【０００１】[0001]
【発明の属する技術分野】本発明は，有機白色顔料から
なるインクジェット記録用インクに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording ink comprising an organic white pigment.
【０００２】[0002]
【従来の技術】インクジェット記録用インクを用いて印
刷するフルカラー印刷において，選択可能な顔料の種類
は，安定に分散可能な顔料の種類が少なく，従来の基本
４色（ブラック，シアン，マゼンタおよびイエロー）で
のフルカラー印刷物の色調を自由に微調整することが困
難であった。従来からホワイトインクによる調色が知ら
れているが，調色による色の濁りやインク自体の分散安
定性不足による保存性の問題から事実上は困難であっ
た。2. Description of the Related Art In full-color printing using an ink jet recording ink, there are few types of pigments that can be stably dispersed, and the conventional four colors (black, cyan, magenta and yellow) can be selected. It has been difficult to freely finely adjust the color tone of the full-color printed matter in the above method. Conventionally, toning with white ink has been known, but it has been practically difficult due to the problem of storability due to color turbidity due to toning and insufficient dispersion stability of the ink itself.
【０００３】従来の記録用インク，特にインクジェット
記録用水性インクの多くは白色着色剤としてクレイ，カ
オリン粘土，タルク，炭酸カルシウム，酸化亜鉛あるい
は酸化チタン等の無機成分を単独又は適宜混合，分散さ
せることで用いられてきた。しかしながらこれらのもの
は無機性のためその比重が大きく，これを分散組成物と
したときは顔料成分が沈降しやすく，均一で安定な分散
組成物をつくりにくい。また，このことは該顔料分散組
成物の保存安定性の面からも好ましいことではない。更
にこのような顔料組成物を例えば紙に塗工した場合，当
然紙の重量をも増大させる結果となる。また，無機性の
顔料は一般にバインダー，その他分散組成物の調整に必
要な添加剤などとの相溶性が劣るといった欠点があっ
た。[0003] Many conventional recording inks, especially aqueous ink jet recording inks, use inorganic components such as clay, kaolin clay, talc, calcium carbonate, zinc oxide or titanium oxide as a white colorant alone or in a suitable mixture and dispersion. Has been used in However, these materials have a high specific gravity due to their inorganic nature, and when they are used as a dispersion composition, the pigment component tends to settle, making it difficult to produce a uniform and stable dispersion composition. This is not preferable from the viewpoint of storage stability of the pigment dispersion composition. Further, when such a pigment composition is applied to paper, for example, it naturally results in increasing the weight of the paper. In addition, inorganic pigments generally have a drawback in that they have poor compatibility with binders and other additives necessary for adjusting the dispersion composition.
【０００４】また，有機顔料を用いたインクジェット記
録用インクにおいて，例えば，特開平１１−１４０３６
５号公報には，有機顔料を樹脂の水溶性アンモニウム塩
で分散させ，更にその樹脂質量比率が１００：２５〜１
００：５０であるインクジェット記録用インク組成物の
記載がされている。Further, in an ink jet recording ink using an organic pigment, for example, JP-A-11-14036
In JP-A-5, an organic pigment is dispersed in a water-soluble ammonium salt of a resin, and the mass ratio of the resin is from 100: 25 to 1: 1.
A description of the ink composition for ink jet recording at 00:50 is given.
【０００５】しかしながら，有機顔料を水溶性アンモニ
ウム塩で分散させた系では，低粘度の液中では沈降しや
すく，容器底部で固形物を生じやすく，インク吐出ノズ
ルで目詰まりを起こしやすい。更に，室温放置では比較
的安定であるが，高温／低温環境下では，沈降が激し
く，インクジェット記録用インクとしては問題点があっ
た。[0005] However, in a system in which an organic pigment is dispersed with a water-soluble ammonium salt, sedimentation tends to occur in a low-viscosity liquid, solids are easily generated at the bottom of the container, and clogging is likely to occur at an ink discharge nozzle. Furthermore, although it is relatively stable when left at room temperature, it sediments violently under high / low temperature environments, and has a problem as an ink for ink jet recording.
【０００６】[0006]
【発明が解決しようとする課題】本発明が解決しようと
する課題は，分散安定性および保存安定性に優れた白色
のインクジェット記録用インクを提供するものである。
また，被記録媒体に印字した印字物の耐久性を向上させ
るインクジェット記録用インクを提供するものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a white ink jet recording ink having excellent dispersion stability and storage stability.
Another object of the present invention is to provide an ink jet recording ink that improves the durability of a printed matter printed on a recording medium.
【０００７】[0007]
【課題を解決するための手段】本発明者は，上記の課題
を解決するために鋭意研究を重ねた結果，インク中に存
在する着色剤が有機白色顔料であって，該有機白色顔料
を皮膜形成性樹脂で被覆した着色樹脂粒子として水性媒
体中に分散させることで，本発明を完成するに至った。
該有機白色顔料としては，下記一般式（Ｉ）The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the coloring agent present in the ink is an organic white pigment. The present invention has been completed by dispersing in an aqueous medium as colored resin particles coated with a forming resin.
As the organic white pigment, the following general formula (I)
【０００８】[0008]
【化３】（ただし，Ｒは水素原子，炭素数１〜４の低級アルキル
基又は脂環式基を示す。また，Ｒ1 ，Ｒ2 ，Ｒ3 ，Ｒ4
はそれぞれ独立に水素原子，炭素数１〜４の低級アルキ
ル基を示し，窒素原子と共に複素環式基を形成してもよ
い。また，Ｘは炭素数２〜３の低級アルキレン基を示
す。）Embedded image (However, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or an alicyclic group. R1 , R2 , R3 , R4
Each independently represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and may form a heterocyclic group together with a nitrogen atom. X represents a lower alkylene group having 2 to 3 carbon atoms. )
【０００９】で表される有機白色顔料が好ましく，中で
も特に下記構造式（ＩＩ）The organic white pigment represented by the following formula (II) is preferable, and among them,
【００１０】[0010]
【化４】Embedded image
【００１１】で表される有機白色顔料が好ましい。The organic white pigment represented by the formula (1) is preferred.
【００１２】上記一般式（Ｉ）で表される有機白色顔料
は，一般に高い融点（３００゜Ｃ以上）を有し，特に，
前記構造式（ＩＩ）で表される有機白色顔料は白色結晶
体で３１４゜Ｃの融点を有することから，耐熱性に優れ
ているため好ましいのである。また，白色度が高く，隠
蔽性も良好であり，有機化合物であるため従来の無機系
化合物に比較して比重が非常に小さい。更に各種溶媒系
に難溶性であるためインクジェットで記録した印字物の
耐溶剤性が良好である。The organic white pigment represented by the general formula (I) generally has a high melting point (300 ° C. or higher).
The organic white pigment represented by the structural formula (II) is preferable because it is a white crystal and has a melting point of 314 ° C. and thus has excellent heat resistance. In addition, it has high whiteness, good hiding power, and is very small in specific gravity as compared with conventional inorganic compounds because it is an organic compound. Furthermore, since it is hardly soluble in various solvent systems, the printed matter recorded by inkjet has good solvent resistance.
【００１３】前記有機白色顔料を用いてインクジェット
記録用インクとするには，環境衛生上の点から，水性媒
体としては水が好ましい。水性媒体として用いる水は，
主としてインクジェット記録用インクとして用いる場合
にはノズル目詰まりを回避するためにイオン交換水以上
のグレードの水が好ましい。In order to prepare an ink for inkjet recording using the organic white pigment, water is preferable as the aqueous medium from the viewpoint of environmental hygiene. The water used as the aqueous medium is
When used mainly as ink for ink jet recording, water of a grade higher than ion exchange water is preferable in order to avoid nozzle clogging.
