JP2002188025A - Actinic energy ray-curable ink-jet ink - Google Patents

Actinic energy ray-curable ink-jet ink

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Publication number
JP2002188025A
JP2002188025A JP2001300185A JP2001300185A JP2002188025A JP 2002188025 A JP2002188025 A JP 2002188025A JP 2001300185 A JP2001300185 A JP 2001300185A JP 2001300185 A JP2001300185 A JP 2001300185A JP 2002188025 A JP2002188025 A JP 2002188025A
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ink
energy ray
pigment
curable
wt
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JP2001300185A
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JP4061876B2 (en )
Inventor
Yoshihiro Fuse
Kaori Nakano
Yasuo Yoshihiro
香緒里 中野
泰男 吉廣
順弘 布施
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Toyo Ink Mfg Co Ltd
東洋インキ製造株式会社
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Abstract

PROBLEM TO BE SOLVED: To provide an actinic energy ray-curable ink-jet ink having low viscosity, excellent in photopolymerizability, having excellent curability in a thick coat, good at heat stability, and to provide the actinic energy ray-curable ink-jet ink good at issue stability with a nozzle, adhesion to printing medium, solvent resistance and water resistance.
SOLUTION: This actinic energy ray-curable ink-jet ink is characterized by being obtained by compounding a liquid component comprising (1) 10-50 wt.% oxirane group-containing compound, (2) 50-90 wt.% oxetane ring-containing compound and (3) 0-40 wt.% vinyl ether compound with (4) a pigment, (5) a photo cationic polymerization initiator and (6) a pigment dispersant.
COPYRIGHT: (C)2002,JPO

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【発明の属する技術分野】本発明は、光重合性に優れ、 The present invention relates is excellent in the photopolymerizable,
硬化性がよく、インキとしての安定性が良好で、硬化膜の強度が強く、ノズルでの吐出安定性、被記録媒体への密着性、耐溶剤性および耐水性の良好な活性エネルギー線硬化型インクジェットインキに関する。 Curable good, a good stability of the ink, the strength of the cured film is strong, the discharge stability at the nozzle, adhesion to a recording medium, solvent resistance and good radiation-curable water-resistant ink-jet on ink.

【0002】 [0002]

【従来の技術】従来、耐水性の良好なインクジェットインキとしては、油溶性染料を高沸点溶剤に分散ないし溶解したもの、油溶性染料を揮発性の溶剤に溶解したものがあるが、染料は耐光性等の諸耐性で顔料に劣るため、 As a conventional, water resistance good inkjet ink, which is dispersed or dissolved oil-soluble dye in a high boiling point solvent, there are obtained by dissolving an oil-soluble dye in a volatile solvent, dye lightfastness It is inferior to the pigment in various resistance properties of sex, etc.,
着色剤として顔料を用いたインキが望まれている。 Ink using a pigment is desired as a colorant. しかしながら、顔料を安定して有機溶剤に分散することは困難であり、安定な分散性および吐出性を確保することも難しい。 However, the pigment stably the it is difficult to disperse in an organic solvent, it is also difficult to ensure a stable dispersibility and discharge properties. 一方、高沸点溶剤を用いたインキは、非吸収性の受像体においては、インキ中の溶剤が揮発せず、溶剤の蒸発による乾燥は困難なので、非吸収性の基材への印字は不可能である。 Meanwhile, ink using a high boiling solvent, in the non-absorbent of the image-receiving member, the solvent is not volatilized in the ink, since the drying by evaporation of the solvent is difficult, printing in a non-absorbing substrate is not it is.

【0003】揮発性の有機溶剤を用いたインキにおいては、使用する樹脂の密着性および溶剤の揮発によって非吸収性の基材においても良好な印字を形成することができる。 [0003] In the ink using a volatile organic solvent, it is possible to form a satisfactory printing in the non-absorbing substrate by volatilization of adhesion and solvent resin used. しかしながら、揮発性の溶剤がインキの主成分となるためヘッドのノズル面において溶剤の揮発による乾燥が非常に早く、頻繁なメンテナンスを必要とする。 However, the volatile solvents are very fast drying by evaporation of the solvent at the nozzle surface of the head for the main component of the ink, and require frequent maintenance. また、インキは本質的に溶剤に対する再溶解性が必要とされるため、溶剤に対する耐性が十分得られないことがある。 Also, ink essentially for remelting resistance is required for the solvent, there may resistance to solvents can not be sufficiently obtained.

【0004】このような特性を満足させるため、揮発性のないモノマー類を使用して、ヘッドでの乾燥を防ぎ、 [0004] To satisfy such characteristics, using a volatile-free monomers, it prevents drying of the head,
その一方、活性エネルギー線を与えることで硬化させる型のインキの利用もおこなわれている。 Meanwhile, are performed also use type ink curing by applying an active energy ray. このようなインキは、例えば、特開昭62−64874号公報、特開昭58−32674号公報等に公開されている。 Such inks are, for example, JP 62-64874 and JP published in JP-58-32674 Publication. これらのインキは、主に、コンティニュアスタイプのプリンターにて使用されるものであり、インキの粘度としては、3 These inks are mainly, which is used in continuous type of printer, the viscosity of the ink, 3
〜5mPa・s程度のものである。 It is of the order of ~5mPa · s. また、このプリンターは、インキを連続的に吐出するため揮発性の溶剤を多量に併用することができ、インキの粘度調整、揮発性の付与も比較的用意に調整できる。 Also, this printer, ink and can be continuously large amount of a combination of volatile solvents for discharging, viscosity of the ink can be adjusted to be relatively prepared impart volatility.

【0005】しかしながら、ピエゾ素子によるオンデマンド方式のプリンターにおいては、揮発性の溶剤を多量に使用することはメンテナンスの頻度を増やし、また、 However, in the printer on-demand method using a piezoelectric element, that using large amounts of volatile solvents increases the frequency of maintenance, also,
プリンター内のインキ接触材料の溶解膨潤という問題を誘発しやすくする。 To easily induce the problem of dissolution swelling of ink contact material in the printer. また、揮発溶剤は、消防法でいう危険物による制約も大きくなる。 In addition, the volatile solvent, the constraint is also increased by the hazardous materials referred to in the Fire Service Act. そこで、ピエゾ素子を用いるオンデマンドタイププリンターにおいては、揮発性溶剤の少ないインキとする必要がある。 Therefore, in the on-demand type printer using a piezo element, it is required to be small ink volatile solvent. しかしながら、 However,
活性エネルギー線硬化型のインキに用いる材料は比較的粘度の高い材料であり、従来のプリンターにて吐出できるような粘度において、硬化性がよく安定性が良好なインキを設計することは困難であった。 Material used for the active energy ray-curable ink is relatively high viscosity material, the viscosity that allows discharge in a conventional printer, is difficult to curable to design good stability good ink It was.

【0006】 [0006]

【発明が解決しようとする課題】本発明は、低粘度で、 SUMMARY OF THE INVENTION It is an object of the present invention is a low viscosity,
かつ光重合性に優れ、厚膜での硬化性が非常によく、熱的安定性が良好な活性エネルギー線硬化型インクジェットインキを提供することにある。 And excellent photopolymerizable, thick-film curability very well is that the thermal stability provide good active energy ray-curable inkjet ink. また、本発明はノズルでの吐出安定性、被記録媒体への密着性、耐溶剤性および耐水性の良好な活性エネルギー線硬化型インクジェットインキを提供することにある。 Further, the present invention is to provide ejection stability at the nozzle, adhesion to a recording medium, the solvent resistance and water resistance of the good active energy ray-curable inkjet ink.

【0007】 [0007]

【課題を解決するための手段】すなわち、本発明は、 Means for Solving the Problems That is, the present invention is,
1)オキシラン基含有化合物10〜50重量%、2)オキセタン環含有化合物50〜90重量%、および3)ビニルエーテル化合物0〜40重量%からなる液状成分に4)顔料を分散してなることを特徴とする活性エネルギー線硬化型インクジェットインキに関する。 1) oxirane group containing compounds 10 to 50 wt%, 2) an oxetane ring-containing compound 50 to 90 wt%, and 3) 4 in a liquid component comprising a vinyl ether compound 0-40 wt%) characterized by being obtained by dispersing the pigment to the active energy ray curable ink-jet inks to.

