JP2008143057A - Laser-engraving printing original plate - Google Patents
Laser-engraving printing original plate Download PDFInfo
- Publication number
- JP2008143057A JP2008143057A JP2006333611A JP2006333611A JP2008143057A JP 2008143057 A JP2008143057 A JP 2008143057A JP 2006333611 A JP2006333611 A JP 2006333611A JP 2006333611 A JP2006333611 A JP 2006333611A JP 2008143057 A JP2008143057 A JP 2008143057A
- Authority
- JP
- Japan
- Prior art keywords
- laser engraving
- photosensitive resin
- original plate
- printing original
- laser
- 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.)
- Granted
Links
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/02—Engraving; Heads therefor
- B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
- B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
Abstract
Description
本発明は、レーザー彫刻法で表面にパターンを形成するレーザー彫刻印刷原版、それを用いた印刷版、およびそれに用いる感光性樹脂組成物に関する。 The present invention relates to a laser engraving printing original plate for forming a pattern on the surface by a laser engraving method, a printing plate using the same, and a photosensitive resin composition used therefor.
近年、フレキソ印刷、ドライオフセット印刷、レタープレス印刷といった樹脂凸版を用いた印刷、あるいはエンボス加工などの表面加工において、レーザー光を照射して照射された部分の樹脂が除去されることにより表面に凹凸パターンを形成するレーザー彫刻法が用いられるようになってきた。レーザー彫刻法に適用される材料としては、加硫ゴム、感光性樹脂組成物を光硬化させて得られる感光性樹脂硬化物、熱硬化性樹脂組成物を熱処理により硬化させたものが用いられている。特に、近年、処理時間の短縮の観点から、感光性樹脂組成物を光硬化させて得られる感光性樹脂硬化物をレーザー彫刻する技術が増えてきた。 In recent years, surface printing such as flexographic printing, dry offset printing, letter press printing, or surface processing such as embossing has been used to remove unevenness on the surface by removing the irradiated resin. Laser engraving to form patterns has come into use. Materials applied to the laser engraving method include vulcanized rubber, a cured photosensitive resin obtained by photocuring a photosensitive resin composition, and a material obtained by curing a thermosetting resin composition by heat treatment. Yes. In particular, in recent years, from the viewpoint of shortening the processing time, a technique for laser engraving a photosensitive resin cured product obtained by photocuring a photosensitive resin composition has increased.
特許文献１（日本国特許２８４６９５４号）では、熱可塑性エラストマーを主原料とする感光性樹脂組成物にカーボンブラックを添加したレーザー彫刻印刷原版の記載がある。この特許文献では、カーボンブラック等で黒色化させているため、印刷原版の透明性が極めて低く、印刷原版中にボイド等の欠陥が存在していても、欠陥を検出することが極めて難しいという問題があった。
特許文献２（特開２００１−３２８３６５号公報）には、グラフト共重合体を用いたレーザー彫刻印刷原版の記載があり、実施例においてカーボンブラック等の黒色顔料や、Ｂｒｉｌｌｉａｎｔ Ｂｌｕｅ Ｒという青色染料、Ｂａｓａｚｏｌ Ｒｅｄ ７１Ｐという赤色染料が用いられている。染料を用いた場合、染料分子は分子レベルで感光性樹脂組成物中に混ざるため、特に紫外線波長領域に吸収の強い化合物を用いた際には、紫外線の光線透過率が極めて低くなり、厚膜での光硬化が非常に困難となる。したがって、染料を添加する場合には、その添加量を極めて低くすることが必要となる。更に、着色が低い場合には、レーザー彫刻法により表面にパターンを形成した際に、パターンコントラストが低くなるという大きな問題があった。
Patent Document 1 (Japanese Patent No. 2846954) describes a laser engraving printing original plate in which carbon black is added to a photosensitive resin composition mainly composed of a thermoplastic elastomer. In this patent document, since blackening is performed with carbon black or the like, the transparency of the printing original plate is very low, and even if a defect such as a void exists in the printing original plate, it is extremely difficult to detect the defect. was there.
Patent Document 2 (Japanese Patent Laid-Open No. 2001-328365) describes a laser engraving printing original plate using a graft copolymer. In Examples, a black pigment such as carbon black, a blue dye called Brilliant Blue R, Basazol Red 71P red dye is used. When dyes are used, the dye molecules are mixed in the photosensitive resin composition at the molecular level. Therefore, particularly when a compound having a strong absorption in the ultraviolet wavelength region is used, the light transmittance of ultraviolet rays is extremely low, resulting in a thick film. The photocuring at is very difficult. Therefore, when adding a dye, it is necessary to make the addition amount extremely low. Further, when the coloring is low, there is a big problem that the pattern contrast is lowered when a pattern is formed on the surface by the laser engraving method.
このように、従来技術のレーザー彫刻印刷原版において、内部の欠陥が検出され易いように透明性が高く、レーザー彫刻した際にコントラストが高いレーザー彫刻印刷版を形成できる材料が存在していなかった。
本発明は、内部の欠陥が検出され易いように透明性が高く、レーザー彫刻した際にコントラストが高いレーザー彫刻印刷版を形成できるレーザー彫刻印刷原版を提供することを目的とする。 It is an object of the present invention to provide a laser engraving printing original plate that is capable of forming a laser engraving printing plate that is highly transparent so that internal defects are easily detected and has high contrast when laser engraving is performed.
本発明者らは鋭意検討し、少なくとも１層の感光性樹脂硬化物からなるレーザー彫刻層を有するレーザー彫刻印刷原版であって、該レーザー彫刻層が顔料を含有し、該顔料の平均粒子径が５ｎｍ以上５μｍ以下であって、前記レーザー彫刻層の最外層の色調が青色であるレーザー彫刻印刷原版を用いることにより、上記の問題を解決できることを見出し、本発明を完成するに至った。
本発明は下記の通りである。
（１）少なくとも１層の感光性樹脂硬化物からなるレーザー彫刻層を有するレーザー彫刻印刷原版であって、該レーザー彫刻層が青色顔料を含有し、該顔料の平均粒子径が５ｎｍ以上５μｍ以下であり、該レーザー彫刻層の最外層の色調が青色であるレーザー彫刻印刷原版。
（２）前記顔料の平均粒子径が１０ｎｍ以上３００ｎｍ以下である、上記（１）のレーザー彫刻印刷原版。
（３）前記顔料が、蛍光あるいは燐光を発する発光性化合物である、上記（１）又は（２）のレーザー彫刻印刷原版。
（４）前記顔料が、吸収スペクトルにおいて４００ｎｍ以下の波長領域にピーク波長を有する、上記（１）〜（３）のいずれかのレーザー彫刻印刷原版。
（５）前記顔料が、フタロシアニン骨格、シアニン骨格、ナフタロシアニン骨格からなる群より選択される少なくとも1種類の分子骨格を有する化合物である、上記（１）〜（５）のいずれかのレーザー彫刻印刷原版。
（６）前記フタロシアニン骨格を有する化合物が中心金属を有する化合物であって、該中心金属が銅、ゲルマニウム、亜鉛、マグネシウム、錫、アルミニウム、インジウム、チタン、ケイ素、コバルト、ニッケル、クロム、パラジウムからなる群より選択される少なくとも１種類の金属イオンである、上記（５）のレーザー彫刻印刷原版。
（７）前記感光性樹脂硬化物が、２０℃において液状の感光性樹脂組成物を光硬化させて形成される感光性樹脂硬化物である、上記（１）〜（６）のいずれかのレーザー彫刻印刷原版。
（８）前記レーザー彫刻層と接する下層が、クッション層あるいは支持体である、上記（１）〜（７）のいずれかのレーザー彫刻印刷原版。
（９）前記クッション層が、感光性樹脂硬化物を含み、且つ気泡あるいは有機系微粒子を含有する、上記（８）のレーザー彫刻印刷原版。
（１０）前記有機系微粒子が中空マイクロカプセルであって、該中空マイクロカプセルの表面に無機系微粒子が付着している、上記（９）のレーザー彫刻印刷原版。
（１１）前記クッション層と前記レーザー彫刻層が直接接着した円筒状積層体であって、該クッション層と該レーザー彫刻層が継ぎ目を有しない、上記（８）〜（１０）のいずれかのレーザー彫刻印刷原版。
（１２）前記クッション層の密度が０．１ｇ／ｃｍ３以上０．９ｇ／ｃｍ３以下である、上記（８）〜（１１）のいずれかのレーザー彫刻印刷原版。
（１３）前記支持体が中空円筒状支持体である、上記（８）のレーザー彫刻印刷原版。
（１４）前記中空円筒状支持体が、繊維強化プラスチック、フィルム強化プラスチック、金属からなる群より選択される少なくとも１種類の材料を構成成分とする中空円筒状支持体である、上記（１３）のレーザー彫刻印刷原版。
（１５）上記（１）〜（１４）のいずれかのレーザー彫刻印刷原版にレーザー光が照射されて、レーザー光が照射された部分が除去されて凹パターンが形成されているレーザー彫刻印刷版。
（１６）前記レーザー光の発振波長１５０ｎｍ以上１５μｍ以下である、上記（１５）のレーザー彫刻印刷版。
（１７）上記（１）〜（１４）のいずれかのレーザー彫刻印刷原版を製造するための感光性樹脂組成物であって、該感光性樹脂組成物が数平均分子量１０００以上３０万以下の樹脂（ａ）、数平均分子量１０００未満で分子内に重合性不飽和基を有する有機化合物（ｂ）、平均粒子径５ｎｍ以上５μｍ以下の青色顔料を含有するレーザー彫刻印刷原版用感光性樹脂組成物。
（１８）前記顔料が前記有機化合物（ｂ）中に微分散処理されたものであって、該微分散処理が超音波分散法、高速撹拌分散法、高速せん断力分散法、ビーズミル分散法からなる群より選択される少なくとも１種類の方法である、上記（１７）のレーザー彫刻印刷原版用感光性樹脂組成物。
（１９）前記感光性樹脂組成物が２０℃において液状感光性樹脂組成物であって、且つ前記青色顔料が銅フタロシアニンである、上記（１７）又は（１８）のレーザー彫刻印刷原版用感光性樹脂組成物。
（２０）前記青色顔料の平均粒子径が、１０ｎｍ以上３００ｎｍ以下である、上記（１７）〜（１９）のいずれかのレーザー彫刻印刷原版用感光性樹脂組成物。
The present inventors have intensively studied and are a laser engraving printing original plate having a laser engraving layer composed of at least one layer of a cured photosensitive resin, the laser engraving layer containing a pigment, and the average particle diameter of the pigment is The inventors have found that the above problem can be solved by using a laser engraving printing original plate having a color tone of 5 nm or more and 5 μm or less and the outermost layer of the laser engraving layer being blue, and has completed the present invention.
The present invention is as follows.
(1) A laser engraving printing original plate having a laser engraving layer composed of at least one photosensitive resin cured product, wherein the laser engraving layer contains a blue pigment, and the average particle diameter of the pigment is 5 nm or more and 5 μm or less A laser engraving printing original plate in which the color tone of the outermost layer of the laser engraving layer is blue.
(2) The laser engraving printing original plate of (1), wherein the average particle diameter of the pigment is 10 nm or more and 300 nm or less.
(3) The laser engraving printing original plate of (1) or (2) above, wherein the pigment is a light emitting compound that emits fluorescence or phosphorescence.
(4) The laser engraving printing original plate according to any one of (1) to (3), wherein the pigment has a peak wavelength in a wavelength region of 400 nm or less in an absorption spectrum.
(5) Laser engraving printing according to any one of (1) to (5), wherein the pigment is a compound having at least one molecular skeleton selected from the group consisting of a phthalocyanine skeleton, a cyanine skeleton, and a naphthalocyanine skeleton. Original edition.
(6) The compound having the phthalocyanine skeleton is a compound having a central metal, and the central metal is made of copper, germanium, zinc, magnesium, tin, aluminum, indium, titanium, silicon, cobalt, nickel, chromium, palladium. The laser engraving printing original plate of (5) above, which is at least one metal ion selected from the group.
(7) The laser according to any one of (1) to (6), wherein the cured photosensitive resin is a cured photosensitive resin formed by photocuring a liquid photosensitive resin composition at 20 ° C. Engraving printing master.
(8) The laser engraving printing original plate according to any one of (1) to (7), wherein the lower layer in contact with the laser engraving layer is a cushion layer or a support.
(9) The laser engraving printing original plate of (8), wherein the cushion layer contains a cured photosensitive resin and contains bubbles or organic fine particles.
(10) The laser engraving printing original plate of (9), wherein the organic fine particles are hollow microcapsules, and the inorganic fine particles are attached to the surface of the hollow microcapsules.
(11) The laser according to any one of (8) to (10) above, wherein the cushion layer and the laser engraving layer are directly bonded to each other, and the cushion layer and the laser engraving layer do not have a seam. Engraving printing master.
(12) The laser engraving printing original plate according to any one of (8) to (11), wherein the cushion layer has a density of 0.1 g / cm 3 or more and 0.9 g / cm 3 or less.
(13) The laser engraving printing original plate according to (8), wherein the support is a hollow cylindrical support.
(14) The hollow cylindrical support according to (13), wherein the hollow cylindrical support is a hollow cylindrical support having at least one material selected from the group consisting of fiber reinforced plastic, film reinforced plastic, and metal as a constituent component. Laser engraving printing master.
(15) A laser engraving printing plate in which a laser beam is irradiated on the laser engraving printing original plate of any one of (1) to (14), and a portion irradiated with the laser beam is removed to form a concave pattern.
(16) The laser engraving printing plate according to (15), wherein the laser light has an oscillation wavelength of 150 nm to 15 μm.
(17) A photosensitive resin composition for producing the laser engraving printing original plate according to any one of (1) to (14) above, wherein the photosensitive resin composition has a number average molecular weight of 1,000 to 300,000. (A) A photosensitive resin composition for a laser engraving printing original plate, comprising an organic compound (b) having a number average molecular weight of less than 1000 and having a polymerizable unsaturated group in the molecule, and a blue pigment having an average particle diameter of 5 nm to 5 μm.
(18) The pigment is finely dispersed in the organic compound (b), and the fine dispersion treatment includes an ultrasonic dispersion method, a high-speed stirring dispersion method, a high-speed shear force dispersion method, and a bead mill dispersion method. The photosensitive resin composition for a laser engraving printing original plate according to (17), which is at least one method selected from the group.
(19) The photosensitive resin for laser engraving printing original plate according to (17) or (18), wherein the photosensitive resin composition is a liquid photosensitive resin composition at 20 ° C., and the blue pigment is copper phthalocyanine. Composition.
(20) The photosensitive resin composition for a laser engraving printing original plate according to any one of (17) to (19), wherein the blue pigment has an average particle size of 10 nm to 300 nm.
本発明は、内部の欠陥が検出され易いように透明性が高く、レーザー彫刻した際にコントラストが高いレーザー彫刻印刷版を形成できるレーザー彫刻印刷原版を提供することを目的とする。 It is an object of the present invention to provide a laser engraving printing original plate that is capable of forming a laser engraving printing plate that is highly transparent so that internal defects are easily detected and has high contrast when laser engraving is performed.
