来公知の方法を利用出来る。即ち両者を無溶剤の状態で混合・撹拌下に反応させる方法、両者を不活性溶剤に溶解させて反応させる方法などがあげられる。反応温度、反応時間などは、両者の反応性や熱安定性などを考慮して最適条件を決めるべきである。またジイソシアネートの使用比率はポリオキシエチレングリコールに対して２．０モル以上、特に２．０５モル以上が望ましい。
The above diisocyanate compound, which is another raw material used for polyether urea urethane, is obtained by reacting a known aliphatic, alicyclic or aromatic diisocyanate with an equimolar or less polyoxyethylene glycol. It is a diisocyanate compound having an isocyanate group at the terminal. A conventionally well-known method can be utilized for the manufacturing method of this diisocyanate compound. That is, a method of reacting both in a solvent-free state while mixing and stirring, a method of reacting both by dissolving in an inert solvent, and the like. The reaction temperature, reaction time, etc. should be determined optimally considering the reactivity and thermal stability of both. The use ratio of diisocyanate is preferably 2.0 mol or more, particularly 2.05 mol or more with respect to polyoxyethylene glycol.
ジイソシアネート化合物を得るために使用するジイソシアネートとしては公知の脂肪族、脂環族、芳香族のジイソシアネートが使用可能である。例えば２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、ｐ－キシリレンジイソシアネート、１，３－シクロヘキサンジメチルイソシアネート、ｐ－キシリレンジイソシアネート、１，５－ナフタレンジイソシアネート、２，６－ジイソシアネートメチルカプロエート、ジフェニルエーテル－４，４’－ジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネートなどが挙げられるが、保存安定性や反応性の面から脂肪族ジイソシアネートが好ましく、特にヘキサメチレンジイソシアネートが好ましい。
As the diisocyanate used for obtaining the diisocyanate compound, known aliphatic, alicyclic and aromatic diisocyanates can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, p-xylylene diisocyanate, 1,3-cyclohexanedimethyl isocyanate, p- Examples include xylylene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-diisocyanate methyl caproate, diphenyl ether-4,4′-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. To aliphatic diisocyanates are preferred, and hexamethylene diisocyanate is particularly preferred.
またジアミンとジイソシアネート化合物との反応比率アミノ基／イソシアネート基（当量比）は１．０以上、望ましくは１．０２以上である。この場合過剰の末端アミノ基が未反応のまま残存しても、それを用いた組成物の性能、物性などに悪影響を及ぼさない限り特にさしつかえない。またアミノ基／イソシアネート基（当量比）が１．０未満の場合はゲル化などの不都合な反応が起こりやすいので好ましくない。アミンとイソシアネートとの反応性は極めて大きいため両者の反応は水、メタノールなどのアルコール類、あるいは水とアルコール類との混合物などの活性溶剤中でも可能である。
The reaction ratio between diamine and diisocyanate compound is amino group / isocyanate group (equivalent ratio) of 1.0 or more, preferably 1.02 or more. In this case, even if an excess terminal amino group remains unreacted, there is no particular problem as long as it does not adversely affect the performance and physical properties of the composition using the terminal amino group. Further, when the amino group / isocyanate group (equivalent ratio) is less than 1.0, an undesirable reaction such as gelation tends to occur, which is not preferable. Since the reactivity between amine and isocyanate is extremely high, the reaction between the two can be carried out in an active solvent such as water, alcohols such as methanol, or a mixture of water and alcohols.
本発明に用いる可溶性高分子化合物はウレアウレタン結合による結晶層を有するブロック共重合体であり、結晶性を乱すことなくソフトセグメントに光重合性化合物の濃度を高く出来、その結果レーザー彫刻時に発生した熱によって境界部分の樹脂（レリーフ)が熱変形を起こしにくくなっていると考えられる。一方、ウレアウレタン結合の結晶層を有するブロック共重合体を用いない場合には、ポリマーの結晶性が光重合性化合物によって乱され、レーザー彫刻時に発生した熱によって境界部分の樹脂（レリーフ)が熱変形を起こしやすいと考えられる。熱変形を防止するためには、光重合性化合物の含有比率を高くすることが考えられるが、樹脂硬度が高くなりすぎるために印刷性の低下が起こり、レーザー彫刻性と印刷性との両者を満足できるものではない。又、シート状成型品の固形化するまでの時間が長くなり、生産性が低下する問題が起こる。
The soluble polymer compound used in the present invention is a block copolymer having a crystal layer with a urea urethane bond, and can increase the concentration of the photopolymerizable compound in the soft segment without disturbing the crystallinity, resulting in the occurrence of laser engraving. It is considered that the resin (relief) at the boundary part is less likely to cause thermal deformation due to heat. On the other hand, when a block copolymer having a urea urethane bond crystal layer is not used, the crystallinity of the polymer is disturbed by the photopolymerizable compound, and the resin (relief) at the boundary is heated by the heat generated during laser engraving. It is thought that deformation is likely to occur. In order to prevent thermal deformation, it is conceivable to increase the content ratio of the photopolymerizable compound. However, since the resin hardness becomes too high, the printability deteriorates, and both the laser engraving property and the printability are reduced. It is not satisfactory. Moreover, the time until solidification of a sheet-like molded product becomes long, and the problem that productivity falls arises.
本発明に用いる光重合性不飽和化合物としては、公知の光重合性不飽和化合物を用いることができる。好適に用いられる光重合性不飽和化合物としては、公知の二価又は三価アルコールのグリシジルエーテルとメタアクリル酸およびアクリル酸との開環付加反応生成物であり、前記多価アルコールとして、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、フタル酸のエチレンオキサイド付加物、グリセリン、ビスフェノールＡ、トリメルロールプロパンやビスフェノールＦのジグリシジルエーテルアクリル酸付加物などが挙げられるが、またこれらの化合物を２種類以上混合して使用することも出来る。なお、本発明においてはレーザー彫刻性の面よりグリセリンジメタクリレート、エチレングリコールジエポキシアクリレート、トリメルロールプロパントリエポキシアクリレートが好ましく、特にグリセリンジメタクリレートを用いることが好ましい。本発明に用いる光重合性不飽和化合物は単独でも良いが、光重合性不飽和基の含有量を特定の範囲とするために混合してもかまわない。
As the photopolymerizable unsaturated compound used in the present invention, known photopolymerizable unsaturated compounds can be used. The photopolymerizable unsaturated compound preferably used is a ring-opening addition reaction product of a known glycidyl ether of a dihydric or trihydric alcohol with methacrylic acid and acrylic acid, and the polyhydric alcohol is ethylene glycol. , Diethylene glycol, triethylene glycol, ethylene oxide adducts of phthalic acid, glycerin, bisphenol A, trimerol propane and diglycidyl ether acrylic acid adducts of bisphenol F, etc. Can also be used. In the present invention, glycerin dimethacrylate, ethylene glycol diepoxy acrylate, and trimerol propane triepoxy acrylate are preferable from the viewpoint of laser engraving, and glycerol dimethacrylate is particularly preferable. The photopolymerizable unsaturated compound used in the present invention may be used alone, but may be mixed in order to bring the content of the photopolymerizable unsaturated group into a specific range.
本発明は光重合性不飽和基の含有量が重要である。本発明は、優れたレーザー彫刻性能と樹脂カス除去性を満足するためには感光性樹脂組成物全体として含有する光重合性不飽和基の含有量を一定量の範囲にコントロールすると共にプロトン酸で４級化した塩基性第３級窒素原子含有量を一定量にコントロールすることが好ましい。
In the present invention, the content of the photopolymerizable unsaturated group is important. In the present invention, in order to satisfy the excellent laser engraving performance and resin residue removal property, the content of the photopolymerizable unsaturated group contained in the photosensitive resin composition as a whole is controlled within a certain range, and a proton acid is used. It is preferable to control the content of the quaternized basic tertiary nitrogen atom to a constant amount.
本発明の好ましい光重合性不飽和基の含有量として、感光性樹脂組成物１０００グラム中に２．２～３．７モル含有させるものであり、さらに好ましくは２．４～３．４モル含有させることである。感光性樹脂凸版組成物１０００グラム中の光重合性不飽和基の含有量が、２．２モル未満ではレーザー彫刻性能が悪く、又３．７モルを超えると印刷版として硬くなりすぎてインキ乗りが低下するので好ましくない。光重合性不飽和基の含有量を感光性樹脂凸版組成物１０００グラム 中に２．２～３．７モル含有させる方法としては、光重合性化合物の配合量を増減させること又は光重合性基間の距離（分子量）を変えることで同じ感光性樹脂組成物への配合量でありながら感光性樹脂組成物中の光重合性基の量を増減させることは可能である。
The preferable content of the photopolymerizable unsaturated group of the present invention is such that it is contained in an amount of 2.2 to 3.7 mol, more preferably 2.4 to 3.4 mol in 1000 g of the photosensitive resin composition. It is to let you. When the content of the photopolymerizable unsaturated group in 1000 grams of the photosensitive resin relief printing composition is less than 2.2 mol, the laser engraving performance is poor, and when it exceeds 3.7 mol, the printing plate becomes too hard and the ink is carried on the surface. Is unfavorable because it decreases. As a method for adding 2.2 to 3.7 moles of the photopolymerizable unsaturated group content in 1000 grams of the photosensitive resin relief printing composition, the amount of the photopolymerizable compound is increased or decreased. By changing the distance (molecular weight) between them, it is possible to increase or decrease the amount of the photopolymerizable group in the photosensitive resin composition while being blended in the same photosensitive resin composition.