【００１４】前記有機白色顔料が皮膜形成性樹脂で被覆
されている着色剤とする好適な製造方法としては，一般
には皮膜形成性樹脂を溶融した有機溶媒中に有機白色顔
料を分散させた着色ミルベースに，更に塩基を混合溶解
して，中和（第１段階），その後，滴下等で水を必須成
分とする水性媒体を混合して乳化させる。即ち，転相乳
化法を行なう（第２段階）のがよい。その後，インク中
の着色樹脂粒子の分散安定性を高めるために，第１段階
の着色ミルベース工程で用いた有機溶媒を除去する脱溶
媒工程を入れる（第３段階）のが好ましい。A preferred method of producing the organic white pigment as a colorant coated with a film-forming resin is generally a coloring mill base obtained by dispersing an organic white pigment in an organic solvent in which the film-forming resin is melted. Then, a base is further mixed and dissolved, neutralized (first step), and thereafter, an aqueous medium containing water as an essential component is mixed and emulsified by dropping or the like. That is, the phase inversion emulsification method is preferably performed (second stage). Thereafter, in order to enhance the dispersion stability of the colored resin particles in the ink, a desolvation step of removing the organic solvent used in the first step of the coloring mill base step is preferably provided (third step).
【００１５】本発明のインクジェット記録用インクは，
前記したような転相乳化法によって得られる。即ち，第
１段階として塩基で中和された皮膜形成性樹脂を含む溶
液に有機白色顔料が分散した着色ミルベースを作成す
る。第２段階として，第１段階で得られた着色ミルベー
スに，着色ミルベースの全量よりも過剰となるように水
性媒体を滴下していき，着色樹脂粒子を得る工程を実施
する。当該水性インクの製造にあたっては，第３段階と
して，インク中の着色樹脂粒子の分散安定性を高めるた
めに，第１段階の着色ミルベース工程で用いた有機溶媒
を除去する脱溶媒工程を入れるのが好ましい。この脱溶
媒工程において必要なら水を除去してもよい。また勿
論，この第３段階の工程は場合によっては省くことも可
能である。この際，第２または３段階の工程が終了した
後，フィルターによるろ過や遠心分離等で大粒径粒子を
除去することが好ましい。The ink-jet recording ink of the present invention comprises:
It is obtained by the phase inversion emulsification method as described above. That is, as a first step, a colored mill base in which an organic white pigment is dispersed in a solution containing a film-forming resin neutralized with a base is prepared. As a second step, an aqueous medium is dropped on the colored mill base obtained in the first step so as to be in excess of the total amount of the colored mill base to obtain colored resin particles. In the production of the aqueous ink, as a third step, in order to enhance the dispersion stability of the colored resin particles in the ink, a desolvation step of removing the organic solvent used in the first step of the coloring mill base step is to be included. preferable. In this desolvation step, water may be removed if necessary. Further, needless to say, this third step can be omitted in some cases. At this time, after completion of the second or third step, it is preferable to remove large-diameter particles by filtration with a filter or centrifugation.
【００１６】有機白色顔料を被覆する皮膜形成性樹脂
は，酸価が５０以上２８０以下の合成樹脂で，少なくと
も一部の酸基が塩基で中和されてなる自己水分散性樹脂
であることが必要である。The film-forming resin for coating the organic white pigment is a synthetic resin having an acid value of 50 or more and 280 or less, and is a self-water dispersible resin in which at least a part of acid groups is neutralized with a base. is necessary.
【００１７】このような皮膜形成性樹脂としては，上記
特性を満足していれば特に限定されるものではないが，
例えばスチレンあるいはα−メチルスチレンのような置
換スチレン，アクリル酸メチル，アクリル酸エチル，ア
クリル酸ブチル，アクリル酸２−エチルヘキシル等のア
クリル酸エステル，メタクリル酸メチル，メタクリル酸
エチル，メタクリル酸ブチル，メタクリル酸２−エチル
ヘキシル等のメタクリル酸エステルから選ばれる少なく
とも一つ以上のモノマー単位と，アクリル酸，メタクリ
ル酸から選ばれる少なくとも一つ以上のモノマー単位を
含む共重合体が使用可能であり，特に自己水分散性樹脂
の必須モノマー成分としてスチレン，アクリル酸，メタ
クリル酸からなる共重合体であり，特にこれら必須モノ
マー成分の構成比率がスチレン６０〜９０モル％，アク
リル酸５〜１５モル％，メタクリル酸５〜２５モル％で
ある場合には，本発明のインクジェット記録用インクと
してノズル目詰まりのない優れた着色樹脂粒子を可能と
する。Such a film-forming resin is not particularly limited as long as it satisfies the above characteristics.
For example, styrene or substituted styrene such as α-methylstyrene, acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid A copolymer containing at least one monomer unit selected from methacrylic acid esters such as 2-ethylhexyl and at least one monomer unit selected from acrylic acid and methacrylic acid can be used. It is a copolymer composed of styrene, acrylic acid and methacrylic acid as essential monomer components of the conductive resin. In particular, the composition ratio of these essential monomer components is 60 to 90% by mole of styrene, 5 to 15% by mole of acrylic acid, and 5 to 5% by weight of methacrylic acid. If it is 25 mol%, To allow no better colored resin particles nozzle clogging as an inkjet recording ink of light.
【００１８】前記皮膜形成性樹脂の分子量範囲について
は特に制限はないが，１０００以上１０万以下の分子量
のものが好ましい。勿論，かかる合成樹脂から得られた
自己水分散性樹脂が水性媒体との組み合わせで安定な着
色樹脂粒子を形成するものであれば，これらに特に限定
されるものではなく，同時に２種類以上を混合して使用
しても良い。The molecular weight range of the film-forming resin is not particularly limited, but is preferably from 1,000 to 100,000. Of course, as long as the self-water-dispersible resin obtained from such a synthetic resin forms stable colored resin particles in combination with an aqueous medium, the resin is not particularly limited to these, and two or more kinds can be mixed simultaneously. You may use it.
【００１９】前記した皮膜形成性樹脂の酸基は塩基によ
って中和されていることが好ましい。即ち，塩基性中和
剤による中和は，皮膜形成性樹脂が水に溶解しない程度
に中和する必要があり，溶解しない程度であれば塩基性
中和剤を過剰に加えても良いが，合成樹脂の酸基の５０
モル％以上で中和するのが好ましい。中和率が５０モル
％以上であると，着色樹脂粒子は粒子径が小さいものが
得られ，分散安定性に優れるからである。It is preferable that the acid group of the film-forming resin is neutralized with a base. That is, the neutralization with the basic neutralizing agent needs to be performed to the extent that the film-forming resin does not dissolve in water, and if it does not dissolve, the basic neutralizing agent may be excessively added. 50 of acid groups of synthetic resin
It is preferable to neutralize at not less than mol%. When the neutralization ratio is 50 mol% or more, the colored resin particles having a small particle diameter are obtained, and the dispersion stability is excellent.
【００２０】皮膜形成性樹脂の使用量は，特に限定され
るものではないが，最終的に得られるインクジェット記
録用インク中で０．５〜２０質量％となるような量が好
ましい。The amount of the film-forming resin used is not particularly limited, but is preferably 0.5 to 20% by mass in the ink jet recording ink finally obtained.
