JP2005084418A - Method for manufacturing photosensitive resin plate - Google Patents
Method for manufacturing photosensitive resin plate Download PDFInfo
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- JP2005084418A JP2005084418A JP2003317174A JP2003317174A JP2005084418A JP 2005084418 A JP2005084418 A JP 2005084418A JP 2003317174 A JP2003317174 A JP 2003317174A JP 2003317174 A JP2003317174 A JP 2003317174A JP 2005084418 A JP2005084418 A JP 2005084418A
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- resin plate
- photosensitive resin
- exposure
- compound
- ink
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- 239000011347 resin Substances 0.000 title claims abstract description 61
- 229920005989 resin Polymers 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 13
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 24
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 238000007639 printing Methods 0.000 abstract description 18
- 230000002411 adverse Effects 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000001846 repelling effect Effects 0.000 description 5
- 230000002459 sustained effect Effects 0.000 description 5
- 238000011109 contamination Methods 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 230000002070 germicidal effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 polyfluorinated ethylene compound Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- WUGOQZFPNUYUOO-UHFFFAOYSA-N 2-trimethylsilyloxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCO[Si](C)(C)C WUGOQZFPNUYUOO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007774 anilox coating Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000647 material safety data sheet Toxicity 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
本発明は、感光性樹脂版の製造方法に関する。 The present invention relates to a method for producing a photosensitive resin plate.
一般的なフレキソ印刷用感光性樹脂版は、例えば特許文献１〜３に記載されるように、露光、現像および後露光工程を経て、製造される。
フレキソ印刷用感光性樹脂版を用いた印刷方式は、凹凸のある樹脂版の凸部の表面に、インキ供給ロール等で、インキを供給し、次に、樹脂版を被印刷体に接触させて、凸部表面のインキを被印刷体に転移させる方式である。
このようなフレキソ印刷においては、しばしば、長時間印刷中に、インキが樹脂版の凸部のショルダー部分に付着してきたり、凹部にインキが入り込んだりして（以下、版面汚れ）、本来の絵柄でない部分まで、印刷されることがある。
このような場合には、一旦、印刷を中止し、樹脂版面をアルコール等の洗浄液を用いて、布等で拭き取る必要があり、経済的に不利になる。
樹脂版の版面汚れに関しては、種々の方法が提案されている。
A general photosensitive resin plate for flexographic printing is manufactured through exposure, development, and a post-exposure process, as described in Patent Documents 1 to 3, for example.
In the printing method using the photosensitive resin plate for flexographic printing, ink is supplied to the surface of the convex portion of the uneven resin plate with an ink supply roll or the like, and then the resin plate is brought into contact with the substrate. In this method, the ink on the surface of the convex portion is transferred to the substrate.
In such flexographic printing, the ink often adheres to the shoulder portion of the convex portion of the resin plate or the ink enters the concave portion (hereinafter referred to as plate surface stain) during long-time printing, which is not the original pattern. Some parts may be printed.
In such a case, it is necessary to stop printing once and wipe the resin plate surface with a cloth or the like using a cleaning liquid such as alcohol, which is economically disadvantageous.
Various methods have been proposed for plate surface contamination of resin plates.
特許文献４には、版表面に有機フッ素化合物を、はけ塗りやスプレー方式で付着させる技術が記載されているが、後露光後に塗布するために、版面汚れ防止の効果が小さく、持続効果も低い。
特許文献５には、版表面にシリコン系化合物やフッ素系化合物の水系エマルジョンと水性樹脂の混合物を塗布する方法が提案されているが、浸透力の低い水系の溶液であることや後露光後に塗布するため、版面汚れ防止の効果は、必ずしも十分ではない。
Patent Document 5 proposes a method of applying a mixture of an aqueous emulsion of a silicon-based compound or a fluorine-based compound and an aqueous resin to the plate surface, but it is an aqueous solution having a low penetrating power or applied after post-exposure. Therefore, the effect of preventing plate surface contamination is not always sufficient.
