JP7005809B1 - Manufacturing method of antibacterial overprint varnish, antibacterial printed matter, and antibacterial printed matter - Google Patents
Manufacturing method of antibacterial overprint varnish, antibacterial printed matter, and antibacterial printed matter Download PDFInfo
- Publication number
- JP7005809B1 JP7005809B1 JP2021109608A JP2021109608A JP7005809B1 JP 7005809 B1 JP7005809 B1 JP 7005809B1 JP 2021109608 A JP2021109608 A JP 2021109608A JP 2021109608 A JP2021109608 A JP 2021109608A JP 7005809 B1 JP7005809 B1 JP 7005809B1
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- JP
- Japan
- Prior art keywords
- antibacterial
- printed matter
- group
- overprint varnish
- silver
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Abstract
【課題】本発明は、印刷物に抗菌性能を付与し、かつ印刷物同士が擦れることによるインキ移りや剥がれなどを防ぎ、ブランケットパイリングの少ない印刷適性が良好な抗菌オーバープリントニスを提供することを目的とする。【解決手段】銀イオン水溶液と、ロジン変性フェノール樹脂と、溶剤とを含有する抗菌オーバープリントニスおよび当該抗菌オーバープリントニスを基材に印刷してなることを特徴とする抗菌印刷物、ならびに当該抗菌オーバープリントニスを塗布する工程を含むことを特徴とする抗菌印刷物の製造方法。【選択図】なしPROBLEM TO BE SOLVED: To provide an antibacterial overprint varnish which imparts antibacterial performance to printed matter, prevents ink transfer and peeling due to rubbing between printed matter, and has good printability with less blanket pilling. do. SOLUTION: An antibacterial overprint varnish containing a silver ion aqueous solution, a rosin-modified phenol resin, and a solvent, an antibacterial printed matter characterized by printing the antibacterial overprint varnish on a base material, and the antibacterial overprint. A method for producing an antibacterial printed matter, which comprises a step of applying a print varnish. [Selection diagram] None
Description
本発明は、オフセット印刷に使用する抗菌オーバープリントニスに関する。 The present invention relates to an antibacterial overprint varnish used for offset printing.
オフセット印刷は、用紙を用いて黄・紅・藍・墨の４色のオフセット印刷インキを紙に印刷する印刷方式で、商業印刷物に多く利用されている。さらに、印刷物の表面保護や、光沢向上あるいは艶消しなどを付与する目的で、上記印刷物の表面にオーバープリントニス層を付与することがある。 Offset printing is a printing method in which four colors of yellow, red, indigo, and black offset printing inks are printed on paper using paper, and is widely used in commercial printed matter. Further, an overprint varnish layer may be imparted to the surface of the printed matter for the purpose of protecting the surface of the printed matter, improving gloss or matting.
一方、近年人々の衛生意識の高まりから、医療分野のみならず、さまざまな分野において、物品に抗菌性、抗ウイルス性、防カビ性などの機能を付与することが求められ、なかでも、不特定多数の人が手に触れる可能性が高い雑誌、チラシ、冊子、カタログ、カレンダー、ガイドブックなどの印刷物について、抗菌性や抗ウイルス性を付与したいという要望が高まってきている。 On the other hand, due to the growing awareness of hygiene among people in recent years, it is required to impart antibacterial, antiviral, antifungal and other functions to articles not only in the medical field but also in various fields. There is an increasing demand for antibacterial and antiviral properties for printed matter such as magazines, leaflets, booklets, catalogs, calendars, and guidebooks that are likely to be touched by a large number of people.
特許文献１には、中空多孔質シリカにより被覆された酸化チタン光触媒を含有するオフセット印刷用ニスが開示され、長期に亘る消臭及び抗菌機能を併せ持つものが提案されている。 Patent Document 1 discloses an offset printing varnish containing a titanium oxide photocatalyst coated with hollow porous silica, and proposes a varnish having both deodorizing and antibacterial functions for a long period of time.
しかし、特許文献１に開示されたオフセット印刷用ニスは、中空多孔質シリカにより被覆された酸化チタン光触媒（光触媒カプセル）が、２～１０μｍ程度の粒子であるため、実機印刷において、ブランケットパイリングや耐摩擦性などの印刷適性が劣るおそれがある。 However, in the offset printing varnish disclosed in Patent Document 1, since the titanium oxide photocatalyst (photocatalyst capsule) coated with hollow porous silica is a particle of about 2 to 10 μm, it is resistant to blanket piring and resistance in actual printing. Printing suitability such as friction may be inferior.
特許文献２には、固形樹脂、植物油、高沸点石油系溶剤および撥水剤を含有してなるＯＰニス１００質量部に対して、酸化銀－リン酸亜鉛カルシウムおよびイソプロピルアルコールを含有してなる抗菌剤を２～５質量部添加してなる抗菌ＯＰニス剤が開示され、意匠印刷層が表示する種々の印刷情報を損なうことなく、その成分であるＯＰニスによって、印刷物の表面を保護することができ、撥水剤によって、印刷物の表面に撥水性を付与することができ、さらに、抗菌剤によって、印刷物の表面に抗菌性を付与することができるものが提案されている。 Patent Document 2 describes an antibacterial substance containing silver oxide-calcium zinc phosphate and isopropyl alcohol against 100 parts by mass of OP varnish containing a solid resin, vegetable oil, a high boiling point petroleum solvent and a water repellent. An antibacterial OP varnish prepared by adding 2 to 5 parts by mass of an agent is disclosed, and the surface of a printed matter can be protected by the OP varnish, which is a component thereof, without impairing various printing information displayed on the design printing layer. It has been proposed that a water-repellent agent can impart water repellency to the surface of a printed matter, and an antibacterial agent can impart antibacterial properties to the surface of the printed matter.
しかし、特許文献２に開示された抗菌ＯＰニス剤は、撥水剤として、シリコーンオイルが含まれ、当該シリコーン類は、ヒートセット型オフ輪印刷で用いられる乾燥装置（ドライヤ）の排気ガスを脱臭処理する触媒として用いられている白金に対して、これらは強い触媒毒であり、白金触媒の被毒による脱臭性能の低下を招くおそれがあるため、ヒートセット型オフ輪印刷には好ましくない。また、抗菌剤に含まれる酸化銀－リン酸亜鉛カルシウムも粒子であるため、実機印刷において、ブランケットパイリングや耐摩擦性などの印刷適性が劣るおそれがある。 However, the antibacterial OP varnish disclosed in Patent Document 2 contains silicone oil as a water repellent, and the silicones deodorize the exhaust gas of the drying device (dryer) used in the heat set type off-wheel printing. These are strong catalytic poisons with respect to platinum used as a catalyst to be treated, and may cause deterioration of deodorizing performance due to poisoning of the platinum catalyst, which is not preferable for heat set type off-wheel printing. In addition, since silver oxide-zinc phosphate calcium contained in the antibacterial agent is also a particle, there is a possibility that printing suitability such as blanket piring and abrasion resistance is inferior in actual printing.
特許文献３には、紙基材の表面にオフセット印刷方式で絵柄印刷層と該絵柄印刷層を設けた面全面にオーバープリント層が順次積層され、前記オーバープリント層が前記絵柄印刷層側から第１透明オフセットインキ層と抗菌剤を含有する第２透明オフセットインキ層の２層からなるオフセット印刷方式で印刷された抗菌性を有する商業印刷物が開示され、紙基材の種類に関係なく、抗菌性を有する商業印刷物とすることができるし、また、生産性よく製造することができるものが提案されている。 In Patent Document 3, an overprint layer is sequentially laminated on the surface of a paper substrate by an offset printing method, and the overprint layer is sequentially laminated on the entire surface provided with the pattern print layer, and the overprint layer is formed from the pattern print layer side to the first. A commercial printed matter having antibacterial properties printed by an offset printing method consisting of two layers of one transparent offset ink layer and a second transparent offset ink layer containing an antibacterial agent is disclosed, and antibacterial properties are disclosed regardless of the type of paper substrate. It is proposed that it can be a commercial printed matter having the above, and that it can be produced with high productivity.
しかし、特許文献３に開示された商業印刷物においては、抗菌剤として、ナノ銀分散溶液を使用しており、当該分散液中の銀についても粒子であるため、実機印刷において、ブランケットパイリングや耐摩擦性などの印刷適性が劣るおそれがある。なお、当該特許文献３には、グロスＯＰニスを用いても同様の効果が得られると記載されているが、抗菌効果は有すると思われるものの、印刷適性についてはまったく記載も示唆もない。 However, in the commercial printed matter disclosed in Patent Document 3, a nano-silver dispersion solution is used as an antibacterial agent, and since silver in the dispersion is also particles, blanket piring and abrasion resistance are used in actual printing. Printability such as sex may be inferior. Although it is described in Patent Document 3 that the same effect can be obtained by using a gloss OP varnish, although it seems to have an antibacterial effect, there is no description or suggestion about printability.
また、特許文献４には、ワニスと、銀イオン含有ゼオライトと、マンガン系金属石鹸及びコバルト系金属石鹸を含む金属石鹸と、を含む低臭インク組成物が開示され、製造直後から使用後（転写して乾燥した後）のいずれの段階においても自身の臭いが少なく低臭性に優れ、かつ、適度な乾燥時間を有し乾燥性に優れるものが提案されている。 Further, Patent Document 4 discloses a low-odor ink composition containing a varnish, a silver ion-containing zeolite, and a metal soap containing a manganese-based metal soap and a cobalt-based metal soap, and the low-odor ink composition is disclosed immediately after production and after use (transfer). It has been proposed that the soap has a low odor, is excellent in low odor, has an appropriate drying time, and is excellent in drying property at any stage of (after drying).
しかし、特許文献４に開示された低臭インク組成物は、銀イオン含有ゼオライトが２～５μｍ程度の粒子であるため、実機印刷において、ブランケットパイリングや耐摩擦性などの印刷適性が劣るおそれがある。 However, in the low-odor ink composition disclosed in Patent Document 4, since the silver ion-containing zeolite is particles of about 2 to 5 μm, there is a possibility that the printability such as blanket piring and friction resistance is inferior in actual printing. ..
また、特許文献５には、銀含有リン酸ジルコニウム粒子、ロジン変性フェノール系樹脂、ドライヤー、植物油を含有し、さらに、平均粒子径１０．０μｍ以下のワックスを全組成物中０．１～１５．０質量％含有する油性抗菌ニス組成物が開示され、耐版摩耗性に優れ、及び乾燥性を有し、かつ、得られた塗膜が、優れた耐摩擦性及び光沢を有するものが提案されている。 Further, Patent Document 5 contains silver-containing zirconium phosphate particles, a rosin-modified phenolic resin, a dryer, and vegetable oil, and further comprises a wax having an average particle diameter of 10.0 μm or less in the entire composition from 0.1 to 15. An oil-based antibacterial varnish composition containing 0% by mass is disclosed, and a coating film having excellent plate wear resistance and drying property and the obtained coating film having excellent friction resistance and gloss is proposed. ing.