以下、さらに詳細に本発明の好ましい実施態様を説明する。
本発明の印刷原版は、少なくとも１層の感光性樹脂硬化物からなるレーザー彫刻層を有するレーザー彫刻印刷原版であって、該レーザー彫刻層が顔料を含有し、前記レーザー彫刻層の最外層の色調が青色である。レーザー彫刻層の最外層の色調が青色であることは、添加する顔料の色も青色であることを意味する。
色調は、ＣＩＥ（国際照明委員会）表色系において、ｘｙｚ色度図を基に定義する。すなわち、ｘｙ色度図のｘｙ座標（ｘ、ｙ）で、（０．０４、０．３４）、（０．０７、０．２）、（０．１、０．１）、（０．１３、０．０５）、（０．１９、０．０１）、（０．２３、０．０３）、（０．２８、０．０６）、（０．３，０．１３）、（０．３２、０．２）、（０．３、０．２４）、（０．２６、０．３）、（０．２、０．３３）、（０．１２、０．３４）、（０．０４、０．３４）の各点を順に線で結んで囲まれる領域を本発明の青色と定義する。
Hereinafter, preferred embodiments of the present invention will be described in more detail.
The printing original plate of the present invention is a laser engraving printing original plate having a laser engraving layer composed of at least one photosensitive resin cured product, the laser engraving layer containing a pigment, and the color tone of the outermost layer of the laser engraving layer Is blue. That the color tone of the outermost layer of the laser engraving layer is blue means that the color of the pigment to be added is also blue.
The color tone is defined based on the xyz chromaticity diagram in the CIE (International Commission on Illumination) color system. That is, the xy coordinates (x, y) of the xy chromaticity diagram are (0.04, 0.34), (0.07, 0.2), (0.1, 0.1), (0.13 , 0.05), (0.19, 0.01), (0.23, 0.03), (0.28, 0.06), (0.3, 0.13), (0.32 , 0.2), (0.3, 0.24), (0.26, 0.3), (0.2, 0.33), (0.12, 0.34), (0.04 , 0.34) is defined by the blue color of the present invention.
レーザー彫刻層の厚さは特に制限はないが、感光性樹脂組成物の硬化性の点から、５０μｍ以上５０ｍｍ以下であることが好ましい。より好ましくは１００μｍ以上１０ｍｍ以下、更に好ましくは５００μｍ以上５ｍｍ以下である。
本発明で用いる顔料は青色顔料である。平均粒子径は５ｎｍ以上５μｍ以下である。より好ましくは５ｎｍ以上８００ｎｍ以下、更に好ましくは１０ｎｍ以上３００ｎｍ以下である。顔料の平均粒子径がこの範囲であれば、感光性樹脂組成物を厚膜で光硬化させることが可能である。感光性樹脂硬化物層中に分散した顔料の平均粒子径は、感光性樹脂硬化物層を深さ方向に切断した切片を高分解能走査型電子顕微鏡あるいは透過型電子顕微鏡で観察することにより求めることとする。顔料粒子がモニター画面に１００個程度入る倍率で、撮影した写真を基に測長する方法やカメラからの信号をデジタル処理して画像解析ソフトウエアーを用いて処理する方法などを挙げることができる。また、感光性樹脂組成物中に分散した顔料粒子の場合、特に粘度の高い分散液や室温で固体状物であるものの中に分散されている顔料をレーザー散乱法で測定することが難しいので、そのような場合は、感光性樹脂組成物を光硬化させて上記と同様にして測定することが好ましい。
The thickness of the laser engraving layer is not particularly limited, but is preferably 50 μm or more and 50 mm or less from the viewpoint of curability of the photosensitive resin composition. More preferably, they are 100 micrometers or more and 10 mm or less, More preferably, they are 500 micrometers or more and 5 mm or less.
The pigment used in the present invention is a blue pigment. The average particle size is 5 nm or more and 5 μm or less. More preferably, they are 5 nm or more and 800 nm or less, More preferably, they are 10 nm or more and 300 nm or less. If the average particle diameter of the pigment is within this range, the photosensitive resin composition can be photocured with a thick film. The average particle size of the pigment dispersed in the cured photosensitive resin layer is obtained by observing a section obtained by cutting the cured photosensitive resin layer in the depth direction with a high-resolution scanning electron microscope or a transmission electron microscope. And Examples include a method for measuring the length based on a photograph taken at a magnification at which about 100 pigment particles enter the monitor screen, and a method for digitally processing a signal from a camera and processing it using image analysis software. In addition, in the case of pigment particles dispersed in the photosensitive resin composition, it is difficult to measure the pigment dispersed in a highly viscous dispersion or a solid material at room temperature by the laser scattering method. In such a case, it is preferable to measure in the same manner as above by photocuring the photosensitive resin composition.
本発明で用いる青色顔料は、有機系顔料であっても無機系顔料であっても構わない。有機系顔料としては、フタロシアニン骨格、シアニン骨格、ナフタロシアニン骨格から選択される少なくとも１種類の分子骨格を有する化合物が好ましい。特にフタロシアニン骨格を有する化合物は、耐候性の観点から好ましい化合物である。更に、フタロシアニン骨格を有する化合物が中心金属を有する化合物であって、該中心金属が銅、ゲルマニウム、亜鉛、マグネシウム、錫、アルミニウム、インジウム、チタン、ケイ素、コバルト、ニッケル、クロム、パラジウムから選択される少なくとも１種類の金属イオンであることが好ましい。また、青色の有機系顔料として、塩基性顔料のメチレンブルー、メチルバイオレット、酸縮合顔料のアルカリブルー、ジオキサジンバイオレット等の化合物を挙げることができる。その中でも特に、銅フタロシアニンは強い青色を示す顔料として好ましい。 The blue pigment used in the present invention may be an organic pigment or an inorganic pigment. As the organic pigment, a compound having at least one molecular skeleton selected from a phthalocyanine skeleton, a cyanine skeleton, and a naphthalocyanine skeleton is preferable. In particular, a compound having a phthalocyanine skeleton is a preferable compound from the viewpoint of weather resistance. Further, the compound having a phthalocyanine skeleton is a compound having a central metal, and the central metal is selected from copper, germanium, zinc, magnesium, tin, aluminum, indium, titanium, silicon, cobalt, nickel, chromium, and palladium. Preferably, it is at least one type of metal ion. Examples of blue organic pigments include compounds such as basic pigments such as methylene blue and methyl violet, acid condensation pigments such as alkali blue and dioxazine violet. Among these, copper phthalocyanine is particularly preferable as a pigment exhibiting a strong blue color.
また、無機系顔料として、２（Ａｌ２・Ｎａ２／Ｓｉ３Ｏ１０）・Ｎａ２Ｓ４を主成分とする群青、Ｆｅ４「Ｆｅ(ＣＮ)６」３を主成分とする紺青、Ｃｏ２Ｏ３とＡｌ２Ｏ３を主成分とするコバルトブルー、ＣｏＯ・ＳｎＯ２を主成分とするセルリアンブルー、ＣａＯ・ＣｕＯ・４ＳｉＯ２を主成分とするエジプトブルー、２ＣｕＣＯ３・Ｃｕ（ＯＨ）２を主成分とする藍銅鉱、２（Ａｌ２Ｎａ２Ｓｉ３Ｏ１０）・Ｎａ２Ｓ４を主成分とする瑠璃、マンガンバイオレット、マルスバイオレット、コバルトバイオレットなどの顔料を挙げることができる。更に、コバルト、アルミニウム、クロム等の元素を有する複合酸化物系焼成無機顔料を用いることもできる。 Further, as an inorganic pigment, ultramarine blue mainly composed of 2 (Al 2 · Na 2 / Si 3 O 10 ) · Na 2 S 4 , bitumen mainly composed of Fe 4 "Fe (CN) 6 " 3 , Co Cobalt blue mainly composed of 2 O 3 and Al 2 O 3 , Cerulean blue mainly composed of CoO · SnO 2 , Egypt blue mainly composed of CaO · CuO · 4SiO 2 , 2CuCO 3 · Cu (OH) 2 And pigments such as soot, manganese violet, mars violet, cobalt violet and the like containing as a main component cyanide or 2 (Al 2 Na 2 Si 3 O 10 ) · Na 2 S 4 as a main component. Furthermore, a composite oxide-based fired inorganic pigment having an element such as cobalt, aluminum, or chromium can also be used.
また、青色顔料は蛍光あるいは燐光を発する化合物であることが好ましい。蛍光あるいは燐光を発する化合物を含有することにより、特に網点等の微細パターンを観察する際に照射する照明の光によって発光することで、パターンのコントラストをより高める効果がある。蛍光あるいは燐光とは、化合物が光を吸収して基底状態から励起状態に遷移し、再度基底状態に戻る際に発する光である。
青色顔料は、感光性樹脂組成物の厚膜状態での光硬化性の点から、吸収スペクトルにおいて４００ｎｍ以下の波長領域にピーク波長を有することが好ましい。
レーザー彫刻層を形成する感光性樹脂組成物は、数平均分子量１０００以上３０万以下の樹脂（ａ）、数平均分子量１０００未満で分子内に重合性不飽和基を有する有機化合物（ｂ）、平均粒子径５ｎｍ以上５μｍ以下の青色顔料を含有することが好ましい。数平均分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ）を用いて示差屈折計あるいは紫外可視分光光度計を用いてモニターすることができる。更に、分子量既知のポリスチレン標準サンプルの値を基準として換算して求めることができる。
The blue pigment is preferably a compound that emits fluorescence or phosphorescence. By containing a compound that emits fluorescence or phosphorescence, light is emitted by illumination light that is irradiated particularly when observing a fine pattern such as a halftone dot, and this has an effect of further increasing the contrast of the pattern. Fluorescence or phosphorescence is light emitted when a compound absorbs light and transitions from a ground state to an excited state and returns to the ground state again.
The blue pigment preferably has a peak wavelength in a wavelength region of 400 nm or less in the absorption spectrum from the viewpoint of photocurability in the thick film state of the photosensitive resin composition.
The photosensitive resin composition for forming the laser engraving layer is a resin (a) having a number average molecular weight of 1000 or more and 300,000 or less, an organic compound (b) having a number average molecular weight of less than 1000 and having a polymerizable unsaturated group in the molecule, an average It is preferable to contain a blue pigment having a particle diameter of 5 nm to 5 μm. The number average molecular weight can be monitored using a differential refractometer or an ultraviolet-visible spectrophotometer using gel permeation chromatography (GPC). Furthermore, it can obtain | require by converting on the basis of the value of a polystyrene standard sample with known molecular weight.
また、青色顔料の濃度は、レーザー彫刻により形成された凹凸パターンの視認性向上の点から、感光性樹脂組成物全重量の５０ｐｐｍ以上が好ましく、厚膜とした場合の感光性樹脂組成物の硬化性の点から１０００ｐｐｍ以下が好ましい。より好ましくは１００ｐｐｍ以上８００ｐｐｍ以下、更に好ましくは１００ｐｐｍ以上５００ｐｐｍ以下である。
青色顔料は、レーザー彫刻層を形成する感光性樹脂組成物で使用する有機化合物（ｂ）が室温で液体の場合には、該有機化合物（ｂ）に分散させて、樹脂（ａ）等に混合されることが好ましい。また、有機化合物（ｂ）に分散させる処理方法として、超音波分散法、高速撹拌分散法、高速せん断力分散法、ビーズミル分散法から選択される少なくとも１種類の方法を用いることが好ましい。特に、超微粒子に分散させる方法として、高速せん断力分散法が効率の観点から好ましい。例えば、特許第２７８８０１０号、特許第３０２１４４８号、特許第３４１２７５３号、特開平１０−３３７４５７号、特開２００５−１４４３２９号に記載の乳化装置を顔料の超微分散処理に用いることができる。前記有機化合物（ｂ）の２０℃における粘度は、１ｍＰａ・ｓ以上２Ｐａ・ｓ以下が好ましい。より好ましくは１ｍＰａ・ｓ以上５００ｍＰａ・ｓ以下、更に好ましくは１ｍＰａ・ｓ以上１００ｍＰａ・ｓ以下である。顔料の微分散の点から分散媒体の粘度が低い方が、好ましい。
Further, the concentration of the blue pigment is preferably 50 ppm or more of the total weight of the photosensitive resin composition from the viewpoint of improving the visibility of the uneven pattern formed by laser engraving, and curing of the photosensitive resin composition when it is a thick film From the viewpoint of properties, 1000 ppm or less is preferable. More preferably, they are 100 ppm or more and 800 ppm or less, More preferably, they are 100 ppm or more and 500 ppm or less.
When the organic compound (b) used in the photosensitive resin composition forming the laser engraving layer is liquid at room temperature, the blue pigment is dispersed in the organic compound (b) and mixed with the resin (a) or the like. It is preferred that Further, as a treatment method for dispersing in the organic compound (b), it is preferable to use at least one method selected from an ultrasonic dispersion method, a high-speed stirring dispersion method, a high-speed shearing force dispersion method, and a bead mill dispersion method. In particular, as a method of dispersing in ultrafine particles, a high-speed shearing force dispersion method is preferable from the viewpoint of efficiency. For example, the emulsifying apparatus described in Japanese Patent No. 2788010, Japanese Patent No. 3021448, Japanese Patent No. 3412753, Japanese Patent Application Laid-Open No. 10-337457, and Japanese Patent Application Laid-Open No. 2005-144329 can be used for the ultrafine dispersion treatment of the pigment. The viscosity of the organic compound (b) at 20 ° C. is preferably 1 mPa · s to 2 Pa · s. More preferably, it is 1 mPa * s or more and 500 mPa * s or less, More preferably, it is 1 mPa * s or more and 100 mPa * s or less. From the viewpoint of fine dispersion of the pigment, it is preferable that the dispersion medium has a lower viscosity.
本発明の印刷原版の用途は、特に限定するものではないが、レーザー彫刻により表面に凹凸パターンを形成するフレキソ印刷原版用シートあるいはロール、グラビア印刷用シートあるいはロール、あるいはレーザー光を照射して貫通した孔状パターンを形成するスクリーン印刷用シートあるいはロータリースクリーン、孔版印刷用原版材料、オフセット印刷法で用いられるブランケット、アニロックスロールに接して用いられるインキ量調整用ロール、印刷用クッションロール、インクジェットプリンター、レーザープリンター、複写機等に搭載されているロール等の印刷基材、あるいは３次元立体成形等の用途として用いることができる。特に、厚膜に光硬化させる必要のあるものである場合に、本発明の効果は一層発揮される。
本発明で用いる感光性樹脂組成物は、２０℃において固体状であっても液状であっても構わないが、成形性の容易さから、２０℃において液状の感光性樹脂組成物であることが特に好ましい。ここで言う液状樹脂とは、容易に流動変形し、かつ冷却により変形された形状に固化できるという性質を有する高分子体を意味し、外力を加えたときに、その外力に応じて瞬時に変形し、かつ外力を除いたときには、短時間に元の形状を回復する性質を有するエラストマーに対する言葉である。
The use of the printing original plate of the present invention is not particularly limited, but it is penetrated by irradiation with laser light, a flexographic printing original sheet or roll that forms an uneven pattern on the surface by laser engraving, or a gravure printing sheet or roll. Screen printing sheet or rotary screen for forming a perforated pattern, stencil printing plate material, blanket used in offset printing, ink amount adjusting roll used in contact with anilox roll, printing cushion roll, inkjet printer, It can be used as a printing substrate such as a roll mounted on a laser printer, a copying machine or the like, or as a three-dimensional solid molding. In particular, the effect of the present invention is further exhibited when the thick film needs to be photocured.
The photosensitive resin composition used in the present invention may be solid or liquid at 20 ° C., but may be a liquid photosensitive resin composition at 20 ° C. for ease of moldability. Particularly preferred. The liquid resin here means a polymer that has the property of being easily deformed by flow and solidified into a deformed shape by cooling. When an external force is applied, the liquid resin is instantly deformed according to the external force. However, it is a term for an elastomer having the property of recovering its original shape in a short time when the external force is removed.
