JP4743848B2 - Water-based radical UV ink and ink jet recording method using the same - Google Patents
Water-based radical UV ink and ink jet recording method using the same Download PDFInfo
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- JP4743848B2 JP4743848B2 JP2005186005A JP2005186005A JP4743848B2 JP 4743848 B2 JP4743848 B2 JP 4743848B2 JP 2005186005 A JP2005186005 A JP 2005186005A JP 2005186005 A JP2005186005 A JP 2005186005A JP 4743848 B2 JP4743848 B2 JP 4743848B2
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- 238000007865 diluting Methods 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- VPWFPZBFBFHIIL-UHFFFAOYSA-L disodium 4-[(4-methyl-2-sulfophenyl)diazenyl]-3-oxidonaphthalene-2-carboxylate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 VPWFPZBFBFHIIL-UHFFFAOYSA-L 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002237 fumaric acid derivatives Chemical class 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 239000007787 solid 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
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、インクジェットインク及びそれを用いるインクジェット記録方法と記録物に関する。 The present invention relates to an inkjet ink, an inkjet recording method using the inkjet ink, and a recorded matter.
インクジェットプリントは情報のデジタル化が進む中で、オフィス、家庭用の印刷機として広く普及しているが、近年では更に応用展開も数多く進められている。そしてインクジェットプリントの用途が広がっていくのに伴い、インクに用いる着色材も従来の酸性染料あるいは直接染料などの水溶性染料から、顔料等の水不溶性色材など用途に応じて様々な色材が使用されるようになってきた。特に、広告や看板用途には、一般的に屋外用途で使われるものが多く、耐光性を必要とし、色材として顔料が使われる例が多い。顔料は、構造的に染料に比べ耐光性、耐水性等が特に優れており、広告、看板用途以外にもさまざまな分野で使用されている。顔料を使用したインクを作製する場合、水や各種溶媒等に顔料分子を分散してインクを作製する。現在までに顔料分散したインクは、水系インク、溶剤インク、ＵＶインク等が提案されている。 Inkjet printing is widely used as a printer for office and home use as information is digitized, but in recent years, many applications have been developed. As the use of inkjet printing expands, the colorants used in inks vary from conventional water-soluble dyes such as acid dyes or direct dyes to various color materials such as pigments and other water-insoluble colorants. Has come to be used. In particular, advertisements and signboards are often used for outdoor purposes, require light resistance, and often use pigments as coloring materials. Pigments are structurally superior in light resistance, water resistance and the like compared to dyes, and are used in various fields other than advertising and billboard applications. When an ink using a pigment is prepared, the ink is prepared by dispersing pigment molecules in water or various solvents. To date, water-based inks, solvent inks, UV inks and the like have been proposed as pigment-dispersed inks.
水系インクの場合は、インクの長所として、後述する溶剤インクと異なり、揮発性の溶剤を使用しておらず、臭いが問題点となることはない。普通紙のような吸収性基材にインクジェットで印刷すると、インクが基材に吸収される。しかし、インク吸収性の悪い基材においては、印刷の後にインクが基材上にたまり、インクの混色の問題がある。たとえば、基材としてポリエステルフィルムに印刷した場合、印刷後、即座に水分を乾燥させなければ、混色の問題がある。 In the case of water-based inks, as a merit of ink, unlike a solvent ink described later, a volatile solvent is not used, and odor does not cause a problem. When ink jet printing is performed on an absorbent substrate such as plain paper, the ink is absorbed by the substrate. However, in a base material with poor ink absorbability, ink accumulates on the base material after printing, and there is a problem of ink color mixing. For example, when printing on a polyester film as a substrate, there is a problem of color mixing unless moisture is dried immediately after printing.
ポリエステルフィルムやポリ塩化ビニル等の非吸水性の基材に適用されるインクとしては、溶剤インクとＵＶインクがある。溶剤インクの場合、普通紙にインクジェットで印刷すると、紙にインクが吸収され、インクの混色の問題はない。しかし、インクによってはにじみやインクの浸透圧が高すぎることに起因した発色性低下の問題がある。また、非吸収性の基材に印刷した場合、インク含有中の溶剤が基材を犯すことで、基材への浸透をはかり、インクが基材に固着する。しかし、溶剤インクの場合、希釈溶剤として、シクロヘキサノン等の揮発性溶剤を使うため、作業環境上問題のあることが知られている。 Examples of inks applied to non-water-absorbing substrates such as polyester films and polyvinyl chloride include solvent inks and UV inks. In the case of solvent ink, when ink is printed on plain paper by ink jet, the ink is absorbed into the paper and there is no problem of ink color mixing. However, depending on the ink, there is a problem that the color developability is deteriorated due to the bleeding or the osmotic pressure of the ink being too high. In addition, when printing is performed on a non-absorbing base material, the solvent containing the ink violates the base material, thereby penetrating the base material and fixing the ink to the base material. However, in the case of a solvent ink, a volatile solvent such as cyclohexanone is used as a diluting solvent.
ＵＶインクには、３つのタイプが知られている。それらは非水系エチレン性不飽和基含有化合物を主に使用する非水系ラジカルＵＶインク、オキセタン樹脂やエポキシ樹脂のように酸素含有環状化合物やビニルエーテル化合物を主に使用するカチオンＵＶインク、および、水系エチレン性不飽和基含有化合物を主に使用する水系ラジカルＵＶインクである。非水系ラジカルＵＶインクは、基材に印刷した場合、インク含有中の非水系エチレン性不飽和基含有化合物の低分子モノマーが基材を犯すことで、基材への浸透をはかり、インクが基材に固着する。そして、その基材にＵＶ照射を行うことで、インクが硬化し、基材に密着し、耐久性の良い、膜が形成される。しかし、非水系ラジカルＵＶインクの問題点としては、含有する低分子モノマーは、皮膚刺激性が強くかつ臭気が高いことが多い。また、それらの低分子モノマーを素早く硬化させるために、光重合開始剤の含有量が多く、光の漏れまたは密閉系で、ラジカルが発生し、部分的に硬化してしまうことがある。 Three types of UV ink are known. They are non-aqueous radical UV inks mainly using non-aqueous ethylenically unsaturated group-containing compounds, cationic UV inks mainly using oxygen-containing cyclic compounds and vinyl ether compounds such as oxetane resins and epoxy resins, and water-based ethylene. This is a water-based radical UV ink mainly using a compound containing a polymerizable unsaturated group. When non-aqueous radical UV inks are printed on a base material, the low molecular weight monomer of the non-aqueous ethylenically unsaturated group-containing compound that contains the ink violates the base material, thereby penetrating the base material. Stick to the material. Then, by irradiating the base material with UV, the ink is cured and adhered to the base material, and a film having good durability is formed. However, as a problem of the non-aqueous radical UV ink, the low molecular monomer contained often has strong skin irritation and high odor. In addition, in order to quickly cure these low molecular weight monomers, the content of the photopolymerization initiator is large, and radicals may be generated due to light leakage or a closed system, which may be partially cured.
