JP2017206577A - Ultraviolet-curable intaglio ink containing polysilane - Google Patents
Ultraviolet-curable intaglio ink containing polysilane Download PDFInfo
- Publication number
- JP2017206577A JP2017206577A JP2016097788A JP2016097788A JP2017206577A JP 2017206577 A JP2017206577 A JP 2017206577A JP 2016097788 A JP2016097788 A JP 2016097788A JP 2016097788 A JP2016097788 A JP 2016097788A JP 2017206577 A JP2017206577 A JP 2017206577A
- Authority
- JP
- Japan
- Prior art keywords
- ultraviolet
- polysilane
- intaglio ink
- ink
- photopolymerization initiator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
Description
本発明は、凹版インキに関し、より詳細には、銀行券、パスポート、証券類、郵便切手等の偽造防止や変造防止が要求されるセキュリティ印刷物、美術印刷物等の製造に利用されるポリシランを含有する紫外線硬化型凹版インキに関する。 The present invention relates to an intaglio ink, and more specifically, contains polysilane used for the production of banknotes, passports, securities, postage stamps and the like that are required to prevent counterfeiting and alteration, and art prints. The present invention relates to an ultraviolet curable intaglio ink.
銀行券、パスポート、証券類及び切手類（以下「銀行券等」という。）は、その性質上、偽造や変造がされにくいことが要求され、美的な要素も求められる。このような要求のために、銀行券等の印刷には、印刷物の仕上りが非常に優れ、製版工程が複雑で容易に偽造されにくい彫刻凹版印刷（以下「凹版印刷」という。）が用いられている。 Banknotes, passports, securities, and stamps (hereinafter referred to as “banknotes”) are required to be difficult to forge or alter due to their nature, and aesthetic elements are also required. Due to such demands, engraving intaglio printing (hereinafter referred to as “intaglio printing”) is used for printing banknotes and the like, which is very excellent in the finish of printed matter, has a complicated plate making process and is not easily counterfeited. Yes.
凹版印刷とは、金属製の版面に凹状の画線を作製し、版面に凹版インキを着肉させて画線凹部に凹版インキを詰め込み、凹版版面上の余剰の凹版インキをふき取り、強い圧力で用紙に凹版インキを転移させる印刷方法である。 Intaglio printing creates a concave image line on a metal plate surface, fills the plate surface with intaglio ink, stuffs the intaglio ink in the image line recess, wipes off the excess intaglio ink on the intaglio plate surface, and with strong pressure This is a printing method for transferring intaglio ink to paper.
前述した凹版インキの一例としては、酸化重合乾燥型、紫外線硬化型又は酸化重合乾燥型と紫外線硬化型を併用したインキがある。 As an example of the intaglio ink described above, there is an oxidation polymerization drying type, an ultraviolet curing type, or an ink in which an oxidation polymerization drying type and an ultraviolet curing type are used in combination.
前述した酸化重合乾燥型と紫外線硬化型を併用した凹版インキは、紫外線硬化型によるインキ表面を瞬時に硬化することができる裏移り防止特性と、酸化重合乾燥型による紫外線で未硬化のインキ深部を硬化できる効果を組み合わせたインキである。 The intaglio ink that uses both the above-mentioned oxidation polymerization drying type and ultraviolet curing type has an anti-set-off property that can instantaneously cure the ink surface by the ultraviolet curing type, and the UV uncured ink deep portion by the oxidation polymerization drying type. This ink combines effects that can be cured.
酸化重合乾燥型と紫外線硬化型を併用した凹版インキの一例としては、酸化重合剤としてアルキド樹脂等、紫外線（ＵＶ）硬化性アクリレートとワックス、更に光重合開始剤としてα−アミノケトン系化合物を使用した凹版印刷インキが開示されている（例えば、特許文献１参照）。 As an example of an intaglio ink using both an oxidation polymerization dry type and an ultraviolet curable type, an alkyd resin, an ultraviolet (UV) curable acrylate and a wax, and an α-aminoketone compound as a photopolymerization initiator are used as an oxidation polymerization agent. An intaglio printing ink is disclosed (for example, see Patent Document 1).