しかし、特許文献５に開示された油性抗菌ニス組成物は、０．５～２．５μｍ程度の高い硬度の銀含有リン酸ジルコニウム粒子を用いているため、依然として実機印刷において、ブランケットパイリングや耐摩擦性などの印刷適性が劣るおそれがある。また、実施例で、光沢の評価を行なっているが、銀含有リン酸ジルコニウム粒子を用いない（従来のニスの）例がないため、耐摩擦性について良好かどうか懸念が生じる。 However, since the oil-based antibacterial varnish composition disclosed in Patent Document 5 uses silver-containing zirconium phosphate particles having a high hardness of about 0.5 to 2.5 μm, blanket pyring and abrasion resistance are still present in actual printing. Printability such as sex may be inferior. In addition, although the gloss is evaluated in the examples, there is no example (of the conventional varnish) in which silver-containing zirconium phosphate particles are not used, so there is a concern as to whether or not the friction resistance is good.
そこで、本発明は、印刷物に抗菌性能を付与し、かつ印刷物同士が擦れることによるインキ移りや剥がれなどを防ぎ、ブランケットパイリングの少ない印刷適性が良好な抗菌オーバープリントニスを提供することを目的とする。 Therefore, an object of the present invention is to provide an antibacterial overprint varnish that imparts antibacterial performance to printed matter, prevents ink transfer and peeling due to rubbing between printed matter, and has good printability with less blanket pilling. ..
本発明者は、鋭意検討した結果、銀イオン水溶液と、ロジン変性フェノール樹脂と、溶剤とを含有することにより上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of diligent studies, the present inventor has found that the above object can be achieved by containing an aqueous silver ion solution, a rosin-modified phenolic resin, and a solvent, and has completed the present invention.
すなわち、本発明は、
（１）銀含有錯体化合物（Ａ）と、ロジン変性フェノール樹脂（Ｂ）と、溶剤（Ｃ）とを含有し、
前記銀含有錯体化合物（Ａ）が、アミノ酸、１～２価のカルボン酸およびイミダゾール誘導体からなる群から選ばれる少なくとも１種の化合物と銀との錯体化合物であり、
かつ、前記溶剤（Ｃ）が、石油系溶剤および植物油類のなかから選ばれる少なくとも１種であることを特徴とする抗菌オーバープリントニス、
（２）前記銀含有錯体化合物（Ａ）が、抗菌オーバープリントニス中に０．００１～１０質量％含有することを特徴とする（１）に記載の抗菌オーバープリントニス、
（３）（１）または（２）に記載の抗菌オーバープリントニスを基材に印刷してなることを特徴とする抗菌印刷物、
（４）オフセット印刷機により印刷を行ない抗菌印刷物を得る抗菌印刷物の製造方法において、
少なくとも一つの印刷ユニットを用いて、（１）または（２）に記載の抗菌オーバープリントニスを塗布する工程を含むことを特徴とする抗菌印刷物の製造方法、
（５）前記塗布工程が、前記抗菌印刷物表面の銀イオン量として０．００００２～０．２５ｇ／ｍ
２
となるように、前記抗菌印刷物に前記抗菌オーバープリントニスを付与することを特徴とする（４）に記載の抗菌印刷物の製造方法、
である。
That is, the present invention
(1) A silver -containing complex compound (A) , a rosin-modified phenolic resin (B) , and a solvent (C) are contained .
The silver-containing complex compound (A) is a complex compound of silver and at least one compound selected from the group consisting of amino acids, monovalent carboxylic acids and imidazole derivatives.
An antibacterial overprint varnish, wherein the solvent (C) is at least one selected from petroleum-based solvents and vegetable oils .
(2) The antibacterial overprint varnish according to (1), wherein the silver -containing complex compound (A) is contained in the antibacterial overprint varnish in an amount of 0.001 to 10% by mass.
(3 ) An antibacterial printed matter characterized by printing the antibacterial overprint varnish according to (1) or (2) on a substrate .
(4) In a method for manufacturing an antibacterial printed matter, which is obtained by printing with an offset printing machine to obtain an antibacterial printed matter.
A method for producing an antibacterial printed matter, which comprises the step of applying the antibacterial overprint varnish according to (1) or (2) using at least one printing unit .
(5) The coating step is characterized in that the antibacterial overprint varnish is applied to the antibacterial printed matter so that the amount of silver ions on the surface of the antibacterial printed matter is 0.00002 to 0.25 g / m 2 . 4) The method for producing an antibacterial printed matter according to the above,
Is.
本発明によれば、印刷物に抗菌性能を付与し、かつ印刷物同士が擦れることによるインキ移りや剥がれなどを防ぎ、ブランケットパイリングの少ない印刷適性が良好な抗菌オーバープリントニスを提供できる。 According to the present invention, it is possible to provide an antibacterial overprint varnish that imparts antibacterial performance to printed matter, prevents ink transfer and peeling due to rubbing between printed matter, and has good printability with less blanket pilling.
以下、本発明を実施するための形態を詳細に説明する。なお、本実施形態は、本発明を実施するための一形態に過ぎず、本発明は本実施形態によって限定されるものではなく、本発明の要旨を逸脱しない範囲で種々の変更実施の形態が可能である。 Hereinafter, embodiments for carrying out the present invention will be described in detail. It should be noted that the present embodiment is merely one embodiment for carrying out the present invention, and the present invention is not limited to the present embodiment, and various modified embodiments can be used without departing from the gist of the present invention. It is possible.
本発明の抗菌オーバープリントニスは、銀イオン水溶液と、ロジン変性フェノール樹脂と、溶剤とを含有することが好ましい。 The antibacterial overprint varnish of the present invention preferably contains an aqueous silver ion solution, a rosin-modified phenolic resin, and a solvent.
前記銀イオン水溶液は、アミノ酸、１～２価のカルボン酸、およびイミダゾール誘導体からなる群から選ばれる少なくとも１種の化合物と錯体化された銀であることが好ましい。 The silver ion aqueous solution is preferably silver complexed with at least one compound selected from the group consisting of amino acids, monovalent carboxylic acids, and imidazole derivatives.
前記アミノ酸としては、ヒスチジン、アルギニン、クレアチニンなどが好ましく、クレアチニンがより好ましい。 As the amino acid, histidine, arginine, creatinine and the like are preferable, and creatinine is more preferable.
前記１～２価のカルボン酸としては、下記一般式（１）で表される１価のカルボン酸または一般式（２）で表される２価のカルボン酸であることが好ましい。
ＨＯＯＣ－Ｘ－Ｒ１ （１）
［ここで、式中、Ｒ１は置換または未置換の炭素数が１～１８の１価の炭化水素基（ただし、カルボキシル基を除く）であり、ＸはＯまたはＮＨである。］
ＨＯＯＣ－Ｒ２－ＣＯＯＨ （２）
［式中、Ｒ２は置換または未置換の炭素数が１～１８の１価の脂肪族炭化水素基、置換または未置換の炭素数が６～１８の１価の芳香族炭化水素基、および置換または未置換の炭素数が２～１８の１価の芳香族複素環基のいずれかである。］
The 1- to divalent carboxylic acid is preferably a monovalent carboxylic acid represented by the following general formula (1) or a divalent carboxylic acid represented by the general formula (2).
HOOC-X-R 1 (1)
[Here, in the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms (excluding the carboxyl group), and X is O or NH. ]
HOOC-R 2 -COOH (2)
[In the formula, R2 is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and It is either a substituted or unsubstituted monovalent aromatic heterocyclic group having 2 to 18 carbon atoms. ]
前記Ｒ１は、置換または未置換の炭素数が１～１８の１価の脂肪族炭化水素基であることが好ましく、炭素数が１～４の１価の脂肪族炭化水素基であることがより好ましい。脂肪族炭化水素基は、直鎖でも分岐鎖でもよい。
また、置換または未置換の炭素数が６～１８の１価の芳香族炭化水素基であることが好ましく、炭素数が６～１２の１価の芳香族炭化水素基であることがより好ましい。
また、置換または未置換の炭素数が２～１８の１価の芳香族複素環基であることが好ましく、炭素数が２～１１の１価の芳香族複素環基であることがより好ましい。
The R 1 is preferably a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and preferably a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms. More preferred. The aliphatic hydrocarbon group may be a straight chain or a branched chain.
Further, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms is preferable, and a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms is more preferable.
Further, a substituted or unsubstituted monovalent aromatic heterocyclic group having 2 to 18 carbon atoms is preferable, and a monovalent aromatic heterocyclic group having 2 to 11 carbon atoms is more preferable.
前記脂肪族炭化水素基の例としては、メチル基、エチル基、プロピル基などのアルキル基、ビニル基、プロペニル基などのアルケニル基、エチニル基、プロピニル基などのアルキニル基、ならびにシクロプロピル基、シクロブチル基などのシクロアルキル基が挙げられる。 Examples of the aliphatic hydrocarbon group include an alkyl group such as a methyl group, an ethyl group and a propyl group, an alkenyl group such as a vinyl group and a propenyl group, an alkynyl group such as an ethynyl group and a propynyl group, and a cyclopropyl group and a cyclobutyl. Cycloalkyl groups such as groups can be mentioned.
前記芳香族炭化水素基の例としては、フェニル基などの単環芳香族炭化水素基、ナフチル基などの縮合環炭化水素基、ならびにビフェニリル基などの環集合炭化水素基が挙げられる。 Examples of the aromatic hydrocarbon group include a monocyclic aromatic hydrocarbon group such as a phenyl group, a fused ring hydrocarbon group such as a naphthyl group, and a ring aggregated hydrocarbon group such as a biphenylyl group.
前記芳香族複素環基の例としては、トリアゾリル基、フラニル基、フリル基、チエニル基、ピロリル基、ピリジル基、ピラジル基、オキサゾリル基、イソオキサゾリル基、チアゾリル基、イソチアゾリル基、イミダゾリル基、ピラゾリル基、キノリル基、イソキノリル基、キノキサリニル基、ベンゾフリル基、ベンゾチエニル基、インドリル基、カルバゾリル基、アクリジニル基、チオフェニル基、ビピリジル基およびオキサジアゾリル基などが挙げられる。 Examples of the aromatic heterocyclic group include a triazolyl group, a furanyl group, a frill group, a thienyl group, a pyrrolyl group, a pyridyl group, a pyrazil group, an oxazolyl group, an isooxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group and a pyrazolyl group. Examples thereof include a quinolyl group, an isoquinolyl group, a quinoxalinyl group, a benzofuryl group, a benzothienyl group, an indolyl group, a carbazolyl group, an acridinyl group, a thiophenyl group, a bipyridyl group and an oxadiazolyl group.