カチオンＵＶインクは、非吸収性の基材にインクジェットで印刷した場合、インクが基材に固着する。そして、この基材にＵＶ照射を行うことで、インクが硬化し、基材に密着し、耐久性の良い、膜が形成される。その上、このインクでは、非水系ラジカルインクと異なり、酸素障害がない。しかし、使用できる化合物の種類が限られていること。また、湿気等の水分の存在下では、硬化が進まないことなどの問題がある。 When the cationic UV ink is printed on a non-absorbing substrate by inkjet, the ink adheres to the substrate. Then, by irradiating the base material with UV, the ink is cured and adhered to the base material, and a highly durable film is formed. In addition, this ink has no oxygen damage unlike non-aqueous radical inks. However, the types of compounds that can be used are limited. In addition, there is a problem that curing does not proceed in the presence of moisture such as moisture.
従来の水系ラジカルＵＶインクでは、多量の水を含んでいるので、非水系ラジカルインクと違い臭気の問題が少ない。使用される水溶性モノマーは、一般的に、ＥＯ（エチレンオキサイド）変性やＰＯ（プロピレンオキサイド）変性モノマーが使用される。これらのモノマーは、ＥＯ変性やＰＯ変性鎖が長くなると（分子量が大きくなると）粘度が上昇し、粘性のある液体または固体となる。それらを多量に含有したインクを硬化させた場合、表面にべたつきが起る。その現象を避けるために、低分子量のＥＯ変性モノマーを使用した場合、モノマーが水溶性ではなく親水性または非水性となり、インク中に十分含有できない。仮に、インクに低分子ＥＯ変性モノマーを多量に入れた場合、インクの分散系を壊し易い等の問題がある。つまり、従来の水系ラジカルＵＶインクは、これらの水溶性モノマーを多量に含むことができなかった。結果として、モノマー濃度が低くなり、含有する水分が増え、印刷後の水分を蒸発させる時間がかかったり、蒸発させた後も膜厚が薄く、酸素阻害や膜の硬度が低い等の問題があった。 Conventional water-based radical UV inks contain a large amount of water, so that there are few odor problems unlike non-aqueous radical inks. As the water-soluble monomer used, EO (ethylene oxide) -modified or PO (propylene oxide) -modified monomer is generally used. These monomers increase in viscosity when an EO-modified or PO-modified chain becomes long (when the molecular weight increases), and become a viscous liquid or solid. When ink containing a large amount of them is cured, the surface becomes sticky. In order to avoid this phenomenon, when a low molecular weight EO-modified monomer is used, the monomer is not water-soluble but hydrophilic or non-aqueous and cannot be contained sufficiently in the ink. If a large amount of low molecular weight EO-modified monomer is added to the ink, there is a problem that the ink dispersion system is easily broken. That is, the conventional water-based radical UV ink cannot contain a large amount of these water-soluble monomers. As a result, the monomer concentration is low, the water content is increased, it takes time to evaporate the water after printing, the film thickness is thin even after evaporation, and there are problems such as oxygen inhibition and low film hardness. It was.
上記３つのタイプのＵＶインクは、以下記述するように公知の文献により開示されている。すなわち非特許文献１には非水系エチレン性不飽和基含有化合物を主に使用する非水系ラジカルＵＶインクが、特許文献１にはオキセタン樹脂やエポキシ樹脂のように酸素含有環状化合物やビニルエーテル化合物を主に使用するカチオンＵＶインクが、また特許文献２には水系エチレン性不飽和基含有化合物を主に使用する水系ラジカルＵＶインクがそれぞれ開示されており、本発明は、これらのうち水系エチレン性不飽和基含有化合物を主に使用する水系ラジカルＵＶインクに関する。また非水系ラジカルＵＶインクに、本発明に用いるアクリロイルモルホリンを使用した例は、非特許文献１に記載がある。 The above three types of UV inks are disclosed in known literature as described below. In other words, Non-Patent Document 1 is a non-aqueous radical UV ink mainly using a non-aqueous ethylenically unsaturated group-containing compound, and Patent Document 1 is mainly an oxygen-containing cyclic compound or vinyl ether compound such as an oxetane resin or an epoxy resin. Patent Document 2 discloses a water-based radical UV ink mainly using a water-based ethylenically unsaturated group-containing compound, and Patent Document 2 discloses a water-based ethylenically unsaturated ink. The present invention relates to an aqueous radical UV ink mainly using a group-containing compound. Non-patent document 1 describes an example in which acryloylmorpholine used in the present invention is used for a non-aqueous radical UV ink.
臭気が少なく、分散安定性に優れ、印刷性も良く、基材への浸透性に優れ、硬化スピードが速いインク、及び前記インクが一度硬化した後は、表面のべたつきも少ない記録物、ならびにそのインクジェット記録方法を提供すること。 Ink with low odor, excellent dispersion stability, good printability, excellent penetrability into the substrate, fast curing speed, and recorded matter with less stickiness on the surface after the ink is cured once, and its To provide an ink jet recording method.
本発明者等は前記課題を解決すべく鋭意研究の結果、インク組成において、水、顔料と水系ラジカル組成物として開始剤と平均分子量５００以上の直鎖ポリエチレングリコールジアクリレートとＮ−アルコキシアルキル（メタ）アクリルアミド及び、またはアクリロイルモルホリンを含有することで、分散系が壊れず、低粘度で硬化後のべたつきのない塗膜を形成するインクが得られることを見出した。 As a result of diligent research to solve the above problems, the present inventors have determined that in the ink composition, water, a pigment, an aqueous radical composition, an initiator, a linear polyethylene glycol diacrylate having an average molecular weight of 500 or more, and an N-alkoxyalkyl (meta It was found that by containing acrylamide and / or acryloylmorpholine, the dispersion system is not broken, and an ink that forms a low-viscosity and non-sticky coating film after curing can be obtained.