【0008】又、本発明は、更に、無溶剤型インキである上記活性エネルギー線硬化型インクジェットインキに関する。 [0008] The present invention further relates to the above active energy ray-curable inkjet ink is a solvent-free ink. 又、本発明は、更に、5)光カチオン重合開始剤を含むことを特徴とする上記活性エネルギー線硬化型インクジェットインキに関する。 The present invention further 5) relates to the active energy ray curable ink-jet ink characterized in that it comprises a cationic photopolymerization initiator. 又、本発明は、更に、 The present invention further
6)顔料分散剤を含むことを特徴とする上記活性エネルギー線硬化型インクジェットインキに関する。 6) regarding the active energy ray curable inkjet ink which comprises a pigment dispersing agent. 又、本発明は、更に、顔料が、平均粒経10〜150nmの微細顔料であることを特徴とする上記活性エネルギー線硬化型インクジェットインキに関する。 The present invention further pigments, relates to the above active energy ray-curable inkjet ink, which is a fine pigment having an average particle diameter 10 to 150 nm. 又、本発明は、25 Further, according to the present invention, 25
℃での粘度が5〜50mPa・sであることを特徴とする上記インクジェットインキに関する。 Viscosity at ℃ relates the inkjet ink, characterized in that the 5 to 50 mPa · s. 又、本発明は、 Further, according to the present invention,
基材に上記活性エネルギー線硬化型インクジェットインキを印刷してなる印刷物に関する。 Printed matter obtained by printing the active energy ray curable ink-jet ink to the substrate.

【0009】 [0009]

【発明の実施の形態】本発明のインクジェットインキに含まれる顔料は、カーボンブラック、酸化チタン、炭酸カルシウム等の無彩色無機顔料または有彩色の有機顔料が使用できる。 Pigment contained in the inkjet ink of the embodiment of the present invention include carbon black, titanium oxide, and organic pigments achromatic inorganic pigments or chromatic colors such as calcium carbonate can be used. 有機顔料としては、トルイジンレッド、 Examples of the organic pigment, toluidine red,
トルイジンマルーン、ハンザエロー、ベンジジンエロー、ピラゾロンレッドなどの不溶性アゾ顔料、リトールレッド、ヘリオボルドー、ピグメントスカーレット、パーマネントレッド2Bなどの溶性アゾ顔料、アリザリン、インダントロン、チオインジゴマルーンなどの建染染料からの誘導体、フタロシアニンブルー、フタロシアニングリーンなどのフタロシアニン系有機顔料、キナクリドンレッド、キナクリドンマゼンタなどのキナクリドン系有機顔料、ペリレンレッド、ペリレンスカーレットなどのペリレン系有機顔料、イソインドリノンエロー、 Toluidine Maroon, Hansa Yellow, Benzidine Yellow, insoluble azo pigments such as pyrazolone, Li tall Red, Helio Bordeaux, Pigment Scarlet, soluble azo pigments such as permanent red 2B, alizarin, indanthrone, from vat dyes such as thioindigo maroon derivatives, phthalocyanine blue, phthalocyanine-based organic pigments such as phthalocyanine green, quinacridone red, quinacridone-based organic pigments such as quinacridone magenta, perylene red, perylene-based organic pigments such as perylene scarlet, isoindolinone yellow,
イソインドリノンオレンジなどのイソインドリノン系有機顔料、ピランスロンレッド、ピランスロンオレンジなどのピランスロン系有機顔料、チオインジゴ系有機顔料、縮合アゾ系有機顔料、ベンズイミダゾロン系有機顔料、キノフタロンエローなどのキノフタロン系有機顔料、イソインドリンエローなどのイソインドリン系有機顔料、その他の顔料として、フラバンスロンエロー、アシルアミドエロー、ニッケルアゾエロー、銅アゾメチンエロー、ペリノンオレンジ、アンスロンオレンジ、ジアンスラキノニルレッド、ジオキサジンバイオレット等が挙げられる。 Isoindolinone-based organic pigments such as isoindolinone orange, pyranthrone red, pyranthrone organic pigments such as pyranthrone Orange, thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthalone yellow quinophthalone of system organic pigments, isoindoline-based organic pigments such as isoindoline yellow, as other pigments, flavanthrone yellow, acylamide yellow, nickel azo yellow, copper Azomechin'ero, Yellow, perinone Orange, Anthrone Orange, Dianthraquinonyl Red, di benzoxazine violet, and the like.

【0010】有機顔料をカラーインデックス(CI)ナンバーで例示すると、CIピグメントエロー12、13、 [0010] To illustrate the organic pigment in the Color Index (CI) number, CI Pigment Yellow 12, 13,
14、17、20、24、74、83、86 93、1 14,17,20,24,74,83,86 93,1
09、110、117、125、128、129、13 09,110,117,125,128,129,13
7、138、139、147、148、150、15 7,138,139,147,148,150,15
1、153、154、155、166、168、18 1,153,154,155,166,168,18
0、185、CIピグメントオレンジ16、36、4 0,185, CI Pigment Orange 16,36,4
3、51、55、59、61、CIピグメントレッド9、48、49、52、53、57、97、122、1 3,51,55,59,61, CI Pigment Red 9,48,49,52,53,57,97,122,1
23、149、168、177、180、192、20 23,149,168,177,180,192,20
2、206、215、216、217、220、22 2,206,215,216,217,220,22
3、224、226、227、228、238、24 3,224,226,227,228,238,24
0、CIピグメントバイオレット19、23、29、3 0, CI Pigment Violet 19,23,29,3
0、37、40、50、CIピグメントブルー15、1 0,37,40,50, CI Pigment Blue 15, 1
5:1、15:3、15:4、15:6、22、60、 5: 1, 15: 3, 15: 4, 15: 6,22,60,
64、CIピグメントグリーン7、36、CIピグメントブラウン23、25、26等が挙げられる。 64, CI Pigment Green 7, 36, such as CI Pigment Brown 23, 25, 26, and the like.

【0011】上記顔料の中で、キナクリドン系有機顔料、フタロシアニン系有機顔料、ベンズイミダゾロン系有機顔料、イソインドリノン系有機顔料、縮合アゾ系有機顔料、キノフタロン系有機顔料、イソインドリン系有機顔料等は耐光性が優れているため好ましい。 [0011] Among the above pigments, quinacridone organic pigments, phthalocyanine organic pigments, benzimidazolone organic pigments, isoindolinone-based organic pigments, condensed azo organic pigments, quinophthalone organic pigments, isoindoline-based organic pigments such as preferred because has excellent light resistance. 有機顔料は、レーザ散乱による測定値で平均粒径10〜150n Organic pigments, the average particle size 10~150n value measured by a laser scattering
mの微細顔料であることが好ましい。 It is preferably m a fine pigment. 顔料の平均粒径が10nm未満の場合は、粒径が小さくなることによる耐光性の低下が生じ、150nmを越える場合は、分散の安定維持が困難になり、顔料の沈澱が生じやすくなる。 When the average particle size of the pigment is less than 10 nm, result in lowering of light resistance due to the particle size decreases, when exceeding 150 nm, stable maintenance of the dispersion becomes difficult, precipitation of the pigment is likely to occur.

【0012】有機顔料の微細化は下記の方法で行うことができる。 [0012] fine organic pigment can be carried out in the following manner. すなわち、有機顔料、有機顔料の3重量倍以上の水溶性の無機塩および水溶性の溶剤の少なくとも3 That is, the organic pigment, at least 3 of 3 times by weight or more water-soluble inorganic salts and water-soluble solvent of the organic pigment
つの成分からなる混合物を粘土状の混合物とし、ニーダー等で強く練りこんで微細化したのち水中に投入し、ハイスピードミキサー等で攪拌してスラリー状とする。 One of a mixture of components a clay-like mixture was poured into water after miniaturized kneaded strongly kneader, and stirred to a slurry with a high speed mixer. 次いで、スラリーの濾過と水洗を繰り返して、水溶性の無機塩および水溶性の溶剤を除去する。 Then, by repeating the washing and filtration of the slurry to remove water-soluble inorganic salts and water-soluble solvent. 微細化工程において、樹脂、顔料分散剤等を添加してもよい。 In refining step, the resin may be added a pigment dispersant. 水溶性の無機塩としては、塩化ナトリウム、塩化カリウム等が挙げられる。 Examples of the water-soluble inorganic salts, sodium chloride, potassium chloride and the like. これらの無機塩は、有機顔料の3重量倍以上、 These inorganic salts are 3 times by weight or more organic pigments,
好ましくは20重量倍以下の範囲で用いる。 Preferably used in the range of 20 times by weight or less. 無機塩の量が3重量倍よりも少ないと、所望の大きさの処理顔料が得られない。 If the amount of the inorganic salt is less than 3 times by weight can not be obtained treated pigment having a desired size. また、20重量倍よりも多いと、後の工程における洗浄処理が多大であり、有機顔料の実質的な処理量が少なくなる。 Further, when it is more than 20 times by weight, the washing treatment in a later step are considerable, substantial throughput of the organic pigment is reduced.

