JP2021021077A - Active energy ray-curable ink, method for producing ink cured product, and printed matter - Google Patents
Active energy ray-curable ink, method for producing ink cured product, and printed matter Download PDFInfo
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- JP2021021077A JP2021021077A JP2020177225A JP2020177225A JP2021021077A JP 2021021077 A JP2021021077 A JP 2021021077A JP 2020177225 A JP2020177225 A JP 2020177225A JP 2020177225 A JP2020177225 A JP 2020177225A JP 2021021077 A JP2021021077 A JP 2021021077A
- Authority
- JP
- Japan
- Prior art keywords
- ink
- active energy
- energy ray
- acrylate
- meth
- Prior art date
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- Pending
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 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
- 150000003573 thiols Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
Abstract
Description
本発明は、活性エネルギー線硬化型インキ、該活性エネルギー線硬化型インキの硬化物の製造方法および印刷物に関する。 The present invention relates to an active energy ray-curable ink, a method for producing a cured product of the active energy ray-curable ink, and a printed matter.
活性エネルギー線硬化型インキは、無溶剤型であり瞬間的に活性エネルギー線硬化乾燥することから、環境対応、印刷作業性に優れ、且つ高品質の印刷物が得られるとして、平版印刷（湿し水を使用する平版印刷や湿し水を使用しない水無し平版印刷）、凸版印刷、凹版印刷、孔版印刷や、これらの版に付けられたインキをブランケット等の中間転写体に転写した後被印刷体に印刷する転写（オフセット）方式を組み合わせた種々の印刷方式におけるインキとして使用されており、フォーム用印刷物、各種書籍印刷物、カルトン紙等の各種包装用印刷物、各種プラスチック印刷物、シール、ラベル用印刷物、美術印刷物、金属印刷物（美術印刷物、飲料缶印刷物、缶詰等の食品印刷物）などの種々の印刷物に適用されている。 The active energy ray-curable ink is a solvent-free type and instantly cures and dries the active energy ray. Therefore, it is said that it is environmentally friendly, has excellent printing workability, and can obtain high-quality printed matter. Flat plate printing using, or waterless flat plate printing without dampening water), letterpress printing, concave printing, stencil printing, and printing after transferring the ink attached to these plates to an intermediate transfer material such as a blanket. It is used as an ink in various printing methods that combine the transfer (offset) method to print on, and is used as an ink for foam prints, various book prints, various packaging prints such as carton paper, various plastic prints, stickers, label prints, etc. It is applied to various printed materials such as art printed matter and metal printed matter (art printed matter, beverage can printed matter, food printed matter such as canned food).
これら活性エネルギー線硬化型インキの光源としては、従来低圧や高圧の水銀灯、キセノンランプ、メタルハライドランプ等の紫外線ランプ（ＵＶランプ）が広く用いられてきたが、近年、紫外線発光ダイオード（ＵＶ−ＬＥＤ）を光源とした照射モジュールが開発され、ＵＶ印刷分野への適用が進んでいる。 As a light source for these active energy ray-curable inks, ultraviolet lamps (UV lamps) such as low-pressure and high-pressure mercury lamps, xenon lamps, and metal halide lamps have been widely used, but in recent years, ultraviolet light emitting diodes (UV-LEDs) have been widely used. An irradiation module using a light source has been developed and is being applied to the UV printing field.
紫外線発光ダイオード（ＵＶ−ＬＥＤ）は、発光ピーク波長が３５０〜４２０ｎｍの範囲の紫外線を発生する。即ち、従来のメタルハライドランプや高圧水銀灯等の光源を用いていたインクをＵＶ−ＬＥＤに適用させようとした場合、波長３５０〜４２０ｎｍ付近に吸収を有する光重合開始剤を使用する必要があるが、インキに使用する顔料自身が波長３５０〜４２０ｎｍの範囲の光を吸収するため、多くの場合、波長３５０〜４２０ｎｍに吸収を有する光重合開始剤を使用しても硬化が不十分となる問題が生じる。 Ultraviolet light emitting diodes (UV-LEDs) generate ultraviolet light with an emission peak wavelength in the range of 350 to 420 nm. That is, when trying to apply an ink using a light source such as a conventional metal halide lamp or a high-pressure mercury lamp to a UV-LED, it is necessary to use a photopolymerization initiator having absorption in the wavelength range of 350 to 420 nm. Since the pigment itself used in the ink absorbs light in the wavelength range of 350 to 420 nm, in many cases, there is a problem that curing is insufficient even if a photopolymerization initiator having absorption in the wavelength range of 350 to 420 nm is used. ..
ＵＶ−ＬＥＤに適用させたインキ組成物としては、例えば、光重合開始剤としてα−（ジメチル）アミノアルキルフェノン化合物および／またはα−モルフォリノアルキルフェノン化合物と、ジアルキルアミノベンゾフェノン化合物（Ａ２−１）および／またはチオキサントン化合物とを併用した活性エネルギー線硬化型インキや（例えば特許文献１参照）、光重合開始剤としてα−アミノアルキルフェノン化合物とアシルフォスフィンオキサイド化合物とを併用し、且つ特定のアルコールを含有した活性エネルギー線硬化型インキ（例えば特許文献２参照）が知られている。しかしながらα−アミノアルキルフェノン化合物は、紫外線吸収領域がより短波長側にあり、ＵＶ−ＬＥＤで硬化させた場合、塗膜表面の硬化性に劣ることがあった。またα−モルフォリノアルキルフェノン化合物として汎用の２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン（Ｉｒｇａｃｕｒｅ９０７）は、紫外線照射直後に特異な臭気を発生させるため、高い衛生性が求められる用途では配合量に限界があり、十分な硬化性を得ることができなかった。 Examples of the ink composition applied to the UV-LED include an α- (dimethyl) aminoalkylphenone compound and / or an α-morpholinoalkylphenone compound as a photopolymerization initiator, and a dialkylaminobenzophenone compound (A2-1). An active energy ray-curable ink in combination with and / or a thioxanthone compound (see, for example, Patent Document 1), an α-aminoalkylphenone compound and an acylphosphine oxide compound in combination as a photopolymerization initiator, and a specific alcohol. An active energy ray-curable ink containing a compound (see, for example, Patent Document 2) is known. However, the α-aminoalkylphenone compound has an ultraviolet absorption region on the shorter wavelength side, and when cured by UV-LED, the curability of the coating film surface may be inferior. In addition, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (Irgacure907), which is generally used as an α-morpholinoalkylphenone compound, generates a peculiar odor immediately after irradiation with ultraviolet rays. Therefore, in applications where high hygiene is required, there is a limit to the blending amount, and sufficient curability cannot be obtained.
本発明者らは、ＵＶ−ＬＥＤ光源を使用した場合であっても非常に硬化が早く、且つ臭気等が生じにくい活性エネルギー線硬化型インキを提供することにある。 The present inventors have provided an active energy ray-curable ink that cures very quickly even when a UV-LED light source is used and does not easily generate odor or the like.
本発明者らは、特定の光重合開始剤を含有する活性エネルギー線硬化型インキが上記課題を解決することを見出した。 The present inventors have found that an active energy ray-curable ink containing a specific photopolymerization initiator solves the above-mentioned problems.
即ち本発明は、エチレン性不飽和二重結合を有するモノマー、及び一般式（１）で表される光重合開始剤を含有する活性エネルギー線硬化型インキを提供する。 That is, the present invention provides an active energy ray-curable ink containing a monomer having an ethylenically unsaturated double bond and a photopolymerization initiator represented by the general formula (1).
（１）
(1)
（一般式（１）中、Ｒ１は炭素原子数１〜１０の直鎖あるいは分岐のアルキル基、又はビニル基を表し、Ｙは水素原子、炭素原子数１〜１０の直鎖あるいは分岐のアルキル基、炭素原子数６〜１０のアリール基、炭素原子数１〜１０の直鎖あるいは分岐のアルコキシ基、または炭素原子数６〜１０のアリールオキシ基を表す。） (In the general formula (1), R 1 represents a linear or branched alkyl group having 1 to 10 carbon atoms or a vinyl group, and Y represents a hydrogen atom or a linear or branched alkyl having 1 to 10 carbon atoms. Represents a group, an aryl group having 6 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.)
また本発明は、前記記載の活性エネルギー線硬化型インキを用いて印刷し、印刷されたインキを活性エネルギー線を用いて硬化させるインキ硬化物の製造方法を提供する。 The present invention also provides a method for producing a cured ink product, which is printed using the above-mentioned active energy ray-curable ink and the printed ink is cured using the active energy ray.
また本発明は、前記記載の活性エネルギー線硬化型インキを用いて平版オフセット印刷し、印刷されたインキを活性エネルギー線を用いて硬化させるインキ硬化物の製造方法を提供する。 The present invention also provides a method for producing a cured ink product in which lithographic offset printing is performed using the active energy ray-curable ink described above and the printed ink is cured using the active energy ray.
また本発明は、前記記載のインキ硬化物の製造方法で得られた印刷物を提供する。 The present invention also provides a printed matter obtained by the method for producing a cured ink product described above.