即ち、本発明は
（１）少なくとも顔料（Ａ）、ポリエチレングリコールジアクリレート（Ｂ）、水溶性（メタ）アクリルアミド（Ｃ）、光重合開始剤（Ｄ）、水（Ｅ）を含有することを特徴とするインクジェット記録用インク、
（２）ポリエチレングリコールジアクリレート（Ｂ）が、平均分子量５００以上の直鎖ポリエチレングリコールジアクリレートである（１）に記載のインクジェット記録用インク、
（３）水溶性（メタ）アクリルアミド（Ｃ）がＮ−アルコキシアルキル（メタ）アクリルアミド（アルキルおよびアルコキシの炭素数がそれぞれ１〜４）及び、またはアクリロイルモルホリンである（１）〜（２）に記載のインクジェット記録用インク、
（４）顔料（Ａ）が０．３〜１０重量％、ポリエチレングリコールジアクリレート（Ｂ）が５〜２５重量％、水溶性アクリルアミド（Ｃ）が２５〜５０重量％、光重合開始剤（Ｄ）が２．５〜１０重量％、水（Ｅ）が１０〜６５％であり、残部が添加剤である（１）〜（３）に記載のインクジェット記録用インク、
（５）インク中のポリエチレングリコールジアクリレート（Ｂ）および水溶性アクリルアミド（Ｃ）の含有量が、合計で４０重量％以上である（１）〜（４）記載のインクジェット記録用インク
（６）２５℃における表面張力が２０〜４０ｍＮ／ｍ、２５℃における粘度が３〜３０ｍＰａ・ｓの範囲であることを特徴とする（１）〜（５）に記載のインク
（７）インクを基材上に０．５〜１００ミクロンの厚さで塗布し、必要に応じ熱などにより塗布したインク中の水分を蒸発させた後、エネルギー線を照射することにより塗布したインクを硬化させることを特徴とする、（１）〜（６）に記載のインクを用いたインクジェット記録方法およびその方法により記録された記録物
に関する。
That is, the present invention is characterized by (1) containing at least a pigment (A), a polyethylene glycol diacrylate (B), a water-soluble (meth) acrylamide (C), a photopolymerization initiator (D), and water (E). An inkjet recording ink,
(2) The inkjet recording ink according to (1), wherein the polyethylene glycol diacrylate (B) is a linear polyethylene glycol diacrylate having an average molecular weight of 500 or more,
(3) The water-soluble (meth) acrylamide (C) is N-alkoxyalkyl (meth) acrylamide (wherein alkyl and alkoxy have 1 to 4 carbon atoms, respectively) and / or acryloylmorpholine (1) to (2) Ink for inkjet recording,
(4) Pigment (A) is 0.3 to 10% by weight, polyethylene glycol diacrylate (B) is 5 to 25% by weight, water-soluble acrylamide (C) is 25 to 50% by weight, and photopolymerization initiator (D). Ink for ink-jet recording according to (1) to (3), wherein 2.5 to 10% by weight, water (E) is 10 to 65%, and the remainder is an additive,
(5) Ink for ink jet recording according to (1) to (4), wherein the total content of polyethylene glycol diacrylate (B) and water-soluble acrylamide (C) in the ink is 40% by weight or more (6) 25 The surface tension at 20 ° C. is 20 to 40 mN / m, and the viscosity at 25 ° C. is in the range of 3 to 30 mPa · s. It is characterized in that it is applied at a thickness of 0.5 to 100 microns, and if necessary, the water in the applied ink is evaporated by heat or the like, and then the applied ink is cured by irradiating energy rays. The present invention relates to an ink jet recording method using the ink described in (1) to (6) and a recorded matter recorded by the method.
本発明の水系ラジカルＵＶインクは、臭気が少なく、分散安定性に優れ、インクジェットの印刷性も良く、基材への浸透性に優れ、硬化スピードが速く、一度硬化した後の記録物は、表面のべたつきも少ない。本発明により、非常に保存安定性且つ印刷安定性にも優れたインク及びインクジェット記録方法が提供できる。さらに皮膚刺激性なども低く抑えられるものと考えられる。 The water-based radical UV ink of the present invention has little odor, excellent dispersion stability, good ink-jet printability, excellent penetrability into the substrate, fast curing speed, There is little stickiness. According to the present invention, it is possible to provide an ink and an ink jet recording method which are extremely excellent in storage stability and printing stability. Furthermore, it is considered that skin irritation can be kept low.
本発明の水系ラジカルＵＶインクは、水中で顔料を分散化した後、これに水系ラジカル組成物を混合させて得られる。また、この水系ラジカルＵＶインクに湿潤剤、表面調製剤、消泡剤、防腐剤、ｐＨ調整剤などを添加することができる。 The aqueous radical UV ink of the present invention is obtained by dispersing a pigment in water and then mixing the aqueous radical composition with the pigment. In addition, wetting agents, surface preparation agents, antifoaming agents, preservatives, pH adjusting agents, and the like can be added to the aqueous radical UV ink.
水中での顔料の分散方法としては、界面活性剤や高分子分散剤による分散方法、顔料を酸化（特許文献３）あるいはスルホン化（特許文献４、特許文献５）等により顔料粒子表面を改質（親水化）し、実質的に分散剤なしで分散化させる方法など公知の方法を用いることができる。 As a method for dispersing the pigment in water, the surface of the pigment particle is modified by a dispersion method using a surfactant or a polymer dispersant, oxidation (Patent Document 3) or sulfonation (Patent Document 4, Patent Document 5) of the pigment. A known method such as a method of (hydrophilizing) and dispersing substantially without a dispersant can be used.
顔料としてはカーボンブラックや公知の顔料を用いることができる。カーボンブラックの例としては、三菱化学製のNo.900, MCF88,No.33,MA7,MA8,MA100、デグザ社製Color Black FW200,Special Black 6,Special Black 5, Special Black 4, Printex 350, Printex 250、コロンビア社製のRaven 700, Raven 1255等が使用できる。イエロー顔料としては、C.I.Pigment Yellow 73, C.I.Pigment Yellow 74, C.I.Pigment Yellow 116, C.I.Pigment Yellow 128, C.I.Pig,emt Yellow 139, C.I.Pigment Yellow 151等が、マゼンタ顔料としてはC.I.Pigment Red 122, C.I.Pigment Red 202, C.I.Pigment Red 207, C.I.Pigment Red 209, C.I.Pigment Violet 19等が、シアン顔料としてはC.I.Pigment Blue15:1, C.I.Pigment Blue15:2,C.I.Pigment Blue15:3, C.I.Pigment Blue 15:4, C.I.Pigment Blue15:6等が挙げられる。またＹＭＣＫの補色インクのグリーン顔料としてC.I.Pigment Green 7,C.I.Pigment Green 36、C.I.Pigment Orange 16, C.I.Pigment Orange 36,C.I.Pigment Orange 43、さらに酸化チタン等を挙げることができる。 As the pigment, carbon black or a known pigment can be used. Examples of carbon black include Mitsubishi Chemical No.900, MCF88, No.33, MA7, MA8, MA100, Degussa Color Black FW200, Special Black 6, Special Black 5, Special Black 4, Printex 350, Printex 250, Columbia Raven 700, Raven 1255, etc. can be used. Examples of yellow pigments include CIPigment Yellow 73, CIPigment Yellow 74, CIPigment Yellow 116, CIPigment Yellow 128, CIPig, emt Yellow 139, CIPigment Yellow 151, etc., and magenta pigments include CIPigment Red 122, CIPigment Red 202, CIPigment Red 207, CIPigment Red 209, CIPigment Violet 19, etc., as cyan pigments CIPigment Blue15: 1, CIPigment Blue15: 2, CIPigment Blue15: 3, CIPigment Blue 15: 4, CI Pigment Blue15: 6 etc. are mentioned. Examples of green pigments for YMCK complementary color inks include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Orange 16, C.I. Pigment Orange 36, C.I. Pigment Orange 43, and titanium oxide.