【0013】水溶性の溶剤は、有機顔料と破砕助剤として用いられる水溶性の無機塩との適度な粘土状態をつくり、充分な破砕を効率よく行うために用いられ、水に溶解する溶剤であれば特に限定されないが、混練時に温度が上昇して溶剤が蒸発し易い状態になるため、安全性の点から沸点120〜250℃の高沸点の溶剤が好ましい。 [0013] water-soluble solvents, create an appropriate clay state of the water-soluble inorganic salt used as an organic pigment crushing aid is used sufficient crushing in order to perform efficiently, with a solvent which dissolves in water It is not particularly limited as long, because the solvent temperature increases during kneading is liable state evaporates, a high-boiling solvent having a boiling point of 120 to 250 ° C. from the viewpoint of safety is preferred. 水溶性溶剤としては、2−(メトキシメトキシ)エタノール、2−ブトキシエタノール、2−(イソペンチルオキシ)エタノール、2−(ヘキシルオキシ)エタノール、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコール、トリエチレングリコールモノメチルエーテル、液体ポリエチレングリコール、1−メトキシ−2−プロパノール、1−エトキシ−2−プロパノール、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、低分子量ポリプロピレングリコール等が挙げられる。 Examples of the water-soluble solvent, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight polypropylene glycol, and the like.

【0014】本発明において顔料は、十分な濃度および十分な耐光性を得るため、インクジェットインキ中に3 [0014] Pigment In the present invention, in order to obtain a sufficient concentration and sufficient light resistance, in the inkjet ink 3
〜15重量%の範囲で含まれることが好ましい。 It is preferably contained in the range of 15 wt%.

【0015】本発明のインクジェットインキに含まれるオキシラン基含有化合物は、分子中に1個以上の下式で示されるオキシラン環 [0015] oxirane group-containing compound contained in the inkjet ink of the present invention, the oxirane ring represented one or more the following formula in the molecule

【化1】 [Formula 1] を有する化合物であり、通常、エポキシ樹脂として用いられているものは、モノマー、オリゴマー又はポリマーいずれも使用可能である。 A compound having a normally, what is used as an epoxy resin, a monomer, any oligomers or polymers can be used. 具体的には、従来公知の芳香族エポキシド、脂環族エポキシドおよび脂肪族エポキシドが挙げられる。 Specifically, conventionally known aromatic epoxides include cycloaliphatic epoxide and aliphatic epoxide. 尚、以下エポキシドとは、モノマーまたはそのオリゴマ−を意味する。 In the following epoxide A, monomer or oligomer - means. これら化合物は、一種または必要に応じて二種以上用いてもよい。 These compounds may be used two or more thereof, if one or needed.

【0016】芳香族エポキシドとして好ましいものは、 [0016] Preferred as the aromatic epoxides,
少なくとも1個の芳香族核を有する多価フェノールあるいはそのアルキレンオキサイド付加体とエピクロルヒドリンとの反応によって製造されるジまたはポリグリシジルエーテルであり、例えばビスフェノールAあるいはそのアルキレンオキサイド付加体のジまたはポリグリシジルエーテル、水素添加ビスフェノールAあるいはそのアルキレンオキサイド付加体のジまたはポリグリシジルエーテル、ならびにノボラック型エポキシ樹脂等が挙げられる。 Polyhydric phenol or a di- or polyglycidyl ethers prepared by the reaction of an alkylene oxide adduct thereof with epichlorohydrin, such as bisphenol A di- or polyglycidyl ethers of alkylene oxide adducts thereof having at least one aromatic nucleus , di- or polyglycidyl ethers of hydrogenated bisphenol a or an alkylene oxide adduct thereof, and novolac epoxy resins. ここでアルキレンオキサイドとしては、エチレンオキサイドおよびプロピレンオキサイド等が挙げられる。 Examples of the alkylene oxide, ethylene oxide and propylene oxide.

【0017】脂環式エポキシドとしては、少なくとも1 [0017] The alicyclic epoxide, at least one
個のシクロへキセンまたはシクロペンテン環等のシクロアルカン環を有する化合物を、過酸化水素、過酸等の適当な酸化剤でエポキシ化することによって得られる、シクロヘキセンオキサイドまたはシクロペンテンオキサイド含有化合物が好ましく、具体例としては、例えば、ダイセル化学工業(株)製、セロキサイド2021、セロキサイド2021A、セロキサイド2021P、セロキサイド2080、セロキサイド3000、セロキサイド2 A compound having a cycloalkane ring such as pieces of hexene or cyclopentene ring cycloheteroalkyl, hydrogen peroxide, obtained by epoxidation with a suitable oxidizing agent such as peracetic acid, cyclohexene oxide or cyclopentene oxide-containing compounds are preferred, particularly examples include, for example, manufactured by Daicel Chemical Industries, Ltd., Celloxide 2021, Celloxide 2021A, Celloxide 2021P, Celloxide 2080, Celloxide 3000, Celloxide 2
000、エポリードGT301、エポリードGT302、エポリードGT401、エポリードGT403、EHPE−3 000, Epolead GT301, Epolead GT302, Epolead GT401, Epolead GT403, EHPE-3
150、EHPEL3150CE、ユニオンカーバイド社製、 150, EHPEL3150CE, manufactured by Union Carbide Corporation,
UVR−6105、UVR−6110、UVR−612 UVR-6105, UVR-6110, UVR-612
8、UVR−6100、UVR−6216、UVR−6 8, UVR-6100, UVR-6216, UVR-6
000等)等が挙げることができる。 It can be 000, etc.) and the like are listed.

【0018】脂肪族エポキシドの好ましいものとしては、脂肪族多価アルコールあるいはそのアルキレンオキサイド付加体のジまたはポリグリシジルエーテル等があり、その代表例としては、エチレングリコールのジグリシジルエーテル、プロピレングリコールのジグリシジルエーテルまたは1,6−ヘキサンジオールのジグリシジルエーテル等のアルキレングリコールのジグリシジルエーテル、グリセリンあるいはそのアルキレンオキサイド付加体のジまたはトリグリシジルエーテル等の多価アルコールのポリグリシジルエーテル、ポリエチレングリコールあるいはそのアルキレンオキサイド付加体のジグリシジルエーテル、ポリプロピレングリコールあるいはそのアルキレンオキサイド付加体のジグリシジルエーテル等のポリアルキレン [0018] Preferred examples of aliphatic epoxides include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and representative examples thereof include diglycidyl ethers of ethylene glycol, di propylene glycol diglycidyl ethers of alkylene glycol such as diglycidyl ether of glycidyl ether or 1,6-hexanediol, polyglycidyl ethers of polyhydric alcohols such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, polyethylene glycol or an alkylene diglycidyl ether of oxide adduct, polypropylene glycol or polyalkylene diglycidyl ether of alkylene oxide adduct thereof リコールのジグリシジルエーテル等が挙げられる。 Diglycidyl ethers of recall and the like. ここでアルキレンオキサイドとしては、エチレンオキサイドおよびプロピレンオキサイド等が挙げられる。 Examples of the alkylene oxide, ethylene oxide and propylene oxide.

【0019】さらに、これらの化合物の他に、脂肪族高級アルコールのモノグリシジルエーテルおよびフェノール、クレゾールのモノグリシジルエーテル等も用いることができる。 Furthermore, in addition to these compounds, aliphatic higher alcohols monoglycidyl ethers and phenols, monoglycidyl ethers of cresol and the like can also be used. これらのエポキシドのうち、速硬化性を考慮すると、芳香族エポキシドおよび脂環式エポキシドが好ましく、特に脂環式エポキシドが好ましい。 Among these epoxides, considering quick curability, aromatic epoxides and alicyclic epoxides are preferable and alicyclic epoxides are preferable.