本発明における技術的課題は、版面のインキ汚れを長期間防止し、かつ印刷に悪影響がない感光性樹脂版の製造方法を提供するものである。 The technical problem in the present invention is to provide a method for producing a photosensitive resin plate that prevents ink stains on the plate surface for a long period of time and does not adversely affect printing.
本発明者らは、上記課題を解決するために鋭意検討した結果、後露光前に、樹脂版の版面に、シリコン系化合物および／またはフッ素系化合物を含有した溶液を、付着させることで、課題を解決できることを見出し、本発明を完成した。
すなわち、本発明は、下記の通りである。
（１）露光工程、現像工程および後露光工程を含む感光性樹脂版の製造方法であって、後露光工程の前に、樹脂版の版面に、シリコン系化合物および／またはフッ素系化合物を含有した溶液を、付着させることを特徴とする感光性樹脂版の製造方法。
（２）現像工程で用いられる現像液が、シリコン系化合物および／またはフッ素系化合物を含有することを特徴とする（１）記載の感光性樹脂版の製造方法。
（３）シリコン系化合物および／またはフッ素系化合物が、（メタ）アクリレート基を有することを特徴とする（１）または（２）記載の感光性樹脂版の製造方法。
（４）露光工程、現像工程および後露光工程を含む感光性樹脂版の製造方法において、後露光工程の前に、樹脂版の版面に、シリコン系化合物および／またはフッ素系化合物を含有した溶液を、付着させることにより得られたことを特徴とする感光性樹脂版。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a solution containing a silicon-based compound and / or a fluorine-based compound is adhered to the plate surface of the resin plate before post-exposure. The present invention has been completed.
That is, the present invention is as follows.
(1) A method for producing a photosensitive resin plate including an exposure step, a development step, and a post-exposure step, wherein a silicon-based compound and / or a fluorine-based compound is contained in the plate surface of the resin plate before the post-exposure step. A method for producing a photosensitive resin plate, comprising attaching a solution.
(2) The method for producing a photosensitive resin plate according to (1), wherein the developer used in the development step contains a silicon compound and / or a fluorine compound.
(3) The method for producing a photosensitive resin plate as described in (1) or (2), wherein the silicon compound and / or the fluorine compound has a (meth) acrylate group.
(4) In a method for producing a photosensitive resin plate including an exposure step, a development step, and a post-exposure step, a solution containing a silicon compound and / or a fluorine-based compound is provided on the plate surface of the resin plate before the post-exposure step. A photosensitive resin plate obtained by adhering.
本発明の製造方法は、樹脂版の版面のインキ汚れを長期間防止し、かつ印刷に悪影響がない感光性樹脂版を提供することができる。 The production method of the present invention can provide a photosensitive resin plate that prevents ink stains on the plate surface of the resin plate for a long period of time and does not adversely affect printing.
以下、本発明について、その好ましい形態を中心に、詳細に説明する。
本発明のフレキソ印刷用感光性樹脂版とは、露光、現像および後露光工程を経て製造されるもので、露光前の樹脂が、室温で流動性があったり、固体であっても構わない。感光性樹脂版として公知の樹脂のものを使用することができる。
本発明でいう、露光工程、現像工程は、通常の感光性樹脂版の製造方法で使用される公知の条件で実施することができる。
本発明では、シリコン系化合物および／またはフッ素系化合物の溶液を、後露光前に、樹脂版面に付着させることが必須である。
Hereinafter, the present invention will be described in detail focusing on preferred forms thereof.
The photosensitive resin plate for flexographic printing of the present invention is produced through exposure, development and post-exposure steps, and the resin before exposure may be fluid at room temperature or may be solid. A known resin can be used as the photosensitive resin plate.
The exposure step and the development step referred to in the present invention can be carried out under known conditions used in a normal method for producing a photosensitive resin plate.
In the present invention, it is essential that the silicon compound and / or fluorine compound solution is adhered to the resin plate surface before post-exposure.