【００２１】塩基（中和剤）としては，例えば水酸化ナ
トリウム，水酸化カリウム，水酸化リチウム等のアルカ
リ金属の水酸化物，アンモニア，トリエチルアミン，モ
ルホリン等の塩基性物質の他，トリエタノールアミン，
ジエタノールアミン，Ｎ−メチルジエタノールアミン等
のアルコールアミンが使用可能である。Examples of the base (neutralizing agent) include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide; basic substances such as ammonia, triethylamine and morpholine;
Alcoholamines such as diethanolamine and N-methyldiethanolamine can be used.
【００２２】皮膜形成性樹脂を溶解する際に用いられる
有機溶媒としては，皮膜形成性樹脂を溶解するものであ
ればどのような有機溶媒であっても使用可能であるが，
例えばアセトン，ジメチルケトン，メチルエチルケトン
等のケトン系溶媒，メタノール，エタノール，イソプロ
ピルアルコール等のアルコール系溶媒，クロロホルム，
塩化メチレン等の塩素系溶媒，ベンゼン，トルエン等の
芳香族系溶媒，酢酸エチル等のエステル系溶媒，エチレ
ングリコールモノメチルエーテル，エチレングリコール
ジメチルエーテル等のグリコールエーテル系溶媒，アミ
ド類等が挙げられる。As the organic solvent used for dissolving the film-forming resin, any organic solvent that can dissolve the film-forming resin can be used.
For example, ketone solvents such as acetone, dimethyl ketone and methyl ethyl ketone, alcohol solvents such as methanol, ethanol and isopropyl alcohol, chloroform,
Examples thereof include chlorine solvents such as methylene chloride, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, glycol ether solvents such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether, and amides.
【００２３】これらの有機溶媒のうち，皮膜形成性樹脂
成分がアクリル系樹脂の場合にはケトン系溶媒とアルコ
ール系溶媒から選ばれる少なくとも１種類以上の組み合
わせが好ましい。かかる有機溶媒の使用量は，本発明に
おける効果を達成すれば特に規定されないが，皮膜形成
性樹脂／該有機溶媒の質量比が１／１〜１／２０となる
ような量が好ましい。When the film-forming resin component is an acrylic resin among these organic solvents, a combination of at least one selected from ketone solvents and alcohol solvents is preferable. The amount of the organic solvent used is not particularly limited as long as the effects of the present invention are achieved, but is preferably such that the mass ratio of the film-forming resin / the organic solvent is 1/1 to 1/20.
【００２４】前記有機溶媒中には，添加剤として，必要
に応じて分散剤，可塑剤，酸化防止剤等を共に用いても
良い。In the organic solvent, a dispersant, a plasticizer, an antioxidant, and the like may be used as additives as needed.
【００２５】また，インクジェット記録用インクが乾燥
するのを防止するためには，水溶性有機溶媒を乾燥防止
剤として当該インク中に存在させておくのが好ましい。
かかる乾燥防止剤は，インクジェットの噴射ノズル口で
のインクの乾燥を防止する効果を与えるものであり，通
常，水の沸点以上の沸点を有するものが使用される。こ
のような乾燥防止剤としては，たとえば従来知られてい
るエチレングリコール，プロピレングリコール，ジエチ
レングリコール，ジプロピレングリコール，ポリエチレ
ングリコール，ポリプロピレングリコール，グリセリン
等の多価アルコール類またはそれらのアルキルエーテル
類，Ｎ−メチル−２−ピロリドン，２−ピロリドン等の
ピロリドン類，アミド類，ジメチルスルホオキサイド，
イミダゾリジノン等が挙げられる。前記乾燥防止剤の使
用量は，種類によって異なるが，通常，水１００質量部
に対して１〜１５０質量部の範囲から適宜選択される。
この範囲のうち，グリセリン及びそれに他の乾燥防止剤
を併用したものを使用する場合には１〜５０質量部が好
ましい。In order to prevent the ink jet recording ink from drying out, it is preferable that a water-soluble organic solvent is present in the ink as a drying inhibitor.
Such an anti-drying agent has an effect of preventing the ink from drying at the ejection nozzle port of the ink jet, and usually, an agent having a boiling point higher than the boiling point of water is used. Examples of such an anti-drying agent include conventionally known polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and glycerin, and alkyl ethers thereof, and N-methyl. Pyrrolidones such as -2-pyrrolidone and 2-pyrrolidone, amides, dimethylsulfoxide,
And imidazolidinone. The amount of the drying inhibitor varies depending on the type, but is usually appropriately selected from the range of 1 to 150 parts by mass with respect to 100 parts by mass of water.
When glycerin and a combination thereof with another drying inhibitor are used, the amount is preferably 1 to 50 parts by mass.
【００２６】本発明のインクジェット記録用インクは水
性インクであることから，必要に応じて水溶性樹脂，Ｐ
Ｈ調整剤，分散・消泡・界面活性剤，防腐剤，キレート
剤等の添加剤を加えることが可能である。Since the ink for ink jet recording of the present invention is an aqueous ink, a water-soluble resin, P
It is possible to add additives such as an H adjuster, a dispersing / defoaming / surfactant, a preservative, and a chelating agent.
【００２７】また，更に，必要に応じてジェット噴射し
て付着したインクを紙によりよく浸透させるために，浸
透性付与剤として浸透性付与効果を示す水溶性有機溶媒
を加えてもよい。かかる浸透性付与剤としてはエタノー
ル，イソプロピルアルコール等の低級アルコール，ジエ
チレングリコール−Ｎ−ブチルエーテル等のグリコール
エーテル等を用いることができるが，これらに限定され
るものではない。浸透性付与剤の使用量は，本発明にお
ける効果を達成すれば特に規定されないが，最終的に得
られる水性インク中で０．１〜１０質量％となるような
量が好ましい。これらの添加剤は，予め水性媒体中に添
加しても，着色剤を含む皮膜形成性樹脂溶液と水性媒体
とを混合するときに添加しても，また，それらの混合後
に添加してもよい。Further, if necessary, a water-soluble organic solvent having a permeation-imparting effect may be added as a permeation-imparting agent so that the ink adhered by jetting and jetting can be more easily permeated into the paper. Examples of the penetrant include lower alcohols such as ethanol and isopropyl alcohol, and glycol ethers such as diethylene glycol-N-butyl ether, but are not limited thereto. The amount of the penetrant used is not particularly limited as long as the effects of the present invention are achieved, but is preferably 0.1 to 10% by mass in the finally obtained aqueous ink. These additives may be added to the aqueous medium in advance, may be added when the film-forming resin solution containing the colorant is mixed with the aqueous medium, or may be added after the mixing. .
【００２８】このようにして得られたインクジェット記
録用インクに，例えばゲル化防止剤，保護コロイド剤，
蛍光増白剤等を水性媒体とともに混合させることにより
インクジェット記録用インクを得ることも可能である。The ink for ink jet recording thus obtained may be added to, for example, an anti-gelling agent, a protective colloid agent,
It is also possible to obtain an ink for inkjet recording by mixing a fluorescent whitening agent and the like with an aqueous medium.
【００２９】更には，活性エネルギー線によりエネルギ
ーを付与することで固化する活性エネルギー線硬化性化
合物をインク分散液中に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を提供する。Further, the present invention provides an ink for ink-jet recording, characterized in that the ink dispersion contains an active energy ray-curable compound which solidifies when energy is applied by an active energy ray.
【００３０】上述の方法等で顔料分散を行った後，活性
エネルギー線硬化性化合物を必要に応じて用い，エネル
ギーの付与でインクジェット記録印字物の皮膜性能を強
固にするものである。After the pigment is dispersed by the above-described method or the like, an active energy ray-curable compound is used as necessary, and the film performance of the ink-jet recorded print is enhanced by applying energy.