【0020】オキシラン基含有化合物は、オキセタン環含有化合物および必要に応じて配合されるビニルエーテル化合物からなる液状成分中、10〜50重量%、好ましくは30〜50重量%配合される。 [0020] oxirane group-containing compound, a liquid component comprising a vinyl ether compound is blended as the oxetane ring-containing compound and requires 10 to 50 wt%, preferably 30 to 50 wt% blend. オキシラン基含有化合物が上記数値より少ないと硬化膜の強度が弱くなってしまい印字物としての耐性が得られず、上記数値より大きいと印字物の耐性はよくなるが粘度が非常に高くなってしまいインクジェットインキとして適用できなくなるため好ましくない。 Oxirane group-containing compound is not obtained resistance as printed matter strength becomes weak cured film is less than the numerical value, resistance may become the viscosity of the printed matter to be greater than the numerical value becomes extremely high inkjet undesirably it can not be applied as an ink.

【0021】本発明におけるオキセタン環含有化合物としては、分子中に1個または2個以上のオキセタン環を有する化合物が挙げられる。 [0021] As the oxetane ring-containing compound in the present invention is a compound having one or more oxetane rings in the molecule.

【0022】分子中に1個のオキセタン環を有する化合物としては、下記式(1)で表される化合物を挙げることができる。 Examples of the compound having one oxetane ring in the molecule include compounds represented by the following formula (1).

【0023】 [0023]

【化2】 ## STR2 ##

【0024】(式(1)中、Zは酸素原子又は硫黄原子、R 1は水素原子、フッ素原子、メチル基、エチル基、プロピル基又はブチル基等の炭素数1〜6個のアルキル基、炭素数1〜6個のフルオロアルキル基、アリル基、アリール基、フリル基又はチエニル基、R 2は、メチル基、エチル基、プロピル基又はブチル基等の炭素数1〜6個のアルキル基、1−プロペニル基、2−プロペニル基、2−メチル−1−プロペニル基、2−メチル− [0024] (In the formula (1), Z an oxygen atom or a sulfur atom, R 1 represents a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, or butyl alkyl group having 1 to 6 carbon atoms such as a group, number 1-6 fluoroalkyl group having a carbon, an allyl group, an aryl group, a furyl group or a thienyl group, R 2 is a methyl group, an ethyl group, a propyl group, or butyl alkyl group having 1 to 6 carbon atoms such as a group, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl group, 2-methyl -
2−プロペニル基、1−ブテニル基、2−ブテニル基又は3−ブテニル基等の炭素数1〜6個のアルケニル基、 2-propenyl, 1-butenyl, 2-butenyl or 3-butenyl number 1-6 alkenyl group having a carbon such as a group,
フェニル基、ベンジル基、フルオロベンジル基、メトキシベンジル基又はフェノキシエチル基等のアリール基、 Phenyl group, a benzyl group, fluorobenzyl group, methoxybenzyl group, or phenoxyethyl aryl group such as a group,
プロピルカルボニル基、ブチルカルボニル基又はペンチルカルボニル基等の炭素数1〜6個のアルキルカルボニル基、エトキシカルボニル基、プロポキシカルボニル基又はブトキシカルボニル基等の炭素数1〜6個のアルコキシカルボニル基、エトキシカルバモイル基、プロピルカルバモイル基又はブチルペンチルカルバモイル基等の炭素数1〜6個のアルコキシカルバモイル基を表す。 Propyl group, butyl group or pentyl group number 1-6 alkylcarbonyl group carbon atoms such as, ethoxycarbonyl group, propoxycarbonyl group, or butoxycarbonyl alkoxycarbonyl group having 1 to 6 carbons such as a group, ethoxy carbamoyl group, an alkoxy carbamoyl group having 1 to 6 carbons such as propylcarbamoyl group, or a butyl pentylcarbamoyl group. )

【0025】本発明で使用するオキセタン環含有化合物としては、上記式(1)において、R 1が低級アルキル基、特にエチル基、R 2がブチル基、フェニル基又はベンジル基、Zは酸素原子であるものが好ましい。 The oxetane ring-containing compound used in the present invention, in the above-mentioned formula (1), R 1 is a lower alkyl group, particularly an ethyl group, R 2 is a butyl group, a phenyl group or a benzyl group, Z is an oxygen atom there are preferred.

【0026】分子中に2個以上のオキセタン環を有する化合物としては、下記式(2)で表わされる化合物を挙げることができる。 Examples of the compound having two or more oxetane rings in the molecule include compounds represented by the following formula (2).

【0027】 [0027]

【化3】 [Formula 3]

【0028】(式(2)中、mは2、3又は4、Zは酸素原子又は硫黄原子、R 3は水素原子、フッ素原子、メチル基、エチル基、プロピル基又はブチル基等の炭素数1〜6個のアルキル基、フェニル基、炭素数1〜6個のフルオロアルキル基、アリル基、アリール基又はフリル基、R 4は、例えば下式(3)で示される炭素数1〜1 [0028] (In the formula (2), m 2, 3 or 4, Z is an oxygen atom or a sulfur atom, R 3 is a hydrogen atom, a fluorine atom, the number of carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group 6 alkyl group, a phenyl group, carbon number 1-6 fluoroalkyl group having a carbon, an allyl group, an aryl group or a furyl group, R 4 is represented by, for example the following formula (3) 1-1
2の線形又は分枝アルキレン基、線形或いは分枝ポリ(アルキレンオキシ)基、 2 linear or branched alkylene group, a linear or branched poly (alkyleneoxy) group,

【0029】 [0029]

【化4】 [Of 4]

【0030】(式(3)中、R 5はメチル基、エチル基又はプロピル基等の低級アルキル基を表す。) [0030] (In the formula (3), R 5 represents a lower alkyl group such as a methyl group, an ethyl group or a propyl group.)

【0031】又は、下記式(4),(5)及び(6)からなる群から選択される多価基を表す。 [0031] or the following formula (4) represents a multivalent group selected from the group consisting of (5) and (6).

【0032】 [0032]

【化5】 [Of 5]

【0033】(式(4)中、nは0又は1〜2000の整数、R 6はメチル基、エチル基、プロピル基又はブチル基等の炭素数1〜10個のアルキル基及び下記式(7)から成る群から選択される基を表す。) [0033] (Equation (4), n is 0 or 1 to 2000 integer, R 6 is a methyl group, an ethyl group, a propyl group or a C 1 -C 10 alkyl groups and the following carbocyclic and butyl group (7 ) represents a group selected from the group consisting of.)

【0034】 [0034]

【化6】 [Omitted]

【0035】(式(7)中、jは0又は1〜100の整数、R 8は1〜10個の炭素原子を有するアルキル、R [0035] (In the formula (7), j is 0 or 1 to 100 of integers, alkyl R 8 is having 1 to 10 carbon atoms, R
7はメチル基、エチル基、プロピル基又はブチル基等の炭素数1〜10のアルキル基を表す。 7 represents a methyl group, an ethyl group, a propyl group or butyl alkyl group having 1 to 10 carbon atoms, such groups. )

【0036】 [0036]

【化7】 [Omitted]

【0037】(式(5)中、R 9は、水素原子、メチル基、エチル基、プロピル基又はブチル基等の炭素数1〜 [0037] (In the formula (5), R 9 is a hydrogen atom, 1 to carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group
10個のアルキル基、炭素数1〜10個のアルコキシ基、ハロゲン原子、ニトロ基、シアノ基、メルカプト基、低級アルキルカルボキシレート基又はカルボキシル基を表す。 10 alkyl group, C 1 -C 10 alkoxy group having a carbon halogen atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxylate group or a carboxyl group. )

【0038】 [0038]

【化8】 [Of 8]

【0039】(式(6)中、R 10は酸素原子、硫黄原子、NH、SO、SO 2 、CH 2 、C(CH 32又はC(CF 32を表す。)) [0039] (In the formula (6), R 10 represents an oxygen atom, a sulfur atom, NH, SO, and SO 2, CH 2, C ( CH 3) 2 or C (CF 3) 2.) )

【0040】本発明で使用されるオキセタン環含有化合物として、上記式(2)において、R 3が低級アルキル基、特にエチル基、R 4が、式(5)においてR 9が水素原子である基、ヘキサメチレン基、式(3)においてR 5がエチル基、R 7及びR The oxetane ring-containing compound used in the present invention, in the above formula (2), R 3 is a lower alkyl group, particularly an ethyl group, is R 4, a R 9 is a hydrogen atom in the formula (5) groups , hexamethylene group, R 5 is an ethyl group in the formula (3), R 7 and R 8はメチル基、Zは酸素原子であるものが好ましい。 8 is a methyl group, Z is what is preferably an oxygen atom.