Ｒ１における、脂肪族炭化水素基、芳香族炭化水素基、および芳香族複素環基の水素原子は、他の置換基で置換されていてもよい。置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子、オキソ基、アリールオキシ基、アリールオキシカルボニル基、ヒドロキシ基、アルコキシ基、アルコキシカルボニル基、置換アミノ基、イミノ基、ニトロ基、シアノ基、アルキルチオ基、アルキルスルホニル基、アリールチオ基、アリールスルホニル基などが挙げられる。 The hydrogen atom of the aliphatic hydrocarbon group, the aromatic hydrocarbon group, and the aromatic heterocyclic group in R1 may be substituted with another substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an oxo group, an aryloxy group, an aryloxycarbonyl group, a hydroxy group, an alkoxy group, an alkoxycarbonyl group, a substituted amino group and an imino group. Examples thereof include a nitro group, a cyano group, an alkylthio group, an alkylsulfonyl group, an arylthio group and an arylsulfonyl group.
Ｒ１は、置換又は未置換の主鎖炭素数１～３の飽和脂肪族炭化水素基、未置換の主鎖炭素数１～２の炭化水素基、あるいは、カルボニル基で置換された主鎖炭素数１～３の炭化水素基であることがより好ましい。
Ｒ１は、メチル基、アセチル基がさらに好ましい。
R 1 is a substituted or unsubstituted backbone hydrocarbon group having 1 to 3 carbon atoms, an unsubstituted backbone group having 1 to 2 carbon atoms, or a backbone carbon substituted with a carbonyl group. More preferably, it is a hydrocarbon group having the number 1 to 3.
R 1 is more preferably a methyl group or an acetyl group.
一般式（１）のカルボン酸の具体例としては、アセチルグリシン、アセトキシ酢酸、メトキシ酢酸などが挙げられる。 Specific examples of the carboxylic acid of the general formula (1) include acetylglycine, acetoxyacetic acid, and methoxyacetic acid.
前記Ｒ２は、置換または未置換の炭素数が１～１８の２価の脂肪族炭化水素基であることが好ましく、炭素数が１～５の２価の脂肪族炭化水素基であることがより好ましい。脂肪族炭化水素基は、直鎖でも分岐鎖でもよい。 The R2 is preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and preferably a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. More preferred. The aliphatic hydrocarbon group may be a straight chain or a branched chain.
前記脂肪族炭化水素基の例としては、メチレン基、エチレン基、プロピレン基などのアルキレン基、ビニレン基、プロペニレン基などのアルケニレン基、ならびにシクロプロピレン基、シクロブチレン基などのシクロアルキレン基が挙げられる。 Examples of the aliphatic hydrocarbon group include an alkylene group such as a methylene group, an ethylene group and a propylene group, an alkenylene group such as a vinylene group and a propenylene group, and a cycloalkylene group such as a cyclopropylene group and a cyclobutylene group. ..
Ｒ２における、脂肪族炭化水素基の水素原子は、他の置換基で置換されていてもよい。置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子、オキソ基、アリールオキシ基、アリールオキシカルボニル基、ヒドロキシ基、アルコキシ基、アルコキシカルボニル基、置換アミノ基、イミノ基、ニトロ基、シアノ基、アルキルチオ基、アルキルスルホニル基、アリールチオ基、アリールスルホニル基などが挙げられる。 The hydrogen atom of the aliphatic hydrocarbon group in R2 may be substituted with another substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an oxo group, an aryloxy group, an aryloxycarbonyl group, a hydroxy group, an alkoxy group, an alkoxycarbonyl group, a substituted amino group and an imino group. Examples thereof include a nitro group, a cyano group, an alkylthio group, an alkylsulfonyl group, an arylthio group and an arylsulfonyl group.
Ｒ２は、主鎖炭素数１～４の飽和脂肪族炭化水素基であることがより好ましい。
Ｒ２は、メチレン基、エチレン基、プロピレン基、ブチレン基、ヒドロキシエチレン基、ビニレン基、ビスヒドロキシエチレン基、フェニレン基、ナフチレン基、カルボキシフェニレン基、ジカルボキシフェニレン基、およびピリジレン基がさらに好ましい。
R2 is more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms in the main chain.
R2 is more preferably a methylene group, an ethylene group, a propylene group, a butylene group, a hydroxyethylene group, a vinylene group, a bishydroxyethylene group, a phenylene group, a naphthylene group, a carboxyphenylene group, a dicarboxyphenylene group, and a pyridylene group.
一般式（２）のカルボン酸の具体例としては、アジピン酸、フマル酸、コハク酸、リンゴ酸、グルタル酸、マロン酸、マレイン酸、酒石酸などが挙げられる。 Specific examples of the carboxylic acid of the general formula (2) include adipic acid, fumaric acid, succinic acid, malic acid, glutaric acid, malonic acid, maleic acid, tartrate acid and the like.
前記イミダゾール誘導体の具体例としては、イミダゾール、１－メチルイミダゾール、２－メチルイミダゾール、１，２－ジメチルイミダゾール、イミダゾリンなどが挙げられる。 Specific examples of the imidazole derivative include imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, imidazoline and the like.
例えば、銀とアミノ酸との錯体、銀とカルボン酸との錯体、銀とカルボン酸とアミノ酸との錯体、銀とイミダゾール誘導体との錯体などが挙げられ、なかでも、クレアチニンと銀の錯体、フマル酸と銀の錯体、イミダゾリンと銀の錯体がより好ましく、クレアチニンと銀との錯体およびフマル酸と銀との錯体の両者を含むことがさらに好ましい。これらのなかから選ばれる少なくとも１種であり、２種以上を併用してもよい。
これらは、（株）Ｊ－ケミカル製ＣＦ－０１（クレアチニンおよびフマル酸と銀との錯体）などで入手することができる。
For example, a complex of silver and an amino acid, a complex of silver and a carboxylic acid, a complex of silver and a carboxylic acid and an amino acid, a complex of silver and an imidazole derivative, and the like, among them, a complex of creatinine and silver, and fumaric acid. And silver complex, imidazoline and silver complex are more preferable, and it is more preferable to contain both a creatinine and silver complex and a fumaric acid and silver complex. It is at least one selected from these, and two or more may be used in combination.
These can be obtained from CF-01 (complex of creatinine and fumaric acid and silver) manufactured by J-Chemical, Inc.
前記銀イオン水溶液は、抗菌オーバープリントニス中に０．００１～１０質量％含有することが好ましく、０．１～５質量％含有することがより好ましく、０．５～３質量％含有することがさらに好ましい。０．００１質量％より少ないと、抗菌機能が発現しにくく、１０質量％より多いと、銀イオン水溶液がニス中で分離するおそれがあり、保存安定性の面で劣る、また変色するおそれがある。 The silver ion aqueous solution is preferably contained in the antibacterial overprint varnish in an amount of 0.001 to 10% by mass, more preferably 0.1 to 5% by mass, and more preferably 0.5 to 3% by mass. More preferred. If it is less than 0.001% by mass, the antibacterial function is difficult to be exhibited, and if it is more than 10% by mass, the silver ion aqueous solution may be separated in the varnish, which may be inferior in terms of storage stability or discoloration. ..
前記ロジン変性フェノール樹脂は、従来よりオーバープリントニスに使用されているものが使用できる。ロジン変性フェノール樹脂は、重量平均分子量が４０，０００～３００，０００の範囲内であることが好ましい。なかでも、特に好ましいのは、重量平均分子量が９０，０００～１７０，０００の範囲内である。重量平均分子量が３００，０００を超えると溶解性が低下するため、溶剤離脱性が早くなることにより、機上安定性が劣り、紙剥けが発生しやすくなる。また高い弾性を有するため、顔料分散性の低下、紙面への着肉低下や、レベリング性、流動性低下による光沢低下が起こりやすくなる。
ここで、重量平均分子量は、ＧＰＣ法（ポリスチレン換算）による測定値である。
As the rosin-modified phenol resin, those conventionally used for overprint varnish can be used. The rosin-modified phenolic resin preferably has a weight average molecular weight in the range of 40,000 to 300,000. Of these, particularly preferred is a weight average molecular weight in the range of 90,000 to 170,000. When the weight average molecular weight exceeds 300,000, the solubility is lowered, so that the solvent withdrawal property is accelerated, so that the on-machine stability is inferior and the paper peeling is liable to occur. Further, since it has high elasticity, the pigment dispersibility is lowered, the inking on the paper surface is lowered, and the leveling property and the fluidity are lowered, so that the gloss is easily lowered.
Here, the weight average molecular weight is a measured value by the GPC method (polystyrene conversion).
前記ロジン変性フェノール樹脂は、抗菌オーバープリントニス中に１０～５０質量％含有することが好ましく、１５～４０質量％含有することがより好ましく、２０～３５質量％含有することがさらに好ましい。１０質量％未満では固形分が少ないため、低粘度となって流動性が過剰となり所望のニスを得ることが困難となり、５０質量％を超えると光沢が低下しやすくなるため好ましくない。 The rosin-modified phenolic resin is preferably contained in an antibacterial overprint varnish in an amount of 10 to 50% by mass, more preferably 15 to 40% by mass, and even more preferably 20 to 35% by mass. If it is less than 10% by mass, the solid content is small, so that the viscosity becomes low and the fluidity becomes excessive, making it difficult to obtain a desired varnish. If it exceeds 50% by mass, the gloss tends to decrease, which is not preferable.
本発明で用いられる溶剤としては、流動性付与などの目的で、ＡＦ溶剤、ノルマルパラフィン系溶剤、イソパラフィン系溶剤、マシン油、シリンダー油などに代表される石油系溶剤、植物油類、ビニリデンオレフィンなどを適宜選択して用いることができる。 Examples of the solvent used in the present invention include AF solvents, normal paraffin solvents, isoparaffin solvents, petroleum solvents such as machine oils and cylinder oils, vegetable oils, vinylidene olefins and the like for the purpose of imparting fluidity. It can be appropriately selected and used.
