JP6973762B2 - 印刷インキ、印刷物、および印刷物の製造方法 - Google Patents
印刷インキ、印刷物、および印刷物の製造方法 Download PDFInfo
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- JP6973762B2 JP6973762B2 JP2021064648A JP2021064648A JP6973762B2 JP 6973762 B2 JP6973762 B2 JP 6973762B2 JP 2021064648 A JP2021064648 A JP 2021064648A JP 2021064648 A JP2021064648 A JP 2021064648A JP 6973762 B2 JP6973762 B2 JP 6973762B2
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- meth
- resin
- printing ink
- acrylate
- antibacterial
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical class OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical class OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
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- Inks, Pencil-Leads, Or Crayons (AREA)
Description
(1)水酸化カルシウムを含む抗菌剤と、
ジアリルフタレート樹脂と、
ワックスとを含み、
前記ジアリルフタレート樹脂100質量部に対して、前記抗菌剤が1〜180質量部であり、
前記抗菌剤の平均粒子径が0.1〜4μmであり、
前記ワックスの含有量が、印刷インキ中に、0.1〜0.75質量%であり、
活性エネルギー線硬化型印刷インキであることを特徴とする印刷インキ、
(2)水酸化カルシウムを含む抗菌剤と、
セラック樹脂、ウレタン樹脂、アクリル樹脂、ポリ塩化ビニリデン樹脂のなかから選ばれる少なくとも1つの樹脂と、
ワックスとを含み、
前記樹脂100質量部に対して、前記抗菌剤が0.3〜20質量部であり、
前記抗菌剤の平均粒子径が0.1〜4μmであり、
前記ワックスの含有量が、印刷インキ中に、1〜5質量%であり、
グラビア印刷インキまたはフレキソ印刷インキのどちらか一方であることを特徴とする印刷インキ、
(3)前記抗菌剤が、さらにホウ素を含むことを特徴とする(1)に記載の印刷インキ、
(4)前記抗菌剤が、さらにホウ素を含むことを特徴とする(2)に記載の印刷インキ、
(5)基材上に、(1)〜(4)のいずれかに記載の印刷インキからなる膜厚が0.1〜10μmとなるように設けられた抗菌層を備えることを特徴とする印刷物、
(6)基材上に、(1)または(3)に記載の印刷インキからなる膜厚が0.1〜10μmとなるように設けられた抗菌層を形成する活性エネルギー線硬化印刷工程からなることを特徴とする印刷物の製造方法、
(7)基材上に、(2)または(4)に記載の印刷インキからなる膜厚が0.1〜10μmとなるように設けられた抗菌層を形成するグラビア印刷工程またはフレキソ印刷工程のどちらか一方の印刷工程からなることを特徴とする印刷物の製造方法、
に関するものである。