【0041】式(8)において、rは25〜200の整数であり、R 11は炭素数1〜4のアルキル基又はトリアルキルシリル基である。 [0041] In the formula (8), r is an integer of 25 to 200, R 11 is an alkyl group or a trialkylsilyl group having 1 to 4 carbon atoms.

【0042】本発明では、組成物として、上記の分子中に一個以上のオキセタン環を有する化合物を2種類以上が併用されたものであってもよい。 [0042] In the present invention, as a composition, or may be a compound having one or more oxetane rings in the molecules described above two or more are used in combination.

【0043】オキセタン環含有化合物は、オキシラン基含有化合物および必要に応じて配合されるビニルエーテル化合物からなる液状成分中、50〜90重量%、好ましくは50〜70重量%配合される。 The oxetane ring-containing compound, a liquid component comprising a vinyl ether compound is blended as an oxirane group-containing compound and requires from 50 to 90 wt%, preferably 50 to 70 wt% blend. オキセタン環含有化合物が上記数値より少ないと硬化性が悪くなってしまい、上記数値より大きいと硬化性はよくなるが、硬化膜の強度が弱く印刷物としての耐性がでなくなるため、好ましくない。 Oxetane ring-containing compound becomes poor curability smaller than the above numerical value, as large as the curable than the above figures better, but the strength of the cured film is not out resistance as weak prints, which is not preferable.

【0044】本発明のインクジェットインキに含まれるビニルエーテル化合物は、例えばエチレングリコールジビニルエーテル、エチレングリコールモノビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールモノビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、ブタンジオールジビニルエーテル、ヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ヒドロキシエチルモノビニルエーテル、 The vinyl ether compound contained in the inkjet ink of the present invention are, for example, ethylene glycol divinyl ether, ethylene glycol monomethyl ether, diethylene glycol divinyl ether, triethylene glycol monomethyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether,
ヒドロキシノニルモノビニルエーテル、トリメチロールプロパントリビニルエーテル等のジ又はトリビニルエーテル化合物、エチルビニルエーテル、n−ブチルビニルエーテル、イソブチルビニルエーテル、オクタデシルビニルエーテル、シクロヘキシルビニルエーテル、ヒドロキシブチルビニルエーテル、2−エチルヘキシルビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、n−プロピルビニルエーテル、イソプロピルビニルエーテル、イソプロペニルエーテル−O−プロピレンカーボネート、ドデシルビニルエーテル、ジエチレングリコールモノビニルエーテル、オクタデシルビニルエーテル等のモノビニルエーテル化合物等が挙げられる。 Hydroxy monovinyl ether, di- or trivinyl ether compounds such as trimethylolpropane trivinyl ether, ethyl vinyl ether, n- butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n- propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether -O- propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

【0045】これらのビニルエーテル化合物のうち、硬化性、密着性、表面硬度を考慮すると、ジ又はトリビニルエーテル化合物が好ましく、特にジビニルエーテル化合物が好ましい。 [0045] Among these vinyl ether compounds, curability, adhesion and surface hardness, di- or trivinyl ether compounds are preferable, particularly divinyl ether compounds are preferred. 本発明では、上記ビニルエーテル化合物の1種を単独で使用してもよいが、2種以上を適宜組み合わせて使用してもよい。 In the present invention, it may be used alone one of the above vinyl ether compounds, or may be used in combination of two or more kinds thereof.

【0046】ビニルエーテル化合物は、任意の配合成分であり、配合させることによってインクジェットインキに要求される低粘度化が実現できる。 The vinyl ether compounds are optional ingredients, low viscosity can be achieved which is required in the inkjet ink by weight. また、硬化速度の向上もできる。 It is also improved in the curing rate. ビニルエーテル化合物は、オキシラン基含有化合物およびオキセタン環含有化合物からなる液状成分中、0〜40重量%、好ましくは0〜20重量%が配合される。 Vinyl ether compounds, the liquid component consisting of an oxirane group-containing compound and an oxetane ring-containing compound, 0 to 40 wt%, preferably 0 to 20 wt% are blended.

【0047】本発明で用いられる光カチオン重合開始剤としては、アリールスルホニウム塩誘導体(例えばユニオン・カーバイド社製のサイラキュアUVI−699 [0047] As the cationic photopolymerization initiator used in the present invention, aryl sulfonium salt derivatives (e.g. made of Union Carbide Cyracure UVI-699
0、サイラキュアUVI−6974、旭電化工業社製のアデカオプトマーSP−150、アデカオプトマーSP 0, CYRACURE UVI-6974, manufactured by Asahi Denka Kogyo KK of ADEKAOPTOMER SP-150, ADEKAOPTOMER SP
−152、アデカオプトマーSP−170、アデカオプトマーSP−172)、アリルヨードニウム塩誘導体(例えばローディア社製のRP−2074)、アレン− -152, Adekaoptomer SP-170, Adekaoptomer SP-172), RP-2074 allyl iodonium salt derivatives (e.g. Rhodia), Allen -
イオン錯体誘導体(例えばチバガイギー社製のイルガキュア261)、ジアゾニウム塩誘導体、トリアジン系開始剤及びその他のハロゲン化物等の酸発生剤が挙げられる。 Ion complex derivatives (e.g. Irgacure 261 manufactured by Ciba-Geigy), diazonium salt derivatives, triazine type initiators and acid generator such as other halides. カチオン重合開始剤は、脂環式エポキシ基を有する化合物100重量部に対して、0.2〜20重量部の比率で含有させることが好ましい。 Cationic polymerization initiator, relative to compound 100 parts by weight having an alicyclic epoxy group, it is preferably contained in a proportion of 0.2 to 20 parts by weight. 重合開始剤の含有量が0.2重量部未満では硬化物を得ることが困難であり、 The content of the polymerization initiator is less than 0.2 part by weight, it is difficult to obtain a cured product,
20重量部を越えて含有させてもさらなる硬化性向上効果はない。 Is contained more than 20 parts by weight does not further curable improving effect even. これら光カチオン重合開始剤は、1種又は2 These photo cationic polymerization initiators, one or
種以上を選択して使用することができる。 It can be used to select the more species.

【0048】光重合促進剤としては、アントラセン、アントラセン誘導体(例えば旭電化工業社製のアデカオプトマーSP−100)が挙げられる。 [0048] As the photopolymerization accelerator, anthracene, (Adekaoptomer SP-100, for example, Asahi Denka Co., Ltd.) anthracene derivatives. これらの光重合促進剤は1種または複数を組み合わせて使用することができる。 These photopolymerization accelerator may be used in combination of one or more.

【0049】本発明の顔料分散剤としては、水酸基含有カルボン酸エステル、長鎖ポリアミノアマイドと高分子量酸エステルの塩、高分子量ポリカルボン酸の塩、長鎖ポリアミノアマイドと極性酸エステルの塩、高分子量不飽和酸エステル、高分子共重合物、変性ポリウレタン、 [0049] As the pigment dispersing agent of the present invention, hydroxyl group-containing carboxylic acid esters, long-chain polyaminoamide and a salt of a high molecular weight acid ester, high molecular weight salt of a polycarboxylic acid, a long chain salts of polyaminoamide and a polar acid ester, high molecular weight unsaturated acid esters, high molecular copolymers, modified polyurethanes,
変性ポリアクリレート、ポリエーテルエステル型アニオン系活性剤、ナフタレンスルホン酸ホルマリン縮合物塩、芳香族スルホン酸ホルマリン縮合物塩、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンノニルフェニルエーテル、ステアリルアミンアセテート、顔料誘導体等を挙げることができる。 Modified polyacrylates, polyether ester type anionic active agents, naphthalenesulfonic acid-formalin condensate salts, aromatic sulfonic acid formalin condensate salts, polyoxyethylene alkyl phosphate esters, polyoxyethylene nonylphenyl ether, stearylamine acetate, pigments mention may be made of the derivatives and the like.