本発明のシリコン系化合物とは、シリコーンオイルやシランカップリング剤等が挙げられる。
シリコンーンオイルは、反応性のものでも、非反応性のものでも構わない。反応性シリコーンオイルとしては、メタクリル変性、アミノ変性、カルボキシル変性物等が挙げられる。トリメチルシロキシエチルメタクリレート等も上げられる。非反応性シリコーンオイルとしては、ポリエーテル変性、メチルスチリル変性、アルキル変性、高級脂肪酸エステル変性、高級アルコキシ変性あるいはフッ素変性物が挙げられる。
本発明のフッ素系化合物とは、ポリフッ化エチレン化合物、ポリ（エチレン−フッ化エチレン）化合物、側鎖にパーフルオロアルキル基を有するアクリル系共重合体、パーフルオロアルキル基を有するウレタン系重合体、パーフルオロアルキル基を有するエステル系重合体あるいはフッ素系のモノマー等が挙げられる。
Examples of the silicon compound of the present invention include silicone oil and silane coupling agents.
Silicone oil may be reactive or non-reactive. Examples of the reactive silicone oil include methacryl-modified, amino-modified and carboxyl-modified products. Trimethylsiloxyethyl methacrylate and the like can also be raised. Non-reactive silicone oils include polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, higher alkoxy-modified or fluorine-modified products.
The fluorine compound of the present invention is a polyfluorinated ethylene compound, a poly (ethylene-fluorinated ethylene) compound, an acrylic copolymer having a perfluoroalkyl group in the side chain, a urethane polymer having a perfluoroalkyl group, Examples thereof include an ester polymer having a perfluoroalkyl group or a fluorine monomer.
シリコン系化合物やフッ素系化合物は、２種類以上を組合わせて用いても良い。
本発明のシリコン系化合物および／またはフッ素系化合物は、溶媒に溶解して使用される。
溶媒は、樹脂版の表面に付着し、表面近傍に浸透するものが良い。樹脂版の表面に浸透する溶媒を選択した上で、後露光工程に処することで、一層、シリコン系化合物および／又はフッ素系化合物が樹脂表面（近傍）に強固に固着されるので好ましい。特に、現像液に塩素系溶剤や炭化水素系溶剤が使用される溶剤現像型感光性樹脂版には、溶媒として、水よりも浸透力の高い溶剤を使用しなければならならい。水よりも浸透力のある溶媒としては、具体的には、炭化水素、酢酸エステル、アルコール、ケトンあるいはグリコールエーテル等の溶剤を用いることができる。これらは単独で使用しても良いし、２種以上を組合わせて用いても良い。樹脂版の表面に浸透させるために、水に上記溶媒のパラフィンやグリコールエーテルを併用したり、浸透力の高いノニオン系界面活性剤を添加して用いることもできる。
Two or more types of silicon compounds and fluorine compounds may be used in combination.
The silicon compound and / or fluorine compound of the present invention is used after being dissolved in a solvent.
The solvent is preferably one that adheres to the surface of the resin plate and permeates near the surface. By selecting a solvent that permeates the surface of the resin plate and then subjecting it to a post-exposure step, the silicon compound and / or fluorine compound is more firmly fixed to the resin surface (near), which is preferable. In particular, in a solvent development type photosensitive resin plate in which a chlorine-based solvent or a hydrocarbon-based solvent is used as a developer, a solvent having a higher penetrating power than water must be used. Specifically, as a solvent having a permeability more than water, a solvent such as hydrocarbon, acetate, alcohol, ketone, or glycol ether can be used. These may be used alone or in combination of two or more. In order to permeate the surface of the resin plate, paraffin or glycol ether of the above solvent can be used in combination with water, or a nonionic surfactant having high penetrating power can be added and used.