炭酸カルシウム源としては、動物性由来のカルシウムを使用することができ、例えばホタテ貝殻、あさり貝殻、しじみ貝殻、アワビ貝殻、サザエ貝殻、ホッキ貝殻、ウニ貝殻、牡蠣貝殻などの天然か養殖の貝類または珊瑚殻、牛骨、豚骨、鳥骨などの動物骨、卵殻などを原料に使用することができ、これらのうち、貝殻組成が均一である点および供給量が多いなどの点から、ホタテ貝殻を使用することが好ましい。これらの貝殻などを、粉砕して粉末(あるいは粒状物) とし、800℃〜1500℃で、より好ましくは850℃〜1200℃で、例えば炭酸ガスを導入しながら焼成する。焼成は空気中で行ってもよいし、窒素などの不活性ガス雰囲気下で行なってもよい。焼成時間は焼成温度などによって適宜設定されるが、通常、雰囲気温度が所定の焼成温度に到達した後、10〜120分、好ましくは15〜90分である。こうした焼成処理により、不要な有機物を熱分解によって除去できる。さらに 焼成後、水和させることにより水酸化カルシウム主体の粉末が得られる。
グラビア印刷インキやフレキソ印刷インキである場合、前記樹脂としては、セラック樹脂、ロジン類、ウレタン樹脂、アクリル樹脂、ポリ塩化ビニリデン樹脂、スチレン樹脂、塩化ゴム、環化ゴム、ポリエステル樹脂、ケトン樹脂、ブチラール樹脂、塩素化ポリプロピレン樹脂、アルキッド樹脂、マレイン酸樹脂、カゼイン、エポキシ樹脂のなかから選ばれる少なくとも1つの樹脂であることがより好ましい。なかでも、セラック樹脂、ウレタン樹脂、アクリル樹脂、ポリ塩化ビニリデン樹脂がより好ましく、これらの樹脂が一種類または二種類以上組み合わせたグラビア印刷インキやフレキソ印刷インキであってもよい。また、2色以上のグラビア印刷インキやフレキソ印刷インキを使用する場合は、同じ樹脂系のグラビア印刷インキやフレキソ印刷インキである必要はなく、別の樹脂系の該印刷インキも適宜使用できる。
活性エネルギー線硬化型印刷インキである場合、ジアリルフタレート樹脂であることがより好ましい。ジアリルフタレート樹脂は、オルソタイプとイソタイプの2種類があり、併用することが好ましい。
また、前記抗菌剤は、活性エネルギー線硬化型印刷インキである場合、前記樹脂100質量部に対して、1〜180質量部であることが好ましく、1〜90質量部であることがより好ましく、4〜50質量部であることがさらに好ましい。1質量部より少ないと、抗菌機能が発現しにくく、180質量部より多いと、反応性希釈剤に分散せず、印刷インキとして使用は困難である。
ヒートシールの際、シールバーに当たる用途には、耐チント変色性など、ボイル・レトルト用途には、耐マイグレーション性、耐熱性など、屋外用途には、耐光性などを考慮して適宜色材を選択することが好ましい。
活性エネルギー線硬化型印刷インキである場合、例えば、常温から100℃の間で、樹脂、光重合開始剤、光沢向上剤、エチレン性不飽和化合物、顔料、体質顔料、重合禁止剤、アミン化合物などの増感剤、その他添加剤などを、ニーダー、三本ロール、アトライター、サンドミル、ゲートミキサーなどの練肉、混合、調整機を用いて製造される。
グラビア印刷インキやフレキソ印刷インキである場合、溶解または分散は、ディゾルバー、ロールミル、ボールミル、ビーズミル、サンドミル、アトライター、ペイントシェーカー、アジテータ、ヘンシェルミキサー、コロイドミル、パールミル、超音波ホモジナイザー、湿式ジェットミル、ニーダー、ホモミキサーなどの各種撹拌機または分散機を使用できる。これらの装置は一種類または二種類以上組み合せて使用してもよい。
該印刷インキ中に気泡や粗大粒子が含まれる場合、印刷適性や印刷物品質を低下させるため、公知のろ過機や遠心分離機などを用いて、取り除くことが好ましい。
前記グラビア印刷インキとしては、粘度は、印刷に支障のない範囲であれば、特に制限はない。グラビア印刷インキやフレキソ印刷インキの製造適性、取扱いなどを考慮すれば、25℃において10〜1,000mPa・sであることが好ましい。10mPa・sより小さいと、粘度が低すぎて、顔料が沈降しやすい傾向になり、1,000mPa・sより大きいと、流動性が悪く、インキ製造時に支障が出たり、容器への充填が困難となる。この場合、ブルックフィールド型粘度計やコーンプレート型粘度計などの市販の粘度計を用いて測定することができる。
ジアリル(オルソ)フタレート樹脂(ダイソーダップA、ダイソー(株)製)を24部、ジペンタエリスリトールヘキサアクリレートを51部、ジトリメチロールプロパンテトラアクリレート25部を配合し、ワニス1を得た。