【0050】顔料分散剤の具体例としては、BYK C [0050] Specific examples of the pigment dispersant, BYK C
hemie社製「Anti−Terra−U(ポリアミノアマイド燐酸塩)」、「Anti−Terra−20 hemie Co. "Anti-Terra-U (polyaminoamide phosphate)", "Anti-Terra-20
3/204(高分子量ポリカルボン酸塩)」、「Dis 3/204 (high molecular weight poly-carboxylic acid salt) "," Dis
perbyk−101(ポリアミノアマイド燐酸塩と酸エステル)、107(水酸基含有カルボン酸エステル)、110(酸基を含む共重合物)、130(ポリアマイド)、161、162、163、164、165、 perbyk-101 (polyaminoamide phosphoric acid salt and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), (copolymer containing an acid group) 110, 130 (polyamide), 161,162,163,164,165,
166、170(高分子共重合物)」、「400」、 166, 170 (polymer copolymer) "," 400 ",
「Bykumen」(高分子量不飽和酸エステル)、 "Bykumen" (high molecular weight unsaturated acid ester),
「BYK−P104、P105(高分子量不飽和酸ポリカルボン酸)」、「P104S、240S(高分子量不飽和酸ポリカルボン酸とシリコン系)」、「Lacti "BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid)", "P104S, 240S (high molecular weight unsaturated acid polycarboxylic acid and silicon-based)", "Lacti
mon(長鎖アミンと不飽和酸ポリカルボン酸とシリコン)」が挙げられる。 mon (silicon and long chain amine and unsaturated acid polycarboxylic acid) "can be mentioned.

【0051】また、Efka CHEMICALS社製「エフカ44、46、47、48、49、54、63、 [0051] In addition, Efka CHEMICALS Co., Ltd. "Efka 44,46,47,48,49,54,63,
64、65、66、71、701、764、766」、 64,65,66,71,701,764,766 "
「エフカポリマー100(変性ポリアクリレート)、1 "Efukaporima 100 (modified polyacrylate), 1
50(脂肪族系変性ポリマー)、400、401、40 50 (aliphatic modified polymer), 400,401,40
2、403、450、451、452、453(変性ポリアクリレート)、745(銅フタロシアニン系)」、 2,403,450,451,452,453 (modified polyacrylate), 745 (copper phthalocyanine) ",
共栄社化学社製「フローレン TG−710(ウレタンオリゴマー)、「フローノンSH−290、SP−10 Kyoeisha Chemical Co., Ltd. "FLOREN TG-710 (urethane oligomer)," Furonon SH-290, SP-10
00」、「ポリフローNo.50E、No.300(アクリル系共重合物)」、楠本化成社製「ディスパロン 00 "," Polyflow No.50E, No.300 (acrylic copolymer) ", manufactured by Kusumoto Chemicals, Ltd." DISPARON
KS−860、873SN、874(高分子分散剤)、 KS-860,873SN, 874 (polymer dispersant),
#2150(脂肪族多価カルボン酸)、#7004(ポリエーテルエステル型)」が挙げられる。 # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester type) "can be mentioned.

【0052】さらに、花王社製「デモールRN、N(ナフタレンスルホン酸ホルマリン縮合物ナトリウム塩)、 [0052] Furthermore, manufactured by Kao Corporation "Demol RN, N (naphthalenesulfonic acid formalin condensate sodium salt),
MS、C、SN−B(芳香族スルホン酸ホルマリン縮合物ナトリウム塩)、EP」、「ホモゲノールL−18 MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP "," HOMOGENOL L-18
(ポリカルボン酸型高分子)、「エマルゲン920、9 (Polycarboxylic acid type polymer), "Emulgen 920,9
30、931、935、950、985(ポリオキシエチレンノニルフェニルエーテル)、「アセタミン24 30,931,935,950,985 (polyoxyethylene nonylphenyl ether), "Acetamin 24
(ココナッツアミンアセテート)、86(ステアリルアミンアセテート)」、ゼネカ社製「ソルスパーズ500 (Coconut amine acetate), 86 (stearylamine acetate) ", manufactured by Zeneca" Solsperse 500
0(フタロシアニンアンモニウム塩系)、13240、 0 (phthalocyanine ammonium salt-based), 13240,
13940(ポリエステルアミン系)、17000(脂肪酸アミン系)、24000、32000」、日光ケミカル社製「ニッコール T106(ポリオキシエチレンソルビタンモノオレート)、MYS−IEX(ポリオキシエチレンモノステアレート)、Hexagline 13940 (polyester amine type), 17000 (fatty acid amine type), 24000,32000 ", Nikko Chemicals Co., Ltd." Nikkol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Hexagline
4−0(ヘキサグリセリルテトラオレート)」等が挙げられる。 4-0 (hexa glyceryl Rute Huwei rate) ", and the like.

【0053】本発明の顔料分散剤はインキ中に0.1〜 [0053] pigment dispersing agent of the present invention is 0.1 in the ink
10重量%の範囲で分散剤を含有させることが好ましい。 Preferably contains a dispersing agent in a range of 10 wt%.

【0054】本発明のインクジェットインキは、活性エネルギー線硬化性化合物、顔料分散剤と共に、顔料をサンドミル等の通常の分散機を用いてよく分散することにより製造される。 [0054] Inkjet inks of the present invention, the active energy ray-curable compound, together with a pigment dispersing agent is prepared by well dispersed using a conventional dispersing machine such as a sand mill pigments. 予め顔料高濃度の濃縮液を作成しておいて活性エネルギー線硬化性化合物で希釈することが好ましい。 It is preferable to dilute the active energy ray-curable compound in advance to prepare a pigment-rich concentrate. 通常の分散機による分散においても充分な分散が可能であり、このため、過剰な分散エネルギーがかからず、多大な分散時間を必要としないため、インキ成分の分散時の変質を招きにくく、安定性に優れたインキが調製される。 It is possible also sufficient dispersion in the dispersion by conventional dispersing machine, and therefore, does not take excess dispersion energy and does not require a great deal of dispersion time, hardly causes deterioration of the dispersion of the ink component, stable excellent ink is prepared to sex. インキは、孔径3μm以下さらには、1μ Ink is more or less pore size 3 [mu] m, 1 [mu]
以下のフィルターにて濾過することが好ましい。 It is preferable that the filtration in the following filter.

【0055】本発明のインクジェットインキは、25℃ [0055] Inkjet inks of the present invention, 25 ° C.
での粘度が5〜50mPa・sと高めに調整することが好ましい。 It is preferable that the viscosity at is adjusted to 5 to 50 mPa · s and enhanced. 25℃での粘度が5〜50mPa・sのインキは、特に通常の4〜10KHzの周波数を有するヘッドから、10〜50KHzの高周波数のヘッドにおいても安定した吐出特性を示す。 Ink viscosity is 5 to 50 mPa · s at 25 ° C., especially from the head with a frequency of normal 4~10KHz, also shows a stable discharge characteristics in the head of the high-frequency 10~50KHz. 粘度が5mPa・s未満の場合は、高周波数のヘッドにおいて、吐出の追随性の低下が認められ、50mPa・sを越える場合は、加熱による粘度の低下機構をヘッドに組み込んだとしても吐出そのものの低下を生じ、吐出の安定性が不良となり、全く吐出できなくなる。 If the viscosity is less than 5 mPa · s, at the head of the high-frequency, observed decrease followers of discharge, if exceeding 50 mPa · s, of the ejection itself a reduction mechanism in viscosity due to heating as incorporated in the head cause deterioration, ejection stability becomes poor, can not be completely discharged.

【0056】また、本発明のインクジェットインキは、 [0056] The ink jet inks of the present invention,
ピエゾヘッドにおいては、10μS/cm以下の電導度とし、ヘッド内部での電気的な腐食のないインキとすることが好ましい。 In piezo head, the following conductivity of 10 [mu] S / cm, it is preferable that the ink without electricity corrosion inside a head. また、コンティニュアスタイプにおいては、電解質による電導度の調整が必要であり、この場合には、0.5mS/cm以上の電導度に調整する必要がある。 In the continuous type, it is necessary to adjust the conductivity by the electrolyte, in this case, it is necessary to adjust the above conductivity 0.5 mS / cm.