樹脂（ａ）が２０℃において液状樹脂である場合に、感光性樹脂組成物も２０℃において液状である。これから得られる感光性樹脂硬化物をシート状、もしくは円筒状に成形する際、良好な厚み精度や寸法精度を得ることができる本発明の感光性樹脂組成物は、好ましくは、２０℃における粘度が１０Ｐａ・ｓ以上１０ｋＰａ・ｓ以下である。さらに好ましくは、５０Ｐａ・ｓ以上５ｋＰａ・ｓ以下である。粘度が１０Ｐａ・ｓ以上であれば、作製される感光性樹脂硬化物の機械的強度が十分であり、円筒状に成形する場合においても形状を保持し易く、加工し易い。粘度が１０ｋＰａ・ｓ以下であれば、常温でも変形し易く、加工が容易である。シート状あるいは円筒状の感光性樹脂硬化物に成形し易く、プロセスも簡便である。特に厚み精度の高い円筒状感光性樹脂硬化物を得るためには、円筒状支持体上に液状感光性樹脂層を形成する際に、該感光性樹脂組成物が重力により液ダレ等の現象を起こさないように粘度を１００Ｐａ・ｓ以上、より好ましくは２００Ｐａ・ｓ以上、更に好ましくは５００Ｐａ・ｓ以上の比較的粘度の高い感光性樹脂組成物であることが望ましい。 When the resin (a) is a liquid resin at 20 ° C., the photosensitive resin composition is also liquid at 20 ° C. The photosensitive resin composition of the present invention, which can obtain good thickness accuracy and dimensional accuracy when the cured photosensitive resin obtained from this is molded into a sheet or cylinder, preferably has a viscosity at 20 ° C. It is 10 Pa · s or more and 10 kPa · s or less. More preferably, it is 50 Pa · s or more and 5 kPa · s or less. When the viscosity is 10 Pa · s or more, the mechanical strength of the produced photosensitive resin cured product is sufficient, and the shape can be easily held and processed even when molded into a cylindrical shape. If the viscosity is 10 kPa · s or less, it is easily deformed even at room temperature and easy to process. It is easy to form into a sheet-like or cylindrical photosensitive resin cured product, and the process is simple. In particular, in order to obtain a cylindrical photosensitive resin cured product with high thickness accuracy, when the liquid photosensitive resin layer is formed on the cylindrical support, the photosensitive resin composition may cause a phenomenon such as liquid dripping due to gravity. It is desirable that the photosensitive resin composition has a relatively high viscosity with a viscosity of 100 Pa · s or more, more preferably 200 Pa · s or more, and even more preferably 500 Pa · s or more so as not to occur.
樹脂（ａ）の数平均分子量は、１０００以上３０万以下、より好ましくは２０００以上１５万以下、更に好ましくは５０００以上５万以下である。樹脂（ａ）の数平均分子量は１０００以上であれば、後に架橋して作成する感光性樹脂硬化物が強度を保ち、印刷用基材などとして用いる場合、繰り返しの使用にも耐えられる。また、樹脂（ａ）の数平均分子量の上限は、２０万以下が好ましい。３０万以下であれば、感光性樹脂組成物の粘度が過度に上昇することもなく、シート状、あるいは円筒状の感光性樹脂硬化物を作製する際に加熱押し出し等の複雑な加工方法は必要ない。ここで言う数平均分子量とは、ゲル浸透クロマトグラフィーを用いて測定し、分子量既知のポリスチレンで検量し換算した値である。 The number average molecular weight of the resin (a) is from 1,000 to 300,000, more preferably from 2,000 to 150,000, and even more preferably from 5,000 to 50,000. If the number average molecular weight of the resin (a) is 1000 or more, the cured photosensitive resin produced by crosslinking later maintains strength, and can be used repeatedly when used as a printing substrate. The upper limit of the number average molecular weight of the resin (a) is preferably 200,000 or less. If it is 300,000 or less, the viscosity of the photosensitive resin composition does not increase excessively, and a complicated processing method such as heat extrusion is necessary when producing a cured resin material in the form of a sheet or cylinder. Absent. The number average molecular weight referred to here is a value measured by gel permeation chromatography, calibrated with polystyrene having a known molecular weight, and converted.
樹脂（ａ）は、分子内に重合性不飽和基を有していても構わない。特に好ましい化合物として１分子あたり平均で０．７以上の重合性不飽和基を有するポリマーを挙げることができる。１分子あたり平均で０．７以上の場合、感光性樹脂組成物より得られる光硬化物の機械強度に優れ、耐久性も良好で、特に印刷用基材として繰り返しの使用にも耐えらるのものとなり好ましい。感光性樹脂硬化物の機械強度を考慮すると、樹脂（ａ）の重合性不飽和基は１分子あたり０．７以上が好ましく、１を越える量が更に好ましい。また、１分子あたりの重合性不飽和基数の上限については特に限定しないが、好ましい範囲としては２０以下である。２０以下であれば、光硬化時の収縮を低く抑えることができ、また表面近傍でのクラック等の発生も抑制できる。「分子内」とは高分子主鎖の末端、高分子側鎖の末端や高分子主鎖中や側鎖中に直接、重合性不飽和基が付いている場合なども含まれる。 The resin (a) may have a polymerizable unsaturated group in the molecule. A particularly preferred compound is a polymer having an average of 0.7 or more polymerizable unsaturated groups per molecule. When the average is 0.7 or more per molecule, the photocured product obtained from the photosensitive resin composition has excellent mechanical strength and good durability, and can withstand repeated use, particularly as a printing substrate. This is preferable. Considering the mechanical strength of the cured photosensitive resin, the polymerizable unsaturated group of the resin (a) is preferably 0.7 or more per molecule, and more preferably more than 1. The upper limit of the number of polymerizable unsaturated groups per molecule is not particularly limited, but is preferably 20 or less. If it is 20 or less, the shrinkage | contraction at the time of photocuring can be suppressed low, and generation | occurrence | production of the crack etc. in the surface vicinity can also be suppressed. “Intramolecular” includes the case where a polymerizable unsaturated group is directly attached to the terminal of the polymer main chain, the terminal of the polymer side chain, the polymer main chain or the side chain.
樹脂（ａ）としては、下記に示すようなポリマーを骨格として、前記特定官能基を有するものを挙げることができる。骨格となるポリマーの例として、ポリエチレン、ポリプロピレンなどのポリオレフィン類、ポリブタジエン、ポリイソプレンなどのポリジエン類、ポリ塩化ビニルポリ塩化ビニリデン等のポリハロオレフィン類、ポリスチレン、ポリアクリロニトリル、ポリビニルアルコール、ポリ酢酸ビニル、ポリビニルアセタール、ポリアクリル酸、ポリ（メタ）アクリル酸エステル類、ポリ（メタ）アクリルアミド、ポリエステル、ポリカーボネート、ポリアセタール、ポリウレタン、ポリアミド、ポリウレア、ポリイミド等の主鎖にヘテロ原子を有する高分子等からなる群より選ばれる１種若しくは２種以上のものを挙げることができる。複数の高分子を用いる場合の形態としては共重合体、ブレンドどちらでもよい。 Examples of the resin (a) include those having the specific functional group with a polymer as shown below as a skeleton. Examples of skeleton polymers include polyolefins such as polyethylene and polypropylene, polydienes such as polybutadiene and polyisoprene, polyhaloolefins such as polyvinyl chloride and polyvinylidene chloride, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyvinyl acetate, and polyvinyl acetate. From the group consisting of polymers having a hetero atom in the main chain such as acetal, polyacrylic acid, poly (meth) acrylic acid esters, poly (meth) acrylamide, polyester, polycarbonate, polyacetal, polyurethane, polyamide, polyurea, polyimide, etc. One or two or more selected ones can be mentioned. When using a plurality of polymers, either a copolymer or a blend may be used.
特にフレキソ印刷版用途のように柔軟なレリーフ画像が必要な場合には、樹脂（ａ）として、一部、ガラス転移温度が２０℃以下の液状樹脂、さらに好ましくはガラス転移温度０℃以下の液状樹脂を添加することもできる。このような液状樹脂として、例えばポリエチレン、ポリブタジエン、水添ポリブタジエン、ポリイソプレン、水添ポイソプレン等の炭化水素類、アジペート、ポリカプロラクトン等のポリエステル類、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリエーテル類、脂肪族ポリカーボネート、ポリジメチルシロキサン等のシリコーン類、（メタ）アクリル酸及び／またはその誘導体の重合体及びこれらの混合物やコポリマー類があげられる。その含有量は、樹脂（ａ）全体に対して３０ｗｔ％以上１００ｗｔ％以下が好ましい。特に耐候性の観点からポリカーボネート構造を有する不飽和ポリウレタン類が好ましい。 In particular, when a flexible relief image is required as in flexographic printing plate applications, the resin (a) is partly a liquid resin having a glass transition temperature of 20 ° C. or lower, more preferably a liquid having a glass transition temperature of 0 ° C. or lower. Resin can also be added. Examples of such a liquid resin include hydrocarbons such as polyethylene, polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated poisoprene, polyesters such as adipate and polycaprolactone, and polymers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples include ethers, aliphatic polycarbonates, silicones such as polydimethylsiloxane, polymers of (meth) acrylic acid and / or derivatives thereof, and mixtures and copolymers thereof. The content is preferably 30 wt% or more and 100 wt% or less with respect to the entire resin (a). In particular, unsaturated polyurethanes having a polycarbonate structure are preferred from the viewpoint of weather resistance.
樹脂（ａ）を構成する化合物に重合性不飽和基を導入する方法として、例えば直接、重合性の不飽和基をその分子末端あるいは分子鎖中に導入したものを用いても良いが、別法として、水酸基、アミノ基、エポキシ基、カルボキシル基、酸無水物基、ケトン基、ヒドラジン残基、イソシアネート基、イソチオシアネート基、環状カーボネート基、エステル基などの反応性基を複数有する化合物に、前記反応性基と結合しうる官能基を複数有する結合剤（例えば水酸基やアミノ基の場合のポリイソシアネートなど）を反応させ、分子量の調節、及び末端の結合性基への変換を行った後に、反応によって得られた化合物と、この化合物の末端結合性基と反応する官能基および重合性不飽和基を有する化合物とを反応させて、末端に重合性不飽和基を導入する方法などの方法が好適にあげられる。 As a method for introducing a polymerizable unsaturated group into the compound constituting the resin (a), for example, a method in which a polymerizable unsaturated group is directly introduced into the molecular end or molecular chain may be used. As a compound having a plurality of reactive groups such as hydroxyl group, amino group, epoxy group, carboxyl group, acid anhydride group, ketone group, hydrazine residue, isocyanate group, isothiocyanate group, cyclic carbonate group, ester group, etc. After reacting with a binder having multiple functional groups that can bind to the reactive group (for example, polyisocyanate in the case of a hydroxyl group or amino group), the molecular weight is adjusted and converted to a terminal binding group. And a compound having a functional group that reacts with the terminal binding group of this compound and a compound having a polymerizable unsaturated group, and a polymerizable unsaturated group at the terminal. Methods such as a method for introducing is suitably raised.
レーザー彫刻性の点から、樹脂（ａ）として熱分解性の高い化合物を使用することが好ましい。例えば、α−メチルスチレン、メタクリル酸エステル、アクリル酸エステル、カーボネート結合、カルバメート結合等を分子内に有する化合物は、熱分解性の高い化合物として知られている。熱分解性の指標として、不活性ガス雰囲気中でサンプルを加熱した際の重量減少を測定した熱重量分析法のデータを用いることができる。樹脂（ａ）の重量が半減する時点の温度が、１５０℃以上４５０℃以下の範囲であることが好ましい。より好ましい範囲は、２５０℃以上４００℃以下、更に好ましくは、２５０℃以上３８０℃以下である。また、熱分解が狭い温度範囲で起こる化合物が好ましい。その指標として、前記熱重量分析において、重量が初期重量の８０％に減少する温度と、重量が初期重量の２０％に減少する温度との差が、１００℃以下であることが好ましい。より好ましくは、８０℃以下、更に好ましくは６０℃以下である。 From the viewpoint of laser engraving property, it is preferable to use a compound having high thermal decomposability as the resin (a). For example, compounds having α-methylstyrene, methacrylic acid ester, acrylic acid ester, carbonate bond, carbamate bond and the like in the molecule are known as highly thermally decomposable compounds. As an index of thermal decomposability, thermogravimetric data obtained by measuring weight loss when a sample is heated in an inert gas atmosphere can be used. The temperature at which the weight of the resin (a) is halved is preferably in the range of 150 ° C. or higher and 450 ° C. or lower. A more preferable range is 250 ° C. or higher and 400 ° C. or lower, and further preferably 250 ° C. or higher and 380 ° C. or lower. Also preferred are compounds that undergo thermal decomposition in a narrow temperature range. As the index, in the thermogravimetric analysis, the difference between the temperature at which the weight is reduced to 80% of the initial weight and the temperature at which the weight is reduced to 20% of the initial weight is preferably 100 ° C. or less. More preferably, it is 80 degrees C or less, More preferably, it is 60 degrees C or less.
本発明の有機化合物（ｂ）は、ラジカル重合反応あるいは開環重合反応に関与する不飽和結合を有した化合物であり、樹脂（ａ）との希釈のし易さを考慮すると数平均分子量は１０００以下が好ましい。有機化合物（ｂ）は例えば、エチレン、プロピレン、スチレン、ジビニルベンゼン等のオレフィン類、アセチレン類、（メタ）アクリル酸及びその誘導体、ハロオレフィン類、アクリロニトリル等の不飽和ニトリル類、（メタ）アクリルアミド及びその誘導体、アリルアルコール、アリルイソシアネート等のアリル化合物、無水マレイン酸、マレイン酸、フマル酸、イタコン酸等の不飽和ジカルボン酸及びそれらの誘導体、酢酸ビニル類、Ｎ−ビニルピロリドン、Ｎ−ビニルカルバゾール、シアネートエステル類等があげられるが、その種類の豊富さ、価格等の観点から（メタ）アクリル酸及び、（メタ）アクリル酸エステル等の誘導体が好ましい例である。 The organic compound (b) of the present invention is a compound having an unsaturated bond involved in radical polymerization reaction or ring-opening polymerization reaction, and the number average molecular weight is 1000 considering the ease of dilution with the resin (a). The following is preferred. Examples of the organic compound (b) include olefins such as ethylene, propylene, styrene and divinylbenzene, acetylenes, (meth) acrylic acid and derivatives thereof, haloolefins, unsaturated nitriles such as acrylonitrile, (meth) acrylamide and Derivatives thereof, allyl compounds such as allyl alcohol and allyl isocyanate, unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid and their derivatives, vinyl acetates, N-vinylpyrrolidone, N-vinylcarbazole, Although cyanate ester etc. are mention | raise | lifted, derivatives, such as (meth) acrylic acid and (meth) acrylic acid ester, are preferable examples from the viewpoint of the abundance of the kind, a price, etc.