特許文献１の技術は、アルキド樹脂系を使用しているため、ワイピング特性に優れるとともに、光重合開始剤としてＡｓ、Ｓｂ又はＦのような毒性のある化学元素を使用しておらず、α−アミノケトン系化合物を使用しているため、環境負荷の低減を図ることができるという利点を有していた。 Since the technique of Patent Document 1 uses an alkyd resin system, it has excellent wiping characteristics and does not use a toxic chemical element such as As, Sb or F as a photopolymerization initiator. Since an aminoketone-based compound is used, it has an advantage that environmental load can be reduced.
しかしながら、特許文献１に使用されているα−アミノケトン系化合物の光重合開始剤についても、近年では、環境負荷（特に、生物系）に対する影響が懸念されてきたため、α−アミノケトン系化合物の光重合開始剤を削減することが望まれてきた。 However, the photopolymerization initiator of α-aminoketone compound used in Patent Document 1 has recently been concerned about the influence on the environmental burden (particularly biological system), and therefore photopolymerization of α-aminoketone compound. It has been desired to reduce initiators.
本発明は、ポリシランを含有することでα−アミノケトン系化合物の光重合開始剤の使用量を削減し、又は含有しないことにより、環境負荷の低減を図ることができる紫外線硬化型凹版インキを提供するものである。 The present invention provides an ultraviolet curable intaglio ink capable of reducing the environmental burden by reducing the use amount or not containing a photopolymerization initiator of an α-aminoketone compound by containing polysilane. Is.
本発明は、紫外線硬化型組成物、酸化重合型組成物、光重合開始剤、酸化重合触媒及び顔料を少なくとも含んで成る凹版インキであって、光重合開始剤は、α−アミノケトン系化合物及び下記式（１）で表される構造を有するポリシランを含有することを特徴とする紫外線硬化型凹版インキである。 The present invention is an intaglio ink comprising at least an ultraviolet curable composition, an oxidation polymerization type composition, a photopolymerization initiator, an oxidation polymerization catalyst and a pigment, the photopolymerization initiator comprising an α-aminoketone compound and the following: An ultraviolet curable intaglio ink comprising polysilane having a structure represented by formula (1).
本発明は、ポリシランを含有した紫外線硬化型凹版インキを用いることで、従来、紫外線硬化型凹版インキに多量に配合していたα−アミノケトン系化合物の光重合開始剤の使用量を削減し、又は含有しないことができることから、環境負荷低減の向上が図られることが可能になった。 The present invention uses an ultraviolet curable intaglio ink containing polysilane, thereby reducing the amount of α-aminoketone compound photopolymerization initiator used in the conventional ultraviolet curable intaglio ink, or Since it can not be contained, it has become possible to improve the environmental load reduction.
本発明は、紫外線硬化型組成物、酸化重合型組成物、光重合開始剤、酸化重合触媒及び顔料を少なくとも含んで成る凹版インキであって、光重合開始剤は、下記式（１）で表される構造を有するポリシランを含有することを特徴とする紫外線硬化型凹版インキである。 The present invention is an intaglio ink comprising at least an ultraviolet curable composition, an oxidation polymerization composition, a photopolymerization initiator, an oxidation polymerization catalyst, and a pigment, and the photopolymerization initiator is represented by the following formula (1). An ultraviolet curable intaglio ink comprising polysilane having a structure as described above.
上記式（１）において、ｎは正の整数を表す。上記式（１）のポリシランは、ケイ素−ケイ素結合を主鎖に有しており、側鎖は後述する置換基が結合したものであり、化学構造は直鎖型又は環状型でもよい。ポリシランの重量平均分子量は、光反応性の観点から５００以上であり３０，０００以下である。５００未満の場合は、光硬化性が不十分となる。また、３０，０００を超えた場合は、インキの保存安定性及び樹脂への溶解性が低下する。 In the above formula (1), n represents a positive integer. The polysilane of the above formula (1) has a silicon-silicon bond in the main chain, the side chain is bonded with a substituent described later, and the chemical structure may be a linear type or a cyclic type. The weight average molecular weight of polysilane is 500 or more and 30,000 or less from the viewpoint of photoreactivity. If it is less than 500, the photocurability is insufficient. On the other hand, when it exceeds 30,000, the storage stability of the ink and the solubility in the resin decrease.