【００３１】尚，活性エネルギー線とは，電子線，紫外
線又は熱線等であるが，中でも電子線，紫外線による処
理が簡便性，安全性の面で好ましく，特に紫外線が好ま
しい。The active energy ray is an electron beam, an ultraviolet ray, a heat ray or the like. Among them, a treatment with an electron beam or an ultraviolet ray is preferable in terms of simplicity and safety, and an ultraviolet ray is particularly preferable.
【００３２】例えば，電子線，紫外線により硬化する硬
化性化合物としては，エポキシ基を有する多官能エポキ
シ樹脂の（メタ）アクリル酸エステル，多価アルコール
のアルキレンオキサイド付加物の（メタ）アクリル酸エ
ステル，ポリエステルの分子鎖末端にアクリル酸エステ
ル基を持つポリエステル（メタ）アクリレート，多価イ
ソシアネートと水酸基を有する（メタ）アクリル酸モノ
マーとの反応物，などの多官能（メタ）アクリレートが
挙げられる。これらの化合物は，分子内にウレタン結合
を有するウレタン変性物であってもよい。また，上記の
多官能（メタ）アクリレートのほか，ヒドロキシエチル
アクリレート，ヒドロキシエチルメタクリレート，ヒド
ロキシプロピルアクリレート，ヒドロキシプロピルメタ
クリレート，テトラヒドロフルフラルアクリレート，２
−エトキシエチルアクリレート，２−エトキシエチルメ
タクリレート等の単官能（メタ）アクリレートも用いる
ことができる。For example, as the curable compound which is cured by an electron beam or an ultraviolet ray, a (meth) acrylate of a polyfunctional epoxy resin having an epoxy group, a (meth) acrylate of an alkylene oxide adduct of a polyhydric alcohol, Polyfunctional (meth) acrylates such as polyester (meth) acrylate having an acrylate group at the molecular chain end of the polyester, and a reaction product of a polyvalent isocyanate and a (meth) acrylic acid monomer having a hydroxyl group are exemplified. These compounds may be urethane modified products having a urethane bond in the molecule. In addition to the above polyfunctional (meth) acrylates, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, tetrahydrofurfural acrylate, 2
Monofunctional (meth) acrylates such as -ethoxyethyl acrylate and 2-ethoxyethyl methacrylate can also be used.
【００３３】本発明のインクジェット記録用インクに含
有される活性エネルギー線硬化性化合物の含有量は，通
常１〜５０質量％の範囲が望ましい。１質量％未満では
硬化性が不十分で，出来上がった皮膜強度が低く，密着
性，耐摩耗性，引っ掻き性などが悪くなり，５０質量％
を越えると粘度が高くなり，吐出性に悪影響を与え，
又，着色樹脂粒子の分散性も悪くなるので好ましくな
い。又，好ましくは５〜３５質量％であり，更に好まし
くは８〜３０質量％であり，この範囲では皮膜密着性や
引っ掻き性ともに良好で，吐出性，着色樹脂粒子分散性
に対しても問題がないという利点がある。The content of the active energy ray-curable compound contained in the ink for ink jet recording of the present invention is usually preferably in the range of 1 to 50% by mass. If the amount is less than 1% by mass, the curability is insufficient, the strength of the resulting film is low, and the adhesion, abrasion resistance, scratching property, etc. are deteriorated.
If it exceeds, the viscosity will increase, adversely affecting the ejection properties,
Further, the dispersibility of the colored resin particles is also deteriorated, which is not preferable. The content is preferably from 5 to 35% by mass, more preferably from 8 to 30% by mass. In this range, both the film adhesion and the scratching property are good, and there are problems with the dischargeability and the dispersibility of the colored resin particles. There is no advantage.
【００３４】これらの特性を有する活性エネルギー線硬
化性化合物を水性媒体とともに混合させることにより，
エネルギーの付与で皮膜性能に優れたインクジェット記
録用インクを得る。By mixing an active energy ray-curable compound having these properties with an aqueous medium,
By applying energy, an ink jet recording ink excellent in film performance is obtained.
【００３５】又，本発明のインクジェット記録用インク
は，カーボンブラックやフタロシアニン顔料やキナクリ
ドン顔料及びベンズイミダゾロン顔料を着色剤とするイ
ンクと組み合わせてなるインクジェット記録用インクと
併用することで，画像形成を行うことも可能にするイン
クジェット記録用インクを提供することも可能である。The ink-jet recording ink of the present invention is used in combination with an ink-jet recording ink obtained by combining carbon black, a phthalocyanine pigment, a quinacridone pigment and a benzimidazolone pigment with a colorant to form an image. It is also possible to provide an ink jet recording ink that is also capable of performing.
【００３６】このようにして得られたインクは，分散安
定性および保存安定性に優れ，調色による色の濁りがな
く，印刷濃度のバランスを損なうことなく，また，活性
エネルギー線で硬化させた皮膜は強固なもので，フルカ
ラー印刷物の色調を自由に微調整可能となるインクジェ
ット記録用インキを提供し，画像形成を行う場合に最適
である。The ink thus obtained is excellent in dispersion stability and storage stability, free of color turbidity due to toning, without impairing the balance of print density, and cured with active energy rays. The film is strong and provides an ink for inkjet recording that allows the color tone of a full-color print to be freely and finely adjusted, and is optimal for image formation.
【００３７】[0037]
【実施例】次に実施例及び比較例を挙げて本発明を更に
具体的に説明する。尚，以下の実施例中における「部」
は『質量部』を表わす。尚，実施例等において，有機白
色顔料の粒子径は，「マイクロトラック粒度分析計」
（リーズ アンド ノースラップ社製）を用いた。Next, the present invention will be described more specifically with reference to examples and comparative examples. In addition, "part" in the following examples
Represents "parts by mass". In the examples and the like, the particle size of the organic white pigment was measured using a “Microtrac particle size analyzer”.
(Leeds and Northrap).
【００３８】（実施例１）有機白色顔料として，アルキ
レンビスメラミン誘導体Ｎ−Ｎ’−ビス（４，６ジアミ
ノ−１，３，５−トリアジン−２−イル）エチレンジア
ミン（構造式（ＩＩ）の化合物）「Ｓｈｉｇｅｎｏｘ
ＯＷＰ」（ハッコーケミカル社製）２５．０部，スチレ
ン−アクリル酸−メタクリル酸樹脂（スチレン／アクリ
ル酸／メタクリル酸＝７７／１０／１３；分子量５万・
酸価１６０）２５．０部の二本ロール混練物を，水４．
０部，トリエタノールアミン６．０部（酸基の５０モル
％相当量），メチルエチルケトン１０．０部，イソプロ
ピルアルコール５．０部の混合溶液に入れ，室温で３時
間撹拌し混練物が溶解したところで，衝突式分散機「ナ
ノマイザー」（ナノマイザー社製）を用いて９８ＭＰａ
の圧力で分散を行い，着色剤懸濁液を得た。Example 1 As an organic white pigment, an alkylenebismelamine derivative N—N′-bis (4,6 diamino-1,3,5-triazin-2-yl) ethylenediamine (compound of the structural formula (II) ) "Shigenox
OWP "(manufactured by Hako Chemical Co., Ltd.) 25.0 parts, styrene-acrylic acid-methacrylic acid resin (styrene / acrylic acid / methacrylic acid = 77/10/13; molecular weight 50,000.multidot.
Acid value 160) 25.0 parts of the two-roll kneaded material was mixed with water 4.