該誘導体は、シクロアルキル基、ビシクロアルキル基、シクロアルケン基、ビシクロアルケン基等の官能基を有する脂環族化合物、ベンジル基、フェニル基、フェノキシ基、メチルスチリル基、スチリル基等の官能基を有する芳香族化合物、アルキル基、ハロゲン化アルキル基、アルコキシアルキル基、ヒドロキシアルキル基、アミノアルキル基、テトラヒドロフルフリル基、グリシジル基等の官能基を有する化合物、アルキレングリコール、ポリオキシアルキレングリコール、（アルキル／アリルオキシ）ポリアルキレングリコールやトリメチロールプロパン等の多価アルコールのエステル化合物等があげられる。
重合性不飽和基を有する有機化合物（ｂ）はその目的に応じて１種若しくは２種以上のものを選択できる。例えば印刷版として用いる場合、印刷インキの溶剤であるアルコールやエステル等の有機溶剤に対する膨潤を押さえるために用いる有機化合物として長鎖脂肪族、脂環族または芳香族の誘導体を少なくとも１種類以上有することが好ましい。
The derivative is an alicyclic compound having a functional group such as a cycloalkyl group, a bicycloalkyl group, a cycloalkene group, or a bicycloalkene group, a functional group such as a benzyl group, a phenyl group, a phenoxy group, a methylstyryl group, or a styryl group. Aromatic compound, alkyl group, halogenated alkyl group, alkoxyalkyl group, hydroxyalkyl group, aminoalkyl group, tetrahydrofurfuryl group, compound having functional group such as glycidyl group, alkylene glycol, polyoxyalkylene glycol, (alkyl / Allyloxy) ester compounds of polyhydric alcohols such as polyalkylene glycol and trimethylolpropane.
The organic compound (b) having a polymerizable unsaturated group can be selected from one type or two or more types according to the purpose. For example, when used as a printing plate, it has at least one long-chain aliphatic, alicyclic or aromatic derivative as an organic compound used to suppress swelling with respect to an organic solvent such as alcohol or ester which is a solvent for printing ink. Is preferred.
感光性樹脂組成物より得られる光硬化物の機械強度を高めるためには、有機化合物（ｂ）としては脂環族または芳香族置換基を有する化合物を少なくとも１種類以上有することが好ましく、この場合、有機化合物（ｂ）の全体量の２０ｗｔ％以上１００ｗｔ％以下であることが好ましく、更に好ましくは５０ｗｔ％以上１００ｗｔ％以下である。
レーザー彫刻層は、上記感光性樹脂組成物に光を照射して硬化させることにより形成される。光としては、紫外線、可視光線の他、電子線、Ｘ線等の高エネルギー線を用いることもできる。特に紫外線、可視光線を用いて光硬化させる場合、光重合開始剤を添加することが好ましい。光重合開始剤としては、水素引き抜き型光重合開始剤（ｄ）あるいは／および崩壊型光重合開始剤（ｅ）を添加することが好ましい。
In order to increase the mechanical strength of the photocured product obtained from the photosensitive resin composition, the organic compound (b) preferably has at least one compound having an alicyclic or aromatic substituent. The total amount of the organic compound (b) is preferably 20 wt% or more and 100 wt% or less, more preferably 50 wt% or more and 100 wt% or less.
The laser engraving layer is formed by irradiating and curing the photosensitive resin composition. As light, in addition to ultraviolet rays and visible rays, high energy rays such as electron beams and X-rays can be used. In particular, when photocuring using ultraviolet light or visible light, it is preferable to add a photopolymerization initiator. As the photopolymerization initiator, it is preferable to add a hydrogen abstraction type photopolymerization initiator (d) and / or a decay type photopolymerization initiator (e).
水素引き抜き型光重合開始剤（ｄ）は特に限定するものではないが、芳香族ケトンを用いることが好ましい。芳香族ケトンは光励起により効率良く励起三重項状態になり、この励起三重項状態は周囲の媒体から水素を引き抜いてラジカルを生成する化学反応機構が提案されている。生成したラジカルが光架橋反応に関与するものと考えられる。本発明で用いる水素引き抜き型光重合開始剤（ｄ）として励起三重項状態を経て周囲の媒体から水素を引き抜きてラジカルを生成する化合物であれば何でも構わない。芳香族ケトンとして、ベンゾフェノン類、ミヒラーケトン類、キサンテン類、チオキサントン類、アントラキノン類を挙げることができ、これらの群から選ばれる少なくとも１種類の化合物を用いることが好ましい。ベンゾフェノン類とは、ベンゾフェノンあるいはその誘導体を指し、具体的には３，３‘，４，４’−ベンゾフェノンテトラカルボン酸無水物、３，３‘，４，４’−テトラメトキシベンゾフェノン等である。 The hydrogen abstraction type photopolymerization initiator (d) is not particularly limited, but an aromatic ketone is preferably used. Aromatic ketone is efficiently converted into an excited triplet state by photoexcitation, and a chemical reaction mechanism has been proposed in which this excited triplet state generates a radical by extracting hydrogen from the surrounding medium. The generated radical is considered to be involved in the photocrosslinking reaction. Any compound can be used as the hydrogen abstraction type photopolymerization initiator (d) used in the present invention as long as it is a compound that generates radicals by extracting hydrogen from the surrounding medium through an excited triplet state. Examples of aromatic ketones include benzophenones, Michler ketones, xanthenes, thioxanthones, and anthraquinones, and it is preferable to use at least one compound selected from these groups. Benzophenones refer to benzophenone or derivatives thereof, specifically 3,3 ′, 4,4′-benzophenone tetracarboxylic anhydride, 3,3 ′, 4,4′-tetramethoxybenzophenone, and the like.
ミヒラーケトン類とはミヒラーケトンおよびその誘導体をいう。キサンテン類とはキサンテンおよびアルキル基、フェニル基、ハロゲン基で置換された誘導体をいう。チオキサントン類とは、チオキサントンおよびアルキル基、フェニル基、ハロゲン基で置換された誘導体をさし、エチルチオキサントン、メチルチオキサントン、クロロチオキサントン等を挙げることができる。アントラキノン類とはアントラキノンおよびアルキル基、フェニル基、ハロゲン基等で置換された誘導体をいう。水素引き抜き型光重合開始剤の添加量は、感光性樹脂組成物全体量の０．３ｗｔ％以上１０ｗｔ％以下、より好ましくは０．５ｗｔ％以上５ｗｔ％以下であることが望ましい。添加量がこの範囲であれば、液状感光性樹脂組成物を大気中で光硬化させた場合、硬化物表面の硬化性は充分に確保でき、また、長期保存時に表面にクラック等が発生せず、退候性を確保することができる。 Michler ketones refer to Michler ketone and its derivatives. Xanthenes refer to derivatives substituted with xanthene and an alkyl group, phenyl group, or halogen group. Thioxanthones refer to thioxanthone and derivatives substituted with an alkyl group, a phenyl group, and a halogen group, and examples thereof include ethylthioxanthone, methylthioxanthone, and chlorothioxanthone. Anthraquinones are anthraquinone and derivatives substituted with alkyl groups, phenyl groups, halogen groups, and the like. The addition amount of the hydrogen abstraction type photopolymerization initiator is desirably 0.3 wt% or more and 10 wt% or less, more preferably 0.5 wt% or more and 5 wt% or less of the total amount of the photosensitive resin composition. If the addition amount is within this range, when the liquid photosensitive resin composition is photocured in the atmosphere, the surface of the cured product can be sufficiently secured, and no cracks or the like are generated on the surface during long-term storage. , Can ensure the fading.
崩壊型光重合開始剤（ｅ）とは、光吸収後に分子内で開裂反応が発生し活性なラジカルが生成する化合物を指し、特に限定するものではない。具体的には、ベンゾインアルキルエーテル類、２，２−ジアルコキシ−２−フェニルアセトフェノン類、アセトフェノン類、アシルオキシムエステル類、アゾ化合物類、有機イオウ化合物類、アシルホスフィンオキシド類、ジケトン類等を挙げることができ、これらの群から選ばれる少なくとも１種類の化合物を用いることが好ましい。ベンゾインアルキルエーテル類としては、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等を挙げることができる。２，２−ジアルコキシ−２−フェニルアセトフェノン類としては、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン等を挙げることができる。 The decay type photopolymerization initiator (e) refers to a compound that generates an active radical by generating a cleavage reaction in the molecule after light absorption, and is not particularly limited. Specific examples include benzoin alkyl ethers, 2,2-dialkoxy-2-phenylacetophenones, acetophenones, acyloxime esters, azo compounds, organic sulfur compounds, acylphosphine oxides, diketones, and the like. It is preferable to use at least one compound selected from these groups. Examples of benzoin alkyl ethers include benzoin isopropyl ether and benzoin isobutyl ether. Examples of 2,2-dialkoxy-2-phenylacetophenones include 2,2-dimethoxy-2-phenylacetophenone and 2,2-diethoxy-2-phenylacetophenone.
アセトフェノン類としては、アセトフェノン、トリクロロアセトフェノン、１−ヒドロキシシクロヘキシルフェニルアセトフェノン、２，２−ジエトキシアセトフェノン等を挙げることができる。アシルオキシムエステル類としては、１−フェニル−１，２−プロパンジオン−２−（ｏ−ベンゾイル）オキシム等を挙げることができる。アゾ化合物としては、アゾビスイソブチロニトリル、ジアゾニウム化合物、テトラゼン化合物等を挙げることができる。ジケトン類としては、ベンジル、メチルベンゾイルホルメート等を挙げることができる。崩壊型光重合開始剤の添加量は、感光性樹脂組成物全体量の０．３ｗｔ％以上１０ｗｔ％以下、より好ましくは０．５ｗｔ％以上５ｗｔ％以下であることが望ましい。添加量がこの範囲であれば、液状感光性樹脂組成物を大気中で光硬化させた場合、硬化物内部の硬化性は充分に確保できる。 Examples of acetophenones include acetophenone, trichloroacetophenone, 1-hydroxycyclohexylphenylacetophenone, 2,2-diethoxyacetophenone, and the like. Examples of acyl oxime esters include 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime. Examples of the azo compound include azobisisobutyronitrile, diazonium compound, and tetrazene compound. Examples of diketones include benzyl and methylbenzoyl formate. The addition amount of the collapsible photopolymerization initiator is desirably 0.3 wt% or more and 10 wt% or less, more preferably 0.5 wt% or more and 5 wt% or less of the total amount of the photosensitive resin composition. If the addition amount is within this range, when the liquid photosensitive resin composition is photocured in the air, the curability inside the cured product can be sufficiently secured.
水素引き抜き型光重合開始剤として機能する部位と崩壊型光重合開始剤として機能する部位を同一分子内に有する化合物を、光重合開始剤として用いることもできる。α−アミノアセトフェノン類を挙げることができる。例えば、２−メチル−１−（４−メチルチオフェニル）−２−モルホリノ−プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン等の化合物を挙げることができる。
水素引き抜き型光重合開始剤として機能する部位と崩壊型光重合開始剤として機能する部位を同一分子内に有する光重合開始剤（ｃ）の添加量としては、感光性樹脂組成物全体量の０．３ｗｔ％以上１０ｗｔ％以下が好ましく、より好ましくは０．５ｗｔ％以上３ｗｔ％以下である。添加量がこの範囲であれば、感光性樹脂組成物を大気中で光硬化させた場合であっても、硬化物の機械的物性は充分に確保できる。
A compound having a site functioning as a hydrogen abstraction type photopolymerization initiator and a site functioning as a decay type photopolymerization initiator in the same molecule can also be used as the photopolymerization initiator. There may be mentioned α-aminoacetophenones. For example, compounds such as 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone are exemplified. be able to.
The addition amount of the photopolymerization initiator (c) having a site functioning as a hydrogen abstraction type photopolymerization initiator and a site functioning as a decay type photopolymerization initiator in the same molecule is 0 of the total amount of the photosensitive resin composition. It is preferably 3 wt% or more and 10 wt% or less, more preferably 0.5 wt% or more and 3 wt% or less. When the addition amount is within this range, the mechanical properties of the cured product can be sufficiently ensured even when the photosensitive resin composition is photocured in the atmosphere.
感光性樹脂組成物には無機系微粒子、有機系微粒子、有機無機複合微粒子を添加することができる。これらの微粒子を添加することにより光硬化させて得られる感光性樹脂硬化物の機械的物性の向上、感光性樹脂硬化物表面の濡れ性改善、あるいは感光性樹脂組成物の粘度の調整、感光性樹脂硬化物の粘弾性特性の調整等が可能となる。無機系微粒子あるいは有機系微粒子の材質は特に限定するものではなく、公知のものを用いることができる。また、有機無機複合微粒子として、無機系微粒子の表面に有機物層あるいは有機系微粒子を形成した微粒子、あるいは有機系微粒子表面に無機物層あるいは無機微粒子を形成した微粒子等をあげることができる。感光性樹脂硬化物の機械的物性を向上させる目的では、窒化珪素、窒化ホウ素、炭化珪素等の剛性の高い無機系微粒子あるいはポリイミド等の有機系微粒子を用いることができる。更に、得られた感光性樹脂硬化物の耐溶剤特性を向上させる目的で、無機系微粒子や、使用する溶剤への膨潤特性の良好な材質で形成された有機系微粒子を添加することもできる。 Inorganic fine particles, organic fine particles, and organic-inorganic composite fine particles can be added to the photosensitive resin composition. Addition of these fine particles improves the mechanical properties of the cured photosensitive resin obtained by photo-curing, improves the wettability of the surface of the cured photosensitive resin, or adjusts the viscosity of the photosensitive resin composition. It becomes possible to adjust the viscoelastic properties of the cured resin. The material of the inorganic fine particles or organic fine particles is not particularly limited, and known materials can be used. Examples of the organic / inorganic composite fine particles include fine particles in which an organic layer or organic fine particles are formed on the surface of inorganic fine particles, or fine particles in which an inorganic layer or inorganic fine particles are formed on the surface of organic fine particles. For the purpose of improving the mechanical properties of the cured photosensitive resin, inorganic fine particles having high rigidity such as silicon nitride, boron nitride and silicon carbide, or organic fine particles such as polyimide can be used. Furthermore, for the purpose of improving the solvent resistance of the obtained photosensitive resin cured product, inorganic fine particles or organic fine particles formed of a material having a good swelling property in the solvent to be used can be added.
また、レーザー彫刻法により感光性樹脂硬化物層表面あるいは感光性樹脂硬化物を貫通したパターンを形成する目的のために、レーザー彫刻時に発生する粘稠性液状残渣の吸着除去特性に優れる無機多孔質微粒子を添加しても構わない。特に限定するものではないが、例えば、多孔質シリカ、メソポーラスシリカ、シリカ−ジルコニア多孔質ゲル、ポーラスアルミナ、多孔質ガラス等を挙げることができる。前記微粒子は、数平均粒径が０．０１〜１００μｍであることが好ましい。この数平均粒径の範囲の微粒子を用いることは、樹脂（ａ）及び有機化合物（ｂ）との混合を行う際に粘度の上昇、気泡の巻き込み、粉塵の大量発生等の不都合を生じることなく、感光性樹脂硬化物表面上の凹凸の発生を抑制できる点から好ましい。より好ましい平均粒子径の範囲は、０．１〜２０μｍであり、更に好ましい範囲は１〜１０μｍである。なお、微粒子の平均粒子径は、レーザー散乱式粒子径分布測定装置を用いて測定した値である。上記微粒子の粒子形状は特に限定するものではなく、球状、扁平状、針状、無定形、あるいは表面に突起のある粒子などを使用することができる。特に耐磨耗性の観点からは、球状粒子が好ましい。上記微粒子の表面をシランカップリング剤、チタンカップリング剤、その他の有機化合物で被覆し表面改質処理を行い、より親水性化あるいは疎水性化した粒子を用いることもできる。これらの微粒子は１種類もしくは２種類以上のものを選択できる。 In addition, for the purpose of forming a pattern that penetrates the surface of the photosensitive resin cured product layer or the photosensitive resin cured product by the laser engraving method, the inorganic porous material has excellent adsorption and removal characteristics of viscous liquid residue generated during laser engraving. Fine particles may be added. Although not particularly limited, for example, porous silica, mesoporous silica, silica-zirconia porous gel, porous alumina, porous glass and the like can be mentioned. The fine particles preferably have a number average particle diameter of 0.01 to 100 μm. The use of fine particles in the range of the number average particle diameter does not cause inconveniences such as increase in viscosity, entrainment of bubbles, and generation of a large amount of dust when mixing with the resin (a) and the organic compound (b). , Which is preferable from the viewpoint of suppressing the occurrence of irregularities on the surface of the cured photosensitive resin. A more preferable range of the average particle diameter is 0.1 to 20 μm, and a further preferable range is 1 to 10 μm. The average particle size of the fine particles is a value measured using a laser scattering type particle size distribution measuring device. The particle shape of the fine particles is not particularly limited, and spherical, flat, needle-like, amorphous, or particles having protrusions on the surface can be used. In particular, spherical particles are preferable from the viewpoint of wear resistance. The surface of the fine particles can be coated with a silane coupling agent, a titanium coupling agent, or other organic compound, and subjected to a surface modification treatment to make the particles more hydrophilic or hydrophobic. These fine particles can be selected from one type or two or more types.