本発明で用いられる植物油類としては、主に大豆油または大豆油由来の脂肪酸エステルが用いられる。その他の植物油としては、例えばアマニ油、菜種油、ヤシ油、オリーブ油、桐油などおよびこれらを再生処理したものが挙げられる。また、その他の植物油由来の脂肪酸エステルとしては、例えば綿実油、アマニ油、サフラワー油、向日葵油、桐油、トール油、脱水ヒマシ油、菜種油、胡麻油などの乾性油または半乾性油を由来とした脂肪酸モノアルキルエステルが例示できる。脂肪酸モノアルキルエステルを構成するアルコール由来のアルキル基の炭素数は１～１２のものが好ましく、具体例としてメチル、エチル、プロピル、ブチル、イソブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、３－メチル－１－ブチル、２，２－ビス（ヒドロキメチル）ブチル、２，４－ジメチル－３－ペンチル、２－エチル－１－ブチル、２－エチル－１－ヘキシル、３，５，５－トリメチル－１－ヘキシル、４－デシル、２－イソプロピル－５－メチル－１－ヘキシル、２－ブチル－１－オクチルなどである。なかでも特に好ましいのはメチル、エチル、プロピル、ブチル、イソブチル、オクチル、２－エチルヘキシル、２，２－ビス（ヒドロキメチル）ブチルなどである。上記植物油類は、樹脂に対する溶解性が上がり、印刷物の光沢向上に優れた効果がある。 As the vegetable oils used in the present invention, soybean oil or fatty acid esters derived from soybean oil are mainly used. Examples of other vegetable oils include flaxseed oil, rapeseed oil, coconut oil, olive oil, tung oil and the like, and those obtained by regenerating them. Examples of fatty acid esters derived from other vegetable oils include dry oils such as cottonseed oil, flaxseed oil, safflower oil, sunflower oil, tung oil, tall oil, dehydrated castor oil, rapeseed oil, and sesame oil, or fatty acids derived from semi-drying oil. A monoalkyl ester can be exemplified. Alkyl groups derived from alcohols constituting fatty acid monoalkyl esters preferably have 1 to 12 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and undecyl. , Dodecyl, 3-Methyl-1-butyl, 2,2-bis (hydrochimethyl) butyl, 2,4-dimethyl-3-pentyl, 2-ethyl-1-butyl, 2-ethyl-1-hexyl, 3, 5,5-trimethyl-1-hexyl, 4-decyl, 2-isopropyl-5-methyl-1-hexyl, 2-butyl-1-octyl and the like. Of these, methyl, ethyl, propyl, butyl, isobutyl, octyl, 2-ethylhexyl, 2,2-bis (hydrochimethyl) butyl and the like are particularly preferable. The above-mentioned vegetable oils have an excellent effect of increasing the solubility in a resin and improving the gloss of printed matter.
本発明の抗菌オーバープリントニスの全量に対し植物油類は、７～３０質量％含有することが好ましい。なかでも、特に好ましいのは１０～２５重量％の範囲内である。７質量％未満では光沢が低下する。３０質量％を超える量を添加しても光沢の向上効果は得られず、溶解性が高くなり、タックの経時での上昇が大きくなるため、ブランケット上に堆積したニスの粘着性が高まり、アフタータックが残り、紙剥けしやすくなる。 It is preferable that the vegetable oil is contained in an amount of 7 to 30% by mass based on the total amount of the antibacterial overprint varnish of the present invention. Of these, the range of 10 to 25% by weight is particularly preferable. If it is less than 7% by mass, the gloss is lowered. Even if an amount exceeding 30% by mass is added, the effect of improving gloss is not obtained, the solubility becomes high, and the increase in tack over time becomes large, so that the adhesiveness of the varnish deposited on the blanket increases, and after-sales The tack remains and the paper is easily peeled off.
大豆油と大豆油由来の脂肪酸エステルの比率は、重量比で１００／０～３０／７０の範囲内であることが好ましい。なかでも、特に好ましいのは９０／１０～５０／５０の範囲内である。大豆油と大豆油由来の脂肪酸エステルの比率において、大豆油由来の脂肪酸エステルが、重量比で７０質量％を超えるとタックが高くなり、紙剥けしやすくなる。 The ratio of soybean oil to the fatty acid ester derived from soybean oil is preferably in the range of 100/0 to 30/70 by weight. Of these, the range of 90/10 to 50/50 is particularly preferable. When the ratio of the fatty acid ester derived from soybean oil to the fatty acid ester derived from soybean oil exceeds 70% by weight by weight, the tack becomes high and the paper is easily peeled off.
本発明の抗菌オーバープリントニスは、さらに 他にニスとしての機能向上を目的として、適宜、顔料、顔料分散剤、キレート剤、乳化剤、乾燥防止剤、乾燥促進剤、整面剤、耐摩擦性剤、ブロッキング防止剤、滑剤などの添加剤を用いることができる。 The antibacterial overprint varnish of the present invention is appropriately used as a pigment, a pigment dispersant, a chelating agent, an emulsifier, an antidrying agent, a drying accelerator, a surface conditioning agent, and an abrasion resistant agent for the purpose of further improving the function as a varnish. , Anti-blocking agents, lubricants and other additives can be used.
本発明で用いられる顔料としては、有機顔料または無機顔料であり、例えばジスアゾイエロー、カーミン６Ｂ、フタロシアニンブルーなどに代表される有機顔料、およびカーボンブラック、炭酸カルシウムなどに代表される無機顔料などであり、特に限定されない。 The pigment used in the present invention is an organic pigment or an inorganic pigment, for example, an organic pigment typified by disazo yellow, carmine 6B, phthalocyanine blue, etc., and an inorganic pigment typified by carbon black, calcium carbonate, etc. , Not particularly limited.
前記有機顔料の多くは、水系で合成されることが多いため、処理されたうえで、ある程度まで水分を絞ったペースト状で使用され、ワニスと、ニーダーや押出機、連続式混練機などの混練機で混練されて、抗菌オーバープリントニスに使用される。さらに詳しくは、有機顔料ペーストとワニスとを混練機で混練し、有機顔料をワニスに移行させ、水を分離、除去した後、残存する水を減圧することにより除去（フラッシング法という）し、有機顔料とワニスの混合物とする。 Since most of the organic pigments are synthesized in an aqueous system, they are treated and used in the form of a paste in which water is squeezed to a certain extent, and the varnish is kneaded with a kneader, an extruder, a continuous kneader, or the like. It is kneaded by machine and used for antibacterial overprint varnish. More specifically, the organic pigment paste and the varnish are kneaded with a kneader, the organic pigment is transferred to the varnish, water is separated and removed, and then the remaining water is removed by reducing the pressure (called a flushing method) to make it organic. A mixture of pigment and varnish.
本発明で用いられるキレート剤はゲル化剤として働くものであるが、金属キレート、特に、エチルアセトアセテートアルミニウムジイソプロポキシド、アルミニウムトリスエチルアセトアセテートなどのアルミニウムキレート化合物が好ましく用いられる。 The chelating agent used in the present invention acts as a gelling agent, and metal chelates, in particular, aluminum chelating compounds such as ethyl acetoacetate aluminum diisopropoxide and aluminum tris ethyl acetoacetate are preferably used.
例えば、耐摩擦性剤、ブロッキング防止剤、滑剤としては、カルナバワックス、パラフィンワックス、マイクロクリスタリンワックスなどの天然ワックス、フィッシャートロプスワックス、ポリエチレンワックス、ポリプロピレンワックス、ポリテトラフルオロエチレンワックス、ポリアミドワックス、シリコーン化合物などの合成ワックスを例示することができる。 For example, as an abrasion resistant agent, an antiblocking agent, and a lubricant, natural waxes such as carnauba wax, paraffin wax, and microcrystalline wax, Fishertropus wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and silicone. A synthetic wax such as a compound can be exemplified.
本発明の抗菌印刷物は、前記抗菌剤オーバープリントニスを基材に印刷してなることが好ましい。 The antibacterial printed matter of the present invention is preferably printed on the base material with the antibacterial agent overprint varnish.
前記基材としては、通常のオフセット印刷が可能な用紙であれば使用できるが、特に、オフセット印刷に適する更紙（非塗工紙）、微塗工紙、コート紙、アート紙、あるいは合成樹脂を主成分とするプラスチックフィルム、あるいは合成樹脂を主成分としてその印刷インキ受容性を改善させた合成紙などが好ましく用いられる。 As the base material, any paper capable of ordinary offset printing can be used, but in particular, stencil paper (non-coated paper), finely coated paper, coated paper, art paper, or synthetic resin suitable for offset printing can be used. A plastic film containing the above as a main component, or a synthetic paper containing a synthetic resin as a main component and having improved printing ink acceptability thereof is preferably used.
さらに、合成紙として、例えば、無孔質のプラスチックフィルムの片面または両面に印刷インキ受容性の塗料を塗布しその塗布膜を形成して、印刷インキ受容性を改善させたものが利用できる。このようなプラスチックフィルムとしては、例えば、ポリ塩化ビニルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、ポリエステルフィルムなどが例示でき、また印刷インキ受容性塗料としては、マット剤を含有するものが使用できる。マット剤としては、シリカ、炭酸カルシウム、硫酸バリウムなどが使用できる。 Further, as the synthetic paper, for example, a non-porous plastic film obtained by applying a printing ink-accepting paint on one side or both sides to form a coating film thereof and improving the printing ink acceptability can be used. Examples of such a plastic film include a polyvinyl chloride film, a polyethylene film, a polypropylene film, a polyester film, and the like, and as a printing ink-accepting paint, those containing a matting agent can be used. As the matting agent, silica, calcium carbonate, barium sulfate and the like can be used.
さらに、合成紙として、プラスチックフィルムを発泡させて多数の微細孔を設けることで印刷インキ受容性を改善させたものや、溶剤に溶解する微粉末を混合して製膜して得られたプラスチックフィルムから溶剤により微粉末を溶解除去し、こうして溶解除去された微粉末が存在していた部位を微細孔とすることで印刷インキ受容性を改善させたもの、あるいは微粉末を混合して製膜して得られたプラスチックフィルムを延伸することで微粉末とプラスチックとの間に微細な亀裂を生じさせ、微細な亀裂とすることで印刷インキ受容性を改善させたものなどが適用できる。 Further, as synthetic paper, a plastic film having improved print ink acceptability by foaming a plastic film to provide a large number of fine pores, or a plastic film obtained by mixing fine powder dissolved in a solvent to form a film. The fine powder was dissolved and removed from the resin with a solvent, and the part where the fine powder was dissolved and removed was made into fine pores to improve the print ink acceptability, or the fine powder was mixed and formed into a film. By stretching the obtained plastic film, fine cracks are generated between the fine powder and the plastic, and by forming the fine cracks, the one having improved printing ink acceptability can be applied.