本発明により、紫外線光源としてＵＶ−ＬＥＤ光源を使用した場合であっても非常に硬化が早く、且つ臭気等が生じにくい活性エネルギー線硬化型インキを得ることができるため、衛生性が求められるパッケージ印刷の分野でも問題なく使用することができる。
本発明のインキは種々の印刷方式におけるインキ、中でも湿し水を使用する平版オフセット印刷インキとして好適に利用することができる。
According to the present invention, even when a UV-LED light source is used as an ultraviolet light source, it is possible to obtain an active energy ray-curable ink that cures very quickly and does not easily generate odors, so that a package that requires hygiene. It can be used without problems in the field of printing.
The ink of the present invention can be suitably used as an ink in various printing methods, particularly as a lithographic offset printing ink using dampening water.
（一般式（１）で表される光重合開始剤）
本発明で使用する一般式（１）で表される光重合開始剤において、Ｒ１は炭素原子数１〜１０の直鎖あるいは分岐のアルキル基、又はビニル基を表し、Ｙは水素原子、炭素原子数１〜１０の直鎖あるいは分岐のアルキル基（−Ｒ２と略す場合がある、但しＲ２はアルキル基を表す）炭素原子数６〜１０のアリール基（−Ａｒ１と略す場合がある。但しＡｒ１はアリール基を表す）、炭素原子数１〜１０の直鎖あるいは分岐のアルコキシ基（−ＯＲ３と略す場合がある。但しＲ３はアルキル基を表す）、または炭素原子数６〜１０のアリールオキシ基（−ＯＡｒ２と略す場合がある。但しＡｒ２はアリール基を表す）を表す。ここで、Ｒ２、Ｒ３はＲ１と同じ基を表わす。
(Photopolymerization initiator represented by the general formula (1))
In the photopolymerization initiator represented by the general formula (1) used in the present invention, R 1 represents a linear or branched alkyl group or vinyl group having 1 to 10 carbon atoms, and Y represents a hydrogen atom or carbon. linear or branched alkyl group having 1 -C 10 (may be abbreviated as -R 2, where R 2 represents an alkyl group) may be abbreviated as an aryl group (-Ar 1 having 6 to 10 carbon atoms However, Ar 1 represents an aryl group), a linear or branched alkoxy group having 1 to 10 carbon atoms (sometimes abbreviated as −OR 3 ; where R 3 represents an alkyl group), or 6 carbon atoms. Represents 10 to 10 aryloxy groups (sometimes abbreviated as −OAr 2 , where Ar 2 represents an aryl group). Here, R 2 and R 3 represent the same group as R 1 .
（１）
(1)
前記Ｒ１〜Ｒ３が表す炭素原子数１〜１０の直鎖上または分岐状のアルキル基としては、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、アミル基、イソアミル基、ヘキシル基、ヘプチル基、イソヘプチル基、オクチル基、イソオクチル基、２−エチルヘキシル基、ノニル基、イソノニル基、デシル基等が挙げられる。 Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by R 1 to R 3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group. , Tert-Butyl group, pentyl group, amyl group, isoamyl group, hexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group and the like.
前記Ａｒ１またはＡｒ２が表す炭素原子数６〜１０のアリール基としては、例えばフェニル基、ナフチル基、アズレニル基、インデニル基、インダニル基、テトラリニル基等が挙げられる。 Examples of the aryl group having 6 to 10 carbon atoms represented by Ar 1 or Ar 2 include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, a tetralinyl group and the like.
前記一般式（１）中、Ｒ１は、炭素原子数１〜５の直鎖または分岐のアルキル基が好ましく、炭素原子数１のメチル基であることがより好ましい。また、Ｙは水素原子もしくは炭素原子数１〜５の直鎖あるいは分岐のアルキル基が好ましく、水素原子であることがさらに好ましい。
本発明にかかる上記光重合開始剤は例えば、１−（[１，１’−ビフェニル]−４−イル）−２−メチル−２−モルフォリノプロパン−１−オン等が挙げられる。
In the general formula (1), R 1 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group having 1 carbon atom. Further, Y is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom.
Examples of the photopolymerization initiator according to the present invention include 1- ([1,1'-biphenyl] -4-yl) -2-methyl-2-morpholinopropane-1-one.
本発明においては、前記一般式（１）で表される光重合開始剤の含有量は、インキ固形分全量に対し０．５〜２０質量％が好ましく、１．０〜１５質量％がより好ましい。０．５質量％以下の場合、紫外線照射で発生した活性なラジカルが空気中の酸素により失活し、インキの硬化性が著しく減少する。そのため、インキ原料の未反応物に由来する臭気が強くなったり、印刷物表面に傷が付き外観不良を起こしたり、印刷物の表面とその印刷物の上に排出された印刷物の裏面が重ねられ積み重なった場合に印刷物の表面とその上部の印刷物の裏面が密着するブロッキングと呼ばれる不具合が生じる。一方、２０質量％以上の場合は、光重合開始剤の析出する可能性が非常に高くなり、インキ製造直後から数日のうちに開始剤がインキ中に析出してしまい、設計通りのインキの硬化性能を発現できなくなる。更に、印刷機のローラーや版に、インキ中に析出した開始剤の粒子が堆積し、正しい画像を形成できなくなる可能性がある。 In the present invention, the content of the photopolymerization initiator represented by the general formula (1) is preferably 0.5 to 20% by mass, more preferably 1.0 to 15% by mass, based on the total amount of solid ink. .. When it is 0.5% by mass or less, active radicals generated by ultraviolet irradiation are deactivated by oxygen in the air, and the curability of the ink is significantly reduced. Therefore, when the odor derived from the unreacted matter of the ink raw material becomes strong, the surface of the printed matter is scratched and the appearance is poor, or the front surface of the printed matter and the back surface of the printed matter discharged on the printed matter are overlapped and stacked. In addition, a problem called blocking occurs in which the front surface of the printed matter and the back surface of the printed matter above it are in close contact with each other. On the other hand, when the content is 20% by mass or more, the possibility that the photopolymerization initiator is precipitated is very high, and the initiator is precipitated in the ink within a few days immediately after the ink is manufactured, so that the ink is as designed. Curing performance cannot be exhibited. In addition, initiator particles deposited in the ink may accumulate on the rollers and plates of the printing press, making it impossible to form a correct image.
〔汎用光重合開始剤の併用〕
本発明においては、本発明の効果を損なわない範囲で、前記一般式（１）で表される光重合開始剤以外に、使用する紫外線光源の種類、紫外線光源の照射強度、紫外線の照射積算光量、色、印刷膜厚、衛生性などを鑑みて、適宜、汎用の光重合開始剤を併用してもよく好ましい。一例を挙げると、例えば、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−ヒロドキシ−１−｛４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］フェニル｝−２−メチル−プロパン−１−オン、フェニル グリオキシリック アシッド メチル エステル、オキシフェニル酢酸、２−［２−オキソ−２−フェニルアセトキシエトキシ］エチルエステルとオキシフェニル酢酸、２−（２−ヒドロキシエトキシ）エチルエステルの混合物、１．２−オクタンジオン，１−［４−（フェニルチオ）−，２−（Ｏ−ベンゾイルオキシム）］、エタノン，１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−，１−（０−アセチルオキシム）、２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］−１−ブタノンなどの化合物が挙げられる。
[Combined use with general-purpose photopolymerization initiator]
In the present invention, in addition to the photopolymerization initiator represented by the general formula (1), the type of ultraviolet light source to be used, the irradiation intensity of the ultraviolet light source, and the integrated light amount of ultraviolet irradiation are used as long as the effects of the present invention are not impaired. , A general-purpose photopolymerization initiator may be used in combination as appropriate in view of color, printing film thickness, hygiene and the like. For example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- On, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hirodoxy-1- {4- [4- (2-hydroxy-) 2-Methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, phenylglycolic acid methyl ester, oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester Oxyphenylacetic acid, a mixture of 2- (2-hydroxyethoxy) ethyl ester, 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4 Compounds such as − (4-morpholinyl) phenyl] -1-butanone can be mentioned.
また、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチル−ペンチルフォスフィンオキサイド等のアシルフォスフィンオキサイド化合物が挙げられる。 In addition, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- Examples thereof include acylphosphine oxide compounds such as pentylphosphine oxide.
また、２，４−ジエチルチオキサントン、２，４−ジメチルチオキサントン、２，４−ジイソプロピルチオキサントン、２−イソプロピルチオキサントン、４−ジイソプロピルチオキサントン、２−イソプロピルチオキサントン、４−イソプロピルチオキサントン、２，４−ジクロロチオキサントン、２−クロロチオキサントン、１−クロロ−４−プロポキシチオキサントン、２−ヒドロキシ−３−（３，４−ジメチル−９−オキソ−９Ｈチオキサントン−２−イロキシ−Ｎ，Ｎ，Ｎ−トリメチル−１−プロパンアミン塩酸塩等のチオキサントン化合物が挙げられる。 In addition, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2-Chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H thioxanthone-2-yloxy-N, N, N-trimethyl-1-propaneamine) Examples thereof include thioxanthone compounds such as hydrochloride.
また、４，４´−ビス−（ジメチルアミノ）ベンゾフェノン、４，４´−ビス−（ジエチルアミノ）ベンゾフェノン等の４，４’−ジアルキルアミノベンゾフェノン類、４−ベンゾイル−４’−メチルジフェニルスルフィド等のベンゾフェノン化合物が挙げられる。 Further, 4,4'-dialkylaminobenzophenones such as 4,4'-bis- (dimethylamino) benzophenone, 4,4'-bis- (diethylamino) benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and the like Benzophenone compounds can be mentioned.