0 parts, triethanolamine 6.0 parts (corresponding to 50 mol% of the acid groups), methyl ethyl ketone 10.0 parts, and isopropyl alcohol 5.0 parts, and stirred at room temperature for 3 hours to dissolve the kneaded material. By the way, 98MPa using a collision type dispersion machine "Nanomizer" (manufactured by Nanomizer)
The colorant was dispersed under the pressure described above to obtain a colorant suspension.
【００３９】得られた着色剤懸濁液を撹拌しながら，水
２５．０部を毎分５ｍｌの速度で滴下し，着色樹脂粒子
分散液を得た。得られた着色樹脂粒子分散液はロータリ
ーエバポレーターを用いてメチルエチルケトンとイソプ
ロピルアルコールを留去し，最終の着色樹脂粒子分散液
を得た。While stirring the obtained colorant suspension, 25.0 parts of water was added dropwise at a rate of 5 ml / min to obtain a colored resin particle dispersion. From the obtained colored resin particle dispersion, methyl ethyl ketone and isopropyl alcohol were distilled off using a rotary evaporator to obtain a final colored resin particle dispersion.
【００４０】この着色樹脂粒子分散液６０．０部（固形
分相当３３．０質量％）に撹拌しながら，乾燥防止剤と
してグリセリン５．０部，浸透性付与剤としてプロピル
プロピレングリコール５．０部，防腐剤として「ＰＲＯ
ＸＥＬ ＧＸＬ」（ゼネカ社製）０．１部，イオン交換
水２９．９部を加え，着色組成物分散液を得た。得られ
た着色組成物分散液は粒子径０．４０μｍの着色組成物
の水分散液であった。濃度調整後，５．０μｍのメンブ
ランフィルターを用いて，ろ過を行い，インクジェット
記録用インクとした。While stirring 60.0 parts (33.0% by mass of solid content) of the colored resin particle dispersion, 5.0 parts of glycerin as a drying inhibitor and 5.0 parts of propylpropylene glycol as a permeation-imparting agent. , "PRO" as a preservative
XEL GXL "(Zeneca) and 29.9 parts of ion-exchanged water were added to obtain a colored composition dispersion. The obtained colored composition dispersion was an aqueous dispersion of the colored composition having a particle diameter of 0.40 μm. After the concentration adjustment, filtration was performed using a 5.0 μm membrane filter to obtain an inkjet recording ink.
【００４１】得られたインクをガラス容器中で室温環境
１ヶ月，２ヶ月，３ヶ月と放置したが，分散性は良好
で，凝集物の発生もなかった。また，４ヶ月放置でも問
題なかった。また，高温／低温環境下で１ヶ月放置した
が，何れも分散性は良好で，凝集物の発生はなかった。
尚，高温環境下放置は６０゜Ｃ，低温環境下放置は−５
゜Ｃの恒温槽で行った。製造直後及び放置後の各種イン
クをピエゾ式インクジェットプリンターにて噴射試験を
した結果，いずれのインクにおいても初期噴射特性は安
定で，ノズル目詰まりもなく，連続噴射試験においても
経時的変化は見られず安定な噴射が可能で，得られた普
通紙印刷物は隠蔽力もあり，耐水性にも優れていた。The obtained ink was allowed to stand in a glass container at room temperature for 1 month, 2 months, and 3 months, but the dispersibility was good and no aggregate was generated. There was no problem even if left for 4 months. In addition, when left for one month in a high-temperature / low-temperature environment, the dispersibility was good in each case, and no aggregate was generated.
In addition, 60 ° C in high temperature environment and -5 in low temperature environment.
The test was performed in a thermostat at の C. As a result of performing a jet test on various inks immediately after production and after leaving the ink using a piezo-type ink jet printer, the initial jet characteristics of each ink were stable, there was no nozzle clogging, and there was a change over time in the continuous jet test. Stable jetting was possible, and the resulting printed matter on plain paper had excellent hiding power and excellent water resistance.
【００４２】（比較例１）有機白色顔料として「Ｓｈｉ
ｇｅｎｏｘ ＯＷＰ」４０．０部，樹脂分散剤として
「ソルスパーズ−２７０００」（ゼネカ社製）８．０部
（有機白色顔料に対して２０．０質量％に相当する
量），水５２．０部を直径１．０ｍｍのジルコニアビー
ズ４５０部と共にペイントシェーカーを用いて６時間分
散した。その分散液を衝突式分散機「ナノマイザー」
（ナノマイザー社製）を用いて９８ＭＰａの圧力で分散
を行い着色剤懸濁液を得た。(Comparative Example 1) As an organic white pigment, "Shi
Genox OWP "40.0 parts," Solspers-27000 "(manufactured by Zeneca) as a resin dispersant 8.0 parts (an amount equivalent to 20.0% by mass based on the organic white pigment), and water 52.0 parts. The mixture was dispersed with 450 parts of zirconia beads having a diameter of 1.0 mm for 6 hours using a paint shaker. The dispersion liquid is used as a collision type dispersion machine "Nanomizer".
Dispersion was performed at a pressure of 98 MPa using (manufactured by Nanomizer) to obtain a colorant suspension.
【００４３】ジルコニアビーズを除いた着色剤懸濁液６
８．０部（固形分相当３３．０質量％）に撹拌しなが
ら，乾燥防止剤としてグリセリン５．０部，浸透防止剤
としてプロピルプロピレングリコール５．０部，防腐剤
として「ＰＲＯＸＥＬ ＧＸＬ」（ゼネカ社製）０．１
部，イオン交換水２１．９部を加え，着色組成物分散液
を得た。得られた着色組成物分散液は粒子径０．４４μ
ｍの着色組成物の水分散液であった。濃度調整後，５．
０μｍのメンブランフィルターを用いて，ろ過を行い，
インクジェット記録用インクとした。Colorant suspension 6 excluding zirconia beads
While stirring to 8.0 parts (33.0% by mass corresponding to solid content), 5.0 parts of glycerin as a drying inhibitor, 5.0 parts of propylpropylene glycol as a penetration inhibitor, and “PROXEL GXL” (Zeneca) as a preservative. 0.1)
And 21.9 parts of ion-exchanged water, to obtain a colored composition dispersion. The resulting colored composition dispersion had a particle size of 0.44 μm.
m was an aqueous dispersion of the colored composition. After adjusting the density, 5.
Perform filtration using a 0 μm membrane filter,
Ink for ink jet recording was used.
【００４４】得られたインクをガラス容器中で室温環境
１ヶ月，２ヶ月と放置したが，分散性は良好で，問題は
なかったものの，３ヶ月放置でインク上層部が透明とな
り，顔料は容器底部に再分散不能な固い沈降物を生じ，
分散性が良好なインクとはいえないものであった。ま
た，高温／低温環境下では１０日放置で，何れもインク
上層部が透明となり，顔料は容器底部に再分散不能な固
い沈降物を生じた。製造直後及び使用可能な放置後の各
種インクをピエゾ式インクジェットプリンターにて噴射
試験をした結果，初期噴射特性は安定であったが，経時
的にノズル目詰まりが発生，不安定な噴射特性を示し
た。得られた普通紙印刷物の隠蔽力はあるものの，耐水
性に乏しく，インクジェット記録用インクとしては実用
に耐えないものであった。The obtained ink was allowed to stand in a glass container at room temperature for 1 month and 2 months, but the dispersibility was good and there was no problem. Forming a hard sediment at the bottom that cannot be redispersed,
The ink was not good in dispersibility. In addition, in a high-temperature / low-temperature environment, after leaving for 10 days, the upper layer of the ink became transparent, and the pigment formed a hard sediment on the bottom of the container that could not be redispersed. As a result of an ejection test of various inks immediately after production and after being left unusable, using a piezo-type inkjet printer, the initial ejection characteristics were stable, but nozzle clogging occurred over time and the ejection characteristics were unstable. Was. Although the obtained plain paper printed matter had a hiding power, it had poor water resistance and was not practical for ink-jet recording ink.