上記式（１）中のＲ１及びＲ２は、各々独立に置換基を表す。Ｒ１及びＲ２の置換基は、ポリシランが紫外線硬化型組成物に析出しない程度に可溶、かつ、後述する吸収波長にピークを有する必要がある。なお、置換基としては、直鎖状、環状又は分岐状のアルキル基、シクロアルキル基、水酸基、ハロゲン基、カルボキシ基、アルコキシ基、アシル基、シアノ基、アシルオキシ基、メチル基、フェニル基等を挙げることができる。 R1 and R2 in the above formula (1) each independently represent a substituent. The substituents R1 and R2 must be soluble to the extent that polysilane does not precipitate in the ultraviolet curable composition and have a peak at the absorption wavelength described below. Examples of the substituent include linear, cyclic or branched alkyl groups, cycloalkyl groups, hydroxyl groups, halogen groups, carboxy groups, alkoxy groups, acyl groups, cyano groups, acyloxy groups, methyl groups, and phenyl groups. Can be mentioned.
ポリシランの吸収波長は、光反応性の観点から紫外線の吸収波長のピークが２００〜３５０ｎｍである。当該範囲であれば、公知の紫外線照射ランプにより硬化することができるため、経済的な観点から好ましい。 The absorption wavelength of polysilane has an absorption wavelength peak of 200 to 350 nm from the viewpoint of photoreactivity. If it is the said range, since it can harden | cure with a well-known ultraviolet irradiation lamp, it is preferable from an economical viewpoint.
また、ポリシランは単独で使用してもよいし、他の光重合開始剤との混合使用でもよいが、環境負荷の低減である本発明の目的を達成するためには、単独使用が好ましい。併用できる光重合開始剤としては、代表的なものとして、ベンゾインメチルエーテル、ベンゾインエチルエーテル、イソプロピルベンゾインエーテル、イソブチルベンゾインエーテル、１−フェニル−１，２−プロパンジオン−２−（ｏ−エトキシカルボニル）オキシム、ベンジル、ジエトキシアセトフェノン、ベンゾフェノン、クロロチオキサントン、２−クロロチオキサントン、イソプロピルチオキサントン、２−メチルチオキサントン、ポリ塩化ポリフェニル、ヘキサクロロベンゼン、α−アミノケトン系等が挙げられる。また、光重合開始剤に加えて、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸イソアミル等の光重合開始助剤を添加してもよい。 Polysilane may be used alone or in combination with other photopolymerization initiators. However, in order to achieve the object of the present invention, which is a reduction in environmental burden, single use is preferred. Representative photopolymerization initiators that can be used in combination include benzoin methyl ether, benzoin ethyl ether, isopropyl benzoin ether, isobutyl benzoin ether, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl). Examples include oxime, benzyl, diethoxyacetophenone, benzophenone, chlorothioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, 2-methylthioxanthone, polychlorinated polyphenyl, hexachlorobenzene, and α-aminoketone. In addition to the photopolymerization initiator, a photopolymerization initiation assistant such as ethyl 4-dimethylaminobenzoate or isoamyl 4-dimethylaminobenzoate may be added.
酸化重合型組成物は、乾性油又は半乾性油、あるいはそれらから誘導される公知のアルキド樹脂等を使用することができる。また、酸化重合触媒は、コバルト、マンガン、鉛、鉄等の金属化合物、ホウ酸コバルト、オクチル酸コバルト、ナフテン酸コバルト等である。 As the oxidative polymerization type composition, it is possible to use a drying oil or a semi-drying oil, or a known alkyd resin derived therefrom. The oxidation polymerization catalyst is a metal compound such as cobalt, manganese, lead, or iron, cobalt borate, cobalt octylate, cobalt naphthenate, or the like.