それ以外には、例えばベンゾフェノン、４−メチル−ベンゾフェノン、２，４，６−トリメチルベンゾフェノン、２，３，４−トリメチルベンゾフェノン、４−フェニルベンゾフェノン、３，３‘−ジメチル−４−メトキシベンゾフェノン、４−（１，３−アクリロイル−１，４，７，１０，１３−ペンタオキソトリデシル）ベンゾフェノン、メチル−ｏ−ベンゾイルベンゾエート、〔４−（メチルフェニルチオ）フェニル〕フェニルメタノン、ジエトキシアセトフェノン、ジブトキシアセトフェノン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾインノルマルブチルエーテルなどが挙げられる。 Other than that, for example, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 2,3,4-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4 -(1,3-Acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, methyl-o-benzoylbenzoate, [4- (methylphenylthio) phenyl] phenylmethanone, diethoxyacetophenone, Examples thereof include dibutoxyacetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and benzoin normal butyl ether.
本発明においては、前記一般式（１）で表される光重合開始剤と併用する前記汎用の光重合開始剤は、１種でも数種併用して使用してもよい。中でも、前記一般式（１）で表される光重合開始剤とアシルフォスフィンオキサイド化合物とを併用することが好ましく、特に樹脂に対する溶解性の点から、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイドを併用することがより好ましい。併用する場合、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイドの含有量は、前記一般式（１）で表される光重合開始剤に対し７０〜２０００質量％となるように含有することが好ましく、７０〜１０００質量％がより好ましい。また併用する場合の２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイドの使用量は、インキ固形分全量に対し１．０〜１５質量％が好ましく、３．０〜１０質量％がより好ましい。１．０質量％未満の場合は、十分な硬化性の向上効果が得られず、１５質量％を超える場合は、ＵＶ照射後でも未反応のアシルフォスフィンオキサイドが硬化塗膜中に残存し、硬化塗膜の色相が許容できないくらい黄味に変色したり、開始剤が析出したり、インキの流動性が著しく低下したりする。 In the present invention, the general-purpose photopolymerization initiator used in combination with the photopolymerization initiator represented by the general formula (1) may be used alone or in combination of several kinds. Above all, it is preferable to use the photopolymerization initiator represented by the general formula (1) in combination with the acylphosphine oxide compound, and particularly from the viewpoint of solubility in a resin, 2,4,6-trimethylbenzoyldiphenylphosphine. It is more preferable to use an oxide in combination. When used in combination, the content of 2,4,6-trimethylbenzoyldiphenylphosphine oxide may be 70 to 2000% by mass with respect to the photopolymerization initiator represented by the general formula (1). It is preferably 70 to 1000% by mass, more preferably 70 to 1000% by mass. The amount of 2,4,6-trimethylbenzoyldiphenylphosphine oxide used in combination is preferably 1.0 to 15% by mass, more preferably 3.0 to 10% by mass, based on the total amount of solid ink. If it is less than 1.0% by mass, a sufficient effect of improving curability cannot be obtained, and if it exceeds 15% by mass, unreacted acylphosphine oxide remains in the cured coating film even after UV irradiation. The hue of the cured coating film is unacceptably yellowish, the initiator is precipitated, and the fluidity of the ink is significantly reduced.
〔増感剤・光開始助剤〕
本発明においては、一般式（１）で表される光重合開始剤や前記の汎用光重合開始剤の他に、光増感剤や三級アミン等の光開始助剤を併用しても良く、好ましい。光増感剤としては、特に限定されないが、チオキサントン系、４，４’−ビス（ジエチルアミノ）ベンゾフェノン等のベンゾフェノン系、アントラキノン系、クマリン系などが挙げられる。
これらの中でも、特に２，４−ジエチルチオキサントン、２，４−ジメチルチオキサントン、２，４−ジクロロチオキサントン、１−クロロ−４−プロポキシチオキサントン、２−クロロチオキサントン、２−イソプロピルチオキサントンなどのチオキサントン系化合物や、ミヒラーケトン、４，４´−ビス−（ジエチルアミノ）ベンゾフェノンなど４，４’−ジアルキルアミノベンゾフェノン類が好ましく、性能、安全性や入手しやすさなどの観点から、２，４−ジエチルチオキサントン，２−イソプロピルチオキサントン、４，４´−ビス−（ジエチルアミノ）ベンゾフェノンが特に好ましい。
増感剤や光開始助剤を併用する場合は、インキ固形分全量に対し０．０５〜１０質量％が好ましく、０．１〜７．０質量％の範囲がより好ましい。０．０５質量％未満の場合は、十分な硬化性の向上効果が得られず、１０質量％を超える場合は、硬化塗膜の色相が許容できないくらい黄味に変色したり、増感剤が析出したり、インキの流動性が著しく低下したりする。
[Sensitizer / Photosensitizer]
In the present invention, in addition to the photopolymerization initiator represented by the general formula (1) and the general-purpose photopolymerization initiator described above, a photoinitiator such as a photosensitizer or a tertiary amine may be used in combination. ,preferable. The photosensitizer is not particularly limited, and examples thereof include thioxanthone type, benzophenone type such as 4,4'-bis (diethylamino) benzophenone, anthraquinone type, and coumarin type.
Among these, thioxanthone compounds such as 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone and the like. , Michler ketone, 4,4'-bis- (diethylamino) benzophenone, etc. 4,4'-dialkylaminobenzophenones are preferable, and 2,4-diethylthioxanthone, 2-, from the viewpoint of performance, safety and availability. Isopropylthioxanthone, 4,4'-bis- (diethylamino) benzophenone is particularly preferred.
When a sensitizer or a photoinitiator is used in combination, it is preferably 0.05 to 10% by mass, more preferably 0.1 to 7.0% by mass, based on the total amount of solid ink. If it is less than 0.05% by mass, a sufficient effect of improving the curability cannot be obtained, and if it exceeds 10% by mass, the hue of the cured coating film becomes unacceptably yellowish or a sensitizer is used. Precipitation or ink fluidity is significantly reduced.
一方、三級アミンとしては、特に限定されないが、ｐ−ジメチルアミノ安息香酸エチル、ｐ−ジメチルアミノ安息香酸イソアミル、Ｎ，Ｎ−ジメチルベンジルアミン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリン、Ｎ，Ｎ−ジメチル−ｐ−トルイジン、Ｎ，Ｎ−ジヒドロキシエチルアニリン、トリエチルアミンおよびＮ，Ｎ−ジメチルヘキシルアミン等が挙げられ、酸素による重合阻害を低減させたり、紫外線により活性化されたチオキサントン類、４，４’−ジアルキルアミノベンゾフェノン類と反応し、活性ラジカル供与体となり、インキの硬化性能を向上させる。三級アミンは本発明の活性エネルギー線硬化型インキの印刷性能を損なわない範囲で併用することが好ましく、インキ固形分全量に対し０．１〜１０質量％が好ましく、０．１〜５．０質量％の範囲で使用することがより好ましい。 On the other hand, the tertiary amine is not particularly limited, but is limited to ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-diethylaniline. , N, N-dimethyl-p-toluidine, N, N-dihydroxyethylaniline, triethylamine and N, N-dimethylhexylamine, etc., and thioxanthones activated by ultraviolet rays or reducing polymerization inhibition by oxygen. , 4,4'-Reacts with dialkylaminobenzophenones to become an active radical donor and improves the curing performance of ink. The tertiary amine is preferably used in combination as long as the printing performance of the active energy ray-curable ink of the present invention is not impaired, preferably 0.1 to 10% by mass, and 0.1 to 5.0% by mass based on the total amount of solid ink. It is more preferable to use it in the range of mass%.
また高い衛生性を求められる用途においては、１分子内に複数の光増感剤や三級アミンを多価アルコール等で分岐させた高分子量化合物も適宜使用することができる。 Further, in applications requiring high hygiene, a high molecular weight compound obtained by branching a plurality of photosensitizers or tertiary amines in one molecule with a polyhydric alcohol or the like can also be appropriately used.
（エチレン性不飽和二重結合を有するモノマー）
本発明で使用する活性エネルギー線硬化性モノマー及び又はオリゴマーは、活性エネルギー線硬化性技術分野で使用されるモノマー及び又はオリゴマーであれば特に限定なく使用することができる。特に反応基として（メタ）アクリロイル基、ビニルエーテル基等を有するものが好ましい。また反応基数や分子量にも特に限定はなく、反応基数の多いものほど反応性は高いが粘度や結晶性が高くなる傾向にあり、また分子量が高いものほど粘度が高くなる傾向にあることから、所望の物性に応じて適宜組み合わせて使用することができる。例えばＵＶ−ＬＥＤのような低エネルギー照射で好適に硬化させるという点では、より反応性の高い３官能以上の活性エネルギー線硬化性モノマーを組み合わせ、用途に応じて印刷基材への接着性、皮膜の柔軟性等の必要物性を得る為に、適宜単官能、２官能のモノマーを単独もしくは併用することが好ましい。
(Monomer with ethylenically unsaturated double bond)
The active energy ray-curable monomer and / or oligomer used in the present invention can be used without particular limitation as long as it is a monomer and / or oligomer used in the active energy ray-curable technical field. In particular, those having a (meth) acryloyl group, a vinyl ether group or the like as a reactive group are preferable. In addition, the number of reactive groups and the molecular weight are not particularly limited, and the higher the number of reactive groups, the higher the reactivity but the viscosity and crystallinity tend to be, and the higher the molecular weight, the higher the viscosity. It can be used in combination as appropriate according to the desired physical properties. For example, in terms of being suitably cured by low-energy irradiation such as UV-LED, a more reactive active energy ray-curable monomer having trifunctionality or higher is combined, and adhesiveness to a printing substrate and a film are used depending on the application. It is preferable to use monofunctional or bifunctional monomers alone or in combination as appropriate in order to obtain necessary physical properties such as flexibility.