必要に応じて、シリコン系化合物やフッ素系化合物を含有する溶液に、消泡剤、酸化防止剤あるいは防腐剤等の添加剤を加えても良い。
シリコン系化合物やフッ素系化合物の溶液を、樹脂版の版面に付着や塗布する工程を省略するため、シリコン系化合物やフッ素系化合物を、現像液に添加して使用するのが好ましい。
現像液中に、シリコン系化合物および／またはフッ素系化合物を添加する場合の濃度は、好ましくは、０.０１ｗｔ％〜５ｗｔ％である。
現像液中にシリコン系化合物および／またはフッ素系化合物を添加しない場合の樹脂版の版面への付着方法としては、スプレーによる溶液塗布、はけ塗り、浸漬、布やスポンジで溶液を塗る方法、現像後リンス液に添加し版面に滴下する等があげられる。これらは、後露光前であれば、現像直後に実施しても良いし、現像し乾燥後に実施してもよい。
If necessary, an additive such as an antifoaming agent, an antioxidant or a preservative may be added to the solution containing a silicon compound or a fluorine compound.
In order to omit the step of adhering or applying the silicon compound or fluorine compound solution to the plate surface of the resin plate, it is preferable to add the silicon compound or fluorine compound to the developer.
The concentration in the case of adding a silicon compound and / or a fluorine compound to the developer is preferably 0.01 wt% to 5 wt%.
As a method of adhering the resin plate to the plate surface when no silicon compound and / or fluorine compound is added to the developer, solution application by spraying, brushing, dipping, applying the solution with a cloth or sponge, development For example, it is added to the post-rinse solution and dropped on the plate surface. If these are before post-exposure, they may be carried out immediately after development, or after development and drying.
現像液中に添加せず、版面に付着させる場合の濃度は、付着時間が現像液の場合より短いので、濃度を高くした方がよく、０.０５ｗｔ％から５０ｗｔ％が好ましい。
本発明の後露光とは、少なくとも波長３００ｎｍ以下の活性光線を、現像後の樹脂版の版面に露光処理することをいう。必要に応じて、３００ｎｍ以上の活性光線を併用しても構わない。これらの波長の異なる活性光線を併用する場合は、同時に露光処理しても、別々に露光処理しても構わない。
The concentration in the case of adhering to the plate surface without being added to the developer is preferably shorter because the adhesion time is shorter than in the case of the developer, and is preferably 0.05 wt% to 50 wt%.
The post-exposure of the present invention means that an actinic ray having a wavelength of 300 nm or less is exposed to the plate surface of the developed resin plate. If necessary, actinic rays of 300 nm or more may be used in combination. When these actinic rays having different wavelengths are used in combination, they may be exposed at the same time or separately.
以下、実施例、及び比較例により本発明についてより具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although an example and a comparative example explain the present invention more concretely, the present invention is not limited to these.
（１）感光性樹脂版の製版
（１−１）露光および現像
溶剤現像型の未露光の感光性樹脂版ＡＦＰ−ＳＨ(旭化成製、商品名、厚み１.１４ｍｍ)のカバーシートをはぎとり、感光性樹脂層の上にある保護膜層の上にネガフィルムを密着させ、ＡＦＰ−１５００露光機（旭化成製、商品名）上で３７０ｎｍに中心波長を有する紫外線蛍光灯を用いて、まず支持体側から８００ｍＪ／ｃｍ2の全面露光をおこなった後、引き続きネガフィルムを通して５０００ｍＪ／ｃｍ2の画像露光をおこなった。このときの露光強度をオ−ク製作所製のＵＶ照度計ＭＯ−２型機でＵＶ−３５フィルタ−を用いて、バック露光を行なう側である下側ランプからの紫外線をガラス板上で測定した強度は４．０ｍＷ／ｃｍ2、レリーフ露光側である上側ランプからの紫外線を測定した強度は７．８ｍＷ／ｃｍ2であった。
次に、ソルビット（ポリファイブロン社製、商品名）を現像液として、クイックライン９１２現像機（旭化成製、商品名）を用いて、液温３０℃で現像を行った。
(1) Plate making of photosensitive resin plate (1-1) Exposure and development Stripping a cover sheet of an unexposed photosensitive resin plate AFP-SH (trade name, thickness 1.14 mm, manufactured by Asahi Kasei) of solvent development type First, from the support side, using a UV fluorescent lamp having a central wavelength of 370 nm on an AFP-1500 exposure machine (trade name, manufactured by Asahi Kasei), a negative film is brought into close contact with the protective film layer on the photosensitive resin layer. after performing the overall exposure of 800 mJ / cm 2, it was subsequently subjected to image exposure of 5000 mJ / cm 2 through a negative film. The exposure intensity at this time was measured on the glass plate for ultraviolet rays from the lower lamp, which is the side that performs back exposure, using a UV illuminometer MO-2 type machine manufactured by Oak Seisakusho using a UV-35 filter. The intensity was 4.0 mW / cm 2 , and the intensity measured by ultraviolet rays from the upper lamp on the relief exposure side was 7.8 mW / cm 2 .