感光性樹脂組成物における樹脂（ａ）、有機化合物（ｂ）、上記微粒子の割合は、通常、樹脂（ａ）１００重量部に対して、有機化合物（ｂ）は５〜２００重量部が好ましく、２０〜１００重量部の範囲がより好ましい。又、微粒子は１〜１００重量部が好ましく、２〜５０重量部の範囲がより好ましい。更に好ましい範囲は、２〜２０重量部である。
有機化合物（ｂ）の割合が、上記の範囲である場合、得られる感光性樹脂硬化物の硬度と引張強伸度のバランスがとりやすく、光硬化時の収縮も小さい範囲に収まり、厚み精度を確保することができる。
本発明で用いる感光性樹脂組成物には用途や目的に応じて重合禁止剤、紫外線吸収剤、滑剤、界面活性剤、可塑剤、香料などを添加することができる。
The proportion of the resin (a), the organic compound (b), and the fine particles in the photosensitive resin composition is usually preferably 5 to 200 parts by weight of the organic compound (b) with respect to 100 parts by weight of the resin (a). The range of 20 to 100 parts by weight is more preferable. The fine particles are preferably 1 to 100 parts by weight, and more preferably 2 to 50 parts by weight. A more preferable range is 2 to 20 parts by weight.
When the ratio of the organic compound (b) is in the above range, it is easy to balance the hardness and tensile strength / elongation of the obtained photosensitive resin cured product, and the shrinkage at the time of photocuring is within a small range, and the thickness accuracy is improved. Can be secured.
A polymerization inhibitor, an ultraviolet absorber, a lubricant, a surfactant, a plasticizer, a fragrance and the like can be added to the photosensitive resin composition used in the present invention according to the purpose and purpose.
感光性樹脂硬化物は、感光性樹脂組成物を光硬化させて形成したものである。したがって、有機化合物（ｂ）の重合性不飽和基、あるいは樹脂（ａ）と有機化合物（ｂ）の重合性不飽和基が反応することにより３次元架橋構造が形成され、通常用いるエステル系、ケトン系、芳香族系、エーテル系、アルコール系、ハロゲン系溶剤に不溶化する。この反応は、有機化合物（ｂ）同士、樹脂（ａ）同士、あるいは樹脂（ａ）と有機化合物（ｂ）との間で起こり、重合性不飽和基が消費される。また、光重合開始剤を用いて光硬化させる場合、光重合開始剤が光により分解されるため、前記光硬化物を溶剤で抽出し、ＧＣ−ＭＳ法（ガスクロマトグラフィーで分離したものを質量分析する方法）、ＬＣ−ＭＳ法（液体クロマトグラフィーで分離したものを質量分析する方法）、ＧＰＣ−ＭＳ法（ゲル浸透クロマトグラフィーで分離し質量分析する方法）、ＬＣ−ＮＭＲ法（液体クロマトグラフィーで分離したものを核磁気共鳴スペクトルで分析する方法）を用いて解析することにより、未反応の光重合開始剤および分解生成物を同定することができる。 The photosensitive resin cured product is formed by photocuring the photosensitive resin composition. Accordingly, a three-dimensional cross-linked structure is formed by the reaction of the polymerizable unsaturated group of the organic compound (b) or the resin (a) with the polymerizable unsaturated group of the organic compound (b). It becomes insoluble in organic, aromatic, etheric, alcoholic and halogenated solvents. This reaction occurs between the organic compounds (b), between the resins (a), or between the resin (a) and the organic compound (b), and the polymerizable unsaturated group is consumed. In addition, when photocuring using a photopolymerization initiator, the photopolymerization initiator is decomposed by light. Therefore, the photocured product is extracted with a solvent, and mass-separated by GC-MS (gas chromatography). Analysis method), LC-MS method (method for mass spectrometry of those separated by liquid chromatography), GPC-MS method (method for separation and mass spectrometry by gel permeation chromatography), LC-NMR method (liquid chromatography) By analyzing using the method of analyzing the product separated in (1) by nuclear magnetic resonance spectrum, unreacted photopolymerization initiator and decomposition products can be identified.
更に、ＧＰＣ−ＭＳ法、ＬＣ−ＭＳ法、ＧＰＣ−ＮＭＲ法を用いることにより、溶剤抽出物中の未反応の樹脂（ａ）、未反応の有機化合物（ｂ）、および重合性不飽和基が反応して得られる比較的低分子量の生成物についても溶剤抽出物の分析から同定することができる。３次元架橋構造を形成した溶剤に不溶の高分子量成分については、熱分解ＧＣ−ＭＳ法を用いることにより、高分子量体を構成する成分として、重合性不飽和基が反応して生成した部位が存在するかを検証することが可能である。例えば、メタクリレート基、アクリレート基、ビニル基等の重合性不飽和基が反応した部位が存在することを質量分析スペクトルパターンから推定することができる。熱分解ＧＣ−ＭＳ法とは、試料を加熱分解させ、生成するガス成分をガスクロマトグラフィーで分離した後、質量分析を行なう方法である。感光性樹脂硬化物中に、未反応の重合性不飽和基又は重合性不飽和基が反応して得られた部位と共に、光重合開始剤に由来する分解生成物や未反応の光重合開始剤が検出されると、感光性樹脂組成物を光硬化させて得られたものであると結論付けることができる。 Furthermore, by using the GPC-MS method, LC-MS method, and GPC-NMR method, the unreacted resin (a), the unreacted organic compound (b), and the polymerizable unsaturated group in the solvent extract are changed. Relatively low molecular weight products obtained by reaction can also be identified from analysis of solvent extracts. For the high molecular weight component insoluble in the solvent in which the three-dimensional cross-linked structure is formed, by using the pyrolysis GC-MS method, the site formed by the reaction of the polymerizable unsaturated group is formed as a component constituting the high molecular weight body. It is possible to verify whether it exists. For example, it can be estimated from the mass spectrometry spectrum pattern that there is a site where a polymerizable unsaturated group such as a methacrylate group, an acrylate group, or a vinyl group has reacted. The pyrolysis GC-MS method is a method in which a sample is thermally decomposed and a generated gas component is separated by gas chromatography and then mass spectrometry is performed. A decomposition product derived from a photopolymerization initiator and an unreacted photopolymerization initiator together with a site obtained by reacting an unreacted polymerizable unsaturated group or a polymerizable unsaturated group in a cured photosensitive resin. When is detected, it can be concluded that the photosensitive resin composition was obtained by photocuring.
感光性樹脂組成物中の樹脂（ａ）あるいは光重合開始剤は、ＧＰＣ法あるいはＬＣ法等の液体クロマトグラフィーを用いて分離精製後、核磁気共鳴スペクトル法（ＮＭＲ法）を用いて分子構造を同定することができる。水素原子に着目したＮＭＲ法（１Ｈ−ＮＭＲ法）を用いて、官能基特有の化学シフトを解析することにより、分子中にどのような官能基が存在するか同定することができ、また特定の官能基を有する炭素原子に直接結合した水素原子（α位水素）の量を積分値から定量的に評価することができる。
本発明の印刷原版の形状は特に限定されず、シート状、円筒状いずれでもよい。またレーザー彫刻層はクッション層や支持体上に直接接するように設けられてもよいし、クッション層や支持体上に他の中間層を設けた後設けられていてもよい。
The resin (a) or photopolymerization initiator in the photosensitive resin composition is separated and purified using liquid chromatography such as GPC method or LC method, and the molecular structure is then determined using nuclear magnetic resonance spectroscopy (NMR method). Can be identified. By analyzing the chemical shift specific to the functional group using the NMR method focusing on hydrogen atoms ( 1 H-NMR method), it is possible to identify what kind of functional group exists in the molecule. The amount of hydrogen atoms (α-position hydrogen) directly bonded to the carbon atom having the functional group can be quantitatively evaluated from the integrated value.
The shape of the printing original plate of the present invention is not particularly limited, and may be either a sheet shape or a cylindrical shape. The laser engraving layer may be provided so as to be in direct contact with the cushion layer or the support, or may be provided after another intermediate layer is provided on the cushion layer or the support.
感光性樹脂組成物をシート状、もしくは円筒状に成形する方法は、既存の樹脂の成形方法を用いることができる。例えば、注型法、ポンプや押し出し機等の機械で樹脂をノズルやダイスから押し出し、ブレードで厚みを合わせる、ロールによりカレンダー加工して厚みを合わせる方法等、スプレー等を用いて噴霧する方法が例示できる。その際、感光性樹脂組成物の熱分解を起こさない範囲で加熱しながら成形を行うことも可能である。また、必要に応じて圧延処理、研削処理などをほどこしても良い。
通常はＰＥＴやニッケルなどの素材からなるシート状支持体上に成形される場合が多いが、直接印刷機のシリンダー上あるいは中空円筒状支持体に成形することも好ましい。中空円筒状支持体が、繊維強化プラスチック、フィルム強化プラスチック、金属から選択される少なくとも１種類の材料を構成成分とする中空円筒状支持体であることが好ましい。また、ガラス繊維、アラミド繊維、炭素繊維等の繊維で強化されたポリエステル樹脂、エポキシ樹脂等のプラスチック製スリーブ、ポリエチレンテレフタレート等のポリエステルチューブ等の円筒状支持体を具体例として挙げることができる。シート状支持体あるいは円筒状支持体の役割は、感光性樹脂硬化物の寸法安定性を確保することである。したがって、寸法安定性の高いものを選択する必要がある。線熱膨張係数を用いて評価すると、好ましい材料の上限値は１００ｐｐｍ／℃以下、更に好ましくは７０ｐｐｍ／℃以下である。
As a method for molding the photosensitive resin composition into a sheet or cylinder, an existing resin molding method can be used. For example, a casting method, a method of spraying resin using a spray, such as a method of extruding a resin from a nozzle or a die with a machine such as a pump or an extruder, adjusting the thickness with a blade, adjusting the thickness by calendaring with a roll, etc. it can. In that case, it is also possible to perform molding while heating the photosensitive resin composition within a range not causing thermal decomposition. Moreover, you may perform a rolling process, a grinding process, etc. as needed.
Usually, it is often formed on a sheet-like support made of a material such as PET or nickel, but it is also preferable to form directly on a cylinder of a printing press or on a hollow cylindrical support. The hollow cylindrical support is preferably a hollow cylindrical support having at least one material selected from fiber reinforced plastic, film reinforced plastic, and metal as a constituent component. Specific examples include cylindrical supports such as polyester resins reinforced with fibers such as glass fibers, aramid fibers, and carbon fibers, plastic sleeves such as epoxy resins, and polyester tubes such as polyethylene terephthalate. The role of the sheet-like support or the cylindrical support is to ensure the dimensional stability of the photosensitive resin cured product. Therefore, it is necessary to select one having high dimensional stability. When evaluated using the linear thermal expansion coefficient, the upper limit value of a preferable material is 100 ppm / ° C. or less, more preferably 70 ppm / ° C. or less.
材料の具体例としては、ポリエステル樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、ポリビスマレイミド樹脂、ポリスルホン樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンチオエーテル樹脂、ポリエーテルスルホン樹脂、全芳香族ポリエステル樹脂からなる液晶樹脂、全芳香族ポリアミド樹脂、エポキシ樹脂などを挙げることができる。また、これらの樹脂を積層して用いることもできる。また、多孔質性のシート、例えば繊維を編んで形成したクロスや、不織布、フィルムに細孔を形成したもの等をシート状支持体として用いることができる。シート状支持体として多孔質性シートを用いる場合、感光性樹脂組成物を孔に含浸させた後に光硬化させることで、感光性樹脂硬化物層とシート状支持体とが一体化するために高い接着性を得ることができる。クロスあるいは不織布を形成する繊維としては、ガラス繊維、アルミナ繊維、炭素繊維、アルミナ・シリカ繊維、ホウ素繊維、高珪素繊維、チタン酸カリウム繊維、サファイア繊維などの無機系繊維、木綿、麻などの天然繊維、レーヨン、アセテート等の半合成繊維、ナイロン、ポリエステル、アクリル、ビニロン、ポリ塩化ビニル、ポリオレフィン、ポリウレタン、ポリイミド、アラミド等の合成繊維を挙げることができる。また、バクテリアの生成するセルロースは、高結晶性ナノファイバーであり、薄くて寸法安定性の高い不織布を作製することのできる材料である。 Specific examples of materials include polyester resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polysulfone resin, polycarbonate resin, polyphenylene ether resin, polyphenylene thioether resin, polyethersulfone resin, all Examples thereof include liquid crystal resins composed of aromatic polyester resins, wholly aromatic polyamide resins, and epoxy resins. Further, these resins can be laminated and used. Moreover, a porous sheet, for example, a cloth formed by knitting fibers, a nonwoven fabric, a film in which pores are formed, or the like can be used as the sheet-like support. When a porous sheet is used as the sheet-like support, it is high because the photosensitive resin cured product layer and the sheet-like support are integrated by photo-curing after impregnating the photosensitive resin composition into the holes. Adhesiveness can be obtained. The fibers forming the cloth or nonwoven fabric include glass fibers, alumina fibers, carbon fibers, alumina / silica fibers, boron fibers, high silicon fibers, potassium titanate fibers, inorganic fibers such as sapphire fibers, natural materials such as cotton and hemp Examples thereof include semi-synthetic fibers such as fibers, rayon and acetate, and synthetic fibers such as nylon, polyester, acrylic, vinylon, polyvinyl chloride, polyolefin, polyurethane, polyimide, and aramid. Further, cellulose produced by bacteria is a highly crystalline nanofiber, and is a material capable of producing a thin nonwoven fabric with high dimensional stability.
また、シート状支持体あるいは円筒状支持体の線熱膨張係数を小さくする方法として、充填剤を添加する方法、全芳香族ポリアミド等のメッシュ状クロス、ガラスクロスなどに樹脂を含浸あるいは被覆する方法などを挙げることができる。充填剤としては、通常用いられる有機系微粒子、金属酸化物あるいは金属等の無機系微粒子、有機・無機複合微粒子など用いることができる。また、多孔質微粒子、内部に空洞を有する微粒子、マイクロカプセル粒子、低分子化合物が内部にインターカレーションする層状化合物粒子を用いることもできる。特に、アルミナ、シリカ、酸化チタン、ゼオライト等の金属酸化物微粒子、ポリスチレン・ポリブタジエン共重合体からなるラテックス微粒子、高結晶性セルロース等の天然物系の有機系微粒子等が有用である。 In addition, as a method of reducing the linear thermal expansion coefficient of a sheet-like support or cylindrical support, a method of adding a filler, a method of impregnating or coating a resin on a mesh cloth such as wholly aromatic polyamide, or a glass cloth And so on. As the filler, generally used organic fine particles, inorganic fine particles such as metal oxide or metal, organic / inorganic composite fine particles, and the like can be used. In addition, porous fine particles, fine particles having cavities inside, microcapsule particles, and layered compound particles in which a low molecular compound intercalates can be used. In particular, metal oxide fine particles such as alumina, silica, titanium oxide, and zeolite, latex fine particles made of polystyrene / polybutadiene copolymer, natural product-based organic fine particles such as highly crystalline cellulose, and the like are useful.