具体的には例えば、単官能（メタ）アクリレート、多官能（メタ）アクリレート、重合性オリゴマー等の、ランプ方式で実績のあるものが、本発明で述べる紫外線発光ダイオード方式においてもそのまま使用することが可能である。 Specifically, for example, monofunctional (meth) acrylate, polyfunctional (meth) acrylate, polymerizable oligomer, etc., which have a proven track record in the lamp method, can be used as they are in the ultraviolet light emitting diode method described in the present invention. It is possible.
単官能（メタ）アクリレートとしては、例えば、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、イソアミル（メタ）アクリレート、イソデシル（メタ）アクリレート、イソステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、ノニルフェノキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、グリシジル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシー３−フェノキシプロピル（メタ）アクリレート、３−クロロ−２−ヒドロキシプロピル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ノニルフェノキシエチルテトラヒドロフルフリル（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニロキシエチル（メタ）アクリレート等が挙げられる。 Examples of the monofunctional (meth) acrylate include ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and hexadecyl. (Meta) acrylate, octadecyl (meth) acrylate, isoamyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxy Ethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-Hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl ( Examples thereof include meta) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.
２官能以上の（メタ）アクリレートとしては、例えば、１，４−ブタンジオールジ（メタ）アクリレート、３−メチル−１，５−ペンタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、２−メチル−１，８−オクタンジオールジ（メタ）アクリレート、２−ブチルー２−エチルー１，３−プロパンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート等の２価アルコールのジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートのジ（メタ）アクリレート、ネオペンチルグリコール１モルに４モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ（メタ）アクリレート、ビスフェノールＡ１モルに２モルのエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールのポリ（メタ）アクリレート等の３価以上の多価アルコールのポリ（メタ）アクリレート、グリセリン１モルに３モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たトリオールのトリ（メタ）アクリレート、トリメチロールプロパン１モルに３モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たトリオールのジ又はトリ（メタ）アクリレート、ビスフェノールＡ１モルに４モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ（メタ）アクリレート等のポリオキシアルキレンポリオールのポリ（メタ）アクリレート等が挙げられる。 Examples of the bifunctional or higher functional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. ) Acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, tricyclodecandy Methanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, etc. Di (meth) acrylate of dihydric alcohol, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, 4 mol per mol of neopentyl glycol Di (meth) acrylate of diol obtained by adding the above ethylene oxide or propylene oxide, di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, trimetyl propane Tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, etc. 3 Poly (meth) acrylate of polyhydric alcohol above valence, tri (meth) acrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of glycerin, 3 mol or more per mol of trimethylolpropane Di or tri (meth) acrylate of triol obtained by adding ethylene oxide or propylene oxide, di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A, etc. Examples thereof include poly (meth) acrylate of oxyalkylene polyol.
重合性オリゴマーとしては、アミン変性ポリエーテルアクリレート、アミン変性エポキシアクリレート、アミン変性脂肪族アクリレート、アミン変性ポリエステルアクリレート、アミノ（メタ）アクリレートなどのアミン変性アクリレート、チオール変性ポリエステルアクリレート、チオール（メタ）アクリレートなどのチオール変性アクリレート、ポリエステル（メタ）アクリレート、ポリエーテル（メタ）アクリレート、ポリオレフィン（メタ）アクリレート、ポリスチレン（メタ）アクリレート、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート等が挙げられる。 Examples of the polymerizable oligomer include amine-modified polyether acrylates, amine-modified epoxy acrylates, amine-modified aliphatic acrylates, amine-modified polyester acrylates, amine-modified acrylates such as amino (meth) acrylate, thiol-modified polyester acrylate, and thiol (meth) acrylate. Thiol-modified acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polyolefin (meth) acrylate, polystyrene (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and the like can be mentioned.
また前記活性エネルギー線硬化性モノマー及び又はオリゴマーとして、４官能以上の（メタ）アクリレートは、上質紙、コート紙、アート紙、模造紙、薄紙、厚紙等の紙への印刷用途において、硬化性や強度の向上に大きく寄与するため使用することが好ましく、インキ固形分全量に対し１５〜７０質量％の範囲で使用することが好ましい。一方、プラスチックへの印刷用途においては、硬化塗膜の架橋密度が上昇するに従って、基材と硬化塗膜との密着性が減少するため、４官能以上の（メタ）アクリレートの含有量を適宜減少させる必要がある。この場合、４官能以上の（メタ）アクリレートはインキ固形分全量に対し０〜５０質量％の範囲で使用することが好ましい。 Further, as the active energy ray-curable monomer and / or oligomer, tetrafunctional or higher (meth) acrylate has curability and curability in printing on paper such as high-quality paper, coated paper, art paper, imitation paper, thin paper, and thick paper. It is preferable to use it because it greatly contributes to the improvement of strength, and it is preferable to use it in the range of 15 to 70% by mass with respect to the total amount of solid ink. On the other hand, in applications for printing on plastics, as the crosslink density of the cured coating film increases, the adhesion between the base material and the cured coating film decreases, so the content of tetrafunctional or higher (meth) acrylate is appropriately reduced. I need to let you. In this case, the tetrafunctional or higher functional (meth) acrylate is preferably used in the range of 0 to 50% by mass with respect to the total amount of solid ink.
本発明の活性エネルギー線硬化型インキは、前記エチレン性不飽和二重結合を有するモノマー、及び前記一般式（１）で表される光重合開始剤とを必須成分とするものであるが、その他、樹脂や顔料、各種添加剤を使用することができる。 The active energy ray-curable ink of the present invention contains the monomer having an ethylenically unsaturated double bond and the photopolymerization initiator represented by the general formula (1) as essential components, but other , Resins, pigments and various additives can be used.
（樹脂）
樹脂としては、公知公用の各種バインダー樹脂を利用することができる。ここで述べるバインダー樹脂とは、適切な顔料親和性と分散性を有し、印刷インキに要求されるレオロジー特性を有する樹脂全般を示しており、例えば非反応性樹脂としては、ジアリルフタレート樹脂、エポキシ樹脂、エポキシエステル樹脂、ポリウレタン樹脂、ポリエステル樹脂、石油樹脂、ロジンエステル樹脂、ポリ（メタ）アクリル酸エステル、セルロース誘導体、塩化ビニル−酢酸ビニル共重合体、ポリアマイド樹脂、ポリビニルアセタール樹脂、ブタジエン−アクリルニトリル共重合体等を挙げることができ、また分子中に少なくとも１つ以上の重合性基を有するエポキシアクリレート化合物、ウレタンアクリレート化合物、ポリエステルアクリレート化合物等を使用することもでき、これらバインダー樹脂は、単独で使用しても、いずれか１種以上を組合せて使用してもよい。
(resin)
As the resin, various publicly known and public binder resins can be used. The binder resin described here refers to all resins having appropriate pigment affinity and dispersibility and having the rheological properties required for printing inks. For example, examples of the non-reactive resin include diallyl phthalate resin and epoxy. Resin, epoxy ester resin, polyurethane resin, polyester resin, petroleum resin, rosin ester resin, poly (meth) acrylic acid ester, cellulose derivative, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, butadiene-acrylic nitrile Examples thereof include copolymers, and epoxy acrylate compounds, urethane acrylate compounds, polyester acrylate compounds, etc. having at least one polymerizable group in the molecule can also be used, and these binder resins can be used alone. It may be used, or any one or more of them may be used in combination.
この中でも、前記一般式（１）で表される光重合開始剤とジアリルフタレート樹脂を併用すると、活性エネルギー線硬化型インキの硬化性が向上する他、インキの流動性が向上し、印刷機上で壺切れ、インキローラ間の転移不良といった印刷適性面での不良の発生を抑制することができる。 Among these, when the photopolymerization initiator represented by the general formula (1) and the diallyl phthalate resin are used in combination, the curability of the active energy ray-curable ink is improved, and the fluidity of the ink is improved, so that the ink can be used on the printing press. It is possible to suppress the occurrence of defects in printability such as jar breakage and transfer defects between ink rollers.
（顔料）
顔料としては、公知公用の着色用有機顔料を挙げることができ、例えば「有機顔料ハンドブック（著者：橋本勲、発行所：カラーオフィス、２００６年初版）」に掲載される印刷インキ用有機顔料等が挙げられ、溶性アゾ顔料、不溶性アゾ顔料、縮合アゾ顔料、金属フタロシアニン顔料、無金属フタロシアニン顔料、キナクリドン顔料、ペリレン顔料、ペリノン顔料、イソインドリノン顔料、イソインドリン顔料、ジオキサジン顔料、チオインジゴ顔料、アンスラキノン系顔料、キノフタロン顔料、金属錯体顔料、ジケトピロロピロール顔料、カーボンブラック顔料、その他多環式顔料等が使用可能である。
(Pigment)
Examples of pigments include publicly known and publicly available organic pigments for coloring, such as organic pigments for printing inks published in "Organic Pigments Handbook (Author: Isao Hashimoto, Publisher: Color Office, 2006 First Edition)". Soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindolin pigments, dioxazine pigments, thioindigo pigments, anthracinone System pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, other polycyclic pigments and the like can be used.