本発明に使用する光重合開始剤としては公知のものが使用可能であり、具体的には、例えば、ベンゾフェノン類、ベンゾイン類、アセトフェノン類、ベンジル類、ベンゾインアルキルエーテル類、ベンジルアルキルケタール類、アンスラキノン類、チオキサントン類などが使用できる。好適な具体例としては、ベンゾフェノン、ベンゾイン、アセトフェノン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンジルジメチルケタール、アンスラキノン、２－クロロアンスラキノン、チオキサントン、２－クロロチオキサントンなどが挙げられる。これらは感光性樹脂組成物中に０．０５～５質量％含有させるのが好ましい。０．０５質量％より少ないと光重合開始能力に支障をきたし、５質量％より多いと印刷用レリーフを作成する場合の生版の厚み方向の光硬化性が低下し、レーザー彫刻性能が低下する。
As the photopolymerization initiator used in the present invention, known ones can be used. Specifically, for example, benzophenones, benzoins, acetophenones, benzyls, benzoin alkyl ethers, benzyl alkyl ketals, anthra Quinones and thioxanthones can be used. Specific examples include benzophenone, benzoin, acetophenone, benzoin methyl ether, benzoin ethyl ether, benzyldimethyl ketal, anthraquinone, 2-chloroanthraquinone, thioxanthone, 2-chlorothioxanthone and the like. These are preferably contained in the photosensitive resin composition in an amount of 0.05 to 5% by mass. When the amount is less than 0.05% by mass, the photopolymerization initiation ability is hindered. When the amount is more than 5% by mass, the photocurability in the thickness direction of the printing plate when producing a relief for printing is lowered, and the laser engraving performance is degraded. .
また必要により公知の熱重合禁止剤を添加してもよい。熱重合禁止剤は、感光性樹脂凸版組成物の調合、製造、成形加工時などの加熱による予定外の熱重合、あるいは該組成物の保存中の暗反応を防止するために添加する。このような化合物の例としては、ハイドロキノン、モノ－tert－ブチルハイドロキノン、２，５－ジ－tert－ブチルハイドロキノン、ハイドロキノンモノメチルエーテルなどのハイドロキノン類、ベンゾキノン、２，５－ジフェニル－ｐ－ベンゾキノンなどのベンゾキノン類、フェノール類、カテコール、ｐ－tert－ブチルカテコールなどのカテコール類、芳香族アミン化合物類、ビクリン酸類、フェノチアジン、α－ナフトキノン類、アンスラキノン類、ニトロ化合物類、イオウ化合物類などが挙げられる。熱重合禁止剤の使用量は全組成物中、０．００１ ～２ 質量％、特に好ましくは０．００５ ～１質量％である。これらの化合物は２種以上併用してもよい。
If necessary, a known thermal polymerization inhibitor may be added. The thermal polymerization inhibitor is added in order to prevent unscheduled thermal polymerization due to heating during preparation, production, molding, etc. of the photosensitive resin letterpress composition, or dark reaction during storage of the composition. Examples of such compounds include hydroquinones such as hydroquinone, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, hydroquinone monomethyl ether, benzoquinone, 2,5-diphenyl-p-benzoquinone, etc. Catechols such as benzoquinones, phenols, catechol, p-tert-butylcatechol, aromatic amine compounds, vicrinic acids, phenothiazine, α-naphthoquinones, anthraquinones, nitro compounds, sulfur compounds, etc. . The amount of the thermal polymerization inhibitor used is from 0.001% to 2% by weight, particularly preferably from 0.005% to 1% by weight, based on the total composition. Two or more of these compounds may be used in combination.
本発明の感光性樹脂組成物は、印刷用レリーフ版を得る場合の溶融成形法の他、例えは、熱プレス、注型、或いは、溶融押出し、溶液キャストなど公知の任意の方法により目的の製品に応じた所望の形状物に成形できる。
The photosensitive resin composition of the present invention is a target product by any known method such as hot pressing, casting, melt extrusion, solution casting, etc. in addition to the melt molding method for obtaining a relief plate for printing. Can be formed into a desired shape.
レーザー彫刻用印刷原版を得る場合は、本発明の感光性樹脂組成物をシート状に成形した成形物（生版）を公知の接着剤を介して、或いは、介さずに支持体に積層して使用することができる。支持体としてはスチール、アルミニウム、ガラス、ポリエチレンテレフタレートなどのプラスチックフィルム、金属蒸着したフィルムなど任意のものが使用できる。シート状成形物（生版）を支持体上に接着層を積層した積層体にして供給する場合には、シート状成形物（生版）に接してさらに保護層を積層しても良い。保護層としては、例えば、ポリエチレンテレフタレートの１２５μｍ厚みのフィルム等のフィルム状のプラスチックに、粘着性のない透明な高分子を１～３μｍの厚みで塗布したものが用いられる。この薄い高分子の皮膜を有する保護層をシート状成形物（生版）に接することによって、シート状成形物（生版）の表面粘着性が強い場合であっても次の露光処理（光硬化）操作時に行う保護層の剥離を容易に行うことができる。
When obtaining a printing original plate for laser engraving, a molded product (raw plate) obtained by molding the photosensitive resin composition of the present invention into a sheet is laminated on a support with or without a known adhesive. Can be used. As the support, any material such as a plastic film such as steel, aluminum, glass, polyethylene terephthalate, or a metal-deposited film can be used. When supplying a sheet-like molded product (raw plate) as a laminate in which an adhesive layer is laminated on a support, a protective layer may be further laminated in contact with the sheet-like molded product (raw plate). As the protective layer, for example, a film-like plastic such as a 125 μm-thick polyethylene terephthalate film coated with a non-sticky transparent polymer with a thickness of 1 to 3 μm is used. Even if the surface adhesiveness of the sheet-like molded product (raw plate) is strong by contacting the protective layer having this thin polymer film with the sheet-shaped molded product (raw plate), the next exposure treatment (photocuring) ) The protective layer can be easily peeled off during operation.
本発明における光硬化とは、例えば、感光性樹脂組成物をシート状に成形・固形化した後に、このシート状成形物（生板）を、表面より高さ５ｃｍの距離から８ｍＷ／ｃｍ２の紫外線露光機（光源：フィリップス社製１０Ｒ）により表裏各１０分露光し、架橋硬化させるものである。
The photocuring in the present invention means, for example, that the photosensitive resin composition is molded and solidified into a sheet shape, and then this sheet-shaped molded product (raw plate) is 8 mW / cm 2 from a distance of 5 cm higher than the surface. The front and back surfaces are exposed for 10 minutes each by an ultraviolet exposure machine (light source: 10R manufactured by Philips), and are cured by crosslinking.
本発明におけるレーザー彫刻用硬化済み凸版印刷原版は、本発明におけるレーザー彫刻用凸版印刷原版を露光処理することによって光硬化（架橋）させて得られるが、露光処理はカバーフィルムを通して処理しても良いし、カバーフィルム剥離後に露光処理しても良い。
The cured letterpress printing original plate for laser engraving in the present invention is obtained by photocuring (crosslinking) the exposure relief printing original plate for laser engraving in the present invention, but the exposure treatment may be performed through a cover film. And you may expose after a cover film peeling.
かくして得られたレーザー彫刻用硬化済み凸版印刷原版は、例えば、レーザー彫刻装置の版装着ドラムの表面に取り付けられ、像に従ったレーザー照射により照射部分の原版が分解されて凹部分を形成し、印刷版が製造される。
The cured letterpress printing original plate for laser engraving thus obtained is attached to the surface of a plate mounting drum of a laser engraving apparatus, for example, and the irradiated portion of the original plate is decomposed by laser irradiation according to the image to form a concave portion, A printing plate is produced.
次に本発明を実施例を用いて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
Next, the present invention will be specifically described using examples, but the present invention is not limited to these examples.
ショアーＤ硬さ及び反発弾性率は感光性樹脂組成物をシート状成形物に成型して光硬化した後に、以下の方法により測定した。なお、測定用サンプルは ２５０μｍのポリエステル支持体上に３ｍｍの感光性樹脂層を設け、更に感光性樹脂層表面に１２５μｍのポリエステルフィルムを積層した感光性樹脂積層体を使って、２５Ｗ／ｍ2のケミカルランプを用いて感光性樹脂積層体表面より高さ５ｃｍの距離から１０分間露光し、光硬化させた。次いで、２０℃、相対湿度６５％の条件で24～36時間保存したものを評価用サンプルとした。
The Shore D hardness and rebound resilience were measured by the following methods after the photosensitive resin composition was molded into a sheet-like molded product and photocured. In addition, the sample for a measurement uses a photosensitive resin laminated body which provided the photosensitive resin layer of 3 mm on the polyester support body of 250 micrometers, and also laminated | stacked the 125-micrometer polyester film on the photosensitive resin layer surface, and is 25 W / m < 2 >. Using a chemical lamp, exposure was performed for 10 minutes from a distance of 5 cm from the surface of the photosensitive resin laminate, and photocuring was performed. Next, samples that were stored for 24 to 36 hours at 20 ° C. and 65% relative humidity were used as samples for evaluation.