これらの顔料は粉末状あるいは塊状の乾燥色材でも、ウエットケーキやスラリーでも良く、色材合成中や合成後に色材粒子の凝集を抑える目的で界面活性剤等の分散剤が少量含有されたものであっても良い。市販のこれらの色材には、工業染色用、樹脂着色用、インキ用、トナー用、インクジェット用などのグレードがあり、製造方法、純度、顔料の粒径等がそれぞれ異なる。粉砕後の凝集性を抑えるには色材としてはより粒子の小さいものが好ましく、また分散安定性及びインクの印刷精度への影響からできるだけ不純物などの少ないものが好ましい。顔料においてはブルー系顔料を主体にオレンジ系顔料及びレッド系顔料を配合する事でブラック用の色材として用いることもできる。また色調調製の範囲内で他の顔料を少量含んでも良い。 These pigments may be powdery or massive dry color materials, wet cakes or slurries, and contain a small amount of a dispersant such as a surfactant for the purpose of suppressing aggregation of the color material particles during or after the color material synthesis. It may be. These commercially available color materials include industrial dyeing grades, resin coloring grades, ink grades, toner grades, and inkjet grades, which differ in production method, purity, pigment particle size, and the like. In order to suppress the cohesiveness after pulverization, the colorant preferably has smaller particles, and preferably has as few impurities as possible from the viewpoint of influence on dispersion stability and ink printing accuracy. The pigment can also be used as a color material for black by blending an orange pigment and a red pigment mainly with a blue pigment. Further, a small amount of other pigments may be contained within the range of color tone preparation.
顔料を微粒子に分散する方法としては、サンドミル（ビーズミル）、ロールミル、ボールミル、ペイントシェーカー、超音波分散機、マイクロフルイダイザー等を用いる方法が挙げられるが、これらの中でもサンドミル（ビーズミル）が好ましい。またサンドミル（ビーズミル）における色材の粉砕においては、径の小さいビーズを使用する、ビーズの充填率を大きくすること等により粉砕効率を高めた条件で処理することが好ましく、更に粉砕処理後に濾過、遠心分離などで粗大粒子を除去することが好ましい。また分散剤の中には発泡性を有するものもあるので、粉砕効率を高める点で粉砕時の泡立ち性をできるだけ抑えた粉砕条件とするのが好ましく、場合によってはシリコーン系、アセチレンアルコール系等の消泡剤等を、顔料粉砕時に極微量添加使用しても良い。但し、消泡剤には分散・微粒子化を阻害するものもあり、微粒子化や分散後の安定性に影響を及ぼさないものを使用する必要がある。 Examples of the method for dispersing the pigment into the fine particles include a method using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, and the like. Among these, a sand mill (bead mill) is preferable. Further, in the pulverization of the coloring material in the sand mill (bead mill), it is preferable to use beads having a small diameter, and to perform the treatment under a condition in which the pulverization efficiency is increased by increasing the filling rate of the beads. It is preferable to remove coarse particles by centrifugation or the like. In addition, some dispersants have foaming properties, so it is preferable to use grinding conditions that suppress foaming as much as possible in order to increase grinding efficiency. In some cases, silicone-based, acetylene alcohol-based, etc. An antifoaming agent or the like may be added in a very small amount during pigment grinding. However, some antifoaming agents inhibit dispersion and micronization, and it is necessary to use those that do not affect the stability after micronization or dispersion.
分散時のスラリー中の顔料濃度は１５〜３５重量％、分散剤は合わせて対顔料比１０〜１００重量％程度で粉砕することが好ましく、このとき適切な顔料分散剤としては、ドデシルベンゼンスルホン酸ナトリウム、ラウリル酸ナトリウム、ナフタレンスルホン酸のホルマリン縮合物、アルキルナフタレンスルホン酸のホルマリン縮合物、クレオソート油スルホン酸のホルマリン縮合物、ポリオキシエチレンアルキルエーテルサルフェートのアンモニウム塩、ポリオキシエチレンアルキルフェニルエーテルサルフェートのアンモニウム、ポリオキシアルキルエーテル燐酸エステル塩等公知のアニオン界面活性剤、ビニルナフタレン誘導体、α、β−エチレン性不飽和カルボン酸の脂肪族アルコールエステル等、スチレン、スチレン誘導体、アクリル酸、アクリル酸誘導体、メタクリル酸、メタクリル酸誘導体、マレイン酸、マレイン酸誘導体、無水マレイン酸、無水マレイン酸誘導体、イタコン酸、イタコン酸誘導体、フマール酸、フマール酸誘導体等から選ばれた少なくとも２つ以上の単量体からなるブロック共重合体、或いはランダム共重合体、またはこれらの塩等の高分子分散剤等が挙げられ、これらの１種以上を顔料に対して１０〜１００重量％の間で使用するのが好ましい。またこれらの分散剤と併せて、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、エチレンオキサイドとプロピレンオキサイドの共重合物等の公知のノニオン系の界面活性剤やシリコーン系、アセチレン系の公知の消泡剤を必要に応じ、顔料分散時及び／または顔料分散化後に添加使用することもできる。顔料（Ａ）は、本発明のインク中、０．３〜１０重量％、好ましくは３〜１０重量％含有するのが良い。 The pigment concentration in the slurry at the time of dispersion is preferably 15 to 35% by weight, and the dispersants are preferably pulverized at a pigment to pigment ratio of about 10 to 100% by weight. In this case, as a suitable pigment dispersant, dodecylbenzenesulfonic acid is used. Formalin condensate of sodium, sodium laurate, naphthalene sulfonic acid, formalin condensate of alkyl naphthalene sulfonic acid, formalin condensate of creosote oil sulfonic acid, ammonium salt of polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate Of known anionic surfactants such as ammonium and polyoxyalkyl ether phosphates, vinyl naphthalene derivatives, aliphatic alcohol esters of α, β-ethylenically unsaturated carboxylic acids, styrene, styrene derivatives, acrylic At least 2 selected from phosphoric acid, acrylic acid derivative, methacrylic acid, methacrylic acid derivative, maleic acid, maleic acid derivative, maleic anhydride, maleic anhydride derivative, itaconic acid, itaconic acid derivative, fumaric acid, fumaric acid derivative, etc. Examples thereof include a block copolymer composed of one or more monomers, a random copolymer, or a polymer dispersant such as a salt thereof. One or more of these may be used in an amount of 10 to 100% by weight based on the pigment. It is preferable to use between. In addition to these dispersants, known nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, copolymers of ethylene oxide and propylene oxide, and silicones A known acetylene-based antifoaming agent can be added and used at the time of pigment dispersion and / or after pigment dispersion, if necessary. The pigment (A) is contained in the ink of the present invention in an amount of 0.3 to 10% by weight, preferably 3 to 10% by weight.