本発明の抗菌印刷物の製造方法は、オフセット印刷機により印刷を行ない抗菌印刷物を得るものであって、少なくとも一つの印刷ユニットを用いて、前記抗菌オーバープリントニスを塗布する工程を含むことが好ましい。 The method for producing an antibacterial printed matter of the present invention is to obtain an antibacterial printed matter by printing with an offset printing machine, and preferably includes a step of applying the antibacterial overprint varnish using at least one printing unit.
前記印刷ユニットは、少なくとも一つの印刷ユニットを有するものが好ましく、複数あってもよい。複数の印刷ユニットを有する場合、抗菌オーバープリントニスを塗布する１つの印刷ユニット以外の印刷ユニットで、オフセット印刷インキ組成物を用いて、単色あるいは複色の印刷物を作製後、抗菌オーバープリントニスを塗布して、抗菌印刷物を作製することが好ましい。抗菌オーバープリントニスは、前記印刷物の全面に塗布されてもよく、一部のみに塗布されてもよい。 The printing unit preferably has at least one printing unit, and may have a plurality of printing units. When having multiple printing units, apply antibacterial overprint varnish to a printing unit other than one printing unit. After producing a single-color or multi-color printed matter using an offset printing ink composition, apply antibacterial overprint varnish. It is preferable to prepare an antibacterial printed matter. The antibacterial overprint varnish may be applied to the entire surface of the printed matter, or may be applied to only a part of the printed matter.
前記抗菌オーバープリントニスを塗布する工程は、オフセット印刷機の印刷ユニットで、オフセット印刷インキ組成物を用いて、単色あるいは複色の印刷物を作製後に続いて、抗菌オーバープリントニスを塗布する工程（インライン工程）であってもよく、前記印刷物を作製後、同印刷機あるいは別の印刷機（塗工機、コーター機なども含む）の印刷ユニットを用いて、抗菌オーバープリントニスを塗布する工程（オフライン工程）であってもよい。 The step of applying the antibacterial overprint varnish is a step of applying the antibacterial overprint varnish (in-line) after producing a single-color or multi-color printed matter by using the offset printing ink composition in the printing unit of the offset printing machine. It may be a step (step), and after producing the printed matter, a step (offline) of applying an antibacterial overprint varnish using the printing unit of the same printing machine or another printing machine (including a coating machine, a coater machine, etc.). Step) may be used.
前記塗布工程は、得られる抗菌印刷物表面の銀イオン量として０．００００２～０．２５ｇ／ｍ２となるように、前記抗菌オーバープリントニスを付与することが好ましく、０．００００５～０．０５ｇ／ｍ２となるように付与することがより好ましく、０．０００１～０．００１ｇ／ｍ２となるように付与することがさらに好ましい。０．００００２ｇ／ｍ２より少ないと、印刷物表面の抗菌機能が発現しにくく、０．２５ｇ／ｍ２より多いと、印刷物の乾燥が劣り、乾燥不良のトラブルが発生するおそれがある。 In the coating step, it is preferable to apply the antibacterial overprint varnish so that the amount of silver ions on the surface of the obtained antibacterial printed matter is 0.00002 to 0.25 g / m 2 , preferably 0.00005 to 0.05 g / m 2. It is more preferable to apply it so as to be m 2 , and it is further preferable to apply it so as to be 0.0001 to 0.001 g / m 2 . If it is less than 0.00002 g / m 2 , the antibacterial function on the surface of the printed matter is difficult to be exhibited, and if it is more than 0.25 g / m 2 , the printed matter is inferior in drying, and there is a possibility that a problem of poor drying may occur.
以下、本発明を実施例によって更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。なお、例中、「部」は「質量部」を、「％」は「質量％」を示す。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the example, "part" indicates "part by mass" and "%" indicates "% by mass".
［ワニスの作製］
＜製造例１＞
ロジン変性フェノール樹脂Ｒ１（重量平均分子量１５０，０００、荒川化学工業（株）製）３０部、ロジン変性フェノール樹脂Ｒ２（重量平均分子量１００，０００、ハリマ化成（株）製）２４部、大豆白絞油１５部、ＡＦソルベント７（ＪＸＴＧエネルギー（株）製）３０．６部、アルミキレート剤（ＡＬＣＨ、川研ファインケミカル（株）製）０．４部を反応容器中に仕込み、窒素ガスを吹き込みながら１８５℃に昇温し、６０分撹拌混合して、ワニスＶ１を得た。
[Making varnish]
<Manufacturing example 1>
Rosin-modified phenolic resin R1 (weight average molecular weight 150,000, manufactured by Arakawa Chemical Industry Co., Ltd.) 30 parts, rosin-modified phenolic resin R2 (weight average molecular weight 100,000, manufactured by Harima Chemicals Co., Ltd.) 24 parts, soybean white squeezed 15 parts of oil, 30.6 parts of AF solvent 7 (manufactured by JXTG Energy Co., Ltd.), 0.4 parts of aluminum chelating agent (ALCH, manufactured by Kawaken Fine Chemicals Co., Ltd.) were charged into the reaction vessel, and while blowing nitrogen gas. The temperature was raised to 185 ° C., and the mixture was stirred and mixed for 60 minutes to obtain varnish V1.
＜製造例２＞
ロジン変性フェノール樹脂Ｒ３（重量平均分子量５０，０００、星光ＰＭＣ（株）製）３２部、ロジン変性フェノール樹脂Ｒ４（重量平均分子量５０，０００、星光ＰＭＣ（株）製）１４部、大豆白絞油２０部、ＡＦソルベント６（ＪＸＴＧエネルギー（株）製）３３．３部、アルミキレート剤（アルゴマー、川研ファインケミカル（株）製）０．７部を反応容器中に仕込み、窒素ガスを吹き込みながら１９０℃に昇温し、６０分撹拌混合して、ワニスＶ２を得た。
<Manufacturing example 2>
Rosin-modified phenolic resin R3 (weight average molecular weight 50,000, manufactured by Starlight PMC Co., Ltd.) 32 parts, rosin-modified phenolic resin R4 (weight average molecular weight 50,000, manufactured by Starlight PMC Co., Ltd.) 14 parts, soybean white squeezed oil 20 parts, AF solvent 6 (manufactured by JXTG Energy Co., Ltd.) 33.3 parts, aluminum chelating agent (Argomer, manufactured by Kawaken Fine Chemical Co., Ltd.) 0.7 parts were charged into the reaction vessel, and 190 while blowing nitrogen gas. The temperature was raised to ° C., and the mixture was stirred and mixed for 60 minutes to obtain varnish V2.
［抗菌オーバープリントニスの作製］
＜実施例１＞
製造例１で得られたワニスＶ１ ６９部、炭酸カルシウム ２５部、ワックスコンパンド １．５部、大豆油脂肪酸エステル １部、ＡＦソルベント７号 ３部を添加し、攪拌し、さらに銀イオン水溶液 ０．５部を添加、攪拌して、抗菌オーバープリントニスを作製した。同様に、表１の処方にしたがって、抗菌オーバープリントニスを作製した。
[Making antibacterial overprint varnish]
<Example 1>
69 parts of varnish V1 obtained in Production Example 1, 25 parts of calcium carbonate, 1.5 parts of wax compound, 1 part of soybean oil fatty acid ester, and 3 parts of AF solvent No. 7 were added, stirred, and further silver ion aqueous solution 0. Five parts were added and stirred to prepare an antibacterial overprint varnish. Similarly, an antibacterial overprint varnish was prepared according to the formulation shown in Table 1.
＜比較例１＞
製造例１で得られたワニスＶ１ ６８．２部、炭酸カルシウム ２５部、ワックスコンパンド １．５部、大豆油脂肪酸エステル １部、ＡＦソルベント７号 ３部、ナノ銀分散溶液 ０．３部を添加、攪拌した後、３本ロールミルで練肉して、抗菌オーバープリントニスを作製した。なお、参考例１は、従来型のオーバープリントニスの例である。
<Comparative Example 1>
Add 68.2 parts of varnish V1 obtained in Production Example 1, 25 parts of calcium carbonate, 1.5 parts of wax compound, 1 part of soybean oil fatty acid ester, 3 parts of AF solvent No. 7, and 0.3 part of nano-silver dispersion solution. After stirring, the meat was kneaded with a three-roll mill to prepare an antibacterial overprint varnish. Reference example 1 is an example of a conventional overprint varnish.
＜実施例７＞
製造例２で得られたワニスＶ２ ８０．５部、ワックスコンパンド １０部、マンガンドライヤ ０．５部、ＡＦソルベント６号 ８部を添加し、攪拌し、さらに銀イオン水溶液 １部を添加、攪拌して、抗菌オーバープリントニスを作製した。同様に、表３の処方にしたがって、抗菌オーバープリントニスを作製した。
<Example 7>
Add 80.5 parts of varnish V2, 10 parts of wax compound, 0.5 part of manganese dryer, and 8 parts of AF solvent No. 6 obtained in Production Example 2 and stir, and further add 1 part of silver ion aqueous solution and stir. To prepare an antibacterial overprint varnish. Similarly, an antibacterial overprint varnish was prepared according to the formulation shown in Table 3.
＜比較例２＞
製造例２で得られたワニスＶ２ ８０．５部、ワックスコンパンド １０部、マンガンドライヤ ０．５部、ＡＦソルベント６号 ８部を添加し、攪拌し、さらに銅イオン水溶液 １部を添加、攪拌して、抗菌オーバープリントニスを作製した。
<Comparative Example 2>
Add 80.5 parts of varnish V2, 10 parts of wax compound, 0.5 part of manganese dryer, and 8 parts of AF solvent No. 6 obtained in Production Example 2 and stir, and further add 1 part of copper ion aqueous solution and stir. To prepare an antibacterial overprint varnish.
＜比較例３＞
製造例２で得られたワニスＶ２ ７５部、ワックスコンパンド １０部、マンガンドライヤ ０．６部、大豆白絞油 １１．９部、銀含有リン酸ジルコニウム粒子 ２．５部を添加、攪拌した後、３本ロールミルで練肉して、抗菌オーバープリントニスを作製した。なお、参考例２は、従来型のオーバープリントニスの例である。
<Comparative Example 3>
After adding 75 parts of varnish V2, 10 parts of wax compound, 0.6 part of manganese dryer, 11.9 parts of soybean white squeezed oil, and 2.5 parts of silver-containing zirconium phosphate particles obtained in Production Example 2 and stirring. An antibacterial overprint varnish was prepared by kneading with a three-roll mill. Reference example 2 is an example of a conventional overprint varnish.