（１）ショアーＤ硬さ ：西独ツビック社製、ショアー式デュロメーター（ショアーＤタイプ）を用いて２５℃で測定した。
(1) Shore D hardness: measured at 25 ° C. using a Shore durometer (Shore D type) manufactured by West German Zbic.
（２）反発弾性率 ：直径１０ｍｍ（重さ４.１６グラム）の鋼球製ボールを２０ｃｍの高さより落下させ、跳ね返る高さ（ａ）を読み取り、（ａ／２０）×１００とした（％表示）。測定は、２５℃、７０％ＲＨの条件で行った。
(2) Rebound resilience: A steel ball ball having a diameter of 10 mm (weight of 4.16 grams) was dropped from a height of 20 cm, and the rebounding height (a) was read to obtain (a / 20) × 100 (% display). The measurement was performed under the conditions of 25 ° C. and 70% RH.
（３）樹脂カス除去性評価（付着した樹脂カスの除去性）
樹脂カス除去性の評価として、レーザー彫刻した後に印刷版表面に付着した樹脂カスを用いて除去のし易さを評価した。直径１６０μｍのポリエチレンテレフタレート製の繊維を植え込みした１０ｃｍ×１０ｃｍのブラシを用いてその除去し易さを以下の通りに評価した。
○：１０回以内の擦り作業で除去可能、△：３０回以内の擦り作業で除去可能、×：３０回以上の擦り作業でも除去できず、ブラシにも樹脂が付着。 (3) Resin residue evaluation (removability of attached resin residue)
As evaluation of the resin residue removal property, the ease of removal was evaluated using the resin residue attached to the printing plate surface after laser engraving. The ease of removal was evaluated as follows using a 10 cm × 10 cm brush in which fibers made of polyethylene terephthalate having a diameter of 160 μm were implanted.
○: Can be removed by rubbing work within 10 times, Δ: Can be removed by rubbing work within 30 times, ×: Can not be removed by rubbing work more than 30 times, and the resin adheres to the brush.
樹脂カス除去性の評価として、レーザー彫刻した後に印刷版表面に付着した樹脂カスを用いて除去のし易さを評価した。直径１６０μｍのポリエチレンテレフタレート製の繊維を植え込みした１０ｃｍ×１０ｃｍのブラシを用いてその除去し易さを以下の通りに評価した。
○：１０回以内の擦り作業で除去可能、△：３０回以内の擦り作業で除去可能、×：３０回以上の擦り作業でも除去できず、ブラシにも樹脂が付着。 (3) Resin residue evaluation (removability of attached resin residue)
As evaluation of the resin residue removal property, the ease of removal was evaluated using the resin residue attached to the printing plate surface after laser engraving. The ease of removal was evaluated as follows using a 10 cm × 10 cm brush in which fibers made of polyethylene terephthalate having a diameter of 160 μm were implanted.
○: Can be removed by rubbing work within 10 times, Δ: Can be removed by rubbing work within 30 times, ×: Can not be removed by rubbing work more than 30 times, and the resin adheres to the brush.
実施例１
Ｎ，Ｎ’－ビス（３－アミノプロピル）ピペラジン７７質量部と２－メチルペンタメチレンジアミン２２質量部をメタノール５５０質量部に溶解した後、該ジアミン溶液にポリエチレングリコール（平均分子量６００）６００質量部とヘキサメチレンジイソシアネート３６９質量部を反応させて得られた実質的に両末端にイソシアネート基を有するウレタンオリゴマー４５１質量部を、撹拌下徐々に添加した。両者の反応はポリマー固形分濃度５０％の条件下に約１５分で完了した。この溶液をテフロン（登録商標）コートしたシャーレに取り、メタノールを蒸発除去後、減圧乾燥して得られた付加重合体は、ジアミン成分中に２－メチルペンタメチレンジアミンを２０重量％、ポリエーテルセグメントを４７重量％含有し、比粘度が１．７１のポリエーテルウレアウレタンであった。
次に得られたポリエーテルウレアウレタン５５．０質量部と４級化剤として乳酸２．１質量部をメタノール２００質量部および水１０質量部に攪拌付き加熱反応釜中６５℃で４時間溶解・４級化反応を行った。その後にグリセリンジメタクリレート３３．７質量部、エチレングリコールジエポキシアクリレート５．０質量部、可塑剤としてＮ－エチルトルエンスルホン酸アミド３．１質量部、ハイドロキノンモノエチルエーテル０．１質量部、ベンジルジメチルケタール１．０質量部を加え、感光性樹脂組成物溶液を得た。得られた感光性樹脂組成物溶液は、メタノール及び水を除く感光性樹脂組成物固形分１０００グラム中に（メタ）アクリロイル基を３．３モル含有し、且つプロトン酸で４級化された３級窒素原子も０．４２モル含有していた。この溶液をテフロン（登録商標）コートしたシャーレに流延し、一昼夜４０℃で減圧乾燥し厚み８００μｍの感光性組成物のシートを得た。 Example 1
After dissolving 77 parts by mass of N, N′-bis (3-aminopropyl) piperazine and 22 parts by mass of 2-methylpentamethylenediamine in 550 parts by mass of methanol, 600 parts by mass of polyethylene glycol (average molecular weight 600) is added to the diamine solution. 451 parts by mass of a urethane oligomer having isocyanate groups at both ends substantially obtained by reacting 369 parts by mass with hexamethylene diisocyanate was gradually added. Both reactions were completed in about 15 minutes under conditions of a polymer solids concentration of 50%. This solution is placed in a petri dish coated with Teflon (registered trademark), and methanol is removed by evaporation, followed by drying under reduced pressure. An addition polymer obtained by adding 20% by weight of 2-methylpentamethylenediamine in the diamine component and a polyether segment Was a polyether urea urethane having a specific viscosity of 1.71.
Next, 55.0 parts by mass of the obtained polyether urea urethane and 2.1 parts by mass of lactic acid as a quaternizing agent were dissolved in 200 parts by mass of methanol and 10 parts by mass of water in a heated reaction kettle with stirring at 65 ° C. for 4 hours. A quaternization reaction was performed. Thereafter, 33.7 parts by mass of glycerin dimethacrylate, 5.0 parts by mass of ethylene glycol diepoxy acrylate, 3.1 parts by mass of N-ethyltoluenesulfonic acid amide as a plasticizer, 0.1 part by mass of hydroquinone monoethyl ether, benzyldimethyl 1.0 part by mass of ketal was added to obtain a photosensitive resin composition solution. The obtained photosensitive resin composition solution contained 3.3 mol of (meth) acryloyl group in 1000 g of the solid content of the photosensitive resin composition excluding methanol and water, and was quaternized with a protonic acid 3 It also contained 0.42 mol of secondary nitrogen atoms. This solution was cast on a Teflon (registered trademark) -coated petri dish and dried under reduced pressure at 40 ° C. overnight to obtain a sheet of a photosensitive composition having a thickness of 800 μm.
Ｎ，Ｎ’－ビス（３－アミノプロピル）ピペラジン７７質量部と２－メチルペンタメチレンジアミン２２質量部をメタノール５５０質量部に溶解した後、該ジアミン溶液にポリエチレングリコール（平均分子量６００）６００質量部とヘキサメチレンジイソシアネート３６９質量部を反応させて得られた実質的に両末端にイソシアネート基を有するウレタンオリゴマー４５１質量部を、撹拌下徐々に添加した。両者の反応はポリマー固形分濃度５０％の条件下に約１５分で完了した。この溶液をテフロン（登録商標）コートしたシャーレに取り、メタノールを蒸発除去後、減圧乾燥して得られた付加重合体は、ジアミン成分中に２－メチルペンタメチレンジアミンを２０重量％、ポリエーテルセグメントを４７重量％含有し、比粘度が１．７１のポリエーテルウレアウレタンであった。
次に得られたポリエーテルウレアウレタン５５．０質量部と４級化剤として乳酸２．１質量部をメタノール２００質量部および水１０質量部に攪拌付き加熱反応釜中６５℃で４時間溶解・４級化反応を行った。その後にグリセリンジメタクリレート３３．７質量部、エチレングリコールジエポキシアクリレート５．０質量部、可塑剤としてＮ－エチルトルエンスルホン酸アミド３．１質量部、ハイドロキノンモノエチルエーテル０．１質量部、ベンジルジメチルケタール１．０質量部を加え、感光性樹脂組成物溶液を得た。得られた感光性樹脂組成物溶液は、メタノール及び水を除く感光性樹脂組成物固形分１０００グラム中に（メタ）アクリロイル基を３．３モル含有し、且つプロトン酸で４級化された３級窒素原子も０．４２モル含有していた。この溶液をテフロン（登録商標）コートしたシャーレに流延し、一昼夜４０℃で減圧乾燥し厚み８００μｍの感光性組成物のシートを得た。 Example 1
After dissolving 77 parts by mass of N, N′-bis (3-aminopropyl) piperazine and 22 parts by mass of 2-methylpentamethylenediamine in 550 parts by mass of methanol, 600 parts by mass of polyethylene glycol (average molecular weight 600) is added to the diamine solution. 451 parts by mass of a urethane oligomer having isocyanate groups at both ends substantially obtained by reacting 369 parts by mass with hexamethylene diisocyanate was gradually added. Both reactions were completed in about 15 minutes under conditions of a polymer solids concentration of 50%. This solution is placed in a petri dish coated with Teflon (registered trademark), and methanol is removed by evaporation, followed by drying under reduced pressure. An addition polymer obtained by adding 20% by weight of 2-methylpentamethylenediamine in the diamine component and a polyether segment Was a polyether urea urethane having a specific viscosity of 1.71.