また、本発明の活性エネルギー線硬化型インキには、体質顔料として無機微粒子を用いてもよい。無機微粒子としては、酸化チタン、グラファイト、亜鉛華等の無機着色顔料；炭酸石灰粉、沈降性炭酸カルシウム、石膏、クレー（ＣｈｉｎａＣｌａｙ）、シリカ粉、珪藻土、タルク、カオリン、アルミナホワイト、硫酸バリウム、ステアリン酸アルミニウム、炭酸マグネシウム、バライト粉、砥の粉等の無機体質顔料； 等の無機顔料や、シリコーン、ガラスビーズなどがあげられる。これら無機微粒子は、インキ中に０．１〜６０重量％の範囲で使用することにより、着色やインキのレオロジー特性を調整したりすることが可能である。 Further, in the active energy ray-curable ink of the present invention, inorganic fine particles may be used as the extender pigment. Inorganic fine particles include inorganic coloring pigments such as titanium oxide, graphite, and zinc oxide; lime carbonate powder, precipitated calcium carbonate, gypsum, clay (ChinaClay), silica powder, diatomaceous soil, talc, kaolin, alumina white, barium sulfate, and stear. Inorganic pigments such as aluminum acid, magnesium carbonate, barite powder, abrasive powder, etc., silicone, glass beads, etc. can be mentioned. By using these inorganic fine particles in the ink in the range of 0.1 to 60% by weight, it is possible to adjust the coloring and the rheological characteristics of the ink.
（その他添加剤）
その他の添加剤としては、例えば耐摩擦性、ブロッキング防止性、スベリ性、スリキズ防止性を付与する添加剤としては、カルナバワックス、木ろう、ラノリン、モンタンワックス、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、およびシリコーン化合物などの合成ワックス等を例示することができる。
(Other additives)
Other additives include, for example, natural additives such as carnauba wax, wood wax, lanolin, montan wax, paraffin wax, and microcrystallin wax that impart abrasion resistance, blocking prevention, slipperiness, and scratch prevention. Examples thereof include waxes, Fishertropus waxes, polyethylene waxes, polypropylene waxes, polytetrafluoroethylene waxes, polyamide waxes, and synthetic waxes such as silicone compounds.
また例えば、インキの保存安定性を付与する添加剤としては、（アルキル）フェノール、ハイドロキノン、カテコール、レゾルシン、ｐ −メトキシフェノール、ｔ −ブチルカテコール、ｔ −ブチルハイドロキノン、ピロガロール、１，１−ピクリルヒドラジル、フェノチアジン、ｐ −ベンゾキノン、ニトロソベンゼン、２，５−ジ−ｔｅｒｔ−ブチル−ｐ −ベンゾキノン、ジチオベンゾイルジスルフィド、ピクリン酸、クペロン、アルミニウムＮ−ニトロソフェニルヒドロキシルアミン、トリ−ｐ −ニトロフェニルメチル、Ｎ−（３−オキシアニリノ−１，３−ジメチルブチリデン）アニリンオキシド、ジブチルクレゾール、シクロヘキサノンオキシムクレゾール、グアヤコール、ｏ−イソプロピルフェノール、ブチラルドキシム、メチルエチルケトキシム、シクロヘキサノンオキシム等の重合禁止剤が例示される。 For example, as additives that impart storage stability of ink, (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picryl Hydradil, phenothiline, p-benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyldisulfide, picric acid, cuperon, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl , N- (3-oxyanilino-1,3-dimethylbutylidene) aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, guayacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxim, cyclohexanone oxime and other polymerization inhibitors are exemplified.
その他、要求性能に応じて、紫外線吸収剤、赤外線吸収剤、抗菌剤等の添加剤を添加することができる。 In addition, additives such as an ultraviolet absorber, an infrared absorber, and an antibacterial agent can be added according to the required performance.
本発明の活性エネルギー線硬化型インキは、無溶剤で使用することもできるし、必要に応じて適当な溶媒を使用する事も可能である。溶媒としては、上記各成分と反応しないものであれば特に限定されるものではなく、単独あるいは２種以上を組み合わせて使用することができる。 The active energy ray-curable ink of the present invention can be used without a solvent, or an appropriate solvent can be used if necessary. The solvent is not particularly limited as long as it does not react with each of the above components, and can be used alone or in combination of two or more.
本発明の活性エネルギー線硬化型インキは、従来と同様の方法によって行えばよく、例えば、常温から１００℃の間で、前記顔料、樹脂、アクリル系モノマーもしくはオリゴマー、重合禁止剤、開始剤およびアミン化合物等の増感剤、その他添加剤などインキ組成物成分を、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。 The active energy ray-curable ink of the present invention may be carried out by the same method as before. For example, the pigment, resin, acrylic monomer or oligomer, polymerization inhibitor, initiator and amine can be used between room temperature and 100 ° C. Ink composition components such as sensitizers such as compounds and other additives are produced by using a kneader, a triple roll, an attritor, a sand mill, a gate mixer, or the like, a kneaded meat, a mixer, and a regulator.
（インキ硬化物の製造方法、印刷物）
本発明のインキ硬化物は、基材上に、活性エネルギー線硬化型インキを用いて印刷し、印刷されたインキを、活性エネルギー線を用いて硬化させることを特徴とする。
(Manufacturing method of cured ink, printed matter)
The ink-cured product of the present invention is characterized in that it is printed on a substrate using an active energy ray-curable ink, and the printed ink is cured using the active energy ray.
(印刷方法
本発明の活性エネルギー線硬化型インキは、前述の通り、平版印刷（湿し水を使用する平版印刷や湿し水を使用しない水無し平版印刷）の平版に付けられたインキをブランケット等の中間転写体に転写した後、被印刷体に印刷する転写（オフセット）方式を組み合わせた平版オフセット印刷方式で特に好ましく使用できる。(以後平版オフセット印刷方式で印刷する活性エネルギー線硬化型インキを、平版オフセット印刷用活性エネルギー線硬化型インキと称する場合がある。)
(Printing method) As described above, the active energy ray-curable ink of the present invention is a blanket of the ink applied to the lithographic printing (lithographic printing using dampening water or waterless lithographic printing without dampening water). It can be particularly preferably used in a lithographic offset printing method that combines a transfer (offset) method of printing on an object to be printed after being transferred to an intermediate transfer material such as (hereinafter, an active energy ray-curable ink to be printed by a lithographic offset printing method). , It may be called active energy ray-curable ink for lithographic offset printing.)
以後、本発明の活性エネルギー線硬化型インキを平版オフセット印刷用活性エネルギー線硬化型インキとして使用する場合の具体的態様について説明する。 Hereinafter, a specific embodiment when the active energy ray-curable ink of the present invention is used as the active energy ray-curable ink for lithographic offset printing will be described.
平版オフセット印刷用活性エネルギー線硬化型インキは、５〜１００Ｐａ・ｓの比較的粘度の高いインキである。平版印刷機の機構は、インキが印刷機のインキ壺から複数のローラーを経由して版面の画線部に供給され、湿し水を使用する平版印刷では非画線部に湿し水が供給されインキを反発し、紙上に画像が形成される。 The active energy ray-curable ink for lithographic offset printing is an ink having a relatively high viscosity of 5 to 100 Pa · s. In the lithographic printing machine mechanism, ink is supplied from the ink fountain of the printing machine to the image area of the plate surface via multiple rollers, and in lithographic printing using dampening water, dampening water is supplied to the non-image area. The ink is repelled and an image is formed on the paper.
湿し水を使用した平版印刷においては、インキと湿し水との乳化バランスが重要であり、インキにおいても耐乳化性の高速印刷適性が求められている。インキは乳化量が高過ぎると非画線部にもインキが着肉し易くなり汚れが発生したり、印刷濃度の低下、水棒ローラー上に乳化したインキが絡み、フライング、給紙外部のブランケットへのインキの溜まりなどの印刷不良が生じる。乳化量が少ないと絵柄の少ない印刷時には、地汚れと呼ばれる非画線部の汚れが顕著となり、安定して印刷する事が難しくなる。
この観点から、本発明の平版オフセット印刷用活性エネルギー線硬化型インキは、インキに使用する樹脂やモノマーの酸価が１.０〜１０.０の範囲内であることが好ましく、１.０〜２．０の範囲内であることがなお好ましい。インキ酸価が１０.０を上回ると、インキが乳化しやすくなり、印刷中に湿し水の供給量を上昇させると、印刷物の濃度が低下したり、版上で親水化処理された非画線部に乳化したインキが付着しやすくなるため、印刷物の非画線部に地汚れと呼ばれる汚れが生じる。一方、インキ酸価が１．０を下回ると、インキの流動性や印刷物の光沢の低下を招く。
In lithographic printing using dampening water, the emulsification balance between the ink and the fountain solution is important, and the ink is also required to have emulsification resistance and high-speed printing suitability. If the amount of emulsified ink is too high, the ink will easily adhere to the non-image area and stains will occur, the print density will decrease, the emulsified ink will get entangled on the water stick roller, and the blanket outside the flying and paper feeding Printing defects such as ink accumulation on the paper occur. If the amount of emulsification is small, when printing with a small number of patterns, stains on non-image areas called background stains become noticeable, and it becomes difficult to print stably.