紫外線硬化型組成物と酸化重合型組成物の構成比は、９５：５〜７５：２５（重量％：重量％）の範囲である。これより紫外線硬化型組成物が少なくなると、印刷後のインキ皮膜表面の紫外線硬化性が低下し裏移りやブロッキングを引き起こす。これより酸化重合型組成物が少なくなると、酸化重合が不十分で、インキの硬化不良が生じたり、基材へのインキの密着性が劣る場合がある。 The composition ratio of the ultraviolet curable composition and the oxidation polymerization type composition is in the range of 95: 5 to 75:25 (wt%: wt%). When the amount of the ultraviolet curable composition is less than this, the ultraviolet curable property on the surface of the ink film after printing is lowered, causing set-off or blocking. If the amount of the oxidative polymerization type composition is less than this, the oxidative polymerization may be insufficient, resulting in poor curing of the ink or poor adhesion of the ink to the substrate.
本発明の紫外線硬化型凹版インキは、紫外線硬化型組成物と酸化重合型組成物の混合成分１００重量部当たり、紫外線硬化型組成物９５〜７５重量部、酸化重合型組成物５〜２５重量部であり、外割でポリシラン１〜１０重量部、光重合開始剤２〜１０重量部、酸化重合触媒０．５〜３重量部の配合範囲である。これよりポリシラン及び光重合開始剤が少ないと印刷後のインキ皮膜表面の紫外線硬化性が低下し裏移りやブロッキングを引き起こす。これよりポリシラン及び光重合開始剤が多いと、顔料を固定する樹脂分が少なくなり、インキ皮膜強度が低下する場合がある。これより酸化重合触媒が少なくても多くてもインキの酸化重合が不十分になる場合がある。 The ultraviolet curable intaglio ink of the present invention comprises 95 to 75 parts by weight of an ultraviolet curable composition and 5 to 25 parts by weight of an oxidative polymerization composition per 100 parts by weight of a mixed component of the ultraviolet curable composition and the oxidative polymerization composition. The blending range is 1 to 10 parts by weight of polysilane, 2 to 10 parts by weight of a photopolymerization initiator, and 0.5 to 3 parts by weight of an oxidation polymerization catalyst. If there is less polysilane and a photoinitiator than this, the ultraviolet sclerosis | hardenability of the ink film surface after printing will fall, and it will cause a setback and blocking. If there are more polysilane and a photoinitiator than this, the resin part which fixes a pigment will decrease, and ink film strength may fall. If the amount of the oxidation polymerization catalyst is less than this, the oxidative polymerization of the ink may be insufficient.
本発明の紫外線硬化型凹版インキは、有機顔料、無機顔料、ワックス等の公知の添加剤を加えて練合することにより作製される。なお、練合方法は、特に限定されるものではない。 The ultraviolet curable intaglio ink of the present invention is produced by adding and kneading known additives such as organic pigments, inorganic pigments and waxes. The kneading method is not particularly limited.
また、インキの保存安定性を向上させるために、重合禁止（抑制）剤としては公知の重合禁止（抑制）剤、例えば、p-メトキシフェノール、ハイドロキノン等が使用できるが、特にハイドロキノン、メチルハイドロキノンが好ましい。重合禁止（抑制）剤の種類によってその添加量は異なる。 Further, in order to improve the storage stability of the ink, a known polymerization inhibitor (suppressor) such as p-methoxyphenol or hydroquinone can be used as the polymerization inhibitor (suppressor). preferable. The amount of addition varies depending on the type of polymerization inhibitor (suppressor).
なお、本発明の凹版インキを用いて印刷物を製造する装置、すなわち凹版版面への凹版インキの着肉、余剰インキのふき取り及び印刷等の一連の工程を行い得る装置としては、公知の凹版印刷機構を使用することが可能である。また、本発明による凹版インキの硬化には、メタルハライドランプを使用した公知の紫外線照射装置を使用することができる。 In addition, as a device for producing a printed matter using the intaglio ink of the present invention, that is, a device capable of performing a series of processes such as inking of intaglio ink on the surface of the intaglio plate, wiping off excess ink and printing, a known intaglio printing mechanism Can be used. For curing the intaglio ink according to the present invention, a known ultraviolet irradiation device using a metal halide lamp can be used.
以下、実施例を用いて本発明を更に詳細に説明するが、本発明の内容は、これらの実施例の範囲に限定されるものではない。本発明において、％は重量％を示し、部は重量部を示し、表中の数字は重量％を示す。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, the content of this invention is not limited to the range of these Examples. In the present invention,% indicates% by weight, part indicates part by weight, and the numbers in the table indicate% by weight.