Next, development was performed at a liquid temperature of 30 ° C. using a quick line 912 developing machine (trade name, manufactured by Asahi Kasei) using Sorbit (trade name, manufactured by Polyfibron) as a developer.
（１−２）後露光
現像直後は、版が現像液に膨潤しているため、後露光の前に、６０℃で１時間乾燥後に、２５４ｎｍに中心波長をもつ殺菌灯を用いて版表面全体に、２０００ｍＪ／ｃｍ2、続いて紫外線蛍光灯を用いて１０００ｍＪ／ｃｍ2の後露光を行なってフレキソ樹脂版を得た。
なおここで殺菌灯による後露光量は、ＭＯ−２型機のＵＶ−２５フィルタ−を用いて測定された照度から算出したものである。
（１−３）シリコン系化合物やフッ素系化合物の付着方法
表１〜４に記載の方法で、シリコン系化合物および／またはフッ素系化合物を含有する溶液を版表面に付着させた。
(1-2) Post-exposure Immediately after development, since the plate is swollen in the developer, the entire plate surface is dried with a germicidal lamp having a central wavelength of 254 nm after drying for 1 hour at 60 ° C. before post-exposure. Further, 2000 mJ / cm 2 , followed by 1000 mJ / cm 2 after exposure using an ultraviolet fluorescent lamp, to obtain a flexographic resin plate.
Here, the post-exposure amount with the germicidal lamp is calculated from the illuminance measured using the UV-25 filter of the MO-2 type machine.
(1-3) Adhesion method of silicon compound and fluorine compound A solution containing a silicon compound and / or a fluorine compound was adhered to the plate surface by the methods described in Tables 1 to 4.
すなわち、実施例１〜５、比較例２においてはメタクリル変性された反応性シリコーンオイルＸ−２２−１６４Ａ(信越化学製、商品名）を用い、表１に記載の条件で行い、実施例６〜１０および比較例３においては高級脂肪酸エステル変性された非反応性シリコーンオイル（信越化学工業製、商品名）を用い、表２の条件で行い、実施例１１〜１５および比較例４においてはアサヒガードＡＧ−５８５０(旭硝子製、商品名、フッ素系化合物、実施例１６〜１９および比較例５においては表４に記載の条件で行った。
なお、フッ素系化合物のアサヒガードＡＧ−５８５０（旭硝子製、商品名）は、製品安全データシートによると、ポリフッ化エチレンおよびパーフルオロアルキル基を有するアクリル系共重合体をミネラルスプリットで希釈したフッ素系化合物が４３ｗｔ％の溶液である。
That is, in Examples 1-5 and Comparative Example 2, methacryl-modified reactive silicone oil X-22-164A (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) was used under the conditions shown in Table 1, and Examples 6- 10 and Comparative Example 3 were performed using a non-reactive silicone oil modified with higher fatty acid ester (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) under the conditions shown in Table 2. In Examples 11 to 15 and Comparative Example 4, Asahi Guard AG-5850 (made by Asahi Glass, trade name, fluorine compound, Examples 16 to 19 and Comparative Example 5 were performed under the conditions described in Table 4.