【0057】本発明で用いる合成樹脂基材としては、従来各種の用途で使用されている広汎な合成樹脂が全て対象となり、具体的には、例えば、ポリエステル、ポリ塩化ビニル、ポリエチレン、ポリウレタン、ポリプロピレン、アクリル樹脂、ポリカーボネート、ポリスチレン、 [0057] As the synthetic resin base material used in the present invention, extensive synthetic resin used in the conventional various applications are all subject, specifically, for example, polyester, polyvinyl chloride, polyethylene, polyurethane, polypropylene , acrylic resin, polycarbonate, polystyrene,
アクリロニトリル−ブタジエン−スチレン共重合体、ポリエチレンテレフタレート、ポリブタジエンテレフタレート等が挙げられ、これらの合成樹脂基材の厚みや形状は何ら限定されない。 Acrylonitrile - butadiene - styrene copolymer, polyethylene terephthalate, polybutadiene terephthalate and the like, the thickness and shape of these synthetic resin substrate is not limited.

【0058】本発明のインクジェットインキを使用するには、まずこのインクジェットインキをインクジェット記録方式用プリンタのプリンタヘッドに供給し、このプリンタヘッドから基材上に吐出し、その後紫外線又は電子線等の活性エネルギー線を照射する。 [0058] To use the inkjet ink of the present invention, first supplies the ink jet ink to the printer head of an ink jet recording method for printers, ejected from the printer head onto a substrate, then UV or activity such as electron beams irradiating an energy beam. これにより印刷媒体上の組成物は速やかに硬化する。 Thus compositions on the print medium is rapidly cured.

【0059】なお、活性エネルギー線の光源としては、 [0059] Incidentally, as the light source of the active energy ray,
紫外線を照射する場合には、例えば水銀アークランプ、 In the case of irradiation with ultraviolet rays, for example, mercury arc lamps,
キセノンアークランプ、螢光ランプ、炭素アークランプ、タングステン−ハロゲン複写ランプおよび太陽光を使用することができる。 It may be used halogen copying lamp and sunlight - Xenon arc lamp, a fluorescent lamp, a carbon arc lamp, a tungsten. 電子線により硬化させる場合には、通常300eVの以下のエネルギーの電子線で硬化させるが、1〜5Mradの照射量で瞬時に硬化させることも可能である。 When cured by electron beam, is cured with the following electron beam energy of usually 300 eV, it is also possible to cure instantly dose of 1~5Mrad.

【0060】 [0060]

【実施例】以下、実施例に基づいて説明する。 EXAMPLES The following will be described based on examples. 例中の部および%は、重量部および重量%をそれぞれ示す。 Parts and% in the examples indicates parts by weight and% by weight respectively. 実施例1〜8 表1に示す顔料と分散剤及びオキシラン基含有化合物、 Dispersing agent and an oxirane group-containing compound and a pigment shown in Examples 1-8 Table 1,
オキセタン環含有化合物、ビニルエーテル化合物を共にサンドミルに入れて分散を4時間行ない、活性エネルギー線硬化型インキ原液を得た。 Oxetane ring-containing compound, together dispersion placed in a sand mill vinyl ether compound subjected 4 hours to obtain an active energy beam-curable ink stock solution. 次いで光開始剤をインキ原液に加え、光開始剤が溶解するまで、穏やかに混合させた後、これをメンブランフィルターで加圧濾過し、活性エネルギー線硬化型IJインキを得た。 Then added photoinitiator in the ink stock solution, until the photoinitiator had dissolved, after mixing gently, which filtered under pressure through a membrane filter to obtain an active energy ray-curable IJ ink. このインキはピエゾヘッドを有するIJプリンタにて各種基材(ポリカーボネイト、ポリスチレン、ABS(アセトニトリル−スチレン−ブタジエン共重合体)、ポリ塩化ビニル、ポリエチレンテレフタラート、ポリブチレンテレフタラート)に印字を行い、その後UV照射装置(メタルハライドランプ1灯:出力120W)により、被印刷体の搬送速度10m/分の条件で硬化を行った。 The ink of various substrates at IJ printer having a piezo head performs printing (polycarbonate, polystyrene, ABS (acetonitrile - - styrene-butadiene copolymer), polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate), the subsequent UV irradiation device (a metal halide lamp 1 lamp: output 120 W) by, it was cured at a conveying speed 10 m / min condition of the printing member.

【0061】 [0061]

【表1】 [Table 1]

【0062】表中の化合物は、下記のものを示す。 The compounds in the table, show the following. 数字は部数を示す。 The numbers indicate the number of copies. 顔料 ・P1 粗製銅フタロシアニン(東洋インキ製造社製「銅フタロシアニン」):250部、塩化ナトリウム:25 Pigment · P1 crude copper phthalocyanine (Toyo Ink Mfg. Co., Ltd. "copper phthalocyanine"): 250 parts, sodium chloride: 25
00部およびポリエチレングリコール(東京化成社製「ポリエチレングリコール300」):160部をスチレン製1ガロンニーダー(井上製作所社製)に仕込み、 00 parts of polyethylene glycol (manufactured by Tokyo Kasei Kogyo Co., Ltd. "polyethylene glycol 300") were charged 160 parts of styrene, Ltd. 1 gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.),
3時間混練した。 3 hours and the mixture was kneaded. 次に、この混合物を2.5リットルの温水に投入し、約80℃に加熱しながらハイスピードミキサーで約1時間攪拌しスラリー状とした後、濾過、水洗を5回繰り返して塩化ナトリウムおよび溶剤を除き、 The mixture was then poured into a 2.5 liter hot water, after the high-speed mixer for about 1 hour stirring slurry while heating to about 80 ° C., filtered, washed with water 5 times repeatedly sodium chloride and the solvent except,
次いでスプレードライをして乾燥した処理顔料を得た。 Then to obtain a treated pigment was dried by spray drying. ・P2 キナクリドン系赤顔料(Ciba Geigy社製「シンカシアマゼンタRT-355-D」):250部、 · P2 quinacridone red pigment (Ciba Geigy Corp. "Shin Cassia Magenta RT-355-D"): 250 parts,
塩化ナトリウム:2500部、および「ポリエチレングリコール300」:160部をスチレン製1ガロンニーダーに仕込み、P1と同様にして処理顔料を得た。 Sodium chloride: 2500 parts, and "polyethylene glycol 300": 160 parts were charged into a styrene-made 1 gallon kneader to obtain and processed pigments as in P1. ・P3 ベンズイミダゾロン系黄顔料(ヘキスト社製「ホスタパーム エロー H3G」):250部、塩化ナトリウム:2500部、および「ポリエチレングリコール300」:160部をスチレン製1ガロンニーダーに仕込み、P1と同様にして処理顔料を得た。 · P3 benzimidazolone yellow pigment (Hoechst "Hostaperm Yellow H3G"): 250 parts of sodium chloride: 2500 parts, and "polyethylene glycol 300": 160 parts were charged into a styrene-made 1 gallon kneader, in the same manner as P1 to obtain a processing pigment Te. ・P4 カーボンブラック顔料「Printex 15 · P4 carbon black pigment "Printex 15
0T」(デグサ社製) 0T "(manufactured by Degussa)

【0063】オキシラン基含有化合物・ セロキサイド3000 脂環式エポキシ(ダイセル社製) ・UVR6110 脂環式エポキシ(ユニオンカーバイド社製) オキセタン環含有化合物 ・XDO 1,4−ビス[[(3−エチル−3−オキセタニル)メトキシ]メチル}ベンゼン(東亞合成社製) ・POX 3−エチル−3−(フェノキシメチル)オキセタン(東亞合成社製) ・OXA 3−エチル−3−ひどろきしメチルオキセタン [0063] oxirane group-containing compound, CELLOXIDE 3000 cycloaliphatic epoxy (manufactured by Daicel Chemical Industries, Ltd.), UVR6110 cycloaliphatic epoxy (manufactured by Union Carbide Corp.) oxetane ring-containing compound, XDO 1,4-bis [[(3-ethyl-3 - oxetanyl) methoxy] methyl} benzene (manufactured by Toagosei Co., Ltd.) · POX 3- ethyl-3- (phenoxymethyl) oxetane (manufactured by Toagosei Co., Ltd.) · OXA 3- ethyl-3-hydroxymethyl oxetane
(東亞合成社製) ビニルエーテル化合物 ・DVE-3 トリエチレングリコールジビニルエーテル(IS (Produced by Toagosei Co., Ltd.) vinyl ether compound · DVE-3 Triethylene glycol divinyl ether (IS
P社製) P Co., Ltd.)