(実施例1)
ワニス1を23部、ワニス2を25部、ジペンタエリスリトールヘキサアクリレートを10部、トリメチロールプロパン3EO変性トリアクリレートを2部、炭酸カルシウム(白艶華O、白石カルシウム(株)製)を10部、ワックスコンパンド(パラフィンワックス、固形分25%)を3部、重合禁止剤(Q1301 富士フイルム和光純薬(株)製)0.1部添加、混合し、活性エネルギー線硬化型ニスベースを作製し、さらに抗菌剤(スカロープレミアムR、平均粒子径4μm、pH12.8、WM(株)製)を10部、Omnirad379(IGM Resins B.V.社製)を6部、Omnirad EMK(IGM Resins B.V.社製)を4部、トリメチロールプロパン3EO変性トリアクリレートを6.9部添加し、撹拌して、UVニス1を作製した。
表1の配合にて、抗菌剤の含有量を変更して、実施例1と同様にして、UVニス2〜8を作製した。
(実施例5)
シェラックニス(固形分32%エタノール溶液)91部に、抗菌剤(スカロープレミアム、平均粒子径3.6μm、WM(株)製)を5部、ポリエチレンワックス(固形分25%、軟化点132℃)を4部添加し、撹拌して、ニス1を作製した。
シェラックニス(固形分32%エタノール溶液)93.5部に、抗菌剤(スカロープレミアム、平均粒子径3.6μm、WM(株)製)を2.5部、ポリエチレンワックス(固形分25%、軟化点132℃)を4部添加し、撹拌して、ニス2を作製した。
ウレタンニス(ウレタン樹脂固形分30%、東京インキ(株)製)91部に、抗菌剤(スカロープレミアム、平均粒子径3.6μm、WM(株)製)を5部、ポリエチレンワックス(固形分25%、軟化点132℃)を4部添加し、撹拌して、ニス3を作製した。
アクリルニスSY(アクリル樹脂固形分30%、東京インキ(株)製)91部に、抗菌剤(スカロープレミアム、平均粒子径3.6μm、WM(株)製)を5部、ポリエチレンワックス(固形分25%、軟化点132℃)を4部添加し、撹拌して、ニス4を作製した。
アクリルニスLG(アクリル樹脂固形分30%、東京インキ(株)製)91部に、抗菌剤(スカロープレミアム、平均粒子径3.6μm、WM(株)製)を5部、ポリエチレンワックス(固形分25%、軟化点132℃)を4部添加し、撹拌して、ニス5を作製した。
塩化ビニリデンニス(塩化ビニリデン樹脂固形分30%、東京インキ(株)製)91部に、抗菌剤(スカロープレミアム、平均粒子径3.6μm、WM(株)(製))を5部、ポリエチレンワックス(固形分25%、軟化点132℃)を4部添加し、撹拌して、ニス6を作製した。
表2の配合にて、抗菌剤の配合量を変更して、実施例5と同様にして、ニス7〜10を作製した。
表2の配合にて、抗菌剤スカロープレミアムをスカロープレミアムR(平均粒子径4μm、pH12.8、WM(株)製)に変更して、実施例5と同様にして、ニス11〜12を作製した。
シェラックニス(固形分32%エタノール溶液)96部に、ポリエチレンワックス(固形分25%、軟化点132℃)を4部添加し、撹拌して、ニス13を作製した。
アクリルニスLG(アクリル樹脂固形分30%、東京インキ(株)製)81部に、抗菌剤(スカロープレミアム、平均粒子径3.6μm、WM(株)製)を15部、ポリエチレンワックス(固形分25%、軟化点132℃)を4部、添加し、撹拌して、ニス14を作製した。
活性エネルギー線硬化型印刷インキである場合、調製した直後のL型粘度計(25℃)による粘度値と、調製1週間後の粘度値の変化の有無により判断した。調製直後の粘度値と1週間後の粘度値の変化率が小さいほど、インキ安定性が良好と判断した。変化率について、〇:5%未満、×:5%以上、の2段階で評価した。
グラビア印刷インキである場合、インキ製造1週間後のインキの状態を目視にて観察し、評価した。インキの状態の変化のないものが、インキ安定性が良好と判断した。状態の変化について、○:製造直後と変化がない、△:わずかに増粘またはゲル化がみられる(実用上問題ない)、×:増粘またはゲル化がみられる、××:インキ製造できない、の4段階で評価した。