使用した材料は、次のものである。
銀イオン水溶液：ＡＧアルファＣＦ－０１（クレアチニンおよびフマル酸と銀との錯体、水溶性銀化合物１３～１４％（銀イオン濃度２．５％）、フマル酸１～２％、水８４～８６％、（株）Ｊ－ケミカル製）
ナノ銀分散溶液：ナノシルバー分散液ＰＲ－ＷＢ１４Ｒ（日本イオン（株）製）
銅イオン水溶液：ｉｏｔｅｃｈ－Ｃｕ（（株）エフ・エル・アイ製）
銀含有リン酸ジルコニウム粒子：ノバロンＡＧ３００（東亞合成（株）製）
炭酸カルシウム：白艶華Ｏ（白石カルシウム（株）製）
大豆油脂肪酸エステル：ＳＦＢ－２（東新油脂（株）製）
ＡＦソルベント７号：ＪＸＴＧエネルギー（株）製
ＡＦソルベント６号：ＪＸＴＧエネルギー（株）製
マンガンドライヤ：オクチル酸マンガン
ワックスコンパンド：ポリエチレンワックス３５部と、大豆白絞油６５部を加熱撹拌した後、室温まで冷却してコンパンドとした。
The materials used are:
Aqueous silver ion solution: AGalpha CF-01 (complex of creatinine and fumaric acid and silver, water-soluble silver compound 13-14% (silver ion concentration 2.5%), fumaric acid 1-2%, water 84-86% , Made by J-Chemical Co., Ltd.)
Nano-silver dispersion solution: Nano-silver dispersion solution PR-WB14R (manufactured by Nippon Ion Co., Ltd.)
Aqueous copper ion solution: iotech-Cu (manufactured by FLI Co., Ltd.)
Silver-containing zirconium phosphate particles: Novalon AG300 (manufactured by Toagosei Co., Ltd.)
Calcium carbonate: Shiraishi Calcium O (manufactured by Shiraishi Calcium Co., Ltd.)
Soybean oil fatty acid ester: SFB-2 (manufactured by Toshin Oil & Fat Co., Ltd.)
AF Solvent No. 7: manufactured by JXTG Energy Co., Ltd. AF Solvent No. 6: manufactured by JXTG Energy Co., Ltd. Manganese dryer: Manganese octylate Wax compound: 35 parts of polyethylene wax and 65 parts of soybean white squeezed oil are heated and stirred, and then at room temperature. It was cooled to compound.
［抗菌性評価］
実施例１で作製した抗菌オーバープリントニスを、ＲＩテスター（（株）明製作所製）で合成紙（ユポＦＧＳ、厚み１５０μｍ、（株）ユポ・コーポレーション製）に、銀イオン量として０．０００４ｇ／ｍ２となるように展色し、紙面乾燥温度が１００℃になるように調節して、展色片を強制乾燥させ、試験用印刷物を得た。実施例２～６、比較例１および参考例１について同様にして、各試験用印刷物を得た。
また、実施例７で作製した抗菌オーバープリントニスを、ＲＩテスター（（株）明製作所製）で合成紙（ユポＦＧＳ、厚み１５０μｍ、（株）ユポ・コーポレーション製）に、銀イオン量として０．０００４ｇ／ｍ２となるように展色し、２５℃で、２４時間乾燥し、試験用印刷物を得た。実施例８～１２、比較例２～３および参考例２について同様にして、各試験用印刷物を得た。
試験用印刷物について、ＪＩＳ Ｚ ２８０１：２０１２に準拠して、以下のようにして実施した。
４０ｍｍ×４０ｍｍに切断した試験用印刷物の表面に、大腸菌（Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ）および黄色ブドウ球菌（Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ）をそれぞれ含む菌液を滴下し、その上から３０ｍｍ×３０ｍｍ×０．０９ｍｍのポリエチレンフィルムを密着させ、温度３５℃、湿度９０％の条件下で２４時間培養した。培養後、ポリエチレンフィルムおよび試験用印刷物に付着している菌体をＳＣＤＬＰ培地１０ｍｌ（Ｖ）で洗い出した。洗い出した液を１ｍｌ取り、リン酸緩衝生理食塩水９ｍｌの入った試験管に加え、混合し、さらに、この試験管から１ｍｌを取り、別の試験管に入ったリン酸緩衝生理食塩水９ｍｌに入れて、混合して、１０倍希釈液を作製し、洗い出し液と１０倍希釈液それぞれ１ｍｌ（１倍希釈：Ｄ）をシャーレ２枚に分注した。シャーレ１枚あたり、４６～４８℃に保温した標準寒天培地１５～２０ｍｌを加え、よく混合し、温度３５℃、湿度９０％の条件下で４０～４８時間培養した後、大腸菌および黄色ブドウ球菌の生菌数をそれぞれカウントした。評価の基準は、無加工の合成紙試験片を用いた。試験はそれぞれ３回行った。表５に結果を示した。
[Antibacterial evaluation]
The antibacterial overprint varnish produced in Example 1 was put on synthetic paper (Yupo FGS, thickness 150 μm, manufactured by YUPO Corporation) with an RI tester (manufactured by Ming Seisakusho Co., Ltd.) as a silver ion amount of 0.0004 g /. The color was developed to be m 2 , the paper surface drying temperature was adjusted to 100 ° C., and the color-developed pieces were forcibly dried to obtain a printed matter for testing. Printed matter for each test was obtained in the same manner for Examples 2 to 6, Comparative Example 1 and Reference Example 1.
Further, the antibacterial overprint varnish produced in Example 7 was put on synthetic paper (Yupo FGS, thickness 150 μm, manufactured by YUPO Corporation) with an RI tester (manufactured by Ming Seisakusho Co., Ltd.), and the amount of silver ions was 0. The color was developed to 0004 g / m 2 and dried at 25 ° C. for 24 hours to obtain a test printed matter. Printed matter for each test was obtained in the same manner for Examples 8 to 12, Comparative Examples 2 to 3, and Reference Example 2.
The test printed matter was carried out as follows in accordance with JIS Z 2801: 2012.
A bacterial solution containing Escherichia coli and Staphylococcus aureus was dropped onto the surface of a test printed matter cut into 40 mm × 40 mm, and a polyethylene film of 30 mm × 30 mm × 0.09 mm was adhered thereto. The mixture was allowed to grow and cultured for 24 hours under the conditions of a temperature of 35 ° C. and a humidity of 90%. After culturing, the cells adhering to the polyethylene film and the test printed matter were washed out with 10 ml (V) of SCDLP medium. Take 1 ml of the washed-out solution, add to a test tube containing 9 ml of phosphate buffered saline, mix, and then take 1 ml from this test tube and add to 9 ml of phosphate buffered saline in another test tube. It was put in and mixed to prepare a 10-fold diluted solution, and 1 ml (1-fold diluted: D) of each of the wash-out solution and the 10-fold diluted solution was dispensed into two chalets. Add 15 to 20 ml of standard agar medium kept at 46 to 48 ° C per petri dish, mix well, incubate for 40 to 48 hours under the conditions of temperature 35 ° C and humidity 90%, and then Escherichia coli and Staphylococcus aureus. The viable cell counts were counted respectively. As the evaluation criteria, unprocessed synthetic paper test pieces were used. Each test was performed 3 times. The results are shown in Table 5.
生菌数（Ｎ）は以下の方法により算出した。
Ｎ＝（Ｃ×Ｄ×Ｖ）／Ａ
Ｎ：生菌数（試験片１ｃｍ２あたり）
Ｃ：集落数（採用した２枚のシャーレの集落数平均値）
Ｄ：希釈倍数（採用したシャーレに分注した希釈液の希釈倍率）
Ｖ：洗い出しに用いたＳＣＤＬＰ培地の液量（ｍｌ）
Ａ：被覆フィルムの表面積（ｃｍ２）
ただし、Ｃが＜１の場合はＣを１として生菌数を算出した。例えば、Ｖ＝１０ｍｌ、Ａ＝９ｃｍ２、Ｄ＝１の場合、Ｎ＜１．１とした。
抗菌活性値（Ｒ）は以下の方法により算出した。
Ｒ＝ｌｏｇ（Ｂ／Ａ）－ｌｏｇ（Ｃ／Ａ）＝ｌｏｇ（Ｂ／Ｃ）
Ａ：無加工試験片の接種直後の生菌数の平均値（個）
Ｂ：無加工試験片の２４時間後の生菌数の平均値（個）
Ｃ：抗菌加工試験片の２４時間後の生菌数の平均値（個）
ただし、生菌数（Ｎ）が＜１．１の場合、１．１で計算した。小数点以下２けた目は切り捨て、小数点以下１けたとした。
抗菌活性値（Ｒ）が２以上のとき、抗菌効果があると判断でき、○：２以上（抗菌効果がある）、△：２未満、１以上（弱い抗菌効果）、×：１未満（抗菌効果がない）の３段階で評価した。
The viable cell count (N) was calculated by the following method.
N = (C × D × V) / A
N: Viable cell count (per 1 cm 2 test piece)
C: Number of settlements (average number of settlements of two petri dishes adopted)
D: Dilution factor (dilution factor of the diluted solution dispensed into the adopted petri dish)
V: Liquid volume (ml) of SCDLP medium used for washing out
A: Surface area of the coating film (cm 2 )
However, when C was <1, the viable cell count was calculated with C as 1. For example, when V = 10 ml, A = 9 cm 2 , and D = 1, N <1.1.
The antibacterial activity value (R) was calculated by the following method.
R = log (B / A) -log (C / A) = log (B / C)
A: Average number of viable bacteria immediately after inoculation of unprocessed test pieces (pieces)
B: Mean value (pieces) of viable cell count after 24 hours of unprocessed test piece
C: Average number of viable bacteria after 24 hours for antibacterial processed test pieces (pieces)
However, when the viable cell count (N) was <1.1, the calculation was made in 1.1. The second digit after the decimal point was rounded down, and the first digit after the decimal point was assumed.
When the antibacterial activity value (R) is 2 or more, it can be judged that there is an antibacterial effect. It was evaluated on a three-point scale (no effect).