Asahi Guard AG-5850 (trade name, manufactured by Asahi Glass Co., Ltd.) is a fluorine compound in which an acrylic copolymer having polyfluorinated ethylene and a perfluoroalkyl group is diluted with a mineral split according to the product safety data sheet. The compound is a 43 wt% solution.
（２）評価方法
（ａ）インキのカラミの防止効果
（ａ−1）印刷条件
水性インキには、ＨＷ５７１ＡＱＰ（東洋インキ製、商品名）、ＵＶインキには、ＦＤＦＬ３９シアン（東洋インキ製、商品名）を使用した。被印刷体には、コート紙パールコート（王子製紙製、商品名）を使用した。アニロックスロールは、６００ｌｐｉ（セル容積３.８ｃｍ3／ｍ2）、クッションテープは、３Ｍ１０２０（３Ｍ製、商品名）を使用し、印刷速度は、１００ｍ／分で印刷を実施した。
（ａ−２）インキのカラミ評価方法
製版後のフレキソ樹脂版を用い、（ａ−１）の条件で、５００ｍ印刷後に、樹脂版の網点部の３％ハイライトと３０％ミッドゾーンの凹部のインキの溜まりの程度を、ルーペで観察し、凹部の谷までインクが流れたものを×、凸部のショルダー部の上層にのみインキが付着している場合を○、その中間を△とした。インキが凹部の谷に到達する時間が長い方が良いので、○を合格とした。
(2) Evaluation method (a) Effect of preventing ink color (a-1) Printing conditions For water-based ink, HW571AQP (product name, manufactured by Toyo Ink), for UV ink, FDFL39 cyan (product name, manufactured by Toyo Ink) )It was used. Coated paper pearl coat (made by Oji Paper Co., Ltd., trade name) was used as the substrate. The anilox roll was 600 lpi (cell volume 3.8 cm 3 / m 2 ), the cushion tape was 3M1020 (manufactured by 3M, trade name), and printing was performed at a printing speed of 100 m / min.
(A-2) Ink Karami Evaluation Method Using the flexographic resin plate after plate making, after printing for 500 m under the conditions of (a-1), 3% highlight of the dot portion of the resin plate and 30% mid-zone recess The degree of ink accumulation was observed with a magnifying glass. The ink flowed up to the valley of the recess was evaluated as x, the case where the ink was only attached to the upper layer of the shoulder of the projection was evaluated as △, and the middle was determined as △ . Since it is better that the time for the ink to reach the valleys of the recesses, the mark “◯” was accepted.
（ｂ）インキのカラミ防止の持続効果
インキのカラミの持続効果を模擬的に評価するため、（ａ−２）で得られた５００ｍ印刷後の樹脂版の表面を、イソプロピルアルコールで布拭きし、インキを除去した後に、ぬれ張力試験用混合液（和光純薬工業株式会社製、商品名）を用いて、樹脂版の版面の表面張力を測定し、３４ｍＮ／ｍ以下であれば、シリコン系化合物やフッ素系化合物が付着していると判断し、○とし、３４ｍＮ／ｍより高ければ持続効果が低いと判断し、×とした。
（ｃ）総合評価
評価（ａ）および評価（ｂ）が共に○で、且つ印刷において、印刷物の１００％画像のベタ部に、インキのはじきが見られない場合を合格とし、○とした。
(B) Sustained effect of preventing ink coloration In order to evaluate the effect of ink colorage in a simulated manner, the surface of the resin plate after 500 m printing obtained in (a-2) was wiped with isopropyl alcohol. After removing the ink, the surface tension of the plate surface of the resin plate is measured using a wet tension test mixture (trade name, manufactured by Wako Pure Chemical Industries, Ltd.). If the surface tension is 34 mN / m or less, a silicon compound And it was judged that the fluorine-containing compound was adhered, and it was judged as ◯.