Next, 55.0 parts by mass of the obtained polyether urea urethane and 2.1 parts by mass of lactic acid as a quaternizing agent were dissolved in 200 parts by mass of methanol and 10 parts by mass of water in a heated reaction kettle with stirring at 65 ° C. for 4 hours. A quaternization reaction was performed. Thereafter, 33.7 parts by mass of glycerin dimethacrylate, 5.0 parts by mass of ethylene glycol diepoxy acrylate, 3.1 parts by mass of N-ethyltoluenesulfonic acid amide as a plasticizer, 0.1 part by mass of hydroquinone monoethyl ether, benzyldimethyl 1.0 part by mass of ketal was added to obtain a photosensitive resin composition solution. The obtained photosensitive resin composition solution contained 3.3 mol of (meth) acryloyl group in 1000 g of the solid content of the photosensitive resin composition excluding methanol and water, and was quaternized with a protonic acid 3 It also contained 0.42 mol of secondary nitrogen atoms. This solution was cast on a Teflon (registered trademark) -coated petri dish and dried under reduced pressure at 40 ° C. overnight to obtain a sheet of a photosensitive composition having a thickness of 800 μm.
次に、得られた組成物シートを厚さ２５０μｍのポリエチレンテレフタレートフィルム上にポリエステル系接着層をコーティングしたフィルムと、厚さ１００μｍのポリエチレンテレフタレートフィルムとで挟み、ヒートプレス機で１００℃、１００ｋｇ／ｃｍ２の圧力で加圧することにより、厚さ１．０５ｍｍのシート状成形物（レーザー彫刻用印刷用原版）を得た。
Next, the obtained composition sheet was sandwiched between a polyethylene terephthalate film having a thickness of 250 μm and a polyethylene terephthalate film having a thickness of 100 μm, and a polyethylene terephthalate film having a thickness of 100 μm. By pressurizing at a pressure of 2 , a sheet-like molded product (laser engraving printing original plate) having a thickness of 1.05 mm was obtained.
次に、このシート状成形物（レーザー彫刻用印刷用原版）を紫外線露光機（光源：フィリップス社製１０Ｒ）により表面より高さ５ｃｍの距離から８ｍＷ／ｃｍ２の紫外線露光機（光源：フィリップス社製１０Ｒ）により厚さ１００μmポリエチレンテレフタレートフィルム側から１０分露光し、架橋硬化させた後、厚さ１００μｍのポリエチレンテレフタレートフィルムを剥がし、レーザー彫刻用硬化済み印刷原版を作製した。作製したレーザー彫刻用硬化済み印刷原版を酢酸エチルに２５℃で４８時間浸漬し、抽出された（メタ）アクリロイル基含有物を定量したところ、（メタ）アクリロイル基の含有量はレーザー彫刻用印刷硬化済み原版を構成する感光性樹脂組成物１０００ｇ中０．３モルであった。
Next, the sheet-like preform (for laser engraving Printing plate precursor) an ultraviolet exposure machine (light source: Philips 10R) by the height from the surface 5cm distance from 8 mW / cm 2 of UV exposure machine (light source: Philips 10R) was exposed from the 100 μm-thick polyethylene terephthalate film side for 10 minutes and crosslinked and cured, and then the 100 μm-thick polyethylene terephthalate film was peeled off to prepare a cured printing original plate for laser engraving. The prepared cured printing original plate for laser engraving was immersed in ethyl acetate at 25 ° C. for 48 hours, and the content of the extracted (meth) acryloyl group was quantified. The content of (meth) acryloyl group was determined by the print curing for laser engraving. It was 0.3 mol in 1000 g of the photosensitive resin composition constituting the finished original plate.
実施例２～３
表１の通りに４級化剤の種類と添加量を変更し、実施例１と同様にして組成物を調整し、実施例１と同様にしてシート状成形物（レーザー彫刻用原版）およびレーザー彫刻用印刷硬化済み原版を得た。 Examples 2 to 3
As shown in Table 1, the type and amount of the quaternizing agent were changed, the composition was adjusted in the same manner as in Example 1, and a sheet-like molded product (laser engraving master) and laser were prepared in the same manner as in Example 1. A print-cured original plate for engraving was obtained.
表１の通りに４級化剤の種類と添加量を変更し、実施例１と同様にして組成物を調整し、実施例１と同様にしてシート状成形物（レーザー彫刻用原版）およびレーザー彫刻用印刷硬化済み原版を得た。 Examples 2 to 3
As shown in Table 1, the type and amount of the quaternizing agent were changed, the composition was adjusted in the same manner as in Example 1, and a sheet-like molded product (laser engraving master) and laser were prepared in the same manner as in Example 1. A print-cured original plate for engraving was obtained.
実施例４～７、１５、１６
表１の通りに実施例１の光重合性不飽和化合物の添加量及び種類を変更して光重合性基含有量を変化させ、またその他の配合の一部を変更して感光性樹脂組成物を作成し、実施例１と同様にして実施例４～７、１５、１６のレーザー彫刻用印刷原版およびレーザー彫刻用印刷硬化済み原版を作製した。 Examples 4-7, 15, 16
As shown in Table 1, the addition amount and type of the photopolymerizable unsaturated compound of Example 1 were changed to change the content of the photopolymerizable group, and a part of other ingredients was changed to change the photosensitive resin composition. In the same manner as in Example 1, laser beam engraving printing original plates and laser engraving print-cured original plates of Examples 4 to 7, 15, and 16 were produced.
表１の通りに実施例１の光重合性不飽和化合物の添加量及び種類を変更して光重合性基含有量を変化させ、またその他の配合の一部を変更して感光性樹脂組成物を作成し、実施例１と同様にして実施例４～７、１５、１６のレーザー彫刻用印刷原版およびレーザー彫刻用印刷硬化済み原版を作製した。 Examples 4-7, 15, 16
As shown in Table 1, the addition amount and type of the photopolymerizable unsaturated compound of Example 1 were changed to change the content of the photopolymerizable group, and a part of other ingredients was changed to change the photosensitive resin composition. In the same manner as in Example 1, laser beam engraving printing original plates and laser engraving print-cured original plates of Examples 4 to 7, 15, and 16 were produced.
実施例９～１１
表１の通りに実施例１のソフトセグメントであるポリエチレングリコールの数平均分子量を変更し、実施例１と同様にして実施例９～１１のレーザー彫刻用印刷原版およびレーザー彫刻用印刷硬化済み原版を作製した。 Examples 9-11
The number average molecular weight of polyethylene glycol, which is the soft segment of Example 1, was changed as shown in Table 1, and the laser engraving printing original plates and laser engraving printing cured original plates of Examples 9 to 11 were prepared in the same manner as in Example 1. Produced.
表１の通りに実施例１のソフトセグメントであるポリエチレングリコールの数平均分子量を変更し、実施例１と同様にして実施例９～１１のレーザー彫刻用印刷原版およびレーザー彫刻用印刷硬化済み原版を作製した。 Examples 9-11
The number average molecular weight of polyethylene glycol, which is the soft segment of Example 1, was changed as shown in Table 1, and the laser engraving printing original plates and laser engraving printing cured original plates of Examples 9 to 11 were prepared in the same manner as in Example 1. Produced.
実施例８、１２～１４
表１の通りに実施例１のジアミン成分を変更し、実施例１と同様にして実施例８、１２～１４のレーザー彫刻用印刷原版およびレーザー彫刻用印刷硬化済み原版を作製した。 Examples 8, 12-14
The diamine component of Example 1 was changed as shown in Table 1, and in the same manner as in Example 1, laser beam engraving printing original plates and laser engraving print-cured original plates of Examples 8 and 12 to 14 were produced.
表１の通りに実施例１のジアミン成分を変更し、実施例１と同様にして実施例８、１２～１４のレーザー彫刻用印刷原版およびレーザー彫刻用印刷硬化済み原版を作製した。 Examples 8, 12-14
The diamine component of Example 1 was changed as shown in Table 1, and in the same manner as in Example 1, laser beam engraving printing original plates and laser engraving print-cured original plates of Examples 8 and 12 to 14 were produced.