支持体の表面に物理的、化学的処理を行うことにより、感光性樹脂組成物層あるいは接着剤層との接着性を向上させることができる。物理的処理方法としては、サンドブラスト法、微粒子を含有した液体を噴射するウエットブラスト法、コロナ放電処理法、プラズマ処理法、紫外線あるいは真空紫外線照射法などを挙げることができる。また、化学的処理方法としては、強酸・強アルカリ処理法、酸化剤処理法、カップリング剤処理法などである。
成形された感光性樹脂組成物層は光照射により架橋せしめ、感光性樹脂硬化物を形成する。また、成型しながら光照射により架橋させることもできる。硬化に用いられる光源としては高圧水銀灯、超高圧水銀灯、紫外線蛍光灯、殺菌灯、カーボンアーク灯、キセノンランプ、メタルハライドランプ等が挙げることができる。感光性樹脂組成物層に照射される光は、２００ｎｍから３００ｎｍの波長の光を有することが好ましい。特に水素引き抜き型光重合開始剤は、この波長領域に強い光吸収を有するものが多いため、２００ｎｍから３００ｎｍの波長の光を有する場合、感光性樹脂硬化物層表面の硬化性を充分に確保することができる。光硬化に用いる光源は、１種類でも構わないが、波長の異なる２種類以上の光源を用いて硬化させることにより、樹脂の硬化性が向上することがあるので、２種類以上の光源を用いることも差し支えない。
By performing physical and chemical treatments on the surface of the support, the adhesion with the photosensitive resin composition layer or the adhesive layer can be improved. Examples of the physical treatment method include a sand blast method, a wet blast method for injecting a liquid containing fine particles, a corona discharge treatment method, a plasma treatment method, an ultraviolet ray or vacuum ultraviolet ray irradiation method, and the like. The chemical treatment method includes a strong acid / strong alkali treatment method, an oxidant treatment method, a coupling agent treatment method, and the like.
The molded photosensitive resin composition layer is crosslinked by light irradiation to form a cured photosensitive resin. Further, it can be crosslinked by light irradiation while molding. Examples of the light source used for curing include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a germicidal lamp, a carbon arc lamp, a xenon lamp, and a metal halide lamp. The light applied to the photosensitive resin composition layer preferably has a wavelength of 200 nm to 300 nm. In particular, since many hydrogen abstraction type photopolymerization initiators have strong light absorption in this wavelength region, when having light with a wavelength of 200 nm to 300 nm, sufficient curability of the surface of the cured photosensitive resin layer is ensured. be able to. The light source used for photocuring may be one type, but the curability of the resin may be improved by curing using two or more types of light sources having different wavelengths, so use two or more types of light sources. There is no problem.
感光性樹脂硬化物層の下部にエラストマーからなるクッション層を形成することもできる。感光性樹脂硬化物の厚さは、０．０５〜５０ｍｍが好ましく、それ以外の下部層は組成の異なる材料であっても構わない。クッション層としては、ショアＡ硬度が１０以上７０度以下、あるいはＡＳＫＥＲ−Ｃ型硬度計で測定したＡＳＫＥＲ−Ｃ硬度が２０度以上８５度以下のエラストマー層であることが好ましい。ショアＡ硬度が１０度以上あるいはＡＳＫＥＲ−Ｃ硬度が２０度以上である場合、適度に変形するため、印刷品質を確保することができる。また、ショアＡ硬度が７０度以下あるいはＡＳＫＥＲ−Ｃ硬度が８５度以下であるものが、クッション層としては好ましい。クッション層のより好ましいショアＡ硬度の範囲は２０〜６０度、ＡＳＫＥＲ−Ｃ硬度では４５〜７５度の範囲である。ショアＡ硬度とＡＳＫＥＲ−Ｃ硬度は、クッション層に使用する材質により使い分けることが好ましい。２種類の硬度の違いは、測定に用いる硬度計の押針形状の違いに由来する。均一な樹脂組成の場合、ショアＡ硬度を用いることが好ましく、発泡ポリウレタン、発泡ポリエチレン等の発泡性基材のように不均一な樹脂組成の場合には、ＡＳＫＥＲ−Ｃ硬度を用いることが好ましい。ＡＳＫＥＲ−Ｃ硬度は、ＪＩＳ Ｋ７３１２規格に準拠する測定法である。 A cushion layer made of an elastomer can also be formed under the photosensitive resin cured product layer. The thickness of the cured photosensitive resin is preferably 0.05 to 50 mm, and other lower layers may be made of materials having different compositions. The cushion layer is preferably an elastomer layer having a Shore A hardness of 10 to 70 degrees, or an ASKER-C hardness of 20 to 85 degrees as measured with an ASKER-C hardness meter. When the Shore A hardness is 10 degrees or more, or the ASKER-C hardness is 20 degrees or more, the print quality can be ensured because it is appropriately deformed. A cushion layer having a Shore A hardness of 70 degrees or less or an ASKER-C hardness of 85 degrees or less is preferable. The more preferable Shore A hardness range of the cushion layer is 20 to 60 degrees, and the ASKER-C hardness is 45 to 75 degrees. The Shore A hardness and the ASKER-C hardness are preferably selected depending on the material used for the cushion layer. The difference between the two types of hardness stems from the difference in the shape of the pushers of the hardness meter used for measurement. In the case of a uniform resin composition, it is preferable to use Shore A hardness, and in the case of a non-uniform resin composition such as a foamable base material such as foamed polyurethane and foamed polyethylene, it is preferable to use ASKER-C hardness. ASKER-C hardness is a measuring method based on JIS K7312 standard.
印刷品質確保の点から、本発明の印刷原版は、クッション層とレーザー彫刻層は直接接着した円筒状積層体であって、該クッション層と該レーザー彫刻層が継ぎ目を有しないことが好ましい。
前記クッション層は、特に限定せず、熱可塑性エラストマー、光硬化型エラストマー、熱硬化型エラストマー等ゴム弾性を有するものであれば何でも構わない。特にシート状あるいは円筒状印刷版への加工性の観点から、光で硬化する液状感光性樹脂組成物を用い、硬化後にエラストマー化する材料を用いることが簡便であり好ましい。
クッション層は、感光性樹脂硬化物を含み、且つ気泡あるいは有機系微粒子を含有することが好ましい。また、前記有機系微粒子が中空マイクロカプセルであって、該中空マイクロカプセルの表面に無機系微粒子が付着しているものを用いることが好ましい。前記有機系微粒子の平均粒子径が１μｍ以上５００μｍ以下であることが好ましい。より好ましい範囲は１０μｍ以上３００μｍ以下、更にこのましくは８０μｍ以上２００μｍ以下である。
From the viewpoint of ensuring printing quality, the printing original plate of the present invention is preferably a cylindrical laminate in which the cushion layer and the laser engraving layer are directly bonded, and the cushion layer and the laser engraving layer preferably have no seam.
The cushion layer is not particularly limited, and any cushion layer may be used as long as it has rubber elasticity, such as a thermoplastic elastomer, a photocurable elastomer, and a thermosetting elastomer. In particular, from the viewpoint of processability to a sheet-like or cylindrical printing plate, it is convenient and preferable to use a liquid photosensitive resin composition that is cured by light and to use a material that becomes elastomer after curing.
The cushion layer preferably contains a cured photosensitive resin and contains bubbles or organic fine particles. The organic fine particles are preferably hollow microcapsules, and those having inorganic fine particles attached to the surface of the hollow microcapsules are preferably used. It is preferable that the average particle diameter of the organic fine particles is 1 μm or more and 500 μm or less. A more preferable range is 10 μm or more and 300 μm or less, and more preferably 80 μm or more and 200 μm or less.
クッション層の密度は、０．１ｇ／ｃｍ３以上０．９ｇ／ｃｍ３以下であることが好ましい。より好ましくは０．３ｇ／ｃｍ３以上０．７ｇ／ｃｍ３以下、更に好ましくは０．４ｇ／ｃｍ３以上０．６ｇ／ｃｍ３以下である。クッション層の密度がこの範囲であれば、印刷工程においてレーザー彫刻層にかかる衝撃を充分に吸収することができる。
クッション層に用いる熱可塑性エラストマーの具体例としては、スチレン系熱可塑性エラストマーであるＳＢＳ（ポリスチレン−ポリブタジエン−ポリスチレン）、ＳＩＳ（ポリスチレン−ポリイソプレン−ポリスチレン）、ＳＥＢＳ（ポリスチレン−ポリエチレン／ポリブチレン−ポリスチレン）等、オレフィン系熱可塑性エラストマー、ウレタン系熱可塑性エラストマー、エステル系熱可塑性エラストマー、アミド系熱可塑性エラストマー、シリコン系熱可塑性エラストマー、フッ素系熱可塑性エラストマー等を挙げることができる。
The density of the cushion layer is preferably 0.1 g / cm 3 or more and 0.9 g / cm 3 or less. More preferably, it is 0.3 g / cm 3 or more and 0.7 g / cm 3 or less, and still more preferably 0.4 g / cm 3 or more and 0.6 g / cm 3 or less. If the density of the cushion layer is within this range, the impact applied to the laser engraving layer in the printing process can be sufficiently absorbed.
Specific examples of the thermoplastic elastomer used for the cushion layer include SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), SEBS (polystyrene-polyethylene / polybutylene-polystyrene), which are styrenic thermoplastic elastomers, and the like. Olefin-based thermoplastic elastomer, urethane-based thermoplastic elastomer, ester-based thermoplastic elastomer, amide-based thermoplastic elastomer, silicon-based thermoplastic elastomer, fluorine-based thermoplastic elastomer, and the like.
光硬化型エラストマーとしては、前記熱可塑性エラストマーに光重合性モノマー、可塑剤および光重合開始剤等を混合したもの、液状樹脂に光重合性モノマー、光重合開始剤等を混合した液状感光性樹脂組成物などを挙げることができる。本発明では、微細パターンの形成機能が重要な要素である感光性樹脂組成物の設計思想とは異なり、光を用いて微細なパターンの形成を行う必要がなく、全面露光により硬化させることにより、必要な機械的強度を確保できれば良いため、材料の選定において自由度が極めて高い。
また、硫黄架橋型ゴム、有機過酸化物、フェノール樹脂初期縮合物、キノンジオキシム、金属酸化物、チオ尿素等の化合物を架橋剤として用いる非硫黄架橋型ゴムでも構わない。
Examples of the photocurable elastomer include those obtained by mixing a photopolymerizable monomer, a plasticizer, a photopolymerization initiator, and the like with the thermoplastic elastomer, and a liquid photosensitive resin obtained by mixing a photopolymerizable monomer, a photopolymerization initiator, and the like with a liquid resin. A composition etc. can be mentioned. In the present invention, unlike the design concept of the photosensitive resin composition, in which the function of forming a fine pattern is an important element, it is not necessary to form a fine pattern using light, and by curing by overall exposure, Since it is only necessary to ensure the required mechanical strength, the degree of freedom in selecting the material is extremely high.
Further, non-sulfur cross-linked rubber using a compound such as sulfur cross-linked rubber, organic peroxide, phenol resin initial condensate, quinone dioxime, metal oxide, thiourea as a cross-linking agent may be used.
更に、テレケリック液状ゴムを反応する硬化剤を用いて３次元架橋させてエラストマー化したものを使用することもできる。
また、発泡ポリウレタン、発泡ポリエチレン等の材質で、独立あるいは連続気泡を層内に有するクッション層であっても構わず、市販品として入手可能なクッション材、クッションテープを使用することもでき、クッション層の片面あるいは両面に接着剤あるいは粘着剤が塗布されたものであっても構わない。
多層化した印刷原版とする場合、シート状支持体あるいは円筒状支持体を設けることも可能であり、その場合前記支持体の位置は、クッション層の下、すなわち印刷基材の最下部、あるいは、感光性樹脂硬化物層とクッション層との間の位置、すなわち印刷基材の中央部、いずれの位置でも構わない。
Furthermore, it is also possible to use a three-dimensionally crosslinked elastomer obtained by using a curing agent that reacts with a telechelic liquid rubber.
Moreover, it may be a cushion layer having a material such as polyurethane foam or polyethylene foam and having independent or open cells in the layer, and a cushion material and cushion tape available as a commercial product can be used. One or both sides may be coated with an adhesive or a pressure-sensitive adhesive.
In the case of a multilayered printing original plate, it is also possible to provide a sheet-like support or a cylindrical support, in which case the position of the support is below the cushion layer, that is, the bottom of the printing substrate, or Any position between the cured photosensitive resin layer and the cushion layer, that is, the central portion of the printing substrate may be used.
感光性樹脂硬化物の表面に改質層を形成させることにより、印刷基材表面のタックの低減、インク濡れ性の向上を行うこともできる。改質層としては、シランカップリング剤あるいはチタンカップリング剤等の表面水酸基と反応する化合物で処理した被膜、あるいは多孔質無機粒子を含有するポリマーフィルムを挙げることができる。
広く用いられているシランカップリング剤は、基材の表面水酸基との反応性の高い官能基を分子内に有する化合物であり、そのような官能基とは、例えばトリメトキシシリル基、トリエトキシシリル基、トリクロロシリル基、ジエトキシシリル基、ジメトキシシリル基、ジモノクロロシリル基、モノエトキシシリル基、モノメトキシシリル基、モノクロロシリル基を挙げることができる。また、これらの官能基は分子内に少なくとも１つ以上存在し、基材の表面水酸基と反応することにより基材表面に固定化される。更に本発明のシランカップリング剤を構成する化合物は、分子内に反応性官能基としてアクリロイル基、メタクリロイル基、活性水素含有アミノ基、エポキシ基、ビニル基、パーフルオロアルキル基、及びメルカプト基から選ばれた少なくとも１個の官能基を有するもの、あるいは長鎖アルキル基を有するものを用いることができる。
By forming a modified layer on the surface of the cured photosensitive resin, it is possible to reduce tack on the surface of the printing substrate and improve ink wettability. Examples of the modified layer include a film treated with a compound that reacts with a surface hydroxyl group such as a silane coupling agent or a titanium coupling agent, or a polymer film containing porous inorganic particles.
A widely used silane coupling agent is a compound having in its molecule a functional group highly reactive with the surface hydroxyl group of the substrate. Examples of such a functional group include a trimethoxysilyl group and a triethoxysilyl group. Group, trichlorosilyl group, diethoxysilyl group, dimethoxysilyl group, dimonochlorosilyl group, monoethoxysilyl group, monomethoxysilyl group, monochlorosilyl group. Further, at least one of these functional groups exists in the molecule, and is immobilized on the surface of the base material by reacting with the surface hydroxyl group of the base material. Further, the compound constituting the silane coupling agent of the present invention is selected from acryloyl group, methacryloyl group, active hydrogen-containing amino group, epoxy group, vinyl group, perfluoroalkyl group, and mercapto group as reactive functional groups in the molecule. Those having at least one functional group or those having a long-chain alkyl group can be used.