【００４５】（比較例２）比較例１の有機白色顔料に変
えて，酸化チタン「ＣＲ−９０」（石原産業社製）を用
いた以外は，比較例１と同様にして着色剤懸濁液を得た
後，インクジェット記録用インクを得た。得られたイン
クをガラス容器中で室温環境放置したところ，１５日で
は問題なかったものの，１ヶ月でインク上層部が透明と
なり，顔料は容器底部に再分散不能な固い沈降物を生
じ，分散性が良好なインクとはいえないものであった。
また，製造直後のインクをピエゾ式インクジェットプリ
ンターにて噴射試験をした結果，この沈降物に依存する
ノズル目詰まりが発生し，安定な噴射は成されず，イン
クジェット記録用インクとしては実用に耐えないもので
あった。Comparative Example 2 A colorant suspension was prepared in the same manner as in Comparative Example 1 except that titanium oxide “CR-90” (manufactured by Ishihara Sangyo) was used instead of the organic white pigment of Comparative Example 1. After that, an ink for inkjet recording was obtained. When the obtained ink was left in a glass container at room temperature, there was no problem in 15 days. However, in 1 month, the upper layer of the ink became transparent and the pigment formed a hard sediment on the bottom of the container that could not be redispersed. Was not a good ink.
In addition, as a result of performing a jet test on the ink immediately after production with a piezo-type ink jet printer, nozzle clogging depending on the sediment occurs, stable jetting is not achieved, and the ink cannot be put to practical use as an ink jet recording ink. Was something.
【００４６】（実施例２）実施例１と同様にして，着色
樹脂粒子分散液を得た。この着色樹脂粒子分散液６０．
０部（固形分相当３３．０質量％）に撹拌しながら，紫
外線硬化性化合物としてポリエチレングリコールジアク
リレート「エベクリル−１１」（ダイセルユーシーピー
社製）２５．０部，グリセリン１．２５部（紫外線硬化
性化合物に対して５．０質量％に相当する量），光重合
開始剤として「ダロキュアー１１７３」（チバ・スペシ
ャルティ・ケミカルズ社製）２．００部（紫外線硬化性
化合物に対して８．０質量％に相当する量），防腐剤と
して「ＰＲＯＸＥＬ ＧＸＬ」０．１部，イオン交換水
１１．６５部を加え，着色紫外線硬化型組成物分散液を
得た。得られた着色組成物分散液は粒子径０．４２μｍ
の着色組成物の水分散液であった。濃度調整後，５．０
μｍのメンブランフィルターを用いて，ろ過を行い，イ
ンクジェット記録用インクとした。Example 2 A colored resin particle dispersion was obtained in the same manner as in Example 1. This colored resin particle dispersion 60.
While stirring to 0 parts (33.0% by mass corresponding to the solid content), 25.0 parts of polyethylene glycol diacrylate "Evecryl-11" (manufactured by Daicel UCP) and 1.25 parts of glycerin (UV An amount equivalent to 5.0% by mass with respect to the curable compound), and 2.00 parts of "Darocur 1173" (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator (8.0 with respect to the ultraviolet curable compound). 0.1% of PROXEL GXL as a preservative and 11.65 parts of ion-exchanged water to obtain a colored ultraviolet curable composition dispersion liquid. The resulting colored composition dispersion had a particle size of 0.42 μm.
Was a water dispersion of the colored composition of Example 1. After density adjustment, 5.0
Filtration was performed using a μm membrane filter to obtain an inkjet recording ink.
【００４７】得られたインクを遮光されたガラス容器中
で室温環境１ヶ月，２ヶ月，３ヶ月と放置したが，分散
性は良好で，凝集物の発生もなかった。また，４ヶ月放
置でも問題なかった。また，高温／低温環境下で１ヶ月
放置したが，何れも分散性は良好で，凝集物の発生もな
かった。製造直後及び放置後の各種インクをピエゾ式イ
ンクジェットプリンターにて噴射試験をした結果，初期
噴射特性も安定で，ノズル目詰まりもなく，連続噴射試
験においても経時的変化は見られず安定な噴射が可能で
あった。また，得られた被記録媒体に印字された印刷物
に，市販の紫外線ランプ（ウシオ電機社製）により紫外
線を照射して完全に硬化させたところ，画像は良好であ
った。また，被記録媒体と画像との密着も良好で，こす
りに対しても剥がれることはなかった。更に，隠蔽力や
耐水性，耐溶剤性も優れていた。The obtained ink was allowed to stand in a light-shielded glass container for 1 month, 2 months, and 3 months at room temperature, but the dispersibility was good, and no agglomerate was generated. There was no problem even if left for 4 months. In addition, the samples were allowed to stand for one month in a high / low temperature environment, but all showed good dispersibility and did not generate aggregates. As a result of performing a jet test of various inks immediately after production and after leaving the ink using a piezo-type ink jet printer, the initial jet characteristics are stable, there is no nozzle clogging, and there is no change over time in the continuous jet test, and stable jets are obtained. It was possible. When the printed matter printed on the obtained recording medium was irradiated with ultraviolet rays by a commercially available ultraviolet lamp (manufactured by Ushio Inc.) and completely cured, the image was good. In addition, the adhesion between the recording medium and the image was good, and the recording medium was not peeled off by rubbing. Furthermore, the hiding power, water resistance and solvent resistance were also excellent.
【００４８】（比較例３）比較例１と同様にして，着色
剤懸濁液を得た。ジルコニアビーズを除いた着色剤懸濁
液６８．０部（固形分相当３３．０質量％）に撹拌しな
がら，紫外線硬化性化合物として「エベクリル−１
１」）２５．０部，グリセリン１．２５部（紫外線硬化
性化合物に対して５．０質量％に相当する量），光重合
開始剤として「ダロキュアー１１７３」２．００部（紫
外線硬化性化合物に対して８．０質量％に相当する
量），防腐剤として「ＰＲＯＸＥＬＧＸＬ」０．１部，
イオン交換水３．６５部を加え，着色紫外線硬化型組成
物分散液を得た。得られた着色組成物分散液は粒子径
０．４５μｍの着色組成物の水分散液であった。濃度調
整後，５．０μｍのメンブランフィルターを用いて，ろ
過を行い，インクジェット記録用インクとした。Comparative Example 3 A colorant suspension was obtained in the same manner as in Comparative Example 1. While stirring the colorant suspension excluding zirconia beads (68.0 parts (solid content: 33.0% by mass)), “Evecryl-1” was used as an ultraviolet curable compound.
1)) 25.0 parts, glycerin 1.25 parts (equivalent to 5.0% by mass based on the ultraviolet curable compound), 2.00 parts of "Darocur 1173" as a photopolymerization initiator (ultraviolet curable compound) 0.1 parts by mass of "PROXELGXL" as a preservative,
3.65 parts of ion-exchanged water was added to obtain a colored ultraviolet-curable composition dispersion. The obtained colored composition dispersion was an aqueous dispersion of the colored composition having a particle diameter of 0.45 μm. After the concentration adjustment, filtration was performed using a 5.0 μm membrane filter to obtain an inkjet recording ink.