また、顔料の表面を改質することで、水に分散する方法としては、例えば、次亜塩素酸ナトリウム等の次亜ハロゲン酸塩による酸化処理、濃硫酸、発煙硫酸、クロロスルホン酸等のスルホン化剤によるスルホン化処理、スルファニル酸等のジアゾニウム塩による親水基導入などの化学的処理による方法を用いることができる。また顔料の表面改質処理と粉砕処理を交互に行ったり、あるいは同時に行う事でより効率良く改質が進行した微粒子顔料を得ることができ、改質および微粒子化後に上記と同様に濾過、遠心分離などで粗大粒子を除去することが好ましい。分散化後あるいは濾過等の後処理後少量の水で分散液を稀釈し所望の色材濃度に調製できる。また分散化された色材を用いインクを調製する場合、色材はインク中へ色材純分として０．３〜２５重量％の範囲で含有するのが好ましい。ただし、これらは、一般的な方法であって、これに限定されるものではない。また、市販品として入手可能な顔料の分散液を利用することもできる。 Examples of the method of dispersing in water by modifying the pigment surface include, for example, oxidation treatment with hypohalite such as sodium hypochlorite, sulfone such as concentrated sulfuric acid, fuming sulfuric acid and chlorosulfonic acid. A method by chemical treatment such as sulfonation treatment with an agent and introduction of a hydrophilic group with a diazonium salt such as sulfanilic acid can be used. In addition, the pigment surface modification treatment and the pulverization treatment can be performed alternately or simultaneously to obtain a fine particle pigment that has been modified more efficiently. After modification and micronization, filtration and centrifugation are performed in the same manner as described above. It is preferable to remove coarse particles by separation or the like. After dispersion or after-treatment such as filtration, the dispersion can be diluted with a small amount of water and adjusted to a desired colorant concentration. Further, when an ink is prepared using a dispersed color material, the color material is preferably contained in the ink in a range of 0.3 to 25% by weight as a pure color material. However, these are general methods and are not limited thereto. Also, a pigment dispersion that is available as a commercial product can be used.
本発明で用いる水性ラジカル組成物は、たとえば、ポリエチレングリコールジアクリレート（Ｂ）成分、水溶性（メタ）アクリルアミド（Ｃ）成分を３０〜８０℃程度の加温下に混合し、光重合開始剤（Ｄ）成分、水、及び必要に応じて酸化防止剤、消泡剤、レベリング剤、光安定剤、重合開始剤等の添加剤類を加え均等に混合、分散することにより、通常液状品として得ることができる。 The aqueous radical composition used in the present invention is prepared by, for example, mixing a polyethylene glycol diacrylate (B) component and a water-soluble (meth) acrylamide (C) component at a temperature of about 30 to 80 ° C. to produce a photopolymerization initiator ( D) It is usually obtained as a liquid product by adding ingredients, water, and if necessary, additives such as antioxidants, antifoaming agents, leveling agents, light stabilizers and polymerization initiators, and mixing and dispersing them uniformly. be able to.
本発明で用いるポリエチレングリコールジアクリレート（Ｂ）であるが、ＥＯ変性を骨格とした水溶性の化合物であることが望ましい。具体例としてはポリエチレングリコール（４００）ジ（メタ）アクリレート、ポリエチレングリコール（６００）ジ（メタ）アクリレート、ポリエチレングリコール（９００）ジ（メタ）アクリレート等があるが、直鎖で分子量が５００以上であり、水に溶解するものであれば用いることが可能である。この成分（Ｂ）で表される化合物は、各々を単独でまたは必要に応じ、混合して用いることもできる。ポリエチレングリコールジアクリレート（Ｂ）は本発明のインク中に５〜２５重量％、好ましくは１０〜２０重量％含有するのが良い。また、これらの化合物をメイン樹脂として、他の水溶性または非水溶性化合物も添加することができる。添加範囲としては、分散液の分散を壊さない程度であることが望ましい。水溶性化合物としては、ＰＯ変性ポリエチレングリコールジアクリレート等があげられる。また、非水溶性化合物としては、１，６−ヘキサンジオールジ（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、トリメチロールプロパントリ（メタ）アクリレート、２−（２−エトキシ）エチル（メタ）アクリレート、ステアリル（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、ラウリル（メタ）アクリレート、２−フェノキシメチル（メタ）アクリレート、イソデシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、トリデシル（メタ）アクリレート、カプロラクトン（メタ）アクリレート、エトキシ化ノニルフェノール（メタ）アクリレート、プロポキシ化ノニルフェノール（メタ）アクリレート、１，３ブタンジオールジ（メタ）アクリレート、１，４−ブタンジオールジ（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、ポリエチレングリコール（２００）ジ（メタ）アクリレート、テトラ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、エトキシ化ビスフェノールＡジ（メタ）アクリレート、プロポキシ化ネオペンチルグリコールジ（メタ）アクリレート、エトキシ化ネオペンチルグリコールジ（メタ）アクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（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、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、プロポキシ化トリメチロールプロパントリ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、プロポキシ化グリセリルトリ（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−ルヒドロキシペンタ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラアクリレート、ペンタ（メタ）アクリレートエステル等が挙げられるが、これ以外の非水溶性化合物も使うことができる。また、各種ウレタンアクリレート、各種ポリエステルアクリレート等も使用することもでき、またそれらを各種混合して使用することもできる。この水溶性または非水溶性化合物は、インク中０〜５％を目安に添加することができる。 The polyethylene glycol diacrylate (B) used in the present invention is preferably a water-soluble compound having an EO-modified skeleton. Specific examples include polyethylene glycol (400) di (meth) acrylate, polyethylene glycol (600) di (meth) acrylate, polyethylene glycol (900) di (meth) acrylate, etc., which are linear and have a molecular weight of 500 or more. Any substance that dissolves in water can be used. The compounds represented by this component (B) can be used alone or in admixture as necessary. The polyethylene glycol diacrylate (B) is contained in the ink of the present invention in an amount of 5 to 25% by weight, preferably 10 to 20% by weight. Also, other water-soluble or water-insoluble compounds can be added using these compounds as the main resin. The range of addition is desirably an extent that does not break the dispersion of the dispersion. Examples of the water-soluble compound include PO-modified polyethylene glycol diacrylate. Examples of water-insoluble compounds include 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and 2- (2-ethoxy) ethyl (meth). Acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxymethyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, tridecyl (meth) acrylate, caprolactone (Meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propoxylated nonylphenol (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanedio Di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol (200) di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) Acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate Lilate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) Examples include acrylate, ethoxylated pentaerythritol tetraacrylate, penta (meth) acrylate ester, and the like, but other water-insoluble compounds can also be used. Moreover, various urethane acrylates, various polyester acrylates, etc. can also be used, and various mixtures thereof can also be used. This water-soluble or water-insoluble compound can be added in an amount of 0 to 5% in the ink.
本発明で用いる水溶性（メタ）アクリルアミド（Ｃ）としては、一次皮膚刺激性が低く、水に溶解し、顔料の分散性を壊さず、結晶が析出しないものであれば良い。また、アミン臭などの臭いも少ないものが良い。このような水溶性（メタ）アクリルアミドの具体例としては、Ｎ−メトキシメチルアクリルアミド（一次皮膚刺激性：０．０８）またはアクリロイルモルホリン（一時皮膚刺激性：０．５）が好ましい。これらはそれぞれ一種類または両者を混合して使用することもできる。水溶性（メタ）アクリルアミド（Ｃ）は、本発明のインク中に２５〜５０重量％、好ましくは２５〜３５重量％含有するのが良い。なお本発明においては、（メタ）アクリルアミドは便宜上、アクリルアミド及びメタクリルアミドのいずれをも意味することとする。 The water-soluble (meth) acrylamide (C) used in the present invention is not particularly limited as long as it has low primary skin irritation, dissolves in water, does not break the dispersibility of the pigment, and does not precipitate crystals. Moreover, the thing with few smells, such as an amine smell, is good. As a specific example of such water-soluble (meth) acrylamide, N-methoxymethylacrylamide (primary skin irritation: 0.08) or acryloylmorpholine (temporary skin irritation: 0.5) is preferable. These can be used alone or in combination. The water-soluble (meth) acrylamide (C) is contained in the ink of the present invention in an amount of 25 to 50% by weight, preferably 25 to 35% by weight. In the present invention, (meth) acrylamide means both acrylamide and methacrylamide for convenience.