本発明の印刷原版のレーザー彫刻層にレーザー彫刻法を用いてパターンを形成する方法としては、例えば、形成したい画像をデジタル型のデータとしてコンピューターを利用してレーザー装置を操作し、印刷基材にレリーフ画像を作成する方法が挙げられる。レーザー彫刻に用いるレーザーは、原版が吸収を有する波長を含むものであればどのようなものを用いてもよいが、彫刻を高速度で行うためには出力の高いものが望ましく、炭酸ガスレーザーやＹＡＧレーザー、半導体レーザー等の赤外線あるいは赤外線放出固体レーザーが好ましいものの一つである。また、可視光線領域に発振波長を有するＹＡＧレーザーの第２高調波、銅蒸気レーザー、紫外線領域に発振波長を有する紫外線レーザー、例えばエキシマレーザー、第３あるいは第４高調波へ波長変換したＹＡＧレーザーは、有機分子の結合を切断するアブレージョン加工が可能であり、微細加工に適する。また、レーザーは連続照射でも、パルス照射でも良い。 As a method of forming a pattern on the laser engraving layer of the printing original plate of the present invention using a laser engraving method, for example, a laser is operated using a computer as an image to be formed as digital data, and a printing substrate is formed. A method for creating a relief image is mentioned. Any laser may be used for the laser engraving as long as the original plate includes a wavelength having absorption. However, in order to perform engraving at a high speed, a laser with a high output is desirable. Infrared or infrared emitting solid lasers such as YAG lasers and semiconductor lasers are preferred. In addition, the second harmonic of a YAG laser having an oscillation wavelength in the visible light region, a copper vapor laser, an ultraviolet laser having an oscillation wavelength in the ultraviolet region, such as an excimer laser, and a YAG laser wavelength-converted to the third or fourth harmonic are It can be ablated by cutting the bonds of organic molecules and is suitable for fine processing. The laser may be continuous irradiation or pulse irradiation.
微細パターン形成の観点から、レーザー光の発振波長は１５０ｎｍ以上１５μｍ以下であることが好ましい。
レーザーによる彫刻は酸素含有ガス下、一般には空気存在下もしくは気流下に実施するが、炭酸ガス、窒素ガス下でも実施できる。彫刻終了後、レリーフ印刷版面にわずかに発生する粉末状もしくは液状の物質は適当な方法、例えば溶剤や界面活性剤の入った水等で洗いとる方法、高圧スプレー等により水系洗浄剤を照射する方法、高圧スチームを照射する方法などを用いて除去しても良い。
レーザー光を照射し凹パターンを形成する彫刻後に、版表面に残存する粉末状あるいは粘性のある液状カスを除去する工程に引き続き、パターンを形成した印刷版表面に波長２００ｎｍ〜４５０ｎｍの光を照射する後露光を実施することもできる。表面のタック除去に効果がある方法である。後露光は大気中、不活性ガス雰囲気中、水中のいずれの環境で行っても構わない。用いる感光性樹脂組成物中に水素引き抜き型光重合開始剤が含まれている場合、特に効果的である。更に、後露光工程前に印刷版表面を、水素引き抜き型光重合開始剤を含む処理液で処理し露光しても構わない。また、水素引き抜き型光重合開始剤を含む処理液中に印刷版を浸漬した状態で露光しても構わない。
From the viewpoint of forming a fine pattern, the oscillation wavelength of the laser light is preferably 150 nm or more and 15 μm or less.
Laser engraving is carried out in an oxygen-containing gas, generally in the presence of air or an air stream, but can also be carried out under carbon dioxide or nitrogen gas. After engraving is finished, the powdery or liquid substance slightly generated on the relief printing plate surface is washed with an appropriate method such as water containing a solvent or a surfactant, or a water-based cleaning agent is irradiated by a high-pressure spray or the like. Alternatively, it may be removed using a method of irradiating high-pressure steam.
After engraving to form a concave pattern by irradiating with laser light, following the process of removing powdery or viscous liquid residue remaining on the plate surface, the surface of the printing plate on which the pattern has been formed is irradiated with light having a wavelength of 200 nm to 450 nm. Post-exposure can also be performed. This is an effective method for removing tack on the surface. The post-exposure may be performed in any environment such as air, inert gas atmosphere, and water. This is particularly effective when the photosensitive resin composition used contains a hydrogen abstraction type photopolymerization initiator. Furthermore, before the post-exposure step, the printing plate surface may be exposed to a treatment liquid containing a hydrogen abstraction type photopolymerization initiator. Moreover, you may expose in the state which immersed the printing plate in the process liquid containing a hydrogen abstraction type photoinitiator.
以下、本発明を実施例に基づいて説明するが、本発明はこれらによって制限されるものではない。
（１）レーザー彫刻
レーザー彫刻は炭酸ガスレーザー彫刻機（商標：ＺＥＤ−ｍｉｎｉ−１０００、英国、ＺＥＤ社製、米国、コヒーレント社製、出力２５０Ｗ炭酸ガスレーザーを搭載、レーザーの発振波長は１０．６μｍ）を用いて行った。彫刻は、網点（１２０線／インチ、面積率１０％)パターンを作成して実施した。彫刻深さは０．５５ｍｍとした。
（２）粘度
感光性樹脂組成物あるいは有機化合物（ｂ）の粘度は、Ｂ型粘度計（商標、Ｂ８Ｈ型；日本国、東京計器社製）を用い、２０℃で測定した。
（３）数平均分子量の測定
樹脂（ａ）、有機化合物（ｂ）の数平均分子量は、ゲル浸透クロマトグラフ法（ＧＰＣ法）を用いて、分子量既知のポリスチレンで換算して求めた。高速ＧＰＣ装置（日本国、東ソー社製、商標、ＨＬＣ−８０２０）とポリスチレン充填カラム（商標：TSKgel GMHXL；日本国、東ソー社製）を用い、テトラヒドロフラン（ＴＨＦ）で展開して測定した。カラムの温度は４０℃に設定した。ＧＰＣ装置に注入する試料としては、樹脂濃度が１ｗｔ％のＴＨＦ溶液を調製し、注入量１０μｌとした。また、検出器としては、示差屈折計を用いた。
EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not restrict | limited by these.
(1) Laser engraving Laser engraving is a carbon dioxide laser engraving machine (trademark: ZED-mini-1000, UK, manufactured by ZED, USA, coherent, output 250W carbon dioxide laser, laser oscillation wavelength is 10.6 μm ). Engraving was performed by creating a dot pattern (120 lines / inch, area ratio 10%). The engraving depth was 0.55 mm.
(2) Viscosity The viscosity of the photosensitive resin composition or the organic compound (b) was measured at 20 ° C. using a B-type viscometer (trademark, B8H type; manufactured by Tokyo Keiki Co., Ltd., Japan).
(3) Measurement of number average molecular weight The number average molecular weights of the resin (a) and the organic compound (b) were determined by conversion with polystyrene having a known molecular weight using a gel permeation chromatography method (GPC method). Using a high-speed GPC apparatus (trademark, HLC-8020, manufactured by Tosoh Corporation, Japan) and a polystyrene-filled column (trademark: TSKgel GMHXL; manufactured by Tosoh Corporation, Japan), the measurement was performed with tetrahydrofuran (THF). The column temperature was set to 40 ° C. As a sample to be injected into the GPC apparatus, a THF solution having a resin concentration of 1 wt% was prepared, and the injection amount was 10 μl. A differential refractometer was used as the detector.
（製造例１）
温度計、攪拌機、還流器を備えた１Ｌのセパラブルフラスコに旭化成株式会社製ポリカーボネートジオールである、商標「ＰＣＤＬＬ４６７２」（数平均分子量１９９０、ＯＨ価５６．４）４４７．２４ｇとトリレンジイソシアナート３０．８３ｇを加え８０℃に加温下に約３時間反応させた後、２−メタクリロイルオキシイソシアネート１４．８３ｇを添加し、さらに約３時間反応させて、末端がメタアクリル基（分子内の重合性不飽和基が1分子あたり平均約２個）である数平均分子量約１００００の樹脂（ア）を製造した。この樹脂は２０℃では水飴状であり、外力を加えると流動し、かつ外力を除いても元の形状を回復しなかった。
(Production Example 1)
A 1 L separable flask equipped with a thermometer, a stirrer, and a refluxer is a polycarbonate diol manufactured by Asahi Kasei Corporation. Trademark “PCDLL4672” (number average molecular weight 1990, OH number 56.4) 447.24 g and tolylene diisocyanate 30 After adding .83 g and reacting at 80 ° C. for about 3 hours, 14.83 g of 2-methacryloyloxyisocyanate is added, and further reacted for about 3 hours, and the terminal is a methacryl group (polymerization within the molecule). A resin (A) having a number average molecular weight of about 10,000 having an average of about 2 unsaturated groups) was produced. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.
（製造例２）
温度計、攪拌機、還流器を備えた１Ｌのセパラブルフラスコに旭化成株式会社製ポリカーボネートジオールである、商標「ＰＣＤＬＬ４６７２」（数平均分子量１９９０、ＯＨ価５６．４）４４７．２４ｇとトリレンジイソシアナート３０．８３ｇを加え８０℃に加温下に約３時間反応させた後、２−メタクリロイルオキシイソシアネート７．４２ｇを添加し、さらに約３時間反応させて、末端がメタアクリル基（分子内の重合性不飽和基が1分子あたり平均約１個）である数平均分子量約１００００の樹脂（イ）を製造した。この樹脂は２０℃では水飴状であり、外力を加えると流動し、かつ外力を除いても元の形状を回復しなかった。
(Production Example 2)
A 1 L separable flask equipped with a thermometer, a stirrer, and a refluxer is a polycarbonate diol manufactured by Asahi Kasei Corporation. Trademark “PCDLL4672” (number average molecular weight 1990, OH number 56.4) 447.24 g and tolylene diisocyanate 30 .83 g was added and reacted at 80 ° C. for about 3 hours. Then, 7.42 g of 2-methacryloyloxyisocyanate was added and further reacted for about 3 hours, and the terminal was a methacrylic group (polymerization within the molecule). A resin (a) having a number average molecular weight of about 10,000 having an average of about 1 unsaturated group per molecule) was produced. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.
（実施例１）
有機化合物（ｂ）の１成分として、フェノキシエチルメタクリレートを用い、フェノキシエチルメタクリレートを分散媒として、青色顔料である銅フタロシアニン（ＢＡＳＦ社製、商標「Ｈｅｌｉｏｇｅｎ Ｂｌｕｅ Ｄ ６７００Ｔ」）を超音波ホモジナイザーで分散させ、分散液を調整した。更に、該顔料を分散させた分散液を、超微細分散装置（吉田機械興業社製、商標「ナノマイザーＭＮ ＩＩ）を用いて平均粒子径が約５０ｎｍの超微粒子とした。顔料粒子の平均粒子径は、レーザー散乱型粒度分布計（大塚電子社製、商標「ＦＰＡＲ−１０００」）を用いて測定した。銅フタロシアニンを微分散させるために使用した分散媒体であるフェノキシエチルメタクリレートの粘度は、Ｂ型粘度計を用いて測定した結果、２０℃において、１０ｍＰａ・ｓであった。
(Example 1)
As a component of the organic compound (b), phenoxyethyl methacrylate is used, and phenoxyethyl methacrylate is used as a dispersion medium, and copper phthalocyanine as a blue pigment (trademark “Heliogen Blue D 6700T”), which is a blue pigment, is dispersed with an ultrasonic homogenizer. The dispersion was adjusted. Furthermore, the dispersion liquid in which the pigment is dispersed is made into ultrafine particles having an average particle diameter of about 50 nm using an ultrafine dispersion apparatus (trade name “Nanomizer MN II” manufactured by Yoshida Kikai Kogyo Co., Ltd.). Was measured using a laser scattering type particle size distribution meter (trademark “FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). The viscosity of phenoxyethyl methacrylate, which is a dispersion medium used for finely dispersing copper phthalocyanine, was 10 mPa · s at 20 ° C. as a result of measurement using a B-type viscometer.
樹脂（ａ）として、製造例１で作製した樹脂（ア）７０重量部、有機化合物（ｂ）として、フェノキシエチルアクリレート（分子量１９２）１０重量部およびポリピレングリコールモノメタクリレート（分子量４００）１０重量部、富士シリシア化学株式会社製、多孔質性微粉末シリカである、商標「サイロスフェアC−１５０４」（以下略してＣ−１５０４、数平均粒子径４．５μｍ、比表面積５２０ｍ２／ｇ、平均細孔径１２ｎｍ、細孔容積１．５ｍｌ／ｇ、灼熱減量２．５ｗｔ％、吸油量２９０ｍｌ／１００ｇ）光重合開始剤としてベンゾフェノンおよび２，２−ジメトキシ−２−フェニルアセトフェノン、その他、安定剤等の添加剤を混合した混合物を調整した。 As resin (a), 70 parts by weight of resin (a) prepared in Production Example 1, as organic compound (b), 10 parts by weight of phenoxyethyl acrylate (molecular weight 192) and 10 parts by weight of polypyrene glycol monomethacrylate (molecular weight 400) Manufactured by Fuji Silysia Chemical Co., Ltd., which is a porous fine-powder silica, the trademark “Pyrospher C-1504” (hereinafter abbreviated as C-1504, number average particle diameter 4.5 μm, specific surface area 520 m 2 / g, average fine Pore diameter 12nm, pore volume 1.5ml / g, ignition loss 2.5wt%, oil absorption 290ml / 100g) Addition of benzophenone and 2,2-dimethoxy-2-phenylacetophenone as photopolymerization initiator, stabilizers, etc. A mixture in which the agent was mixed was prepared.
更に、得られた混合物に、前記分散液１０重量部を混合し、顔料を含む感光性樹脂組成物を得た。顔料の濃度は、感光性樹脂組成物全重量の２００ｐｐｍとした。
用いた光重合開始剤の濃度は、ベンゾフェノンが１ｗｔ％、２，２−ジメトキシ−２−フェニルアセトフェノンが０．６ｗｔ％とした。
得られた感光性樹脂組成物をＰＥＴフィルム上に厚さ１．４ｍｍのシート状に成形し、旭化成株式会社製ＡＬＦ型２１３Ｅ露光機を用い、大気中でレリーフ面 ２０００ｍＪ／ｃｍ２、バック面１０００ｍＪ／ｃｍ２の条件で露光し、シート状レーザー彫刻印刷原版を作製した。露光に用いた光は紫外線蛍光灯（ケミカルランプ、中心波長：３７０ｎｍ）と殺菌灯（ジャーミサイダルランプ、中心波長：２５３ｎｍ）の光であった。感光性樹脂組成物は、完全に光硬化していた。深さ方向に切断し、断面の状況を確認したところ、未硬化部分は存在していなかった。
Furthermore, 10 parts by weight of the dispersion was mixed with the obtained mixture to obtain a photosensitive resin composition containing a pigment. The concentration of the pigment was 200 ppm of the total weight of the photosensitive resin composition.
The concentration of the photopolymerization initiator used was 1 wt% for benzophenone and 0.6 wt% for 2,2-dimethoxy-2-phenylacetophenone.
The obtained photosensitive resin composition was molded into a sheet having a thickness of 1.4 mm on a PET film, and a relief surface of 2000 mJ / cm 2 and a back surface of 1000 mJ were used in the atmosphere using an ALF type 213E exposure machine manufactured by Asahi Kasei Corporation. It exposed on the conditions of / cm < 2 >, and produced the sheet-form laser engraving printing original plate. The light used for exposure was ultraviolet fluorescent light (chemical lamp, center wavelength: 370 nm) and germicidal lamp (germicidal lamp, center wavelength: 253 nm). The photosensitive resin composition was completely photocured. When it was cut in the depth direction and the condition of the cross section was confirmed, there was no uncured portion.