比較例１及び比較例２
比較例１及び比較例２は感光性樹脂組成物１０００グラム中に含有する光重合性基の総モル数が請求項１の範囲外の値を含有する感光性樹脂組成物であり、実施例１と同様にしてレーザー彫刻用印刷原版およびレーザー彫刻用印刷硬化済み原版を作製した。 Comparative Example 1 and Comparative Example 2
Comparative Example 1 and Comparative Example 2 are photosensitive resin compositions in which the total number of moles of photopolymerizable groups contained in 1000 grams of the photosensitive resin composition contains values outside the range of claim 1. In the same manner as described above, a laser engraving printing original plate and a laser engraving print cured original plate were prepared.
比較例１及び比較例２は感光性樹脂組成物１０００グラム中に含有する光重合性基の総モル数が請求項１の範囲外の値を含有する感光性樹脂組成物であり、実施例１と同様にしてレーザー彫刻用印刷原版およびレーザー彫刻用印刷硬化済み原版を作製した。 Comparative Example 1 and Comparative Example 2
Comparative Example 1 and Comparative Example 2 are photosensitive resin compositions in which the total number of moles of photopolymerizable groups contained in 1000 grams of the photosensitive resin composition contains values outside the range of claim 1. In the same manner as described above, a laser engraving printing original plate and a laser engraving print cured original plate were prepared.
比較例３
ポリエーテルウレアウレタンとは構造が異なるε－カプロラクタム５５．０質量部、Ｎ，Ｎ’－ビス（γ－アミノプロピル）ピペラジンとアジピン酸のナイロン塩４０．０質量重量部と１，３－ビスアミノメチルシクロヘキサンとアジピン酸のナイロン塩７．５質量部とを溶融重縮合して共重合ポリアミドを得た。得られたポリアミド５０．０質量部をメタノール１００質量部および水２０質量部に攪拌付き加熱溶解釜中６０℃で２時間溶解し、乳酸３．６質量部、グリセリンジメタクリレート３４．４質量部、エチレングリコールジエポキシアクリレート５質量部、Ｎ－エチルトルエンスルホン酸アミド３．１質量部、ハイドロキノンモノエチルエーテル０．１質量部、ベンジルジメチルケタール１．０質量部を加え、感光性樹脂組成物溶液を得た。この溶液をテフロン（登録商標）コートしたシャーレに流延し、一昼夜４０℃で減圧乾燥し厚み８００μｍの組成物シートを得た。得られた組成物シート中のメタクリロイル基含有量は組成物１０００グラム中に３．４６モルであった。 Comparative Example 3
55.0 parts by mass of ε-caprolactam having a different structure from polyether urea urethane, 40.0 parts by mass of N, N′-bis (γ-aminopropyl) piperazine and adipic acid nylon salt, and 1,3-bisamino Methylcyclohexane and 7.5 parts by mass of adipic acid nylon salt were melt polycondensed to obtain a copolymerized polyamide. 50.0 parts by mass of the obtained polyamide was dissolved in 100 parts by mass of methanol and 20 parts by mass of water in a heat-dissolved kettle with stirring at 60 ° C. for 2 hours, 3.6 parts by mass of lactic acid, 34.4 parts by mass of glycerol dimethacrylate, 5 parts by mass of ethylene glycol diepoxy acrylate, 3.1 parts by mass of N-ethyltoluenesulfonic acid amide, 0.1 part by mass of hydroquinone monoethyl ether and 1.0 part by mass of benzyl dimethyl ketal were added to prepare a photosensitive resin composition solution. Obtained. This solution was cast on a Teflon (registered trademark) -coated petri dish and dried under reduced pressure at 40 ° C. overnight to obtain a composition sheet having a thickness of 800 μm. The methacryloyl group content in the obtained composition sheet was 3.46 mol in 1000 grams of the composition.
ポリエーテルウレアウレタンとは構造が異なるε－カプロラクタム５５．０質量部、Ｎ，Ｎ’－ビス（γ－アミノプロピル）ピペラジンとアジピン酸のナイロン塩４０．０質量重量部と１，３－ビスアミノメチルシクロヘキサンとアジピン酸のナイロン塩７．５質量部とを溶融重縮合して共重合ポリアミドを得た。得られたポリアミド５０．０質量部をメタノール１００質量部および水２０質量部に攪拌付き加熱溶解釜中６０℃で２時間溶解し、乳酸３．６質量部、グリセリンジメタクリレート３４．４質量部、エチレングリコールジエポキシアクリレート５質量部、Ｎ－エチルトルエンスルホン酸アミド３．１質量部、ハイドロキノンモノエチルエーテル０．１質量部、ベンジルジメチルケタール１．０質量部を加え、感光性樹脂組成物溶液を得た。この溶液をテフロン（登録商標）コートしたシャーレに流延し、一昼夜４０℃で減圧乾燥し厚み８００μｍの組成物シートを得た。得られた組成物シート中のメタクリロイル基含有量は組成物１０００グラム中に３．４６モルであった。 Comparative Example 3
55.0 parts by mass of ε-caprolactam having a different structure from polyether urea urethane, 40.0 parts by mass of N, N′-bis (γ-aminopropyl) piperazine and adipic acid nylon salt, and 1,3-bisamino Methylcyclohexane and 7.5 parts by mass of adipic acid nylon salt were melt polycondensed to obtain a copolymerized polyamide. 50.0 parts by mass of the obtained polyamide was dissolved in 100 parts by mass of methanol and 20 parts by mass of water in a heat-dissolved kettle with stirring at 60 ° C. for 2 hours, 3.6 parts by mass of lactic acid, 34.4 parts by mass of glycerol dimethacrylate, 5 parts by mass of ethylene glycol diepoxy acrylate, 3.1 parts by mass of N-ethyltoluenesulfonic acid amide, 0.1 part by mass of hydroquinone monoethyl ether and 1.0 part by mass of benzyl dimethyl ketal were added to prepare a photosensitive resin composition solution. Obtained. This solution was cast on a Teflon (registered trademark) -coated petri dish and dried under reduced pressure at 40 ° C. overnight to obtain a composition sheet having a thickness of 800 μm. The methacryloyl group content in the obtained composition sheet was 3.46 mol in 1000 grams of the composition.
比較例４及び５
比較例４では、比較例３のポリアミドを用いて表２の組成比率を基にして比較例３と同様にして配合し、組成物中１０００グラム中に光重合性基量２．４８モルを含有する感光性樹脂組成物を得た。又、比較例５では比較例３においてポリアミドを４０．０質量部に減らして、表２の組成比率の通りに光重合性化合物含有率が５３．７質量％と高い感光性樹脂組成物を用いて実施例１と同様に評価してレーザー彫刻用印刷原版およびレーザー彫刻用印刷硬化済み原版を作製した。 Comparative Examples 4 and 5
In Comparative Example 4, the polyamide of Comparative Example 3 was used and blended in the same manner as in Comparative Example 3 based on the composition ratio in Table 2, and the photopolymerizable group amount of 2.48 mol was contained in 1000 grams of the composition. A photosensitive resin composition was obtained. In Comparative Example 5, the polyamide was reduced to 40.0 parts by mass in Comparative Example 3, and a photosensitive resin composition having a high photopolymerizable compound content of 53.7% by mass as shown in the composition ratio of Table 2 was used. In the same manner as in Example 1, a laser engraving printing original plate and a laser engraving print cured original plate were prepared.
比較例４では、比較例３のポリアミドを用いて表２の組成比率を基にして比較例３と同様にして配合し、組成物中１０００グラム中に光重合性基量２．４８モルを含有する感光性樹脂組成物を得た。又、比較例５では比較例３においてポリアミドを４０．０質量部に減らして、表２の組成比率の通りに光重合性化合物含有率が５３．７質量％と高い感光性樹脂組成物を用いて実施例１と同様に評価してレーザー彫刻用印刷原版およびレーザー彫刻用印刷硬化済み原版を作製した。 Comparative Examples 4 and 5
In Comparative Example 4, the polyamide of Comparative Example 3 was used and blended in the same manner as in Comparative Example 3 based on the composition ratio in Table 2, and the photopolymerizable group amount of 2.48 mol was contained in 1000 grams of the composition. A photosensitive resin composition was obtained. In Comparative Example 5, the polyamide was reduced to 40.0 parts by mass in Comparative Example 3, and a photosensitive resin composition having a high photopolymerizable compound content of 53.7% by mass as shown in the composition ratio of Table 2 was used. In the same manner as in Example 1, a laser engraving printing original plate and a laser engraving print cured original plate were prepared.
比較例６
比較例６では、実施例１においてシート状成形物に対する紫外線照射時間を１分間としてレーザー彫刻用硬化済み印刷原版を作製した。 Comparative Example 6
In Comparative Example 6, a cured printing original plate for laser engraving was prepared by setting the ultraviolet irradiation time for the sheet-like molded product in Example 1 to 1 minute.
比較例６では、実施例１においてシート状成形物に対する紫外線照射時間を１分間としてレーザー彫刻用硬化済み印刷原版を作製した。 Comparative Example 6
In Comparative Example 6, a cured printing original plate for laser engraving was prepared by setting the ultraviolet irradiation time for the sheet-like molded product in Example 1 to 1 minute.