本発明で用いる光重合開始剤（Ｄ）であるが、公知のどのような光重合開始剤であってもよい。例えば、次のものをあげられる。これらのうち１種類を使用することもできるし、２種類以上を組み合わせて使用することもできる。また、増感剤やアミン化合物として、公知のどのような増感剤を組み合わせてもしくは単独で使用してもよい。光重合開始剤として、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、ベンゾフェノン、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、オキシ−フェニル−アセチック−アシッド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、オキシ−フェニル−アセチック−アシッド２−[２−ヒドロキシ−エトキシ]−エチルエステル、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、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、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、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等があげられる。また、増感剤として、２，４−ジエチルチオキサントン、２−クロロチオキサントン、[４−（メチルフェニルチオ）フェニル]フェニルメタン、エチルアントラキノン、ｐ−ジメチルアミノ安息香酸イソアミルエステル、ｐ−ジメチルアミノ安息香酸エチルエステル等があげられる。光重合開始剤（Ｄ）は、本発明のインク中に２．５〜１０重量％、好ましくは２．５〜７重量％含有するのが良い。 Although it is a photoinitiator (D) used by this invention, what kind of well-known photoinitiator may be sufficient. For example, the following can be mentioned. One of these can be used, or two or more can be used in combination. Further, any known sensitizer may be used in combination or alone as the sensitizer or amine compound. 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one as photopolymerization initiator Benzophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oxy-phenyl-acetic acid 2- [2-oxo-2- Phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, 2-methyl-1- “4- (methylthio) phenyl” -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phos Examples include fin oxides. As sensitizers, 2,4-diethylthioxanthone, 2-chlorothioxanthone, [4- (methylphenylthio) phenyl] phenylmethane, ethylanthraquinone, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid Examples include ethyl ester. The photopolymerization initiator (D) is contained in the ink of the present invention in an amount of 2.5 to 10% by weight, preferably 2.5 to 7% by weight.
本発明の水系ラジカル組成物には、さらに必要に応じて、たとえば酸化防止剤、消泡剤、レベリング剤、光安定剤、重合禁止剤等の添加剤類を添加することもできる。酸化防止剤としては、たとえばＢＨＴスワノックス（精工化学（株）製）、消泡剤としては、たとえばＢＹＫ−０５７（ビックケミー製）、レベリング剤としては、たとえばＢＹＫ−３５４（ビックケミー製）、光安定剤としては、たとえばＬＡ−８２（旭電化（株）製）、重合禁止剤としては、メチルハイドロキノン等がある。 If necessary, additives such as an antioxidant, an antifoaming agent, a leveling agent, a light stabilizer, and a polymerization inhibitor can be further added to the aqueous radical composition of the present invention. Examples of the antioxidant include BHT Swanox (manufactured by Seiko Chemical Co., Ltd.), examples of the antifoaming agent include BYK-057 (manufactured by BYK Chemie), and examples of the leveling agent include BYK-354 (manufactured by BYK Chemie), a light stabilizer. Examples include LA-82 (manufactured by Asahi Denka Co., Ltd.), and examples of the polymerization inhibitor include methyl hydroquinone.
［本発明で使用するインクの調製方法の例］
上記顔料水分散液に、攪拌下、水系ラジカル組成物をゆっくり滴下し、混合することで本発明のインクを得ることができる。この工程は、水系ラジカル組成物および／または水系ラジカルＵＶインクが重合することをさけるため、遮光または、黄色光の下で行われることが好ましい。
[Example of method for preparing ink used in the present invention]
The ink of the present invention can be obtained by slowly dropping and mixing the aqueous radical composition into the pigment aqueous dispersion with stirring. This step is preferably performed under light shielding or under yellow light in order to avoid polymerization of the aqueous radical composition and / or aqueous radical UV ink.
上記の方法により得られたインクを、インクジェット法により基材に印刷する。必要に応じ、インクおよびまたは、この基材に熱をかけ、インク中の水分を蒸発させる。このときの熱源は、例えば、熱風をあてる方法、基材に赤外線を放射する方法等があるが、これらの方法にとらわれず、インク中の水分を蒸発させるのが目的で使用する。その後、電子線、紫外線や可視光線等のエネルギー線を照射することによって硬化物を得ることができる。例えば、紫外線を使用するとき、光源としては、たとえば、メタハライドランプ、高圧水銀ランプ等をあげることができる。インクおよび、または基材に熱がかかったときに、光重合開始剤が開裂して部分的にまたは全体的に重合が起ることもある。また、本発明のインクは、インク中の水分残存量には左右されず、仮に水分の蒸発工程を行わない場合でも、インクの硬化性が良好である。 The ink obtained by the above method is printed on a substrate by an inkjet method. If necessary, heat is applied to the ink and / or the substrate to evaporate moisture in the ink. The heat source at this time includes, for example, a method of applying hot air, a method of radiating infrared rays to the base material, and the like, but it is used for the purpose of evaporating moisture in the ink without being limited to these methods. Thereafter, a cured product can be obtained by irradiating an energy beam such as an electron beam, an ultraviolet ray or a visible ray. For example, when ultraviolet rays are used, examples of the light source include a metahalide lamp and a high-pressure mercury lamp. When heat is applied to the ink and / or the substrate, the photopolymerization initiator may be cleaved to cause partial or complete polymerization. Further, the ink of the present invention does not depend on the residual amount of water in the ink, and has good ink curability even when the water evaporation step is not performed.
基材としては例えば、ポリエチレンテレフタレートやポリ塩化ビニル等が挙げられるが、それらにコロナ処理のような表面処理されている物も使用することができる。しかし、基材に対する表面処理のあるなしにかかわらず、本発明のインクを用いた記録物、特に本発明のインク硬化物の薄膜を表面に有する記録物は、べたつきの少ない、皮膜を形成することができる。 Examples of the base material include polyethylene terephthalate and polyvinyl chloride, and those subjected to surface treatment such as corona treatment can also be used. However, a recorded matter using the ink of the present invention, particularly a recorded matter having a thin film of the cured ink of the present invention on its surface, forms a film with little stickiness regardless of whether or not the substrate is surface-treated. Can do.