【００４９】得られたインクを遮光されたガラス容器中
で室温環境１ヶ月，２ヶ月と放置したが，分散性は良好
で，問題はなかったものの，３ヶ月放置でインク上層部
が透明となり，顔料は容器底部に再分散不能な固い沈降
物を生じ，分散性が良好なインクとはいえないものであ
った。また，高温／低温環境下では１０日放置で，何れ
もインク上層部が透明となり，顔料は容器底部に再分散
不能な固い沈降物を生じた。製造直後及び使用可能な放
置後の各種インクをピエゾ式インクジェットプリンター
にて噴射試験をした結果，初期噴射特性は安定であった
が，経時的にノズル目詰まりが発生し，不安定な噴射特
性を示した。また，得られた被記録媒体に印字された印
刷物に，市販の紫外線ランプにより紫外線を照射して完
全に硬化させたところ，画像の隠蔽度に著しいムラを生
じた。The obtained ink was allowed to stand in a light-shielded glass container at room temperature for 1 month and 2 months. The dispersibility was good and there was no problem. However, the ink upper layer became transparent after 3 months. The pigment formed a hard sediment on the bottom of the container that could not be redispersed, and was not a good dispersible ink. In addition, in a high-temperature / low-temperature environment, after leaving for 10 days, the upper layer of the ink became transparent, and the pigment formed a hard sediment on the bottom of the container that could not be redispersed. As a result of performing a jet test using a piezo-type inkjet printer with various inks immediately after production and after being left unusable, the initial jetting characteristics were stable, but nozzle clogging occurred over time, resulting in unstable jetting characteristics. Indicated. Further, when the printed matter printed on the obtained recording medium was completely cured by irradiating ultraviolet rays with a commercially available ultraviolet lamp, remarkable unevenness occurred in the degree of hiding of the image.
【００５０】（比較例４）比較例２と同様にして，着色
剤懸濁液を得た。ジルコニアビーズを除いた着色剤懸濁
液を，比較例３と同様にして，インクジェット記録用イ
ンクを得た。得られたインクを遮光されたガラス容器中
で室温環境放置したところ，１５日では問題なかったも
のの，１ヶ月でインク上層部が透明となり，顔料は容器
底部に再分散不能な固い沈降物を生じ，分散性が良好な
インクとはいえないものであった。また，ピエゾ式イン
クジェットプリンターを用いて噴射試験をした結果，こ
の沈降物に依存するノズル目詰まりが発生し，経時安定
な噴射は成されず，インクジェット記録用インクとして
は実用に耐えないものであった。Comparative Example 4 A colorant suspension was obtained in the same manner as in Comparative Example 2. The colorant suspension excluding the zirconia beads was used in the same manner as in Comparative Example 3 to obtain an ink jet recording ink. When the obtained ink was left at room temperature in a light-shielded glass container, there was no problem in 15 days, but in one month the upper layer of the ink became transparent and the pigment formed a hard sediment at the bottom of the container that could not be redispersed. In addition, the ink did not have good dispersibility. In addition, as a result of an ejection test using a piezo-type inkjet printer, nozzle clogging due to the sediment occurred, and stable ejection with time was not achieved, and the ink was not practically usable as an inkjet recording ink. Was.
【００５１】（実施例３）実施例２において，紫外線硬
化性化合物として水性ウレタンアクリレート「ネオラッ
ドＱＣ４６」（ゼネカ社製）２５．０部を使用した以外
は，実施例２と同様にして，インクジェット記録用イン
クを得た。得られたインクを遮光されたガラス容器中で
室温環境１ヶ月，２ヶ月，３ヶ月と放置したが，分散性
は良好で，凝集物の発生もなかった。また，４ヶ月放置
でも問題なかった。また，高温／低温環境下で１ヶ月放
置したが，何れも分散性は良好で，凝集物の発生もなか
った。製造直後及び放置後の各種インクをピエゾ式イン
クジェットプリンターにて噴射試験をした結果，初期噴
射特性も安定で，ノズル目詰まりもなく，連続噴射試験
においても経時的な変化は見られず安定な噴射が可能で
あった。また，得られた被記録媒体に印字された印刷物
に，市販の紫外線ランプで紫外線を照射して完全に硬化
させたところ，画像は良好であった。また，被記録媒体
と画像との密着も良好で，こすりに対しても剥がれるこ
とはなかった。更に，隠蔽力や耐水性，耐溶剤性も優れ
ていた。Example 3 Ink jet recording was carried out in the same manner as in Example 2, except that 25.0 parts of an aqueous urethane acrylate "Neorad QC46" (manufactured by Zeneca) were used as the ultraviolet curable compound. Ink was obtained. The obtained ink was allowed to stand in a light-shielded glass container at room temperature for 1 month, 2 months, and 3 months, but the dispersibility was good and no aggregate was generated. There was no problem even if left for 4 months. In addition, the samples were allowed to stand for one month in a high / low temperature environment, but all showed good dispersibility and did not generate aggregates. As a result of performing a jet test of various inks immediately after production and after leaving the ink with a piezo-type ink jet printer, the initial jet characteristics are stable, there is no nozzle clogging, and there is no change over time even in the continuous jet test, and stable jet is performed. Was possible. Further, when the printed matter printed on the obtained recording medium was completely cured by irradiating ultraviolet rays with a commercially available ultraviolet lamp, the image was good. In addition, the adhesion between the recording medium and the image was good, and the recording medium was not peeled off by rubbing. Furthermore, the hiding power, water resistance and solvent resistance were also excellent.
【００５２】（比較例５）比較例３において，紫外線硬
化性化合物として「ネオラッドＱＣ４６」を使用した以
外は，比較例３と同様にしてインクジェット記録用イン
クを得た。得られたインクを遮光されたガラス容器中で
室温環境１ヶ月，２ヶ月と放置したが，分散性は良好
で，問題はなかったものの，３ヶ月放置でインク上層部
が透明となり，顔料は容器底部に再分散不能な固い沈降
物を生じ，分散性が良好なインクとはいえないものであ
った。また，高温／低温環境下では１０日放置で，何れ
もインク上層部が透明となり，顔料は容器底部に再分散
不能な固い沈降物を生じた。製造直後及び使用可能な放
置後の各種インクをピエゾ式インクジェットプリンター
にて噴射試験をした結果，初期噴射特性は安定であった
が，経時的にノズル目詰まりが発生，不安定な噴射特性
を示した。また，得られた被記録媒体に印字された印刷
物に，市販の紫外線ランプにより紫外線を照射して完全
に硬化させたところ，画像の隠蔽度に著しいムラを生じ
た。Comparative Example 5 An ink for ink-jet recording was obtained in the same manner as in Comparative Example 3, except that "Neorad QC46" was used as the ultraviolet curable compound. The obtained ink was left in a light-shielded glass container at room temperature for 1 month and 2 months, but the dispersibility was good and there was no problem. A non-redispersible hard sediment was formed at the bottom, and the ink was not good in dispersibility. In addition, in a high-temperature / low-temperature environment, after leaving for 10 days, the upper layer of the ink became transparent, and the pigment formed a hard sediment on the bottom of the container that could not be redispersed. As a result of an ejection test of various inks immediately after production and after being left unusable, using a piezo-type inkjet printer, the initial ejection characteristics were stable, but nozzle clogging occurred over time and the ejection characteristics were unstable. Was. Further, when the printed matter printed on the obtained recording medium was completely cured by irradiating ultraviolet rays with a commercially available ultraviolet lamp, remarkable unevenness occurred in the degree of hiding of the image.