表１に示す配合により紫外線硬化型組成物（Ａ１）から（Ａ４）までを作製し、ゲル分率の評価を行った。なお、比較として、比較用紫外線硬化型組成物（Ｂ１）も合わせて作製した。 Ultraviolet curable compositions (A1) to (A4) were prepared according to the formulation shown in Table 1, and the gel fraction was evaluated. For comparison, a comparative ultraviolet curable composition (B1) was also prepared.
紫外線硬化型組成物は、ポリ（エチレングルコール）ジアクリレート（日本化薬製：ＰＥＧ４００ＤＡ）、ジペンタエリスリトールペンタ／ヘキサアクリレート（東亜合成製：Ｍ４０３）及びＮ−（２-ヒドロキシメチル）アクリルアミド（興人製：ＨＥＡＡ）を用いた。また、ビスフェノールＡジグリシジンエーテルアクリル酸付加物（大阪有機化学工業製：Ｖ５４０）を２６０部、無水コハク酸（新日本理化製：リカシッドＳＡ）を１００部、希釈アクリレートとして、ポリ（エチレングルコール）ジアクリレートを７２部及びメチルハイドロキノン（和光純薬工業製）０．４部を撹拌機付きセパラプルフラスコに仕込み、空気を吹き込みながら８０℃で１時間反応させた。得られた反応生成物について、ＪＩＳ Ｋ ００７０に準拠した酸価を測定した結果、１３９ｍｇ／ＫＯＨのカルボシル基を有する酸変性エポキシアクリレート（Ｖ５４０＿ＳＡ）を得た。 The ultraviolet curable composition includes poly (ethylene glycol) diacrylate (Nippon Kayaku: PEG400DA), dipentaerythritol penta / hexaacrylate (Toa Gosei: M403) and N- (2-hydroxymethyl) acrylamide (X Human product: HEAA) was used. In addition, 260 parts of bisphenol A diglycidin ether acrylic acid adduct (manufactured by Osaka Organic Chemical Industry: V540), 100 parts of succinic anhydride (manufactured by Shin Nippon Chemical Co., Ltd .: Ricacid SA), poly (ethylene glycol) as dilute acrylate 72 parts of diacrylate and 0.4 part of methyl hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) were charged into a separable flask equipped with a stirrer and reacted at 80 ° C. for 1 hour while blowing air. As a result of measuring the acid value based on JIS K0070 about the obtained reaction product, the acid-modified epoxy acrylate (V540_SA) which has a carbosil group of 139 mg / KOH was obtained.
炭素系ラジカルの光重合開始剤は、イルガキュア３６９（ＢＡＳＦ製：Ｉ-３６９）を用いた。ケイ素系ラジカル種を生成するポリシランとしては、分子構造が直鎖型で分子量が異なるオグゾールＳＩ-１０-１０（大阪ガスケミカル製：ＳＩ-１０-１０）及びオグソールＳＩ-１０-２０（大阪ガスケミカル製：ＳＩ-１０-２０）、環状型のポリシランとして、オグゾールＳＩ-３０-１０（大阪ガスケミカル製：ＳＩ-３０-１０）を用いた。 Irgacure 369 (manufactured by BASF: I-369) was used as a photopolymerization initiator for the carbon radical. Polysilanes that generate silicon radical species include OGSOL SI-10-10 (Osaka Gas Chemical: SI-10-10) and OGSOL SI-10-20 (Osaka Gas Chemical), which have a linear molecular structure and a different molecular weight. Manufactured by SI-10-20) and OGSOL SI-30-10 (manufactured by Osaka Gas Chemical Co., Ltd .: SI-30-10) was used as the cyclic polysilane.
ゲル分率は、表１に示した紫外線硬化型組成物を用いて、ガラス板上に約１００μｍの厚さで塗布し、種々の紫外線積算光量で紫外線を照射して硬化皮膜を作製した後、アセトンに１分間浸漬させ、溶解しない部分の割合（ゲル分率）を求めた。 The gel fraction was applied to a glass plate with a thickness of about 100 μm using the ultraviolet curable composition shown in Table 1, and after irradiating ultraviolet rays with various ultraviolet integrated light amounts to produce a cured film, It was immersed in acetone for 1 minute, and the ratio (gel fraction) of the part which does not melt | dissolve was calculated | required.