得られた感光性樹脂組成物は、２０℃において液状であった。また、Ｂ型粘度計を用いて測定した粘度は、２０℃において、１２００Ｐａ・ｓであった。
得られたレーザー彫刻印刷原版の表面に、炭酸ガスレーザー彫刻機を用いて凹凸パターンを形成した。得られたパターンのコントラストが良好であった。図１に網点部を顕微鏡で観察した際の写真を示す。
また、レーザー彫刻印刷原版を深さ方向に切断し、ミクロトームを用いて切片サンプルを作製し、透過型電子顕微鏡で観察し撮影した写真を基に解析した結果、顔料粒子の平均粒子径は約５０ｎｍであることがわかった。
The obtained photosensitive resin composition was liquid at 20 ° C. The viscosity measured using a B-type viscometer was 1200 Pa · s at 20 ° C.
An uneven pattern was formed on the surface of the obtained laser engraving printing original plate using a carbon dioxide laser engraving machine. The contrast of the obtained pattern was good. FIG. 1 shows a photograph of the halftone dot portion observed with a microscope.
Further, the laser engraving printing original plate was cut in the depth direction, a section sample was prepared using a microtome, and the result was analyzed based on a photograph taken by observation with a transmission electron microscope. As a result, the average particle size of the pigment particles was about 50 nm. I found out that
用いた青色顔料である銅フタロシアニンの吸収スペクトルは、紫外可視分光光度計（日本分光社製、商標「Ｖ−５７０」）で測定した。サンプルは、前記分散液を分散媒であるフェノキシエチルアクリレートで１０倍に希釈して調整した。その結果、３００ｎｍから３６０ｎｍにピークを有するブロードな吸収スペクトルを示した。また、前記銅フタロシアニンが分散した分散液を、蛍光分光光度計（日立製作所社製、商標「Ｆ−４０１０」）を用いて波長３６５ｎｍの光で励起して発光スペクトルを解析した結果、４３５ｎｍ、４５１ｎｍ、４６９ｎｍに発光ピークを有することを確認した。
得られたレーザー彫刻印刷原版表面の色調を分光測色計計（コニカミノルタ社製、商標「ＣＭ−２０２２」）を用いて測定した。ＣＩＥ（国際照明委員会）表色系のｘｙ色度図において、ｘ＝０．１５６４、ｙ＝０．１９５７の青色であった。
The absorption spectrum of copper phthalocyanine, which is the blue pigment used, was measured with an ultraviolet-visible spectrophotometer (trade name “V-570” manufactured by JASCO Corporation). The sample was prepared by diluting the dispersion liquid 10 times with phenoxyethyl acrylate as a dispersion medium. As a result, a broad absorption spectrum having a peak from 300 nm to 360 nm was shown. Moreover, as a result of analyzing the emission spectrum by exciting the dispersion in which the copper phthalocyanine was dispersed with light having a wavelength of 365 nm using a fluorescence spectrophotometer (trademark “F-4010” manufactured by Hitachi, Ltd.), 435 nm and 451 nm. It was confirmed to have an emission peak at 469 nm.
The color tone of the surface of the obtained laser engraving printing original plate was measured using a spectrocolorimeter (trade name “CM-2022” manufactured by Konica Minolta, Inc.). In the xy chromaticity diagram of the CIE (International Commission on Illumination) color system, blue was x = 0.1564 and y = 0.1957.
（実施例２）
実施例１と同じ感光性樹脂組成物を用いて、円筒状の感光性樹脂硬化物を形成した。直径２００ｍｍのエアーシリンダーに、内径が同径で厚さ１．５ｍｍのガラス繊維強化プラスチック製のスリーブを嵌め込み、エアーシリンダーを回転させながら、前記スリーブ上に前記感光性樹脂組成物を厚さ１．４ｍｍにドクターブレードを用いて塗布した。その後、エアーシリンダーを回転させながら、大気雰囲気下でケミカルランプ（中心波長：３７０ｎｍ）および殺菌灯（中心波長：２５３ｎｍ）の光をそれぞれ２０００ｍＪ／ｃｍ２、５００ｍＪ／ｃｍ２照射し、厚さ約１．４ｍｍの感光性樹脂硬化物を得た。得られた感光性樹脂硬化物は、表面および内部まで完全に硬化していた。
円筒表面の状態を観察できる顕微鏡（独国、Ｍサービス社製、商標「Ｍｅｔｒｉｃ Ｍタイプ」）を用いて網点部を観察した結果、コントラストが良好であった。
また、レーザー彫刻層中に故意に約５０μｍの大きさの気泡を含有させた場合、高速微小欠陥検査装置（富士オプト社製、商標「ＳＤＲ５０Ｐ０２５−００」）を用いて検査した結果、前記気泡を発見することができた。
(Example 2)
Using the same photosensitive resin composition as in Example 1, a cylindrical photosensitive resin cured product was formed. A glass fiber reinforced plastic sleeve having the same inner diameter and a thickness of 1.5 mm is fitted into an air cylinder having a diameter of 200 mm, and the photosensitive resin composition has a thickness of 1. It apply | coated to 4 mm using a doctor blade. Thereafter, while rotating the air cylinder, a chemical lamp (center wavelength: 370 nm) in an air atmosphere and bactericidal lamp (center wavelength: 253 nm) light was irradiated respectively 2000mJ / cm 2, 500mJ / cm 2 in a thickness of about 1 A 4 mm photosensitive resin cured product was obtained. The obtained photosensitive resin cured product was completely cured to the surface and inside.
As a result of observing the halftone dots using a microscope (trademark “Metric M type”, manufactured by M Service, Germany) that can observe the state of the cylindrical surface, the contrast was good.
In addition, when bubbles of about 50 μm were intentionally included in the laser engraving layer, as a result of inspection using a high-speed micro defect inspection apparatus (trademark “SDR50P025-00” manufactured by Fuji Opto), the bubbles were I was able to find it.
（実施例３）
実施例１で用いた内側の感光性樹脂硬化物を形成する際に用いた感光性樹脂組成物を窒素ガス中で激しく撹拌し、感光性樹脂組成物中に微細な気泡を形成した。得られた感光性樹脂組成物を実施例２と同じ方法で、ガラス繊維強化プラスチック製スリーブ上に厚さ０．５ｍｍで塗布し、大気雰囲気下で光照射することにより硬化させた。得られた感光性樹脂硬化物の表面および内部は完全に硬化していた。このようにして感光性樹脂硬化物からなるクッション層を形成した。別途、ＰＥＴフィルム上に形成したクッション層を、ＰＥＴフィルムから剥離して密度を測定したところ、０．５５ｇ／ｃｍ３であった。
次に、実施例２と同様に、形成したクッション層の上にレーザー彫刻層を形成し、クッション層を有する円筒状のレーザー彫刻印刷原版を作製した。
実施例１と同じ炭酸ガスレーザー彫刻機を用いて同様の網点パターンを形成した。円筒表面の状態を観察できる顕微鏡（独国、Ｍサービス社製、商標「Ｍｅｔｒｉｃ Ｍタイプ」）を用いて網点部を観察した結果、コントラストが良好であった。
(Example 3)
The photosensitive resin composition used in forming the inner photosensitive resin cured product used in Example 1 was vigorously stirred in nitrogen gas to form fine bubbles in the photosensitive resin composition. The obtained photosensitive resin composition was applied in a thickness of 0.5 mm on a glass fiber reinforced plastic sleeve in the same manner as in Example 2, and cured by light irradiation in an air atmosphere. The surface and the inside of the obtained photosensitive resin cured product were completely cured. Thus, the cushion layer which consists of photosensitive resin hardened | cured material was formed. Separately, the cushion layer formed on the PET film was peeled from the PET film and the density was measured, and it was 0.55 g / cm 3 .
Next, in the same manner as in Example 2, a laser engraving layer was formed on the formed cushion layer to produce a cylindrical laser engraving printing original plate having the cushion layer.
The same dot pattern was formed using the same carbon dioxide laser engraving machine as in Example 1. As a result of observing the halftone dots using a microscope (trademark “Metric M type”, manufactured by M Service, Germany) that can observe the state of the cylindrical surface, the contrast was good.
（実施例４）
樹脂（ａ）として、樹脂（ア）の代わりに製造例２で作製した樹脂（イ）を用いる以外は、実施例１と同様にして、感光性樹脂組成物を調製した。
得られた感光性樹脂組成物を用いて、実施例１と同様にしてシート状のレーザー彫刻印刷原版を作製した。感光性樹脂組成物は、完全に光硬化していた。深さ方向に切断し、断面の状況を確認したところ、未硬化部分は存在していなかった。
また、実施例１と同じ炭酸ガスレーザー彫刻機を用いて同様の網点パターンを形成した。得られたパターンのコントラストが良好であった。
Example 4
A photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin (a) prepared in Production Example 2 was used instead of the resin (a) as the resin (a).
Using the obtained photosensitive resin composition, a sheet-form laser engraving printing original plate was prepared in the same manner as in Example 1. The photosensitive resin composition was completely photocured. When it was cut in the depth direction and the condition of the cross section was confirmed, there was no uncured portion.
Moreover, the same halftone dot pattern was formed using the same carbon dioxide laser engraving machine as in Example 1. The contrast of the obtained pattern was good.
（比較例１）
実施例１で用いた青色顔料を添加しない以外は、実施例１と同じ成分の感光性樹脂組成物を調製し、調整した感光性樹脂組成物を用いて実施１と同様にしてレーザー彫刻印刷原版を形成し、同じく炭酸ガスレーザー彫刻機を用いて実施例１と同様のパターンを形成した。
顕微鏡を用いて網点部を観察したが、コントラストが明確ではなかった。図２に網点部を顕微鏡で観察した際の写真を示す。
(Comparative Example 1)
Except not adding the blue pigment used in Example 1, a photosensitive resin composition having the same components as in Example 1 was prepared, and a laser engraving printing original plate was prepared in the same manner as in Example 1 using the prepared photosensitive resin composition. The same pattern as in Example 1 was formed using the same carbon dioxide laser engraving machine.
Although the halftone dot portion was observed using a microscope, the contrast was not clear. FIG. 2 shows a photograph of the halftone dot portion observed with a microscope.
（比較例２）
実施例１で用いた青色顔料の代わりに青色染料（チバスペシャリティーケミカル社製、商標「Ｂｒｉｌｌｉａｎｔ Ｂｌｕｅ Ｒ」）を同濃度添加する以外は、実施例１と同じ成分の感光性樹脂組成物を調製した。
実施例１と同様にしてレーザー彫刻印刷原版を作製したが、ＰＥＴフィルムとの界面で光硬化が不十分であった。深さ方向に切断し、断面の状況を観察したところ、ＰＥＴフィルムとの界面で未硬化の部分が存在することが確認された。
(Comparative Example 2)
A photosensitive resin composition having the same components as in Example 1 was prepared except that a blue dye (trade name “Brillant Blue R” manufactured by Ciba Specialty Chemical Co., Ltd.) was added in the same concentration instead of the blue pigment used in Example 1. did.
A laser engraving printing original plate was produced in the same manner as in Example 1, but photocuring was insufficient at the interface with the PET film. When cutting in the depth direction and observing the state of the cross section, it was confirmed that an uncured portion was present at the interface with the PET film.
本発明の印刷原版は、内部の欠陥が検出され易いように透明性が高く、レーザー彫刻した際にコントラストが高いレーザー彫刻印刷版を形成できるレーザー彫刻印刷原版として好適である。 The printing original plate of the present invention is suitable as a laser engraving printing original plate that has high transparency so that internal defects can be easily detected and can form a laser engraving printing plate with high contrast when laser engraved.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010162733A (en) * | 2009-01-14 | 2010-07-29 | Asahi Kasei E-Materials Corp | Thermosetting resin composition, printing original plate, and printing plate |
| JP5371119B2 (en) * | 2008-09-12 | 2013-12-18 | 旭化成イーマテリアルズ株式会社 | Production method of resin relief printing plate, resin relief printing plate, and production apparatus of resin relief printing plate |
| KR101376129B1 (en) | 2009-09-01 | 2014-03-20 | 주식회사 엘지화학 | Blanket for reverse off-set printing, and method of manufacturing the same |
| ITUA20162250A1 (en) * | 2016-04-01 | 2017-10-01 | Trelleborg Coated Systems Italy S P A | RUBBER FABRIC FOR OFFSET PRINTING |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09254351A (en) * | 1996-03-25 | 1997-09-30 | Daicel Chem Ind Ltd | Printing plate material and its production |
| JPH1073917A (en) * | 1996-07-03 | 1998-03-17 | E I Du Pont De Nemours & Co | Flexo printing element having powder layer, and method for manufacturing flexo printing plate therefrom |
| JP2004255812A (en) * | 2003-02-27 | 2004-09-16 | Asahi Kasei Chemicals Corp | Cylindrical flexographic printing original plate capable of undergoing laser engraving |
| JP2006035092A (en) * | 2004-07-27 | 2006-02-09 | Sanyo Chem Ind Ltd | Method for producing mixture of hollow resin particle and inorganic fine particle |
| JP2006082301A (en) * | 2004-09-14 | 2006-03-30 | Techno Polymer Co Ltd | Laser marking method |
| JP2006248190A (en) * | 2005-03-14 | 2006-09-21 | Asahi Kasei Chemicals Corp | Method for producing cylindrical cushion layer for printing base material |
-
2006
- 2006-12-11 JP JP2006333611A patent/JP5305587B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09254351A (en) * | 1996-03-25 | 1997-09-30 | Daicel Chem Ind Ltd | Printing plate material and its production |
| JPH1073917A (en) * | 1996-07-03 | 1998-03-17 | E I Du Pont De Nemours & Co | Flexo printing element having powder layer, and method for manufacturing flexo printing plate therefrom |
| JP2004255812A (en) * | 2003-02-27 | 2004-09-16 | Asahi Kasei Chemicals Corp | Cylindrical flexographic printing original plate capable of undergoing laser engraving |
| JP2006035092A (en) * | 2004-07-27 | 2006-02-09 | Sanyo Chem Ind Ltd | Method for producing mixture of hollow resin particle and inorganic fine particle |
| JP2006082301A (en) * | 2004-09-14 | 2006-03-30 | Techno Polymer Co Ltd | Laser marking method |
| JP2006248190A (en) * | 2005-03-14 | 2006-09-21 | Asahi Kasei Chemicals Corp | Method for producing cylindrical cushion layer for printing base material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5371119B2 (en) * | 2008-09-12 | 2013-12-18 | 旭化成イーマテリアルズ株式会社 | Production method of resin relief printing plate, resin relief printing plate, and production apparatus of resin relief printing plate |
| JP2010162733A (en) * | 2009-01-14 | 2010-07-29 | Asahi Kasei E-Materials Corp | Thermosetting resin composition, printing original plate, and printing plate |
| KR101376129B1 (en) | 2009-09-01 | 2014-03-20 | 주식회사 엘지화학 | Blanket for reverse off-set printing, and method of manufacturing the same |
| ITUA20162250A1 (en) * | 2016-04-01 | 2017-10-01 | Trelleborg Coated Systems Italy S P A | RUBBER FABRIC FOR OFFSET PRINTING |
| WO2017167606A1 (en) * | 2016-04-01 | 2017-10-05 | Trelleborg Coated Systems Italy S.P.A. | Rubber blanket for offset printing |
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