【0064】分散剤 ・32000 脂肪族変性系分散剤(「ソルスパーズ32000」 [0064] dispersants, 32000 aliphatic modified dispersant ( "Solsperse 32000"
ゼネカ社製) Zeneca Co., Ltd.)

【0065】開始剤・ SP-150 トリフェニルスルホニウム塩 (「アデカオプトマーSP-150」旭電化社製)・ SP-170 トリフェニルスルホニウム塩 (「アデカオプトマーSP-170」旭電化社製)・ UVI6990トリフェニルスルホニウム塩 (「サイラキュアU [0065] (manufactured by "ADEKAOPTOMER SP-170" manufactured by Asahi Denka Co., Ltd.) Initiator-SP-0.99 triphenylsulfonium salt ( "Adekaoptomer SP-0.99" manufactured by Asahi Denka Co., Ltd.), SP-170 triphenylsulfonium salt, UVI6990 triphenylsulfonium salt ( "CYRACURE U
VI6990」ユニオンカーバイド社製) VI6990 "manufactured by Union Carbide Corporation)

【0066】比較例1〜4 表2に示す顔料と分散剤及びモノマを共にサンドミルに入れて分散を4時間行ない、活性エネルギー線硬化型I [0066] performed and pigments shown in Comparative Examples 1-4 Table 2 dispersants and monomer together 4 hours a dispersion placed in a sand mill, an active energy ray-curable I
Jインキ原液を得た。 To obtain a J ink stock. 次いで光開始剤をインキ原液に加え、光開始剤が溶解するまで、穏やかに混合させた後、 Then added photoinitiator in the ink stock solution, until the photoinitiator had dissolved, after gentle mixing,
これをメンブランフィルターで加圧濾過し、活性エネルギー線硬化型IJインキを得た。 This filtered under pressure through a membrane filter to obtain an active energy ray-curable IJ ink. このインキはピエゾヘッドを有するIJプリンタにて上記の基材に印字を行い、その後UV照射装置(メタルハライドランプ1灯: The ink performs the printing on the base material by IJ printer having a piezo head, then UV irradiation apparatus (a metal halide lamp 1 lamp:
出力120W)により、被印刷体の搬送速度10m/分の条件で硬化を行った。 The output 120 W), was cured at a conveying speed 10 m / min condition of the printing member.

【0067】 [0067]

【表2】 [Table 2]

【0068】表中の化合物は、実施例1〜8に使用したものと同じものを使用した。 The compounds in the table were the same as those used in Examples 1-8. 数字は部数を示す。 The numbers indicate the number of copies.

【0069】実施例1〜8、比較例1〜4で得られたインキおよび印刷物について、下記の評価を行った。 [0069] Examples 1-8, the obtained ink and printed in Comparative Examples 1 to 4 were evaluated as follows. 結果を表3に示す。 The results are shown in Table 3.

【0070】 [0070]

【表3】 [Table 3]

【0071】表中の評価方法 [粘度]インキの粘度を、B型粘度計を用いて25℃にて測定したときの値。 [0071] The viscosity of the evaluation methods Viscosity ink in the table, the value when measured at 25 ° C. using a B-type viscometer. 単位はmPa・s [硬化性]指触によりタックがなくなるまでのココンベアUVランプのパス回数。 The number of passes of Kokonbea UV lamp until the unit is tack is eliminated by mPa · s [curing] finger touch. [経時安定性]インキを25℃で1ヵ月保存後の分散状態を目視および粘度変化により評価した。 [Temporal stability] The ink was visually evaluated and the change in viscosity of the dispersion state after 1 month storage at 25 ° C.. ○:沈殿物の発生が認められず、粘度の変化なし △:沈殿物の発生が認められず、粘度が増加 ×:沈殿物の発生が認められる。 ○: not observed the occurrence of precipitates, no change in viscosity △: not observed the occurrence of precipitates, viscosity increases ×: occurrence of precipitation is observed. [膜強度] 硬化膜の強度を爪の引っ掻き試験で行った。 Membrane Strength was carried out the strength of the cured film in the scratch test of the nail. ○:引っ掻いても全くとれない △:強く引っ掻くと若干とれる ×:引っ掻くと簡単にとれてしまう ○: scratched not be taken at all even if △: strongly scratching and some take ×: scratching and easily become caught

【発明の効果】本発明により、活性エネルギー線硬化性化合物に顔料を分散したインクジェットにおいて、低粘度で、硬化膜の強度が強く、硬化性がよく、安定性が良好でノズルでの吐出安定性がよいインクジェットインキを得ることができた。 Effect of the Invention] The present invention, in an inkjet dispersed pigment in the active energy ray-curable compound, a low viscosity, the strength of the cured film is strong, good curability, stability ejection stability in good nozzle it was possible to obtain a good inkjet ink. 又、本発明のインクジェットインキにより記録した記録物は、透明性が高く、記録物の耐性に優れ、光沢に優れる。 Moreover, it recorded matter recorded by the ink-jet ink of the present invention has high transparency, good resistance of the recording material, excellent in gloss.

フロントページの続き Fターム(参考) 2C056 EA13 FC01 FC02 2H086 BA55 BA59 BA60 BA61 4J005 AA04 AA07 AA11 BA00 4J039 AD21 AE07 BD02 BE01 BE22 BE27 EA04 EA38 EA39 EA43 EA44 EA46 EA48 GA24 Front page of the continued F-term (reference) 2C056 EA13 FC01 FC02 2H086 BA55 BA59 BA60 BA61 4J005 AA04 AA07 AA11 BA00 4J039 AD21 AE07 BD02 BE01 BE22 BE27 EA04 EA38 EA39 EA43 EA44 EA46 EA48 GA24

Claims (7)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】1)オキシラン基含有化合物10〜50重量%、2)オキセタン環含有化合物50〜90重量%、 1. A 1) oxirane group containing compounds 10 to 50 wt%, 2) an oxetane ring-containing compound 50 to 90 wt%,
    および3)ビニルエーテル化合物0〜40重量%からなる液状成分に、4)顔料を分散してなることを特徴とする活性エネルギー線硬化型インクジェットインキ。 And 3) a liquid component comprising a vinyl ether compound 0-40 wt%, 4) active-energy ray curable ink-jet inks, characterized in that by dispersing pigment.
  2. 【請求項2】無溶剤型インキである請求項1記載の活性エネルギー線硬化型インクジェットインキ。 2. A according to claim 1, wherein the solvent-free inks active energy ray-curable inkjet ink.
  3. 【請求項3】更に、5)光カチオン重合開始剤を含む請求項1または2記載の活性エネルギー線硬化型インクジェットインキ。 3. Furthermore, 5) the active energy ray curable ink-jet ink of claim 1 or 2, wherein including an optical cationic polymerization initiator.
  4. 【請求項4】更に6)顔料分散剤を含む請求項1ないし3いずれか記載の活性エネルギー線硬化型インクジェットインキ。 4. A further 6) according to claim 1 to 3 active energy ray-curable inkjet ink according to any one containing a pigment dispersing agent.
  5. 【請求項5】顔料が平均粒経10〜150nmの微細顔料である請求項1ないし4請求項3いずれか記載の活性エネルギー線硬化型インクジェットインキ。 5. A pigment is the average particle diameter is fine pigment 10~150nm claims 1 to 4 claim 3 active energy ray-curable inkjet ink according to any one.
  6. 【請求項6】25℃での粘度が5〜50mPa・sである請求項1ないし5いずれか記載の活性エネルギー線硬化型インクジェットインキ。 6. 25 viscosity at ℃ is 5 to 50 mPa · s according to claim 1 to 5 active energy ray-curable inkjet ink according to any one.
  7. 【請求項7】基材に請求項1ないし7いずれか記載の活性エネルギー線硬化型インクジェットインキを印刷してなる印刷物。 7. claims 1 to substrates to 7 prints made by printing the active energy ray-curable inkjet ink according to any one.
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