上述の試験結果について、図１を用いて説明する。紫外線硬化型ワニス（以下、ＵＶワニスと略す）に対して、ポリシラン（ＳＩ−１０−２０）を１％以上配合すると、紫外線照射による皮膜の硬化を確認することができた。また、１％以上のポリシランを配合すると、ゲル分率が向上することを確認した。さらに、紫外線の積算光量を増やすと、ゲル分率が高くなることを確認した。 The above test results will be described with reference to FIG. When 1% or more of polysilane (SI-10-20) was blended with an ultraviolet curable varnish (hereinafter abbreviated as UV varnish), curing of the film by ultraviolet irradiation could be confirmed. Moreover, when 1% or more of polysilane was mix | blended, it confirmed that a gel fraction improved. Furthermore, it was confirmed that the gel fraction increases as the cumulative amount of ultraviolet light increases.
粘弾性測定装置（ＨＡＡＫＥ社製 ＲｈｅｏＳｔｒｅｓｓ６００）を用いた紫外線硬化性（以下「ＵＶ硬化性」という。）の評価方法について以下に示す。表２に示す配合により、紫外線硬化型組成物（Ａ５）から（Ａ１１）までを作製した。 An evaluation method of ultraviolet curability (hereinafter referred to as “UV curability”) using a viscoelasticity measuring apparatus (Rheo Stress 600 manufactured by HAAKE) will be described below. Ultraviolet curable compositions (A5) to (A11) were prepared according to the formulation shown in Table 2.
ＵＶ硬化性、皮膜の柔軟性の評価は、回転センサと石英セルとのギャップを１００μｍ、回転速度を１ｃｍ／ｓとし、紫外線照射装置（２００Ｗの水銀キセノンランプ）を使用して、試料を充填して回転開始３０秒後に、下方から紫外線を照射して、せん断応力への変化を測定した。 The UV curability and film flexibility were evaluated by filling the sample with an ultraviolet irradiation device (200 W mercury xenon lamp) with a gap of 100 μm between the rotation sensor and the quartz cell and a rotation speed of 1 cm / s. Then, 30 seconds after the start of rotation, ultraviolet rays were irradiated from below, and the change to shear stress was measured.
上述の試験結果について、図２を用いて説明する。ポリシランを配合した紫外線硬化型組成物に紫外線を照射すると、ラジカル重合反応が進行して、試料の粘度が増し、せん断応力が高くなった。また、着色顔料を含まない紫外線硬化型組成物は、炭素系ラジカル種を生成する光重合開始剤Ｉ−３６９を加えなくても、高いＵＶ硬化性が得られた。さらに、分子構造や分子量が異なったポリシランを用いても高いＵＶ硬化性があることを確認した。 The above test results will be described with reference to FIG. When the ultraviolet curable composition containing polysilane was irradiated with ultraviolet rays, the radical polymerization reaction proceeded to increase the viscosity of the sample and increase the shear stress. In addition, the UV curable composition containing no coloring pigment obtained high UV curability without adding a photopolymerization initiator I-369 that generates carbon-based radical species. Furthermore, it was confirmed that even if polysilanes having different molecular structures and molecular weights were used, there was high UV curability.
表３に示した配合に従い、各成分を三本ロールミルで練合し、常法により凹版インキ（Ｖ１）から（Ｖ３）までを作製して、ブロッキングと裏移りの評価を行った。 In accordance with the formulation shown in Table 3, each component was kneaded with a three-roll mill, and intaglio inks (V1) to (V3) were prepared by a conventional method, and blocking and setback were evaluated.