次にレーザー彫刻性能評価について説明する。レーザー彫刻装置はＬｕｅｓｃｈｅｒ Ｆｌｅｘｏ社製の３００Ｗ炭酸ガスレーザーを搭載したＦｌｅｘＰｏｓｅ！ｄｉｒｅｃｔを用いた。本装置の仕様はレーザー波長１０．６μｍ、ビーム直径３０μｍ、版装着ドラム直径は３００ｍｍ、加工速度は１．５時間／０．５ｍ２であった。レーザー彫刻の条件は、以下のとおりである。なお、（１）～（３）は装置固有の条件である。（４）～（７）は任意に条件設定が可能であり、それぞれの条件は本装置の標準条件を採用した。
（１）解像度：２５４０ｄｐｉ
（２）レーザーピッチ：１０μｍ
（３）ドラム回転数：９８２ｃｍ／秒
（４）トップパワー：９％
（５）ボトムパワー：１００％
（６）ショルダー幅：０．３０ｍｍ
（７）評価画像：１５０ｌｐｉ、０～１００％まで１％刻みの網点、直径１００μｍ
～６００μｍの独立点について画像形成し、評価した。 Next, laser engraving performance evaluation will be described. The laser engraving machine is a FlexPose equipped with a 300W carbon dioxide laser from Luescher Flexo! direct was used. The specifications of this apparatus were a laser wavelength of 10.6 μm, a beam diameter of 30 μm, a plate mounting drum diameter of 300 mm, and a processing speed of 1.5 hours / 0.5 m 2 . The conditions for laser engraving are as follows. Note that (1) to (3) are conditions specific to the apparatus. Conditions can be arbitrarily set in (4) to (7), and the standard conditions of this apparatus are adopted for each condition.
(1) Resolution: 2540 dpi
(2) Laser pitch: 10 μm
(3) Drum rotation speed: 982 cm / sec (4) Top power: 9%
(5) Bottom power: 100%
(6) Shoulder width: 0.30mm
(7) Evaluation image: 150 lpi, halftone dots in 1% increments from 0 to 100%, diameter 100 μm
Images were formed and evaluated for independent points of ˜600 μm.
（１）解像度：２５４０ｄｐｉ
（２）レーザーピッチ：１０μｍ
（３）ドラム回転数：９８２ｃｍ／秒
（４）トップパワー：９％
（５）ボトムパワー：１００％
（６）ショルダー幅：０．３０ｍｍ
（７）評価画像：１５０ｌｐｉ、０～１００％まで１％刻みの網点、直径１００μｍ
～６００μｍの独立点について画像形成し、評価した。 Next, laser engraving performance evaluation will be described. The laser engraving machine is a FlexPose equipped with a 300W carbon dioxide laser from Luescher Flexo! direct was used. The specifications of this apparatus were a laser wavelength of 10.6 μm, a beam diameter of 30 μm, a plate mounting drum diameter of 300 mm, and a processing speed of 1.5 hours / 0.5 m 2 . The conditions for laser engraving are as follows. Note that (1) to (3) are conditions specific to the apparatus. Conditions can be arbitrarily set in (4) to (7), and the standard conditions of this apparatus are adopted for each condition.
(1) Resolution: 2540 dpi
(2) Laser pitch: 10 μm
(3) Drum rotation speed: 982 cm / sec (4) Top power: 9%
(5) Bottom power: 100%
(6) Shoulder width: 0.30mm
(7) Evaluation image: 150 lpi, halftone dots in 1% increments from 0 to 100%, diameter 100 μm
Images were formed and evaluated for independent points of ˜600 μm.
得られた印刷版について以下の評価項目を評価した。
The following evaluation items were evaluated for the obtained printing plate.
（１）印刷版表面への樹脂カスの付着具合
１０倍の拡大ルーペを使用して、印刷表面への樹脂カスの付着具合を目視により検査し、◎：ほとんど付着なし、○：少し付着有り、△：かなり付着有り、×：付着激しい、の４段階で示した。 (1) Using a magnifier with a magnification of 10 times the resin residue on the printing plate surface, visually inspect the resin residue adhesion on the printing surface, ◎: almost no adhesion, ○: little adhesion, The results are shown in four stages: Δ: considerably adhered, ×: severely adhered.
１０倍の拡大ルーペを使用して、印刷表面への樹脂カスの付着具合を目視により検査し、◎：ほとんど付着なし、○：少し付着有り、△：かなり付着有り、×：付着激しい、の４段階で示した。 (1) Using a magnifier with a magnification of 10 times the resin residue on the printing plate surface, visually inspect the resin residue adhesion on the printing surface, ◎: almost no adhesion, ○: little adhesion, The results are shown in four stages: Δ: considerably adhered, ×: severely adhered.
（２）レリーフ縁部エッジ丸み
超深度カラー３Ｄ形状測定顕微鏡（キーエンス社製ＶＫ－９５１０）を使用して、直径２００μの独立点を拡大し、頂部レリーフの縁部エッジ丸みの判定を行った。縁部エッジに丸みが発生すると印刷物が不明瞭となるために、丸みが発生しないことが必要である。
◎：エッジがシャープで丸み全く発生なし。
○：僅かにエッジに丸みが発生。
△：エッジに少し丸みが発生。
×：エッジに激しい丸みが発生し、エッジが不鮮明。 (2) Relief Edge Edge Roundness Using an ultra-deep color 3D shape measuring microscope (VK-9510 manufactured by Keyence Corporation), an independent point having a diameter of 200 μ was enlarged to determine the edge edge roundness of the top relief. When the edge edge is rounded, the printed matter becomes unclear, so it is necessary that the rounded edge does not occur.
A: The edge is sharp and rounded at all.
○: Slightly rounded edges.
Δ: The edge is slightly rounded.
X: The edge is severely rounded and the edge is unclear.
超深度カラー３Ｄ形状測定顕微鏡（キーエンス社製ＶＫ－９５１０）を使用して、直径２００μの独立点を拡大し、頂部レリーフの縁部エッジ丸みの判定を行った。縁部エッジに丸みが発生すると印刷物が不明瞭となるために、丸みが発生しないことが必要である。
◎：エッジがシャープで丸み全く発生なし。
○：僅かにエッジに丸みが発生。
△：エッジに少し丸みが発生。
×：エッジに激しい丸みが発生し、エッジが不鮮明。 (2) Relief Edge Edge Roundness Using an ultra-deep color 3D shape measuring microscope (VK-9510 manufactured by Keyence Corporation), an independent point having a diameter of 200 μ was enlarged to determine the edge edge roundness of the top relief. When the edge edge is rounded, the printed matter becomes unclear, so it is necessary that the rounded edge does not occur.
A: The edge is sharp and rounded at all.
○: Slightly rounded edges.
Δ: The edge is slightly rounded.
X: The edge is severely rounded and the edge is unclear.
（３）１５０ｌｐｉ最小網点再現性
１０倍の拡大ルーペを使用して、１５０ｌｐｉ最小網点再現性を測定した。 (3) 150 lpi minimum halftone dot reproducibility The 150 lpi minimum halftone dot reproducibility was measured using a 10 × magnification magnifier.
１０倍の拡大ルーペを使用して、１５０ｌｐｉ最小網点再現性を測定した。 (3) 150 lpi minimum halftone dot reproducibility The 150 lpi minimum halftone dot reproducibility was measured using a 10 × magnification magnifier.
（４）高速印刷時の印刷性
レタープレス印刷機としてシール印刷用輪転印刷機を使って１００ｍ／分の速度でＵＶインキを用いて１０００部の印刷を実施し、ハイライト印刷性及びベタインキ乗りを判定した。
〔ハイライト印刷性〕
○：１５０ｌｐｉの３％ハイライトでムラなく鮮明に印刷できる。
△：１５０ｌｐｉの３％ハイライトでわずかに濃度ムラが有る。
×：１５０ｌｐｉの３％ハイライトで濃度ムラが有る。
〔ベタ部インキ乗り〕
○：ベタ部のインキ乗りにムラがなく印刷できる。
△：ベタ部のインキ乗りにわずかに濃度ムラが有る。
×：ベタ部のインキ乗りに濃度ムラが有る。 (4) Printability during high-speed printing Using a rotary printing press for seal printing as a letter press printer, 1000 copies were printed using UV ink at a speed of 100 m / min, and highlight printability and solid ink riding were achieved. Judged.
[Highlight printability]
◯: Printing can be performed clearly and uniformly with 3% highlight at 150 lpi.
Δ: 3% highlight at 150 lpi, slightly uneven density
X: There is uneven density at 3% highlight of 150 lpi.
[Solid ink riding]
◯: Printing can be performed without unevenness on the solid ink.
(Triangle | delta): There exists a slight density | concentration nonuniformity in the ink riding of a solid part.
X: Density unevenness in the solid ink.