以下、本発明を実施例によりさらに具体的に説明するが、実施例の範囲に限定されるものではない。なお、文中の「部」および「％」は特に断らない限りは、それぞれ、「重量部」および「重量％」を示す。
［シアン顔料水分散液調製例］
イオン交換水 ８９ｇ、スルファニル酸１ｇ、市販銅フタロシアニン顔料１０ｇを０．５ｍｍ径ビーズ１００ｍｌをサンドミルにて水冷下で約３０分粉砕処理後、亜硝酸ソーダ１ｇを追加し水冷下にて更に３０分処理した。スルファニル酸１ｇ、亜硝酸ソーダ１ｇを３０分後に計３回追加しながら、水冷下で合計約２時間粉砕処理を行った。得られた分散液を乾燥し水分を蒸発させた後、メタノールにて洗浄してジアゾ分解物などを除去した。更に乾燥後、得られた顔料粉末をイオン交換水中に再分散させ、平均粒径８０ｎｍの表面改質された銅フタロシアニンの２０％分散液を得た。これに分散剤としてポリオキシエチレン（２０）フェニルエーテル硫酸アンモニウムを対銅フタロシアニン顔料の１０％を添加し、更にイオン交換水で希釈し、顔料濃度１０％の分散液を得た。これをガラス繊維ろ紙ＧＣ−５０（東洋濾紙株式会社製）で濾過し、粗大粒子を除去した。
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to the range of an Example. In the text, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively, unless otherwise specified.
[Cyan pigment aqueous dispersion preparation example]
89g of ion-exchanged water, 1g of sulfanilic acid, and 10g of commercially available copper phthalocyanine pigment were pulverized for about 30 minutes in a sand mill under water cooling with a 0.5mm diameter bead and added with 1g of sodium nitrite for further 30 minutes under water cooling. did. While adding 1 g of sulfanilic acid and 1 g of sodium nitrite 30 minutes later, a total of about 2 hours of pulverization was performed under water cooling. The obtained dispersion was dried to evaporate water, and then washed with methanol to remove diazo decomposition products and the like. Further, after drying, the obtained pigment powder was redispersed in ion-exchanged water to obtain a 20% dispersion of surface-modified copper phthalocyanine having an average particle size of 80 nm. To this, 10% of polyoxyethylene (20) phenyl ether ammonium sulfate as a dispersant was added to the copper phthalocyanine pigment, and further diluted with ion-exchanged water to obtain a dispersion having a pigment concentration of 10%. This was filtered with glass fiber filter paper GC-50 (manufactured by Toyo Filter Paper Co., Ltd.) to remove coarse particles.
［マゼンタ顔料水分散液調製例］
イオン交換水 ８９ｇ、スルファニル酸１ｇ、市販のＰｉｇｍｅｎｔ Ｒｅｄ１２２の顔料１０ｇを０．５ｍｍ径ビーズ１００ｍｌをサンドミルにて水冷下で約３０分粉砕処理後、亜硝酸ソーダ１ｇを追加し水冷下にて更に３０分処理した。スルファニル酸１ｇ、亜硝酸ソーダ１ｇを３０分後に計４回追加しながら、水冷下で合計約３時間粉砕処理を行った。得られた分散液を乾燥し水分を蒸発させた後、メタノールにて洗浄してジアゾ分解物などを除去した。更に乾燥後、得られた顔料粉末をイオン交換水中に再分散させ、平均粒径１０２ｎｍの表面改質されたＰｉｇｍｅｎｔ Ｒｅｄ１２２の２０％分散液を得た。これに分散剤としてポリオキシエチレン（２０）フェニルエーテル硫酸アンモニウムを対顔料の１０％を添加し、更にイオン交換水で希釈し、顔料濃度１０％の分散液を得た。これをガラス繊維ろ紙ＧＣ−５０（東洋濾紙株式会社製）で濾過し、粗大粒子を除去した。
[Magenta pigment aqueous dispersion preparation example]
89 g of ion-exchanged water, 1 g of sulfanilic acid, and 10 g of commercially available Pigment Red 122 pigment were pulverized in 100 ml of 0.5 mm diameter beads in a sand mill for about 30 minutes under water cooling, and then added with 1 g of sodium nitrite and further 30 under water cooling. Minute processed. While adding 1 g of sulfanilic acid and 1 g of sodium nitrite 30 times later in total 4 times, the mixture was pulverized for about 3 hours under water cooling. The obtained dispersion was dried to evaporate water, and then washed with methanol to remove diazo decomposition products and the like. Further, after drying, the obtained pigment powder was redispersed in ion-exchanged water to obtain a 20% dispersion of Pigment Red 122 having an average particle diameter of 102 nm and surface-modified Pigment Red122. To this, 10% of the pigment was added polyoxyethylene (20) phenyl ether ammonium sulfate as a dispersant, and further diluted with ion-exchanged water to obtain a dispersion having a pigment concentration of 10%. This was filtered with glass fiber filter paper GC-50 (manufactured by Toyo Filter Paper Co., Ltd.) to remove coarse particles.
［ブラック顔料水分散液調製例］
イオン交換水 ８９ｇ、スルファニル酸１ｇ、市販のカーボンブラック顔料１０ｇを０．５ｍｍ径ビーズ１００ｍｌをサンドミルにて水冷下で約３０分粉砕処理後、亜硝酸ソーダ１ｇを追加し水冷下にて更に３０分処理した。スルファニル酸１ｇ、亜硝酸ソーダ１ｇを３０分後に計３回追加しながら、水冷下で合計約２時間粉砕処理を行った。得られた分散液を乾燥し水分を蒸発させた後、メタノールにて洗浄してジアゾ分解物などを除去した。更に乾燥後、得られた顔料粉末をイオン交換水中に再分散させ、平均粒径１０２ｎｍの表面改質されたカーボンブラックの２０％分散液を得た。
[Black pigment aqueous dispersion preparation example]
89 g of ion-exchanged water, 1 g of sulfanilic acid, and 10 g of commercially available carbon black pigment were pulverized with 100 ml of 0.5 mm diameter beads in a sand mill under water cooling for about 30 minutes, and then added with 1 g of sodium nitrite and further 30 minutes under water cooling. Processed. While adding 1 g of sulfanilic acid and 1 g of sodium nitrite 30 minutes later, a total of about 2 hours of pulverization was performed under water cooling. The obtained dispersion was dried to evaporate water, and then washed with methanol to remove diazo decomposition products and the like. Further, after drying, the obtained pigment powder was redispersed in ion-exchanged water to obtain a 20% dispersion of surface-modified carbon black having an average particle size of 102 nm.