紫外線硬化型組成物は、紫外線硬化型組成物（Ａ５）、（Ａ６）、（Ａ７）を使用した。酸化重合型組成物は、常法によって作製した油長５５のアマニ油変性アルキド樹脂を使用した。顔料は、青色顔料１５．０重量部、黄色顔料３．０重量部、赤色顔料２．７重量部、黒色顔料２．０重量部、体質顔料２７．３重量部を使用した。酸化重合触媒は、オクチル酸コバルトを使用した。なお、比較例として、比較用紫外線硬化型組成物（Ｂ１）を同様な方法により使用して、比較用凹版インキ（Ｗ１）を作製した。 As the ultraviolet curable composition, ultraviolet curable compositions (A5), (A6), and (A7) were used. As the oxidative polymerization type composition, linseed oil-modified alkyd resin having an oil length of 55 produced by a conventional method was used. The pigment used was 15.0 parts by weight of a blue pigment, 3.0 parts by weight of a yellow pigment, 2.7 parts by weight of a red pigment, 2.0 parts by weight of a black pigment, and 27.3 parts by weight of an extender pigment. Cobalt octylate was used as the oxidation polymerization catalyst. As a comparative example, a comparative intaglio ink (W1) was prepared using the comparative ultraviolet curable composition (B1) by the same method.
表３に示す凹版インキ（Ｖ１）から（Ｖ３）までを使用して、画線深度が１００μｍの凹版版面で９０ｍｍ×１７７ｍｍの坪量８６ｇ/ｍ2の用紙を使用して凹版印刷を行った。印刷後に紫外線（空冷式１２０Ｗ/ｃｍメタルハライドランプ）を８０及び１６０ｍＪ／ｃｍ２照射して、印刷面側と同じ大きさの用紙を重ね、ガラス板に挟んで、４２９ｋｇ／ｍ２の加重をかけた。１週間後、用紙の裏面に付着した凹版インキを目視で観察した。 Using intaglio inks (V1) to (V3) shown in Table 3, intaglio printing was performed on a 90 mm × 177 mm basis weight 86 g / m 2 paper on an intaglio plate surface with an image line depth of 100 μm. After printing, ultraviolet rays (air-cooled 120 W / cm metal halide lamp) were irradiated at 80 and 160 mJ / cm 2, a sheet of the same size as the printed surface was stacked, sandwiched between glass plates, and a load of 429 kg / m 2 was applied. . One week later, the intaglio ink adhered to the back surface of the paper was visually observed.
上述の試験結果について、表４を用いて説明する。 The above test results will be described with reference to Table 4.
着色顔料を含んだ凹版インキを用いた印刷物に紫外線を１６０ｍＪ／ｃｍ２照射すると、炭素系ラジカル種を生成する光重合開始剤Ｉ−３６９を低減させても裏移りがないことを確認した。また、ポリシランを凹版インキに配合すると、光重合開始剤Ｉ−３６９を低減した凹版インキを用いた場合、紫外線積算光量が８０ｍＪ／ｃｍ２でも、裏移りがないことを確認した。 It was confirmed that when the printed matter using the intaglio ink containing the color pigment was irradiated with ultraviolet rays of 160 mJ / cm 2, there was no setback even if the photopolymerization initiator I-369 that generates carbon-based radical species was reduced. Moreover, when polysilane was mix | blended with the intaglio ink, when the intaglio ink which reduced the photoinitiator I-369 was used, even if the ultraviolet rays integrated light quantity was 80 mJ / cm < 2 >, it confirmed that there was no setback.
これにより、ポリシランを紫外線硬化型組成物として使用した場合は、凹版インキに配合するα−アミノケトン系化合物を含有する光重合開始剤の使用量を低減することができた。よって、ポリシランを用いた環境負荷の少ない凹版インキを得ることができた。 Thereby, when polysilane was used as an ultraviolet curable composition, the usage-amount of the photoinitiator containing the alpha-amino ketone type compound mix | blended with an intaglio ink was able to be reduced. Therefore, an intaglio ink with a low environmental load using polysilane could be obtained.