レタープレス印刷機としてシール印刷用輪転印刷機を使って１００ｍ／分の速度でＵＶインキを用いて１０００部の印刷を実施し、ハイライト印刷性及びベタインキ乗りを判定した。
〔ハイライト印刷性〕
○：１５０ｌｐｉの３％ハイライトでムラなく鮮明に印刷できる。
△：１５０ｌｐｉの３％ハイライトでわずかに濃度ムラが有る。
×：１５０ｌｐｉの３％ハイライトで濃度ムラが有る。
〔ベタ部インキ乗り〕
○：ベタ部のインキ乗りにムラがなく印刷できる。
△：ベタ部のインキ乗りにわずかに濃度ムラが有る。
×：ベタ部のインキ乗りに濃度ムラが有る。 (4) Printability during high-speed printing Using a rotary printing press for seal printing as a letter press printer, 1000 copies were printed using UV ink at a speed of 100 m / min, and highlight printability and solid ink riding were achieved. Judged.
[Highlight printability]
◯: Printing can be performed clearly and uniformly with 3% highlight at 150 lpi.
Δ: 3% highlight at 150 lpi, slightly uneven density
X: There is uneven density at 3% highlight of 150 lpi.
[Solid ink riding]
◯: Printing can be performed without unevenness on the solid ink.
(Triangle | delta): There exists a slight density | concentration nonuniformity in the ink riding of a solid part.
X: Density unevenness in the solid ink.
評価結果を以下の表１～３に示す。
Evaluation results are shown in Tables 1 to 3 below.
なお、表１～３において、「－」は未測定であることを示す。また、化合物名の略号は下記のとおりである；
ＢＡＰＰ：Ｎ，Ｎ’－ビス（３－アミノプロピル）ピペラジン
ＢＡＣ：１，３－ビス（アミノメチル）シクロヘキサン
ＭＰＤＡ：２－メチルペンタメチレンジアミン
ＨＭＤＡ：ヘキサメチレンジアミン
ＡＥＰ：Ｎ－（２－アミノエチル）ピペラジン
ＢＡＰＩＡ：Ｎ，Ｎ－ジ（３－アミノプロピル）イソプロピルアミン
ＰＥＧ：ポリエチレングリコール、ＰＥＧに続く数値はＰＥＧの数平均分子量を表す
ＨＤＩ：ヘキサメチレンジイソシアネート In Tables 1 to 3, “-” indicates that no measurement was performed. The abbreviations of the compound names are as follows:
BAPP: N, N′-bis (3-aminopropyl) piperazine BAC: 1,3-bis (aminomethyl) cyclohexane MPDA: 2-methylpentamethylenediamine HMDA: hexamethylenediamine AEP: N- (2-aminoethyl) Piperazine BAPIA: N, N-di (3-aminopropyl) isopropylamine PEG: Polyethylene glycol, the number following PEG represents the number average molecular weight of PEG HDI: Hexamethylene diisocyanate
ＢＡＰＰ：Ｎ，Ｎ’－ビス（３－アミノプロピル）ピペラジン
ＢＡＣ：１，３－ビス（アミノメチル）シクロヘキサン
ＭＰＤＡ：２－メチルペンタメチレンジアミン
ＨＭＤＡ：ヘキサメチレンジアミン
ＡＥＰ：Ｎ－（２－アミノエチル）ピペラジン
ＢＡＰＩＡ：Ｎ，Ｎ－ジ（３－アミノプロピル）イソプロピルアミン
ＰＥＧ：ポリエチレングリコール、ＰＥＧに続く数値はＰＥＧの数平均分子量を表す
ＨＤＩ：ヘキサメチレンジイソシアネート In Tables 1 to 3, “-” indicates that no measurement was performed. The abbreviations of the compound names are as follows:
BAPP: N, N′-bis (3-aminopropyl) piperazine BAC: 1,3-bis (aminomethyl) cyclohexane MPDA: 2-methylpentamethylenediamine HMDA: hexamethylenediamine AEP: N- (2-aminoethyl) Piperazine BAPIA: N, N-di (3-aminopropyl) isopropylamine PEG: Polyethylene glycol, the number following PEG represents the number average molecular weight of PEG HDI: Hexamethylene diisocyanate
表１～３の評価結果の実施例１～１０、１５、１６より、可溶性高分子化合物としてポリエーテルウレアウレタンを用いた感光性樹脂組成物中に（メタ）アクリロイル基の含有量が感光性樹脂組成物１０００質量グラム中に２．２ｍｏｌ以上３．７ｍｏｌ以下含有するものがレーザー彫刻性及び印刷性に優れたレーザー彫刻用原版であることが分かり、特に２．４～３．４モルを含有することでさらに優れたレーザー彫刻性が得られることが分かる。
From Examples 1 to 10, 15, and 16 of the evaluation results in Tables 1 to 3, the photosensitive resin composition using polyether urea urethane as the soluble polymer compound has a (meth) acryloyl group content in the photosensitive resin. It can be seen that a composition containing 2.2 mol or more and 3.7 mol or less in 1000 mass grams of the composition is an original plate for laser engraving excellent in laser engraving properties and printability, and particularly contains 2.4 to 3.4 mol. It can be seen that even better laser engraving properties can be obtained.
又、実施例１１～１４ではジアミン成分を実施例１より変更した可溶性高分子化合物を用いたものであるが、塩基性第３級窒素原子含有ジアミンとしてはピペラジン環を有するジアミンがレーザー彫刻性の面から好ましいことが分かる。
In Examples 11 to 14, a soluble polymer compound in which the diamine component is changed from that in Example 1 is used. As a basic tertiary nitrogen atom-containing diamine, a diamine having a piperazine ring is used for laser engraving. It turns out that it is preferable from a surface.
一方、比較例１及び２では、感光性樹脂組成物中の(メタ）アクリロイル基の含有量が特許請求項の範囲外の場合であり、レーザー彫刻性及び印刷性の両者を満足できていないことは明らかである。又比較例３及び４では、ポリエーテルウレアウレタンを用いない感光性樹脂組成物であり、レーザー彫刻性及び印刷性の両者を満足できていない。さらに、比較例５は比較例３のポリアミドを用いて光重合性不飽和化合物を５０質量％以上含有させた場合であるが、光重合性不飽和化合物を５０質量％以上含有させることでレーザー彫刻性は満足できるが、印刷性でベタ部インキ乗りを満足できない。
On the other hand, in Comparative Examples 1 and 2, the content of the (meth) acryloyl group in the photosensitive resin composition is outside the scope of the claims, and both the laser engraving property and the printability cannot be satisfied. Is clear. Further, Comparative Examples 3 and 4 are photosensitive resin compositions that do not use polyether urea urethane and do not satisfy both the laser engraving property and the printability. Further, Comparative Example 5 is a case where 50% by mass or more of the photopolymerizable unsaturated compound is contained using the polyamide of Comparative Example 3, and laser engraving by containing 50% by mass or more of the photopolymerizable unsaturated compound. Although satisfactory, the printing performance cannot satisfy solid ink.
また、比較例６は、紫外線照射時間を短縮して、レーザー彫刻を行う時点での感光性樹脂組成物層中に残留する（メタ）アクリロイル基の残留量が過剰な状態とした場合であるが、レーザー彫刻性及び印刷性の両者を満足できていないことが明らかである。
Comparative Example 6 is a case where the amount of residual (meth) acryloyl groups remaining in the photosensitive resin composition layer at the time of laser engraving is shortened by reducing the ultraviolet irradiation time. It is clear that both the laser engraving property and the printability are not satisfied.
以上の結果から、本発明の樹脂組成物及びそれより得られた印刷原版、硬化済み印刷原版を使用すればレーザー彫刻性に優れ、しかも印刷性に優れた凸版用印刷版を製造することができることが明らかである。
From the above results, it is possible to produce a relief printing plate excellent in laser engraving property and excellent in printability by using the resin composition of the present invention and the printing original plate obtained from the resin composition and the cured printing original plate. Is clear.
本発明の樹脂組成物は、印刷版作製の際のレーザー照射時の版表面への樹脂カス付着が少なく且つレリーフエッジの丸み発生が殆どないので、レーザー彫刻性と高速印刷性能との両者を満足できるレーザー彫刻用印刷原版および硬化済み印刷原版を提供することができる。
The resin composition of the present invention satisfies both the laser engraving property and the high-speed printing performance because there is little resin residue adhesion to the plate surface at the time of laser irradiation during printing plate preparation and almost no rounding of the relief edge. Laser engraving printing plate and cured printing plate can be provided.
The resin composition of the present invention satisfies both the laser engraving property and the high-speed printing performance because there is little resin residue adhesion to the plate surface at the time of laser irradiation during printing plate preparation and almost no rounding of the relief edge. Laser engraving printing plate and cured printing plate can be provided.