実施例１，２，３，４および比較例１，２，３，４
前記の顔料水分散液に表１に示す配合組成に従って、各成分を配合し、２０ｍｌのインクを調製した。そのインクを０．８μｍのフィルターでろ過し、カートリッジに詰め、印刷テストを行った。プリンターは、ＥＰＳＯＮ ＰＭ−７４０ＤＵを使用した。
１）分散安定性
撹拌している顔料水分散液に水系ラジカル組成物を滴下し、よく撹拌した。その分散液２０ｍｌを０．８μｍのフィルターでろ過をした。結果を下記の要領で判断した。
○・・・全量ろ過できる。
△・・・１０ｍｌ程度で詰まる。
×・・・０．１〜１ｍｌ程度で詰まる。
２）硬化性、べたつき性
１）で分散したインクをプリンターで印刷し、（i）基材とともに５０℃で２分間放置し水分を蒸発させた後、または、（ii）乾燥作業を行わず、（i）と（ii）にそれぞれＵＶを照射した。ＵＶの照射条件は、ランプが高圧水銀ランプ、照射光量が３６５ｎｍにおいて５００ｍＪ／ｃｍ2である。結果を下記の要領で指触にて判断した。
◎・・・３５０ｍＪ／ｃｍ2でべたつきがなくなる。
○・・・べたつきがない。
△・・・ややべたつく。
×・・・べたつきで指からフィルムが離れない。
Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3, 4
Each component was blended in the pigment aqueous dispersion according to the blending composition shown in Table 1 to prepare 20 ml of ink. The ink was filtered through a 0.8 μm filter, packed in a cartridge, and a printing test was performed. The printer used was EPSON PM-740DU.
1) Dispersion stability The aqueous radical composition was added dropwise to the stirred pigment aqueous dispersion and stirred well. 20 ml of the dispersion was filtered through a 0.8 μm filter. The result was judged as follows.
○: The entire amount can be filtered.
Δ: Clogged with about 10 ml.
X: Clogged with about 0.1 to 1 ml.
2) Curability, stickiness 1) The ink dispersed in 1) is printed with a printer, and (i) after standing for 2 minutes at 50 ° C. together with the substrate to evaporate the water, or (ii) without performing a drying operation. (I) and (ii) were each irradiated with UV. The UV irradiation condition is 500 mJ / cm 2 when the lamp is a high-pressure mercury lamp and the irradiation light quantity is 365 nm. The result was judged by finger touch in the following manner.
◎ ・ ・ ・ No stickiness at 350 mJ / cm 2
○ ・ ・ ・ There is no stickiness.
Δ: Slightly sticky.
X: The film does not come off the finger due to stickiness.
表１ 各成分に対応する数値は、各実施例のインク中における重量部を示す。
実施例 比較例
１ ２ ３ ４ １ ２ ３ ４
Ａ成分（１） １０ １０ １０ １０ １０ １０
（２） １０
（３） １０
Ｂ成分（１） ３ ３ ３ ３ ６
（２） ３
（３） ０．５ ３
（４） ３
Ｃ成分（１）６．５ ６．５ ６．５ ６．５ ６．５ ６．５ ６．５
Ｄ成分（１） １ １ １ １ １ １ １ １
水 ４．５
添加剤（１）０．１ ０．１ ０．１ ０．１ ０．１ ０．１ ０．１ ０．１
結果
分散安定性 ○ ○ ○ ○ × × × ○
乾燥条件（i)
硬化性 ○ ○ ○ ○ − − − △
べたつき性 ○ ○ ○ ◎ − − − ×
乾燥条件（ii）
硬化性 ○ ○ ○ ○ − − − △
べたつき性 ○ ○ ○ ◎ − − − ×
Ａ成分（１）：実施例の分散液：マゼンタ：顔料濃度１０％
（２）：実施例の分散液：シアン ：顔料濃度１０％
（３）：実施例の分散液：ブラック：顔料濃度２０％
Ｂ成分（１）：ポリエチレングリコール（４００）ジアクリレート
（２）：エトキシ化ビスフェノールＡジアクリレート （ＥＯ変性１０モル付加物）
（３）：トリス（２−ヒドロキシエチル）イソシアヌレートトリアクリレート
（４）：エトキシ化トリメチロールプロパントリアクリレート
（ＥＯ変性１５モル付加物）
Ｃ成分（１）：Ｎ−メトキシメチルアクリルアミド
Ｄ成分（１）：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
添加剤（１）：ビックケミー製 ＢＹＫ−３８０Ｎ
Table 1 The numerical value corresponding to each component indicates the weight part in the ink of each example.
Examples Comparative examples
1 2 3 4 1 2 3 4
A component (1) 10 10 10 10 10 10
(2) 10
(3) 10
B component (1) 3 3 3 3 6
(2) 3
(3) 0.5 3
(4) 3
C component (1) 6.5 6.5 6.5 6.5 6.5 6.5 6.5
D component (1) 1 1 1 1 1 1 1 1
Water 4.5
Additive (1) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Result Dispersion stability ○ ○ ○ ○ × × × ○
Drying conditions (i)
Curability ○ ○ ○ ○ − − − △
Stickiness ○ ○ ○ ◎ − − − ×
Drying conditions (ii)
Curability ○ ○ ○ ○ − − − △
Stickiness ○ ○ ○ ◎ − − − ×
Component A (1): Example dispersion: Magenta: Pigment concentration 10%
(2): Dispersion liquid of Examples: Cyan: Pigment concentration 10%
(3): Example dispersion: Black: Pigment concentration 20%
Component B (1): Polyethylene glycol (400) diacrylate (2): Ethoxylated bisphenol A diacrylate (EO-modified 10 mol adduct)
(3): Tris (2-hydroxyethyl) isocyanurate triacrylate (4): Ethoxylated trimethylolpropane triacrylate
(EO-modified 15 mol adduct)
Component C (1): N-methoxymethylacrylamide Component D (1): 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one additive ( 1) BYK-380N manufactured by Big Chemie
表１の結果より、比較例１〜３のインクは分散安定性に乏しく、唯一分散安定性の良い比較例４のインクも、硬化性や特にべたつき性に関して問題が生じることが判明した。これと比較し、本発明の分散液を使用したインクは、明らかにその優れた分散安定性、乾燥性及びべたつきの無い性質を示した。また実施例１と実施例４との比較により、非水溶性のエチレン性不飽和基含有化合物（トリス（２−ヒドロキシエチル）イソシアヌレートトリアクリレート）を添加することも可能であることが示された。 From the results shown in Table 1, it was found that the inks of Comparative Examples 1 to 3 have poor dispersion stability, and the ink of Comparative Example 4 having only good dispersion stability has problems with respect to curability and particularly stickiness. In comparison with this, the ink using the dispersion of the present invention clearly showed excellent dispersion stability, drying property and non-stickiness. In addition, comparison between Example 1 and Example 4 showed that it is possible to add a water-insoluble ethylenically unsaturated group-containing compound (tris (2-hydroxyethyl) isocyanurate triacrylate). .
Claims (6)
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| JP2015147418A (en) * | 2010-01-27 | 2015-08-20 | セイコーエプソン株式会社 | Inkjet recording system and recording method |
| WO2021002307A1 (en) | 2019-07-03 | 2021-01-07 | 株式会社Adeka | Amide compound, polymerizable composition, cured product, and production method thereof |
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| JP5270073B2 (en) * | 2006-05-24 | 2013-08-21 | 富士フイルム株式会社 | Ink composition for inkjet recording |
| JP5448924B2 (en) | 2010-02-25 | 2014-03-19 | 富士フイルム株式会社 | Ink composition, ink set, and image forming method using the same |
| JP5579468B2 (en) * | 2010-03-10 | 2014-08-27 | 富士フイルム株式会社 | Ink composition, ink set, and image forming method using the same |
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