【００５３】（比較例６）比較例４において，紫外線硬
化性化合物として「ネオラッドＱＣ４６」を使用した以
外は，比較例４と同様にしてインクジェット記録用イン
クを得た。得られたインクを遮光されたガラス容器中で
室温環境放置したところ，１５日では問題なかったもの
の，１ヶ月でインク上層部が透明となり，顔料は容器底
部に再分散不能な固い沈降物を生じ，分散性が良好なイ
ンクとはいえないものであった。また，ピエゾ式インク
ジェットプリンターを用いて噴射試験をした結果，この
沈降物に依存するノズル目詰まりが発生し，経時安定な
噴射は成されず，インクジェット記録用インクとしては
実用に耐えないものであった。Comparative Example 6 An ink for ink jet recording was obtained in the same manner as in Comparative Example 4, except that "Neorad QC46" was used as the ultraviolet curable compound. When the obtained ink was left at room temperature in a light-shielded glass container, there was no problem in 15 days, but in one month the upper layer of the ink became transparent and the pigment formed a hard sediment at the bottom of the container that could not be redispersed. In addition, the ink did not have good dispersibility. In addition, as a result of an ejection test using a piezo-type inkjet printer, nozzle clogging due to the sediment occurred, and stable ejection with time was not achieved, and the ink was not practically usable as an inkjet recording ink. Was.
【００５４】[0054]
【発明の効果】本発明のインクジェット記録用インク
は，着色剤が有機白色顔料からなり，インク中の有機白
色顔料を皮膜形成性樹脂で被覆した着色樹脂粒子とする
ことにより，分散安定性，保存安定性に優れ，また，調
色による色の濁りがなく，印刷濃度のバランスを損なう
ことなく，印刷物の色調を自由に微調整することができ
る。また，活性エネルギー線硬化性化合物を添加させて
被記録媒体に印字した印字物を硬化させるので，皮膜強
度を向上させることができ，被記録媒体と画像との密着
も良好で，こすれに対しても剥がれることのない，高品
質の画像を得ることができる。The ink for ink jet recording according to the present invention is characterized in that the coloring agent is composed of an organic white pigment, and that the organic white pigment in the ink is coated with a film-forming resin to form colored resin particles, so that the dispersion stability and storage stability can be improved. It is excellent in stability, free of color turbidity due to toning, and can finely adjust the color tone of printed matter freely without impairing the balance of print density. In addition, since the printed matter printed on the recording medium is cured by adding an active energy ray-curable compound, the film strength can be improved, the adhesion between the recording medium and the image is good, and A high-quality image can be obtained without peeling.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36960199AJP4196243B2 (en) | 1999-12-14 | 1999-12-27 | Ink for inkjet recording |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35428499 | 1999-12-14 | ||
| JP11-354284 | 1999-12-14 | ||
| JP36960199AJP4196243B2 (en) | 1999-12-14 | 1999-12-27 | Ink for inkjet recording |
| Publication Number | Publication Date |
|---|---|
| JP2001234093Atrue JP2001234093A (en) | 2001-08-28 |
| JP4196243B2 JP4196243B2 (en) | 2008-12-17 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36960199AExpired - Fee RelatedJP4196243B2 (en) | 1999-12-14 | 1999-12-27 | Ink for inkjet recording |
| Country | Link |
|---|---|
| JP (1) | JP4196243B2 (en) |
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| JP2002167536A (en)* | 2000-06-14 | 2002-06-11 | Mitsubishi Chemicals Corp | Recording liquid and ink jet recording method |
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| WO2010138191A1 (en) | 2009-05-29 | 2010-12-02 | Eastman Kodak Company | Aqueous compositions with improved silicon corrosion characteristics |
| WO2011066117A1 (en) | 2009-11-24 | 2011-06-03 | Eastman Kodak Company | Continuous inkjet printer aquous ink composition |
| WO2011066091A1 (en) | 2009-11-24 | 2011-06-03 | Eastman Kodak Company | Continuous inkjet printer aqueous ink composition |
| US8517528B2 (en) | 2007-08-30 | 2013-08-27 | Seiko Epson Corporation | Ink jet recording method for recording pattern layer and white overlaying layer on longitudinal sheet |
| US8628184B2 (en) | 2010-03-23 | 2014-01-14 | Seiko Epson Corporation | Recording method, recording apparatus, and ink set |
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| US9085150B2 (en) | 2011-02-07 | 2015-07-21 | Seiko Epson Corporation | Ink jet recording method and ink used for the same |
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| EP3199366A1 (en) | 2016-01-27 | 2017-08-02 | Canon Finetech Inc. | Transfer material, printed material, manufacturing apparatus for printed material, and manufacturing method for printed material |
| US10300727B2 (en) | 2016-09-02 | 2019-05-28 | Canon Finetech Nisca Inc. | Print medium, printed material, and manufacturing method for printed material |
| WO2020149017A1 (en) | 2019-01-16 | 2020-07-23 | サカタインクス株式会社 | Anchor coat agent |
| WO2023276427A1 (en) | 2021-06-30 | 2023-01-05 | サカタインクス株式会社 | Primer composition for surface printed flexible packaging, ink set, surface printed material, and inkjet printing method |
| WO2023276426A1 (en) | 2021-06-30 | 2023-01-05 | サカタインクス株式会社 | Water-based white ink composition for surface-printed flexible packaging |
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|---|---|---|---|---|
| JP2002167536A (en)* | 2000-06-14 | 2002-06-11 | Mitsubishi Chemicals Corp | Recording liquid and ink jet recording method |
| WO2006075451A1 (en)* | 2005-01-13 | 2006-07-20 | Konica Minolta Medical & Graphic, Inc. | White ink composition for inkjet recording |
| JP2008001072A (en)* | 2006-06-26 | 2008-01-10 | Fujifilm Corp | Inkjet recording device |
| EP1964896A2 (en) | 2007-02-28 | 2008-09-03 | Konica Minolta Holdings, Inc. | Ink-jet ink and ink-jet recording method |
| US8702222B2 (en) | 2007-08-30 | 2014-04-22 | Seiko Epson Corporation | Ink jet recording method for recording pattern layer and white overlaying layer on longitudinal sheet |
| USRE47981E1 (en) | 2007-08-30 | 2020-05-12 | Seiko Epson Corporation | Ink jet recording method for recording pattern layer and white overlaying layer on longitudinal sheet |
| US8517528B2 (en) | 2007-08-30 | 2013-08-27 | Seiko Epson Corporation | Ink jet recording method for recording pattern layer and white overlaying layer on longitudinal sheet |
| USRE49081E1 (en) | 2007-08-30 | 2022-05-24 | Seiko Epson Corporation | Ink jet recording method for recording pattern layer and white overlaying layer on longitudinal sheet |
| US8721062B2 (en) | 2007-08-30 | 2014-05-13 | Seiko Epson Corporation | Ink jet recording method for recording pattern layer and white overlaying layer on longitudinal sheet |
| WO2010138191A1 (en) | 2009-05-29 | 2010-12-02 | Eastman Kodak Company | Aqueous compositions with improved silicon corrosion characteristics |
| WO2011066091A1 (en) | 2009-11-24 | 2011-06-03 | Eastman Kodak Company | Continuous inkjet printer aqueous ink composition |
| WO2011066117A1 (en) | 2009-11-24 | 2011-06-03 | Eastman Kodak Company | Continuous inkjet printer aquous ink composition |
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| US8876276B2 (en) | 2010-03-23 | 2014-11-04 | Seiko Epson Corporation | Recording method, recording apparatus, and ink set |
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