From this point of view, the active energy ray-curable ink for lithographic offset printing of the present invention preferably has an acid value of the resin or monomer used in the ink in the range of 1.0 to 10.0. It is still preferably in the range of 2.0. When the ink acid value exceeds 10.0, the ink is easily emulsified, and when the amount of dampening water supplied is increased during printing, the density of the printed matter decreases or the non-image which has been hydrolyzed on the plate is treated. Since the emulsified ink easily adheres to the line portion, a stain called ground stain occurs on the non-image portion of the printed matter. On the other hand, when the ink acid value is less than 1.0, the fluidity of the ink and the gloss of the printed matter are deteriorated.
(印刷基材)
使用する基材としては特に限定は無くオフセット印刷分野で通常使用されている紙もしくはプラスチック基材、食品包装分野で使用される軟包装基材を使用すればよい。例えば紙であれば、カタログ、ポスター、チラシ、ＣＤジャケット、ダイレクトメール、パンフレット、化粧品や飲料、医薬品、おもちゃ、機器等のパッケージ等の印刷に用いられる上質紙、クラフト紙、純白ロール紙、グラシンペーパー、パーチメント紙、マニラボール、白ボール、コート紙、アート紙、模造紙、薄紙、厚紙等の紙、各種合成紙、等が挙げられる。
(Printing substrate)
The base material to be used is not particularly limited, and a paper or plastic base material usually used in the offset printing field or a flexible packaging base material used in the food packaging field may be used. For example, in the case of paper, high-quality paper, kraft paper, pure white roll paper, glassin paper used for printing catalogs, posters, leaflets, CD jackets, direct mail, brochures, packages for cosmetics and beverages, pharmaceuticals, toys, equipment, etc. , Parchment paper, Manila balls, white balls, coated paper, art paper, imitation paper, thin paper, thick paper and other papers, various synthetic papers, and the like.
またプラスチック基材や軟包装基材としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリ乳酸（ＰＬＡ）などのポリエステル樹脂フィルム；ＯＰＰ（２軸延伸ポリプロピレン）フィルム等のポリオレフィン樹脂フィルム；ポリスチレン樹脂フィルム；ナイロン６、ポリ−ｐ−キシリレンアジパミド（ＭＸＤ６ナイロン）などのポリアミド樹脂フィルム；ポリカーボネート樹脂フィルム；ポリアクリルニトリル樹脂フィルム；ポリイミド樹脂フィルム；これらの複層体（例えば、ナイロン６／ＭＸＤ６／ナイロン６、ナイロン６／エチレン−ビニルアルコール共重合体／ナイロン６）や混合体等や、特にシーラントフィルムとして使用される低密度ポリエチレン（ＬＤＰＥ）や直鎖状低密度ポリエチレン（ＬＬＤＰＥ）や高密度ポリエチレン（ＨＤＰＥ）などのポリエチレン、酸変性ポリエチレン、ポリプロピレン（ＰＰ）、酸変性ポリプロピレン、共重合ポリプロピレン、ＶＭＣＰＰ（アルミ蒸着無延伸ポリプロピレン）、ＶＭＬＤＰＥ（アルミ蒸着低密度ポリエチレン）、エチレン−ビニルアセテート共重合体、エチレン−（メタ）アクリル酸エステル共重合体、エチレン−（メタ）アクリル酸共重合体、アイオノマーなどのポリオレフィン樹脂等の樹脂フィルムがあげられる。
また前記樹脂フィルムに各種バリア機能等の機能性を付与するための、アルミニウム箔などの軟質金属箔、アルミ蒸着、シリカ蒸着、アルミナ蒸着、シリカアルミナ２元蒸着などの蒸着層、塩化ビニリデン系樹脂、変性ポリビニルアルコール、エチレンビニルアルコール共重合体、ＭＸＤナイロンなどからなる有機バリア層等が設けられた複合フィルムも挙げられる。
Examples of the plastic base material and the flexible packaging base material include polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polylactic acid (PLA); and polyolefin resins such as OPP (biaxially stretched polypropylene) film. Film; Polystyrene resin film; Polyethylene resin film such as nylon 6, poly-p-xylylene adipamide (MXD6 nylon); Polycarbonate resin film; Polyacrylic nitrile resin film; Polyethylene resin film; These multilayers (for example, Nylon 6 / MXD6 / Nylon 6, Nylon 6 / Ethylene-Vinyl Alcohol Copolymer / Nylon 6) and mixtures, especially low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) used as sealant films. ) And high-density polyethylene (HDPE), acid-modified polyethylene, polypropylene (PP), acid-modified polypropylene, copolymerized polypropylene, VMCPP (aluminum-deposited unstretched polypropylene), VMLDPE (aluminum-deposited low-density polyethylene), ethylene-vinyl Examples thereof include an acetate copolymer, an ethylene- (meth) acrylic acid ester copolymer, an ethylene- (meth) acrylic acid copolymer, and a resin film such as a polyolefin resin such as ionomer.
In addition, soft metal foils such as aluminum foils, vapor deposition layers such as aluminum vapor deposition, silica vapor deposition, alumina vapor deposition, and silica-alumina binary vapor deposition, vinylidene chloride-based resins, for imparting functionality such as various barrier functions to the resin film. Examples thereof include a composite film provided with an organic barrier layer made of modified polyvinyl alcohol, ethylene vinyl alcohol copolymer, MXD nylon and the like.
前記基材において、プラスチック基材や軟包装基材に使用される樹脂フィルムは一般的に表面エネルギーが低く、紫外線硬化型オフセットインキに対する濡れが悪いため、密着性不良を引き起こしやすい。その為、高周波電源により供給される高周波・高電圧出力を、コロナ処理装置が備える放電電極とアースロールとの間に印加することでコロナ放電を発生させ、このコロナ放電下に前記フィルムを通過させることにより、前記基材の表面エネルギーを向上させることが好ましい。 In the base material, the resin film used for the plastic base material and the flexible packaging base material generally has a low surface energy and is poorly wetted with the ultraviolet curable offset ink, so that it tends to cause poor adhesion. Therefore, a high-frequency / high-voltage output supplied by a high-frequency power supply is applied between the discharge electrode provided in the corona processing device and the earth roll to generate a corona discharge, and the film is passed under the corona discharge. Thereby, it is preferable to improve the surface energy of the base material.
また、一般的にプライマーもしくはアンカー（コート剤）と称される密着性付与剤を予め前記プラスチック基材、軟包装基材上に塗布してもよく好ましい。 Further, it is preferable to apply an adhesion imparting agent generally called a primer or an anchor (coating agent) on the plastic base material or the flexible packaging base material in advance.
これら基材に、平版オフセット印刷方式により活性エネルギー線硬化型インキを転写印刷しインキ層を設ける。
平版オフセット印刷方式による印刷は、カラープロセスインキや特色インキを、単色や多色使いで刷重ね印刷を行う方法が一般的である。
平版オフセット印刷機は多数の印刷機メーカーによって製造販売されており、一例としてハイデルベルグ社、小森コーポレーション社、リョービＭＨＩグラフィックテクノロジー社、マンローランド社、ＫＢＡ社等を挙げることができ、またシート形態の印刷用紙を用いる枚葉オフセット印刷機、リール形態の印刷用紙を用いるオフセット輪転印刷機、いずれの用紙供給方式においても本発明を好適に利用することが可能である。更に具体的には、ハイデルベルグ社製スピードマスターシリーズ、小森コーポレーション社製リスロンシリーズ、リョービＭＨＩグラフィックテクノロジー社製ＲＭＧＴシリーズ等のオフセット印刷機を挙げることができる。
An active energy ray-curable ink is transferred and printed on these base materials by a lithographic offset printing method to provide an ink layer.
Printing by the lithographic offset printing method is generally performed by overprinting color process inks and special color inks in a single color or in multiple colors.
Flat plate offset printing machines are manufactured and sold by a large number of printing machine manufacturers, and examples include Heidelberg, Komori Corporation, Ryobi MHI Graphic Technology, Munroland, KBA, etc., and sheet-type printing. The present invention can be suitably used in any of a sheet-fed offset printing machine that uses paper and an offset rotary printing machine that uses reel-type printing paper. More specifically, offset printing machines such as the Speedmaster series manufactured by Heidelberg, the Lithrone series manufactured by Komori Corporation, and the RMGT series manufactured by Ryobi MHI Graphic Technology can be mentioned.