Claims (10)
- 少なくとも可溶性合成高分子化合物、光重合性不飽和化合物、光重合開始剤を基本成分とする感光性樹脂組成物から得られる感光性樹脂組成物層を紫外線照射によって硬化させた後にレーザー光照射により画像形成して印刷版を形成するレーザー彫刻用凸版印刷原版において、前記感光性樹脂層が可溶性合成高分子化合物としてポリエーテルウレアウレタン、光重合性不飽和化合物としてエチレン性不飽和モノマーおよび光重合開始剤を必須成分とする前記感光性樹脂組成物からなり、前記感光性樹脂組成物中の（メタ）アクリロイル基の含有量が前記感光性樹脂組成物１０００質量グラム中に２．２モル以上３．７モル以下含有すること特徴とするレーザー彫刻用凸版印刷原版。 A photosensitive resin composition layer obtained from a photosensitive resin composition containing at least a soluble synthetic polymer compound, a photopolymerizable unsaturated compound and a photopolymerization initiator as basic components is cured by ultraviolet irradiation, and then imaged by laser light irradiation. In the relief printing original plate for laser engraving to form a printing plate, the photosensitive resin layer is a polyether urea urethane as a soluble synthetic polymer compound, an ethylenically unsaturated monomer and a photopolymerization initiator as a photopolymerizable unsaturated compound Is an essential component of the photosensitive resin composition, and the content of (meth) acryloyl groups in the photosensitive resin composition is 2.2 mol or more and 3.7 mol per 1000 mass grams of the photosensitive resin composition. A letterpress printing original plate for laser engraving characterized by containing a molar amount or less.
- 前記エチレン性不飽和モノマーが少なくとも２個以上のアクリロイル基またはメタクリロイル基を有し、且つ、前記感光性樹脂組成物中に２０質量％～４２質量％含有することを特徴とする請求項１のレーザー彫刻用印刷原版。 2. The laser according to claim 1, wherein the ethylenically unsaturated monomer has at least two acryloyl groups or methacryloyl groups and is contained in the photosensitive resin composition in an amount of 20% by mass to 42% by mass. Printing master for engraving.
- 前記エチレン性不飽和モノマーが、多価アルコールのポリグリシジルエーテルとメタクリル酸あるいはアクリル酸との開環付加反応生成物を含むことを特徴とする請求項１又は２に記載のレーザー彫刻用印刷原版。 3. The printing original plate for laser engraving according to claim 1, wherein the ethylenically unsaturated monomer contains a ring-opening addition reaction product of polyglycidyl ether of polyhydric alcohol and methacrylic acid or acrylic acid.
- ポリエーテルウレタンウレアが塩基性第３級窒素原子を含有し、ポリエーテルウレタンウレア１０００質量グラム中に塩基性第３級窒素原子を０．５０～２．００モル含有し、数平均分子量が４００～１５００のポリエチレングリコールをソフトセグメントとするブロック共重合体であることを特徴とする請求項１～３のいずれかに記載のレーザー彫刻用印刷原版。 The polyether urethane urea contains a basic tertiary nitrogen atom, 0.50 to 2.00 mol of the basic tertiary nitrogen atom is contained in 1000 mass grams of the polyether urethane urea, and the number average molecular weight is 400 to The printing original plate for laser engraving according to any one of claims 1 to 3, which is a block copolymer having 1,500 polyethylene glycol as a soft segment.
- ポリエーテルウレタンウレアがプロトン性４級化剤によって２５モル％以上を４級化された塩基性第３級窒素原子を含有することを特徴とする請求項４に記載のレーザー彫刻用印刷原版。 5. The printing master plate for laser engraving according to claim 4, wherein the polyether urethane urea contains a basic tertiary nitrogen atom quaternized by 25 mol% or more with a protic quaternizing agent.
- 請求項１～５のいずれかに記載のレーザー彫刻用印刷原版より得られることを特徴とする感光性樹脂凸版印刷版。 A photosensitive resin relief printing plate obtained from the printing plate precursor for laser engraving according to any one of claims 1 to 5.
- 請求項１～５のいずれかに記載のレーザー彫刻用印刷原版に紫外線を照射し、感光性樹脂組成物層中の（メタ）アクリロイル基含有量を紫外線照射前の３０モル％未満としたレーザー彫刻用硬化済み凸版印刷原版。 Laser engraving wherein the printing original plate for laser engraving according to any one of claims 1 to 5 is irradiated with ultraviolet rays, and the content of (meth) acryloyl groups in the photosensitive resin composition layer is less than 30 mol% before ultraviolet irradiation. Cured letterpress printing plate.
- 請求項１～５のいずれかに記載のレーザー彫刻用印刷原版に紫外線を照射し、感光性樹脂組成物層中の（メタ）アクリロイル基含有量を、前記感光性樹脂組成物１０００質量グラム中に１モル未満としたレーザー彫刻用硬化済み凸版印刷原版。 6. The laser engraving printing original plate according to claim 1 is irradiated with ultraviolet rays, and the (meth) acryloyl group content in the photosensitive resin composition layer is added to 1000 mass grams of the photosensitive resin composition. Cured relief printing original plate for laser engraving with less than 1 mole.
- 少なくとも可溶性合成高分子化合物、光重合性不飽和化合物、光重合開始剤を基本成分とする感光性樹脂組成物から得られる感光性樹脂組成物層を紫外線照射によって硬化させたレーザー彫刻用硬化済み印刷原版であって、
紫外線照射後の感光性樹脂組成物層が可溶性合成高分子化合物としてポリエーテルウレアウレタン、光重合性不飽和化合物としてエチレン性不飽和モノマー、および前記エチレン性不飽和モノマーのラジカル重合反応生成物を含有し、
紫外線照射後の感光性樹脂組成物層中の（メタ）アクリロイル基の含有量が前記感光性樹脂組成物１０００質量グラム中に１モル未満であることを特徴とするレーザー彫刻用硬化済み凸版印刷原版。 Cured printing for laser engraving in which a photosensitive resin composition layer obtained from a photosensitive resin composition containing at least a soluble synthetic polymer compound, a photopolymerizable unsaturated compound, and a photopolymerization initiator as basic components is cured by ultraviolet irradiation. The original version
The photosensitive resin composition layer after ultraviolet irradiation contains polyether urea urethane as a soluble synthetic polymer compound, an ethylenically unsaturated monomer as a photopolymerizable unsaturated compound, and a radical polymerization reaction product of the ethylenically unsaturated monomer. And
Cured letterpress printing original plate for laser engraving, characterized in that the content of (meth) acryloyl groups in the photosensitive resin composition layer after ultraviolet irradiation is less than 1 mol in 1000 mass grams of the photosensitive resin composition . - 請求項７～９のいずれかに記載のレーザー彫刻用硬化済み凸版印刷原版より得られることを特徴とする感光性樹脂凸版印刷版。
A photosensitive resin relief printing plate obtained from the cured relief printing original plate for laser engraving according to any one of claims 7 to 9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010508649A JP5316534B2 (en) | 2008-12-25 | 2009-12-25 | Letterpress printing plate for laser engraving and letterpress printing plate obtained therefrom |
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| JP2008329947 | 2008-12-25 | ||
| JP2008-329947 | 2008-12-25 |
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| WO2010074210A1 true WO2010074210A1 (en) | 2010-07-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2009/071554 WO2010074210A1 (en) | 2008-12-25 | 2009-12-25 | Relief printing original plate for laser engraving and relief printing plate obtained therefrom |
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| JP (1) | JP5316534B2 (en) |
| WO (1) | WO2010074210A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017021111A (en) * | 2015-07-08 | 2017-01-26 | 東洋紡株式会社 | Photosensitive resin composition for relief printing plate precursor, and relief printing plate precursor obtained from the same |
| CN114258350A (en) * | 2019-08-23 | 2022-03-29 | 东洋纺株式会社 | Flexographic printing plate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0497154A (en) * | 1990-08-09 | 1992-03-30 | Toyobo Co Ltd | Photosensitive resin composition |
| JP2008225464A (en) * | 2007-02-14 | 2008-09-25 | Toyobo Co Ltd | Photosensitive resin relief printing plate precursor |
| WO2009081899A1 (en) * | 2007-12-26 | 2009-07-02 | Toyo Boseki Kabushiki Kaisha | Relief printing original plate for laser engraving and relief printing plate obtained therefrom |
-
2009
- 2009-12-25 WO PCT/JP2009/071554 patent/WO2010074210A1/en active Application Filing
- 2009-12-25 JP JP2010508649A patent/JP5316534B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0497154A (en) * | 1990-08-09 | 1992-03-30 | Toyobo Co Ltd | Photosensitive resin composition |
| JP2008225464A (en) * | 2007-02-14 | 2008-09-25 | Toyobo Co Ltd | Photosensitive resin relief printing plate precursor |
| WO2009081899A1 (en) * | 2007-12-26 | 2009-07-02 | Toyo Boseki Kabushiki Kaisha | Relief printing original plate for laser engraving and relief printing plate obtained therefrom |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017021111A (en) * | 2015-07-08 | 2017-01-26 | 東洋紡株式会社 | Photosensitive resin composition for relief printing plate precursor, and relief printing plate precursor obtained from the same |
| CN114258350A (en) * | 2019-08-23 | 2022-03-29 | 东洋纺株式会社 | Flexographic printing plate |
| CN114258350B (en) * | 2019-08-23 | 2023-05-26 | 东洋纺株式会社 | Flexographic printing plate |
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| Publication number | Publication date |
|---|---|
| JPWO2010074210A1 (en) | 2012-06-21 |
| JP5316534B2 (en) | 2013-10-16 |
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