(C) Comprehensive evaluation Both the evaluation (a) and the evaluation (b) were ◯, and when printing, no repelling of the ink was observed in the solid portion of the 100% image of the printed matter, and the result was ◯.
実施例１〜５、比較例１および２で得られた水性インキ使用における評価試験結果の一覧を表１に記載する。樹脂版の版面には、付着および塗布ムラは無かった。また、得られた印刷物のベタ部（１００％画像部）に、インキのはじきも無く、きれいに印刷できた。表１に示す通り、後露光前に、シリコン系化合物の溶液を、版面に付着させることで、インキのカラミを抑えられ、且つ持続効果が得られた。
実施例６〜１０、比較例１および３で得られた水性インキにおける評価結果を表２に記載する。樹脂版の版面には、付着および塗布ムラは無かった。また、得られた印刷物のベタ部（１００％画像部）に、インキのはじきも無く、きれいに印刷できた。表２に示す通り、後露光前に、シリコン系化合物の溶液を、版面に付着させることで、インキのカラミを抑えられ、且つ持続効果が得られた。
Table 1 shows a list of evaluation test results in the use of water-based inks obtained in Examples 1 to 5 and Comparative Examples 1 and 2. There was no adhesion or coating unevenness on the plate surface of the resin plate. In addition, the solid portion (100% image portion) of the obtained printed matter could be printed neatly without ink repelling. As shown in Table 1, by applying a silicon compound solution to the plate surface before post-exposure, it was possible to suppress ink coloration and to obtain a sustained effect.
Table 2 shows the evaluation results of the water-based inks obtained in Examples 6 to 10 and Comparative Examples 1 and 3. There was no adhesion or coating unevenness on the plate surface of the resin plate. In addition, the solid portion (100% image portion) of the obtained printed matter could be printed neatly without ink repelling. As shown in Table 2, by applying a silicon compound solution to the plate surface before post-exposure, it was possible to suppress ink coloration and to obtain a sustained effect.
実施例１１〜１５、比較例１および４で得られた水性インキにおける結果を表３に記載する。樹脂版の版面には、付着および塗布ムラは無かった。また、得られた印刷物のベタ部（１００％画像部）に、インキのはじきも無く、きれいに印刷できた。表３に示す通り、後露光前に、フッ素系化合物の溶液を、版面に付着させることで、インキのカラミを抑えられ、且つ持続効果が得られた。
実施例１６〜１９および比較例５で得られたＵＶインキにおける結果を表４に記載する。表４に示す通り、ＵＶインキにおいても、後露光前に、フッ素系化合物やシリコン系化合物の溶液を版面に付着させることで、インキカラミを抑えられ、且つ持続効果が得られた。また、得られた印刷物のベタ部（１００％画像部）に、インキのはじきも無く、きれいに印刷できた。
Table 3 shows the results of the water-based inks obtained in Examples 11 to 15 and Comparative Examples 1 and 4. There was no adhesion or coating unevenness on the plate surface of the resin plate. In addition, the solid portion (100% image portion) of the obtained printed matter could be printed neatly without ink repelling. As shown in Table 3, by adhering the fluorine compound solution to the plate surface before post-exposure, the ink color was suppressed and a sustained effect was obtained.
The results for the UV inks obtained in Examples 16 to 19 and Comparative Example 5 are listed in Table 4. As shown in Table 4, also in the UV ink, the ink color was suppressed and the sustaining effect was obtained by adhering the fluorine compound or silicon compound solution to the plate surface before post-exposure. In addition, the solid portion (100% image portion) of the obtained printed matter could be printed neatly without ink repelling.
本発明は、印刷中の版面の汚れ防止に好適な感光性樹脂印刷版の製造方法として利用することができる。 INDUSTRIAL APPLICATION This invention can be utilized as a manufacturing method of the photosensitive resin printing plate suitable for the stain | pollution | contamination prevention of the plate surface during printing.
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