（光源）
前記印刷されたインキを硬化させる目的で使用する活性エネルギー源としては、例えば、殺菌灯、紫外線用蛍光灯、紫外線発光ダイオード（ＵＶ−ＬＥＤ）、カーボンアーク、キセノンランプ、複写用高圧水銀灯、中圧又は高圧水銀灯、超高圧水銀灯、無電極ランプ、メタルハライドランプ、自然光等を光源とする紫外線が挙げられる。前記紫外線発光ダイオード（ＵＶ−ＬＥＤ）としては、そのピーク波長が３５０〜４２０ｎｍ程度であるものが好ましく３５０〜４００ｎｍの範囲であるものがより好ましく、積算光量が５ｍＪ／ｃｍ２〜２００ｍＪ／ｃｍ２程度であり、より好ましくは、１０〜１００ｍＪ／ｃｍであることが好ましい。
(light source)
Examples of the active energy source used for curing the printed ink include a sterilizing lamp, an ultraviolet fluorescent lamp, an ultraviolet light emitting diode (UV-LED), a carbon arc, a xenon lamp, a high-pressure mercury lamp for copying, and a medium pressure. Alternatively, ultraviolet rays using high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc. as light sources can be mentioned. The ultraviolet light emitting diode (UV-LED) preferably has a peak wavelength of about 350 to 420 nm, more preferably one having a peak wavelength in the range of 350 to 400 nm, and has an integrated light intensity of about 5 mJ / cm 2 to 200 mJ / cm 2. It is more preferably 10 to 100 mJ / cm.
また紫外線発光ダイオードの照射強度（ｍＷ／ｃｍ２）に関しては、印刷方向に並べる紫外線発光ダイオード光源の個数、光源から組成物までの照射距離等の諸条件によっても適切な照射強度範囲が変動することから特に規定はしないが、本発明で述べる印刷方式における印刷基材の移動速度は６０〜４００ｍ／ｍｉｎ．程度であるから、該印刷速度で移動する印刷基材上のＵＶ硬化性組成物に対して、積算光量値が先に述べた程度となる照射強度であることが好ましい。 Regarding the irradiation intensity (mW / cm 2 ) of the ultraviolet light emitting diode, the appropriate irradiation intensity range varies depending on various conditions such as the number of ultraviolet light emitting diode light sources arranged in the printing direction and the irradiation distance from the light source to the composition. Although not particularly specified, the moving speed of the printing substrate in the printing method described in the present invention is 60 to 400 m / min. Therefore, it is preferable that the irradiation intensity is such that the integrated light amount value is about the above-mentioned degree with respect to the UV curable composition on the printing substrate that moves at the printing speed.
本発明の活性エネルギー線硬化型印刷インキは、通常湿し水を使用する平版オフセット印刷に適用されるが、湿し水を使用しない水無し印刷にも好適に用いることができる。また本発明の活性エネルギー線硬化型印刷インキは、フォーム用印刷物、各種書籍用印刷物、カルトン紙等の各種包装用印刷物、各種プラスチック印刷物、シール／ラベル用印刷物、美術印刷物、金属印刷物（美術印刷物、飲料缶印刷物、缶詰等の食品印刷物）などの印刷物に適用される。さらにオーバーコートワニスとして使用されることもある。 The active energy ray-curable printing ink of the present invention is usually applied to lithographic offset printing using dampening water, but can also be suitably used for waterless printing using dampening water. The active energy ray-curable printing ink of the present invention includes foam printed matter, various book printed matter, various packaging printed matter such as carton paper, various plastic printed matter, seal / label printed matter, art printed matter, metal printed matter (art printed matter, art print, etc.). It is applied to printed matter such as beverage can printed matter, canned food printed matter). It may also be used as an overcoat varnish.
次に実施例により更に具体的に説明するが、本発明はこれらに限定されるものでは無い。 Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
〔活性エネルギー線硬化型インキの製造方法〕
表１、表２の組成に従って、実施例１〜７及び比較例１〜７の活性エネルギー線硬化型インキを３本ロールミルにて練肉することによって、各種の活性エネルギー線硬化型インキを得た。尚、表中の空欄は、未配合を意味している。
[Manufacturing method of active energy ray-curable ink]
Various active energy ray-curable inks were obtained by kneading the active energy ray-curable inks of Examples 1 to 7 and Comparative Examples 1 to 7 with a three-roll mill according to the compositions of Tables 1 and 2. .. The blanks in the table mean that the mixture has not been mixed.
〔展色物の製造方法〕
この様にして得られた活性エネルギー線硬化型インキを、簡易展色機（ＲＩテスター、豊栄精工社製）を用い、インキ０．１０ｍｌを使用して、ＲＩテスターのゴムロール及び金属ロール上に均一に引き伸ばし、ＰＥＴ原反（ＤＩＣ社製、ダイタックＵＶＰＥＴ透明２５ＦＬ）上、約２２０ｃｍ２の面積範囲にわたって印字濃度１．８（Ｘ−Ｒｉｔｅ社製ＳｐｅｃｔｒｏＥｙｅ濃度計で計測）で均一に塗布されるように展色し、展色物を作製した。なおＲＩテスターとは、紙やフィルムにインキを展色する試験機であり、インキの転移量や印圧を調整することが可能である。
[Manufacturing method of colored products]
The active energy ray-curable ink thus obtained is uniformly applied onto a rubber roll and a metal roll of the RI tester using a simple color developer (RI tester, manufactured by Hoei Seiko Co., Ltd.) and 0.10 ml of ink. On the PET original fabric (DIC UVPET transparent 25FL), the print density is 1.8 (measured with a X-Rite SpectroEye densitometer) over an area of about 220 cm 2 so that it is evenly applied. Colors were spread and colored products were produced. The RI tester is a testing machine that spreads ink on paper or film, and can adjust the amount of ink transfer and printing pressure.
（紫外線発光ダイオード光源による乾燥方法）
水冷式ＵＶ−ＬＥＤ（中心発光波長３８５ｎｍ±５ｎｍＵＶ−ＬＥＤの出力１００％）およびベルトコンベアを搭載したＵＶ照射装置（アイグラフィックス社製）を使用し、展色物をコンベア上に載せ、コンベアスピード１００ｍ／ｍｉｎの速度で、ＬＥＤ直下（照射距離９ｃｍ）を通過させた。前記の方法で得られた光硬化性インキ塗布後の展色物に紫外線（ＵＶ）照射を行いインキ皮膜を硬化乾燥させた。
(Drying method using an ultraviolet light emitting diode light source)
Using a water-cooled UV-LED (center emission wavelength 385 nm ± 5 nm UV-LED output 100%) and a UV irradiation device (manufactured by Eye Graphics) equipped with a belt conveyor, the colored object is placed on the conveyor and the conveyor speed. It passed directly under the LED (irradiation distance 9 cm) at a speed of 100 m / min. After applying the photocurable ink obtained by the above method, the color-developed material was irradiated with ultraviolet rays (UV) to cure and dry the ink film.
〔活性エネルギー線硬化型インキの硬化性評価方法〕
硬化直後に硬化インキ層を爪で擦ることにより硬化皮膜の硬化性を評価した。
評価基準は以下とした。
◎：強い力で擦っても傷が付かず、ＵＶ硬化性は非常に良好である。
〇：強い力で擦ると僅かに傷が付く。
△：強い力で擦ると明確に傷が付く
×：弱い力で擦っても明確に傷が付き、ＵＶ硬化性は不良である。
[Method for evaluating curability of active energy ray-curable ink]
Immediately after curing, the curability of the cured film was evaluated by rubbing the cured ink layer with a nail.
The evaluation criteria were as follows.
⊚: The UV curability is very good without being scratched even when rubbed with a strong force.
〇: Slightly scratched when rubbed with strong force.
Δ: Clearly scratched when rubbed with a strong force ×: Clearly scratched even when rubbed with a weak force, and UV curability is poor.
〔硬化塗膜の臭気評価方法〕
前記硬化方法で硬化させた硬化物を縦５ｃｍ横２．５ｃｍに切り取り、この切片を１０枚用意した。この切片１０枚を素早く外径４０ｍｍ、高さ７５ｍｍ、口内径２０．１ｍｍ、容量５０ｍｌのコレクションバイアルに入れ、ふたを閉めて６０℃の恒温槽に１時間保管し、コレクションバイアル中に臭気を充満させた。つぎに、このコレクションバイアルを室温になるまで放置し、臭気の強さを評価するモニター１０名により、各サンプルの臭気の強さを１０段階で評価した。
１０名の臭気評価結果を平均し、そのサンプルの臭気の強さとした。なお、数値が高い方が、低臭であることを意味している。
○： １０〜７
△： ６〜３
×： ２〜０
[Odor evaluation method for cured coating film]
The cured product cured by the above curing method was cut into 5 cm in length and 2.5 cm in width, and 10 sections thereof were prepared. The 10 sections were quickly placed in a collection vial having an outer diameter of 40 mm, a height of 75 mm, an inner diameter of 20.1 mm, and a capacity of 50 ml, closed and stored in a constant temperature bath at 60 ° C. for 1 hour, and the collection vial was filled with odor. I let you. Next, the collection vial was allowed to stand until it reached room temperature, and the odor intensity of each sample was evaluated on a scale of 10 by 10 monitors for evaluating the odor intensity.
The odor evaluation results of 10 people were averaged and used as the odor intensity of the sample. The higher the value, the lower the odor.