［抗ウイルス性評価］
前記［抗菌性評価］と同様に作成した試験用印刷物について、以下のようにして実施した。
５０ｍｍ×５０ｍｍに切断した試験用印刷物の表面に、エンベローブ型ウイルス（バクテリオファージφ６）およびノンエンベローブ型ウイルス（バクテリオファージＱβ）をそれぞれ含む懸濁液を０．４ｍＬ滴下した。その上から４０ｍｍ×４０ｍｍ×０．０９ｍｍのポリエチレンフィルムを密着させ、温度２５℃、湿度９０％以上の条件下で２４時間静置した。静置後、ポリエチレンフィルムおよび試験用印刷物に付着しているウイルスをＳＣＤＬＰ培地１０ｍＬで洗い出し、洗い出し液から１０倍希釈系列を作成した。洗い出し液および各希釈液０．１ｍＬ、宿主細菌培養液０．１ｍＬ、軟寒天培地５ｍＬを試験管に加え攪拌し、寒天平板培地に重層した後、３７℃で１８時間培養し、宿主細菌にバクテリオファージを感染させた。培養後、シャーレのプラーク数を測定した。評価の基準は、無加工の合成紙試験片を用いた。試験はそれぞれ３回行った。表５に結果を示した。
[Antiviral evaluation]
The test printed matter prepared in the same manner as the above [antibacterial evaluation] was carried out as follows.
0.4 mL of a suspension containing an enveloped virus (bacteriophage φ6) and a non-enveloped virus (bacteriophage Qβ) was added dropwise to the surface of a test printed matter cut into 50 mm × 50 mm. A polyethylene film having a size of 40 mm × 40 mm × 0.09 mm was brought into close contact with the film, and allowed to stand for 24 hours under the conditions of a temperature of 25 ° C. and a humidity of 90% or more. After standing, the virus adhering to the polyethylene film and the test printed matter was washed out with 10 mL of SCDLP medium, and a 10-fold dilution series was prepared from the washout solution. Add 0.1 mL of washout solution and each diluted solution, 0.1 mL of host bacterial culture solution, and 5 mL of soft agar medium to a test tube, stir, layer on an agar plate medium, and incubate at 37 ° C. for 18 hours to inoculate the host bacteria. Infected the phage. After culturing, the number of plaques in the petri dish was measured. As the evaluation criteria, unprocessed synthetic paper test pieces were used. Each test was performed 3 times. The results are shown in Table 5.
ウイルス感染価（Ｖ）は以下の方法により算出した。
Ｖ＝（１０×Ｃ×Ｄ×Ｎ）／Ａ
Ｖ：ウイルス感染価（試験片１ｃｍ２あたり）（ＰＦＵ／ｃｍ２）
Ｃ：プラーク数
Ｄ：希釈倍数（採用したウェルに分注した希釈液の希釈倍率）
Ｎ：洗い出しに用いたＳＣＤＬＰ培地の液量（ｍｌ）
Ａ：被覆フィルムの表面積（ｃｍ２）
ただし、Ｃが＜１の場合はＣを１としてプラーク数を算出した。例えば、Ｎ＝１０ｍｌ、Ａ＝１６ｃｍ２、Ｄ＝１（洗い出し液）の場合、ｌｏｇＶ＜０．８０とした。
抗ウイルス活性値（Ｒ）は以下の方法により算出した。
Ｒ＝ｌｏｇ（Ｖｂ）－ｌｏｇ（Ｖｃ）
ｌｏｇ（Ｖｂ）：無加工試験片のウイルス感染価の常用対数値
ｌｏｇ（Ｖｃ）：加工試験片のウイルス感染価の常用対数値
ただし、ｌｏｇＶが＜０．８０の場合、０．８０で計算した。小数点以下２けた目は切り捨て、小数点以下１けたとした。
抗ウイルス活性値（Ｒ）が２以上のとき、抗ウイルス効果があると判断でき、○：２以上（抗ウイルス効果がある）、△：２未満、１以上（弱い抗ウイルス効果）、×：１未満（抗ウイルス効果がない）の３段階で評価した。
The virus infectivity titer (V) was calculated by the following method.
V = (10 x C x D x N) / A
V: Viral load (per 1 cm 2 test piece) (PFU / cm 2 )
C: Number of plaques D: Dilution factor (dilution factor of the diluted solution dispensed into the adopted wells)
N: Liquid volume (ml) of SCDLP medium used for washing out
A: Surface area of the coating film (cm 2 )
However, when C is <1, the number of plaques is calculated with C as 1. For example, in the case of N = 10 ml, A = 16 cm 2 , and D = 1 (washout liquid), logV <0.80.
The antiviral activity value (R) was calculated by the following method.
R = log (Vb) -log (Vc)
log (Vb): Common logarithmic value of viral infectivity of unprocessed test piece log (Vc): Common logarithmic value of viral infectivity of processed test piece However, when logV is <0.80, it was calculated as 0.80. .. The second digit after the decimal point was rounded down, and the first digit after the decimal point was assumed.
When the antiviral activity value (R) is 2 or more, it can be judged that there is an antiviral effect, ○: 2 or more (having an antiviral effect), Δ: less than 2, 1 or more (weak antiviral effect), ×: It was evaluated on a three-point scale of less than 1 (no antiviral effect).
表１および表２の抗菌オーバープリントニスについて、下記の条件にて連続印刷試験を行ない、抗菌印刷物を作製した。
印刷機：（株）小森コーポレーション製 システム３８Ｓ ６色オフセット輪転機
印刷回転数：４１０ｒｐｍ
印刷インキ：東京インキ（株）製 ガイア墨、藍、紅、黄
用紙：王子製紙（株）製 ＯＫコートＬ 厚み５３μｍ 坪量６４ｇ／ｍ２
ドライヤー設定温度：第１ゾーン１９０℃、第２ゾーン１７５℃、第３ゾーン１２０℃
The antibacterial overprint varnishes in Tables 1 and 2 were subjected to continuous printing tests under the following conditions to prepare antibacterial printed matter.
Printing machine: Komori Corporation System 38S 6-color offset rotary press Printing rotation speed: 410 rpm
Printing ink: Gaia ink, indigo, red, yellow manufactured by Tokyo Ink Co., Ltd. Paper: OK coat L manufactured by Oji Paper Co., Ltd. Thickness 53 μm Basis weight 64 g / m 2
Dryer set temperature: 1st zone 190 ° C, 2nd zone 175 ° C, 3rd zone 120 ° C
＜実施例１３＞
上記印刷試験条件にて、印刷ユニット１で墨インキ、印刷ユニット２で藍インキ、印刷ユニット３で紅インキ、印刷ユニット４で黄インキ、および印刷ユニット５で実施例１の抗菌オーバープリントニスを印刷し、印刷用紙巻取４本分（Ａ１換算、約８万部）を連続印刷した。得られた抗菌印刷物表面の銀イオン量としては０．０００３ｇ／ｍ２となった。抗菌印刷物表面の銀イオン量は、印刷部数と抗菌オーバープリントニスの使用量から換算した。
なお、抗菌オーバープリントニスは、全面に印刷した（全ベタ印刷）。
同様に、表６にしたがって、実施例１４～１５、比較例４および参考例３の抗菌印刷物を作製した。
<Example 13>
Under the above printing test conditions, the printing unit 1 prints black ink, the printing unit 2 prints indigo ink, the printing unit 3 prints red ink, the printing unit 4 prints yellow ink, and the printing unit 5 prints the antibacterial overprint varnish of Example 1. Then, four rolls of printing paper (A1 conversion, about 80,000 copies) were continuously printed. The amount of silver ions on the surface of the obtained antibacterial printed matter was 0.0003 g / m 2 . The amount of silver ions on the surface of the antibacterial printed matter was converted from the number of printed copies and the amount of antibacterial overprint varnish used.
The antibacterial overprint varnish was printed on the entire surface (all solid printing).
Similarly, according to Table 6, antibacterial printed matter of Examples 14 to 15, Comparative Example 4 and Reference Example 3 was prepared.
表３および表４の抗菌オーバープリントニスについて、下記の条件にて連続印刷試験を行ない、抗菌印刷物を作製した。
印刷機：（株）小森コーポレーション製 リスロンＬ－６４０ ６色枚葉印刷機
印刷回転数：１０，０００ｓｐｈ
印刷インキ：東京インキ（株）製 ジップセットニューセルボ墨、藍、紅、黄
用紙：日本製紙（株）製 オーロラコート 厚み６２μｍ 坪量７９．１ｇ／ｍ２
The antibacterial overprint varnishes in Tables 3 and 4 were subjected to continuous printing tests under the following conditions to prepare antibacterial printed matter.
Printing machine: Komori Corporation Lithrone L-640 6-color sheet-fed printing machine Printing rotation speed: 10,000 sph
Printing ink: Zip set made by Tokyo Ink Co., Ltd. New selvo ink, indigo, red, yellow Paper: Aurora coat made by Nippon Paper Industries Co., Ltd. Thickness 62 μm Basis weight 79.1 g / m 2
＜実施例１６＞
上記印刷試験条件にて、印刷ユニット１で墨インキ、印刷ユニット２で藍インキ、印刷ユニット３で紅インキ、印刷ユニット４で黄インキ、および印刷ユニット５で実施例７の抗菌オーバープリントニスを連続印刷した。得られた抗菌印刷物表面の銀イオン量としては０．０００３ｇ／ｍ２となった。抗菌印刷物表面の銀イオン量は、印刷部数と抗菌オーバープリントニスの使用量から換算した。
なお、抗菌オーバープリントニスは、全面に印刷した（全ベタ印刷）。
同様に、表６にしたがって、実施例１７～１８、比較例５～６および参考例４の抗菌印刷物を作製した。
<Example 16>
Under the above printing test conditions, the printing unit 1 is used for black ink, the printing unit 2 is used for indigo ink, the printing unit 3 is used for red ink, the printing unit 4 is used for yellow ink, and the printing unit 5 is used for the antibacterial overprint varnish of Example 7. I printed it. The amount of silver ions on the surface of the obtained antibacterial printed matter was 0.0003 g / m 2 . The amount of silver ions on the surface of the antibacterial printed matter was converted from the number of printed copies and the amount of antibacterial overprint varnish used.
The antibacterial overprint varnish was printed on the entire surface (all solid printing).
Similarly, antibacterial printed matter of Examples 17 to 18, Comparative Examples 5 to 6 and Reference Example 4 were prepared according to Table 6.
［抗菌性評価］
抗菌試験は、上記印刷用紙では正確な評価が困難であるため、次の方法で確認した。
ジップセットニューセルボ紅（東京インキ（株）製）を、ＲＩテスター（（株）明製作所製）で合成紙（ユポＦＧＳ、厚み１５０μｍ、（株）ユポ・コーポレーション製）に展色し、２４時間乾燥した。さらに、実施例１３で用いた実施例１の抗菌オーバープリントニスを、上記紅インキ塗布面に銀イオン量として０．０００３ｇ／ｍ２となるように同ＲＩテスターで塗布し、十分乾燥し、試験用印刷物を得た。
得られた試験用印刷物を、上記抗菌性評価（大腸菌を使用）と同様にして評価した。
抗菌活性値（Ｒ）が２以上のとき、抗菌効果があると判断でき、○：２以上（抗菌効果がある）、△：２未満、１以上（弱い抗菌効果）、×：１未満（抗菌効果がない）の３段階で評価した。
同様に、表６にしたがって、各印刷物を作製した。
[Antibacterial evaluation]
Since it is difficult to make an accurate evaluation of the antibacterial test using the above printing paper, the antibacterial test was confirmed by the following method.