なお、<インキ安定性>の評価で、「×」のものについては、後述の評価を行なわなかった。
LED−UV照射装置を搭載したオフセット印刷機を用いて、OKトップコート+(王子製紙(株)製)に、UVニス1を約1μmの厚みで全面印刷し、活性エネルギー線硬化印刷物1を作製した。同様に、UVニス2〜7を用いて、活性エネルギー線硬化印刷物2〜7を作製した。
グラビア印刷機を用いて、OKトップコート+(王子製紙(株)製)に、ニス1を印刷し、乾燥後膜厚1μmのグラビア印刷物1を作成した。同様に、ニス2〜13を用いて、グラビア印刷物2〜13を作製した。
各印刷物について、表面pHを測定し、抗菌性を評価した。
印刷物の表面に、ピペットで蒸留水を0.5ml滴下し、直後にpH・水質分析計(LAQUA F74T、フラットISFET pH電極使用、(株)堀場製作所製)により、蒸留水滴下部の表面pHを計測した。計測は、同じ印刷物について異なる3箇所で実施し、その平均値を求めた。表面pHが10以上のとき、抗菌機能があると判断でき、〇:pH10以上、×:pH10未満、の2段階で評価した。
印刷物の表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、○: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3段階で評価した。
抗菌剤を所定量以上含まない印刷インキからなる抗菌層を有する印刷物(比較例1および2)は、抗菌機能が発現しないことが明確である。
また、活性エネルギー線硬化型印刷、グラビア印刷およびフレキソ印刷にて、抗菌層を形成できることから、包装用途、食品保存用途、農業用途、土木用途、漁業用途、自動車内外装用途、船舶用途、日用品用途、建材内外装用途、住設機器用途、医療・医療機器用途、医薬用途、家電品用途、家具類用途、文具類・事務用品用途、出版用途、衣料用途、販売促進用途、商業用途、電機電子産業用途などの各種フィルム、シール、ラベル、シートなど、さらにそれを利用した容器に広く適用できる。
Claims (7)
- 水酸化カルシウムを含む抗菌剤と、
ジアリルフタレート樹脂と、
ワックスとを含み、
前記ジアリルフタレート樹脂100質量部に対して、前記抗菌剤が1〜180質量部であり、
前記抗菌剤の平均粒子径が0.1〜4μmであり、
前記ワックスの含有量が、印刷インキ中に、0.1〜0.75質量%であり、
活性エネルギー線硬化型印刷インキであることを特徴とする印刷インキ。 - 水酸化カルシウムを含む抗菌剤と、
セラック樹脂、ウレタン樹脂、アクリル樹脂、ポリ塩化ビニリデン樹脂のなかから選ばれる少なくとも1つの樹脂と、
ワックスとを含み、
前記樹脂100質量部に対して、前記抗菌剤が0.3〜20質量部であり、
前記抗菌剤の平均粒子径が0.1〜4μmであり、
前記ワックスの含有量が、印刷インキ中に、1〜5質量%であり、
グラビア印刷インキまたはフレキソ印刷インキのどちらか一方であることを特徴とする印刷インキ。 - 前記抗菌剤が、さらにホウ素を含むことを特徴とする請求項1に記載の印刷インキ。
- 前記抗菌剤が、さらにホウ素を含むことを特徴とする請求項2に記載の印刷インキ。
- 基材上に、請求項1〜4のいずれかに記載の印刷インキからなる膜厚が0.1〜10μmとなるように設けられた抗菌層を備えることを特徴とする印刷物。
- 基材上に、請求項1または3に記載の印刷インキからなる膜厚が0.1〜10μmとなるように設けられた抗菌層を形成する活性エネルギー線硬化印刷工程からなることを特徴とする印刷物の製造方法。
- 基材上に、請求項2または4に記載の印刷インキからなる膜厚が0.1〜10μmとなるように設けられた抗菌層を形成するグラビア印刷工程またはフレキソ印刷工程のどちらか一方の印刷工程からなることを特徴とする印刷物の製造方法。
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