Claims (1)
前記光重合開始剤は、α−アミノケトン系化合物及び下記式（１）で表される構造を有するポリシランを含有することを特徴とする紫外線硬化型凹版インキ。
The photopolymerization initiator contains an α-aminoketone compound and a polysilane having a structure represented by the following formula (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016097788A JP2017206577A (en) | 2016-05-16 | 2016-05-16 | Ultraviolet-curable intaglio ink containing polysilane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016097788A JP2017206577A (en) | 2016-05-16 | 2016-05-16 | Ultraviolet-curable intaglio ink containing polysilane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2017206577A true JP2017206577A (en) | 2017-11-24 |
Family
ID=60415265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016097788A Pending JP2017206577A (en) | 2016-05-16 | 2016-05-16 | Ultraviolet-curable intaglio ink containing polysilane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2017206577A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019151699A (en) * | 2018-03-01 | 2019-09-12 | 株式会社リコー | Active energy ray-curable composition, active energy ray-curable ink, composition storage container, two-dimensional or three-dimensional image formation device, method for producing cured product and cured product |
| JP2020015790A (en) * | 2018-07-24 | 2020-01-30 | 株式会社リコー | Curable composition, curable ink, accommodation container, two-dimensional or three-dimensional image forming apparatus, two-dimensional or three-dimensional image forming method, cured product, and printed matter |
-
2016
- 2016-05-16 JP JP2016097788A patent/JP2017206577A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019151699A (en) * | 2018-03-01 | 2019-09-12 | 株式会社リコー | Active energy ray-curable composition, active energy ray-curable ink, composition storage container, two-dimensional or three-dimensional image formation device, method for producing cured product and cured product |
| JP7101938B2 (en) | 2018-03-01 | 2022-07-19 | 株式会社リコー | Active energy ray-curable ink for inkjet, ink container, two-dimensional or three-dimensional image forming device, method for producing cured product, and cured product |
| JP2020015790A (en) * | 2018-07-24 | 2020-01-30 | 株式会社リコー | Curable composition, curable ink, accommodation container, two-dimensional or three-dimensional image forming apparatus, two-dimensional or three-dimensional image forming method, cured product, and printed matter |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3428187B2 (en) | Active energy ray-curable ink composition | |
| JP4852953B2 (en) | Ink composition and image forming method using the same | |
| JPWO2018003381A1 (en) | UV curable silicone composition and cured product thereof | |
| JP7101938B2 (en) | Active energy ray-curable ink for inkjet, ink container, two-dimensional or three-dimensional image forming device, method for producing cured product, and cured product | |
| JPH11152441A (en) | Ultraviolet-curing composition for coating can | |
| JP2008075067A (en) | Photocurable ink set, and printing method, printing apparatus and printed matter each using the same | |
| JP5939369B1 (en) | Active energy ray curable composition, active energy ray curable printing ink using the same, and printed matter | |
| JP5725511B2 (en) | Intaglio ink | |
| JP2007045989A (en) | Ink composition | |
| JP2008174713A (en) | Two-component photo-curable ink composition set, inkjet recording method using the same, apparatus for inkjet recording and printed material | |
| JP2006257302A (en) | Ink composition | |
| CN110770245B (en) | Compound, photopolymerization initiator, photocurable composition, cured product thereof, photocurable ink, and printed matter using the same | |
| JP2008120991A (en) | Two-pack photocurable ink set | |
| JP2017206577A (en) | Ultraviolet-curable intaglio ink containing polysilane | |
| JP2010143974A (en) | Photocurable ink composition, inkjet recording method, recorded matter, ink set, ink cartridge, and recording device | |
| JP2003292606A (en) | Cationic-polymerizable composition | |
| JP2010132827A (en) | Energy beam curable type inkjet ink composition and printed matter | |
| JP2010209198A (en) | Photocurable ink composition, inkjet recording method, record matter, ink set, ink cartridge and recording device | |
| JP2008239958A (en) | Polysilane compound and its synthetic method, ultraviolet-ray curable ink composition using the polysilane compound, inkjet recording method using the ultraviolet-ray curable ink composition, and ink container and inkjet recording apparatus, both containing the ultraviolet ray-curable ink composition | |
| JP2021024970A (en) | Active energy ray-curable lithographic ink, method for producing a printed matter using the same, and varnish for active energy ray-curable lithographic ink | |
| JP2008223014A (en) | Ultraviolet-ray curable ink composition, inkjet recording method using the same ultraviolet-ray curable ink composition, ink container and inkjet recording apparatus containing the same composition | |
| JP2008291172A (en) | Curable composition and method for curing the same | |
| JP5915919B1 (en) | Active energy ray curable composition, active energy ray curable printing ink using the same, and printed matter | |
| JP2006182971A (en) | Ink for inkjet recording and lithographic printing plate using the same | |
| JP2011174076A (en) | Ink composition for inkjet recording, inkjet recording method, and inkjet recording device |