Zip set New Cervo Beni (manufactured by Tokyo Ink Co., Ltd.) is spread on synthetic paper (Yupo FGS, thickness 150 μm, manufactured by Yupo Corporation) with an RI tester (manufactured by Ming Seisakusho Co., Ltd.) for 24 hours. It was dry. Further, the antibacterial overprint varnish of Example 1 used in Example 13 was applied to the red ink coated surface with the same RI tester so that the amount of silver ions was 0.0003 g / m 2 , dried sufficiently, and tested. Obtained printed matter.
The obtained test printed matter was evaluated in the same manner as in the above antibacterial property evaluation (using Escherichia coli).
When the antibacterial activity value (R) is 2 or more, it can be judged that there is an antibacterial effect. It was evaluated on a three-point scale (no effect).
Similarly, each printed matter was prepared according to Table 6.
［ブランケットパイリング］
上記連続印刷試験時において、一定印刷部数ごとに抗菌印刷物をサンプリングし、印刷画像を目視にて観察し、ブランケットパイリングの発生状況を確認した。
実施例１３～１５、比較例４、および参考例３については、ブランケットパイリングの発生について、◎：７万部以上印刷しても発生しない、○：７万部未満、５万部以上印刷しても発生しない、△：５万部未満、２万部以上印刷した時点で発生はみられるが、印刷物として許容できる（実用上問題ない）、×：２万部未満の印刷で発生し印刷物として許容できない、の４段階で評価した。
また、実施例１６～１８、比較例５～６、および参考例４については、ブランケットパイリングの発生について、◎：１万部以上印刷しても発生しない、○：１万部未満、５千部以上印刷しても発生しない、△：５千部未満、３千部以上印刷した時点で発生はみられるが、印刷物として許容できる（実用上問題ない）、×：３千部未満の印刷で発生し印刷物として許容できない、の４段階で評価した。
表６に、ブランケットパイリングの結果を記載した。
[Blanket pyring]
During the continuous printing test, antibacterial printed matter was sampled for each fixed number of copies, and the printed image was visually observed to confirm the occurrence of blanket pyring.
Regarding Examples 13 to 15, Comparative Example 4, and Reference Example 3, regarding the occurrence of blanket piring, ⊚: does not occur even if 70,000 or more copies are printed, ○: less than 70,000 copies are printed, and 50,000 or more copies are printed. No occurrence, Δ: Occurrence occurs when less than 50,000 copies are printed, but it is acceptable as a printed matter (no problem in practical use), ×: Occurs when printing less than 20,000 copies and is acceptable as a printed matter. It was evaluated on a four-point scale: not possible.
Further, in Examples 16 to 18, Comparative Examples 5 to 6, and Reference Example 4, regarding the occurrence of blanket piring, ⊚: not generated even if 10,000 or more copies are printed, ○: less than 10,000 copies and 5,000 copies. It does not occur even if it is printed more than 5,000 copies. It was evaluated on a four-point scale, which was unacceptable as a printed matter.
Table 6 shows the results of blanket pyring.
［耐摩擦性試験］
実施例１～６、比較例１、および参考例１については、ＲＩテスター（（株）明製作所製）でコート紙（ＯＫコートＬ）に、ガイア紅インキを１．２５ｃｃ／ｍ２で展色し、すぐに温度調整可能なオーブンを用いて、１２０℃、１０秒間、加熱し、乾燥させた後に、抗菌ＯＰニスを１．２５ｃｃ／ｍ２で展色し、すぐに同オーブンを用いて、１２０℃、１０秒間、試料片を加熱し、乾燥させた。加熱後、試料片を１分間放冷し、放冷した試料片のインキ面を学振型耐摩擦性試験機にて白紙で擦り、色落ちの程度を目視にて評価した。色落ちが少ないものほど、耐摩擦性が優れる。色落ちの程度について、◎：非常に少ないもの、○：少ないもの、△：やや多いもの（実用上問題ない程度）、×：多いもの（実用できない）、の４段階で評価した。
また、実施例７～１２、比較例２～３、および参考例２については、ＲＩテスター（（株）明製作所製）でコート紙（オーロラコート）に、ニューセルボ紅インキを１．２５ｃｃ／ｍ２で展色し、２５℃で、２４時間乾燥後、抗菌ＯＰニスを１．２５ｃｃ／ｍ２で展色し、２５℃で、２４時間乾燥させた。乾燥した試料片のインキ面を学振型耐摩擦性試験機にて白紙で擦り、色落ちの程度を目視にて評価した。色落ちが少ないものほど、耐摩擦性が優れる。色落ちの程度について、◎：非常に少ないもの、○：少ないもの、△：やや多いもの（実用上問題ない程度）、×：多いもの（実用できない）、の４段階で評価した。
表６に、耐摩擦性試験の結果を記載した。
[Abrasion resistance test]
For Examples 1 to 6, Comparative Example 1, and Reference Example 1, a RI tester (manufactured by Ming Seisakusho Co., Ltd.) was used to spread the color of Gaia red ink at 1.25 cc / m 2 on coated paper (OK coat L). Then, using an oven whose temperature can be adjusted immediately, the mixture was heated at 120 ° C. for 10 seconds and dried, and then the antibacterial OP varnish was developed at 1.25 cc / m 2 and immediately used in the same oven. The sample pieces were heated and dried at 120 ° C. for 10 seconds. After heating, the sample piece was allowed to cool for 1 minute, and the ink surface of the released sample piece was rubbed with a blank sheet of paper using a Gakushin type friction resistance tester, and the degree of discoloration was visually evaluated. The less discoloration, the better the abrasion resistance. The degree of discoloration was evaluated on a four-point scale: ⊚: very few, ○: few, Δ: slightly high (no problem in practical use), and ×: high (not practical).
For Examples 7 to 12, Comparative Examples 2 to 3, and Reference Example 2, RI tester (manufactured by Akira Seisakusho Co., Ltd.) was used to apply 1.25 cc / m of New Cervo red ink to coated paper (Aurora coat). The color was developed at 2 and dried at 25 ° C. for 24 hours, then the antibacterial OP varnish was developed at 1.25 cc / m 2 and dried at 25 ° C. for 24 hours. The ink surface of the dried sample piece was rubbed with a blank sheet of paper using a Gakushin type friction resistance tester, and the degree of discoloration was visually evaluated. The less discoloration, the better the abrasion resistance. The degree of discoloration was evaluated on a four-point scale: ⊚: very few, ○: few, Δ: slightly high (no problem in practical use), and ×: high (not practical).
Table 6 shows the results of the abrasion resistance test.
表５～６より、実施例１～１２の抗菌オーバープリントニスは、抗菌性および抗ウイルス性について良好であり、実機印刷において、ブランケットパイリングおよび耐摩擦性試験といった印刷適性が良好であることが明確である。比較例１のナノ銀分散溶液を含有するものは、耐摩擦性試験は実用上問題ないものであるが、抗菌性および抗ウイルス性が劣り、ブランケットパイリングが劣ることが明確である。比較例２の銅イオン水溶液を含有するものは、印刷適性は良好であるものの抗菌性および抗ウイルス性が劣ることが明確である。特許文献５に類似の比較例３の銀含有リン酸ジルコニウム粒子を含有するものは、耐摩擦性試験は実用上問題ないものであるが、抗菌性および抗ウイルス性が劣り、ブランケットパイリングが劣ることが明確である。また、従来品（参考例１および２）は、抗菌性が劣ることが明確である。 From Tables 5 to 6, it is clear that the antibacterial overprint varnishes of Examples 1 to 12 have good antibacterial and antiviral properties, and have good printability such as blanket piring and abrasion resistance test in actual printing. Is. The one containing the nano-silver dispersion solution of Comparative Example 1 has no problem in practical use in the abrasion resistance test, but it is clear that the antibacterial and antiviral properties are inferior and the blanket piring is inferior. It is clear that the one containing the copper ion aqueous solution of Comparative Example 2 has good printability but is inferior in antibacterial and antiviral properties. Those containing the silver-containing zirconium phosphate particles of Comparative Example 3 similar to Patent Document 5 have no problem in practical use in the abrasion resistance test, but are inferior in antibacterial and antiviral properties and inferior in blanket pyring. Is clear. Further, it is clear that the conventional products (Reference Examples 1 and 2) are inferior in antibacterial properties.
Claims (5)
前記銀含有錯体化合物（Ａ）が、アミノ酸、１～２価のカルボン酸およびイミダゾール誘導体からなる群から選ばれる少なくとも１種の化合物と銀との錯体化合物であり、
かつ、前記溶剤（Ｃ）が、石油系溶剤および植物油類のなかから選ばれる少なくとも１種であることを特徴とする抗菌オーバープリントニス。 It contains a silver -containing complex compound (A) , a rosin-modified phenolic resin (B) , and a solvent (C) .
The silver-containing complex compound (A) is a complex compound of silver and at least one compound selected from the group consisting of amino acids, monovalent carboxylic acids and imidazole derivatives.
Moreover, the antibacterial overprint varnish is characterized in that the solvent (C) is at least one selected from petroleum-based solvents and vegetable oils .
少なくとも一つの印刷ユニットを用いて、請求項１または２に記載の抗菌オーバープリントニスを塗布する工程を含むことを特徴とする抗菌印刷物の製造方法。 In a method for manufacturing an antibacterial printed matter, which is printed by an offset printing machine to obtain an antibacterial printed matter.
A method for producing an antibacterial printed matter, which comprises the step of applying the antibacterial overprint varnish according to claim 1 or 2 using at least one printing unit.
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| JP3143581B2 (en) * | 1996-03-18 | 2001-03-07 | 東洋インキ製造株式会社 | Overprint varnish composition |
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| JP2008037100A (en) * | 2006-07-11 | 2008-02-21 | Sakata Corp | Manufacturing process of printed matter and printed matter obtained by its method |
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| JP2005170976A (en) | 2003-12-08 | 2005-06-30 | Shinto Paint Co Ltd | Printing varnish composition |
| JP2008179691A (en) | 2007-01-24 | 2008-08-07 | Toyo Ink Mfg Co Ltd | Ink composition for water-less lithography |
| WO2009081850A1 (en) | 2007-12-21 | 2009-07-02 | Dic Corporation | Pigment composition for printing ink, method for production thereof, and method for production of printing ink |
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