◯: 10 to 7
Δ: 6 to 3
×: 2 to 0
〔活性エネルギー線硬化型インキの評価方法３：流動性〕
インキ流動性はスプレッドメーター法（平行板粘度計）によりＪＩＳ Ｋ５１０１，５７０１に則った方法で測定を実施し、水平に置いた２枚の平行板の間に挟まれたインキが、荷重板の自重（１１５グラム）によって、同心円状に広がる特性を経時的に観察し、６０秒後のインキの広がり直径をダイアメーター値（ＤＭ［ｍｍ］）とし、インキ印刷適性が良好となる次の３段階で評価した。本評価項目においてＤＭが２７ｍｍ未満となる組成では、印刷機上で壺切れ、インキローラ間の転移不良といった印刷適性面での不良が発現し易くなる。
○：ＤＭ３０ｍｍ以上
△：ＤＭ２７ｍｍ以上〜３０ｍｍ未満
×：ＤＭ２７ｍｍ未満
[Evaluation method for active energy ray-curable ink 3: Fluidity]
The ink fluidity was measured by the spread meter method (parallel plate viscometer) according to JIS K5101,5701. The ink sandwiched between two horizontally placed parallel plates is the weight of the load plate (115). Gram) was used to observe the characteristics of concentric spread over time, and the spread diameter of the ink after 60 seconds was used as a viscometer value (DM [mm]), and the ink printability was evaluated in the following three stages. .. When the DM is less than 27 mm in this evaluation item, defects in printability such as jar breakage on the printing machine and transfer defects between ink rollers are likely to occur.
◯: DM 30 mm or more Δ: DM 27 mm or more to less than 30 mm ×: DM 27 mm or more
[活性エネルギー線硬化型インキの平版オフセット印刷方法]
製造された実施例１〜７、比較例１〜７の活性エネルギー線硬化型インキについて、オフセット印刷適性を評価した。紫外線照射装置としてアイグラフィックス社製水冷メタルハライドランプ（出力１６０Ｗ／ｃｍ、３灯使用）を搭載したマンローランド製オフセット印刷機（ローランドＲ７００印刷機、幅４０インチ機）を用いて、毎時９０００枚の印刷速度にてオフセット印刷を実施した。印刷用紙には王子製紙社製ＯＫトップコートプラス（５７．５ｋｇ、Ａ判）を使用した。版面に供給される湿し水は、水道水９８重量％とエッチ液（ＦＳＴ−７００、ＤＩＣグラフィックス社製）２重量％を混合した水溶液を用いた。
[Planographic offset printing method for active energy ray-curable ink]
The offset printing suitability of the produced active energy ray-curable inks of Examples 1 to 7 and Comparative Examples 1 to 7 was evaluated. Using a Munroland offset printing machine (Roland R700 printing machine, 40-inch wide machine) equipped with a water-cooled metal halide lamp (output 160 W / cm, using 3 lights) manufactured by Eye Graphics Co., Ltd. as an ultraviolet irradiation device, 9000 sheets per hour Offset printing was performed at the printing speed. As the printing paper, OK Top Coat Plus (57.5 kg, A size) manufactured by Oji Paper Co., Ltd. was used. As the dampening water supplied to the plate surface, an aqueous solution obtained by mixing 98% by weight of tap water and 2% by weight of an etchant (FST-700, manufactured by DIC Graphics) was used.
〔活性エネルギー線硬化型インキ組成物の評価方法３：オフセット印刷適性〕
オフセットインキ印刷適性の評価方法としては、まず印刷機の水供給ダイヤルを４０（標準水量）にセットし、印刷物濃度が標準プロセス藍濃度１．６（Ｘ−Ｒｉｔｅ社製ＳｐｅｃｔｒｏＥｙｅ濃度計で計測）となるようインキ供給キーを操作し、濃度が安定した時点でインキ供給キーを固定した。その後インキ供給キーを固定したままの条件で、水供給ダイヤルを４０から５５に変更し水供給量を増やした条件で３００枚印刷し、３００枚後の印刷物の藍濃度を測定した。水供給量を増やした状態においても印刷物の濃度低下が少ないほど、乳化適性に優れ、印刷適性に優れたインキと評価できる。下記の基準に従って活性エネルギー線硬化型インキの印刷適性を評価した。
○：印刷物の藍濃度が１．５以上であり、オフセット印刷適性は良好である。
△：印刷物の藍濃度が１．４以上〜１．５未満であり、オフセット印刷適性は中位である。
×：印刷物の藍濃度が１．４未満であり、オフセット印刷適性は不良である。
[Evaluation method of active energy ray-curable ink composition 3: Offset printing suitability]
As an evaluation method of offset ink printability, first set the water supply dial of the printing machine to 40 (standard water volume), and the printed matter density is standard process indigo density 1.6 (measured with a SpectroEye densitometer manufactured by X-Rite). The ink supply key was operated so that the ink supply key was fixed when the density became stable. After that, under the condition that the ink supply key was fixed, the water supply dial was changed from 40 to 55, and 300 sheets were printed under the condition that the water supply amount was increased, and the indigo density of the printed matter after 300 sheets was measured. Even when the amount of water supplied is increased, the smaller the decrease in the density of the printed matter, the better the emulsification suitability and the better the printability. The printability of the active energy ray-curable ink was evaluated according to the following criteria.
◯: The indigo density of the printed matter is 1.5 or more, and the offset printing suitability is good.
Δ: The indigo density of the printed matter is 1.4 or more and less than 1.5, and the offset printing suitability is medium.
X: The indigo density of the printed matter is less than 1.4, and the offset printing suitability is poor.
結果を表に示す。 The results are shown in the table.
使用した原料の詳細は下記の通りである。
「ラーベン１０６０Ｕｌｔｒａ」：ＢＩＲＬＡ ＣＡＲＢＯＮ製 カーボンブラック
「ＦＡＳＴＯＧＥＮ ＢＬＵＥ ＴＧＲ−１」：ＤＩＣ製 Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３
「ホスタパームバイオレット ＲＬ ０２」：クラリアント製 Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ ２３
「ハイフィラー＃５０００ＰＪ」：松村産業製 タルク
「Ｓ−３８１−Ｎ１」：シャムロック製 オレフィン系微粉末ワックス
「Ｍｉｒａｍｅｒ ＰＥ−２１０」：Ｍｉｗｏｎ製 ビスフェノールＡエポキシアクリレートオリゴマー
「ジアリルフタレート樹脂ワニス」：大阪ソーダ製ダイソーダップ ３５質量％をＳＲ３５５ＮＳ ６５質量％に溶解させた混合物
「ステアラーＴＢＨ」：精工化学製 ｔｅｒｔ−ブチルハイドロキノン
「アロニックスＭ−４００」：東亞合成製 ジペンタエリスリトールペンタ及びヘキサアクリレート
「ＳＲ３５５ＮＳ」：アルケマ製 ジトリメチロールプロパンテトラアクリレート
「光重合開始剤Ｂ」：（１）に記載の光重合開始剤において、下記の構造式で表される化合物 １−（[１，１’−ビフェニル]−４−イル）−２−メチル−２−モルフォリノプロパン−１−オン
Details of the raw materials used are as follows.
"Raven 1060 Ultra": BIRLA CARBON carbon black "FASTOGEN BLUE TGR-1": DIC Pigment Blue 15: 3
"Hosta Palm Violet RL 02": Clariant Pigment Violet 23
"High Filler # 5000PJ": Matsumura Sangyo Talk "S-381-N1": Shamrock Olefin Fine Powder Wax "Miramer PE-210": Miwon Bisphenol A Epoxy Acrylate Oligomer "Diarylphthalate Resin Wanith": Osaka Soda Daisodap 35% by mass dissolved in SR355NS 65% by mass "Stairer TBH": Seiko Kagaku tert-butyl hydroquinone "Aronix M-400": Toa Synthetic dipentaerythritol penta and hexaacrylate "SR355NS": Alchema Ditrimethylol Propanetetraacrylate "Photopolymerization Initiator B": In the photopolymerization initiator according to (1), the compound 1-([1,1'-biphenyl] -4-yl) represented by the following structural formula ) -2-Methyl-2-morpholinopropan-1-one
以下の光重合開始剤は全てＩＧＭ ＲＥＳＩＮＳ 製である。
Ｏｍｎｉｒａｄ ９０７ ２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン
Ｏｍｎｉｒａｄ ＴＰＯ ２，４，６−トリメチルベンゾイル−ジフェニルフォスフィンオキシド
Ｏｍｎｉｒａｄ ＤＥＴＸ ２，４−ジエチルチオキサントン
Ｏｍｎｉｒａｄ ＥＭＫ ４，４’−ビス（ジエチルアミノ）ベンゾフェノン
Ｏｍｎｉｒａｄ ＥＤＢ ４−（ジメチルアミノ）安息香酸エチル
The following photopolymerization initiators are all manufactured by IGM RESINS.
Omnirad 907 2-Methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one Omnirad TPO 2,4,6-trimethylbenzoyl-diphenylphosphine oxide Omnirad DETX 2,4-diethylthioxanthone Omnirad EMK 4,4'-bis (diethylamino) benzophenone Omnirad EDB 4- (dimethylamino) ethyl benzoate
この結果、実施例１〜７の活性エネルギー線硬化型インキは硬化性に優れることが明らかである。 As a result, it is clear that the active energy ray-curable inks of Examples 1 to 7 are excellent in curability.
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| JP2018002958A (en) * | 2016-07-07 | 2018-01-11 | Dic株式会社 | Active energy ray-curable printing ink and printed matter of the same |
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- 2019-11-21 WO PCT/JP2019/045568 patent/WO2020116180A1/en active Application Filing
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| WO2020116180A1 (en) | 2020-06-11 |
| JP7066833B2 (en) | 2022-05-13 |
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