JPH1088056A - Recording fluid and method for recording image - Google Patents
Recording fluid and method for recording imageInfo
- Publication number
- JPH1088056A JPH1088056A JP26530896A JP26530896A JPH1088056A JP H1088056 A JPH1088056 A JP H1088056A JP 26530896 A JP26530896 A JP 26530896A JP 26530896 A JP26530896 A JP 26530896A JP H1088056 A JPH1088056 A JP H1088056A
- Authority
- JP
- Japan
- Prior art keywords
- recording liquid
- fine particles
- recording
- weight
- resin fine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は記録液及び画像記録
方法に関し、さらに詳細には、着色剤、水及び樹脂微粒
子を含有する記録液、並びにそれを使用した画像記録方
法に関する。The present invention relates to a recording liquid and an image recording method, and more particularly to a recording liquid containing a colorant, water and resin fine particles, and an image recording method using the same.
【0002】[0002]
【従来の技術】コンピューター等の情報機器の出力装置
として、最近ランニングコストが安く且つカラー化が容
易な方式として、記録液の液滴を記録ヘッドから吐出さ
せて記録体上に記録を行う画像記録方法であるインクジ
ェット方式が注目されている。インクジェットプリンタ
用の記録液としては、従来、水と染料を主成分とする染
料水溶液が使用されてきたが、ノズルから飛ばされた記
録液が記録紙に付着したときに、記録液が記録紙で滲
み、これにより飛翔時に形成した記録液滴粒よりも著し
く大きなドットになってしまったり、記録された画像の
濃度が低く、画質が低いという問題があった。また、記
録された画像の耐水性が低いため、水により容易に画像
が滲んだり、画像が流れるという問題があった。さら
に、耐光性が低く、太陽光等の光の照射により容易に画
像が退色するという問題があった。2. Description of the Related Art Recently, as an output device of an information device such as a computer, a system in which droplets of a recording liquid are ejected from a recording head to perform recording on a recording medium has been used as a system which has a low running cost and is easy to colorize. Attention has been paid to the inkjet method, which is a method. As a recording liquid for an ink jet printer, a dye aqueous solution containing water and a dye as a main component has been used.However, when the recording liquid ejected from a nozzle adheres to the recording paper, the recording liquid is applied to the recording paper. There are problems such as bleeding, which results in dots that are significantly larger than the recording droplets formed during flight, and that the density of the recorded image is low and the image quality is low. Further, since the recorded image has low water resistance, there has been a problem that the image easily bleeds or flows due to water. Furthermore, there is a problem that the light resistance is low and the image is easily discolored by irradiation with light such as sunlight.
【0003】従来、インクジェットプリンタ用の記録液
では染料水溶液のこれらの問題を解決するために、造膜
性の樹脂微粒子を記録液に添加する技術が提案されてい
る。例えば、樹脂微粒子としてラテックスが添加された
記録液が特公昭60−32663号公報に、カルボキシ
ル基とノニオン親水性基を有する水分散性樹脂が添加さ
れた記録液が特開平5−239392号公報に、非架橋
構造のビニル系高分子が添加された記録液が特開平5−
255628号公報に、及びイオン性基を有するポリエ
ステル粒子が添加された記録液が特開平6−34083
5号公報にそれぞれ開示されている。また、ポリエステ
ル等の樹脂微粒子と架橋剤とが配合された記録液の該樹
脂を記録体上で架橋させる技術が特公平7−47355
号公報に開示されている。Conventionally, in order to solve these problems of a dye aqueous solution for a recording liquid for an ink jet printer, a technique of adding film-forming resin fine particles to the recording liquid has been proposed. For example, JP-B-60-32663 discloses a recording liquid containing latex as resin fine particles, and JP-A-5-239392 discloses a recording liquid containing a water-dispersible resin having a carboxyl group and a nonionic hydrophilic group. A recording liquid to which a non-crosslinked vinyl polymer is added is disclosed in
Japanese Patent Application Laid-Open No. 6-34083 discloses a recording liquid containing polyester particles having an ionic group.
No. 5, each of which is disclosed. Japanese Patent Publication No. 7-47355 discloses a technique of crosslinking a resin of a recording liquid containing resin fine particles such as polyester and a crosslinking agent on a recording medium.
No. 6,086,045.
【0004】[0004]
【発明が解決しようとする課題】しかし、上記の公報に
開示されている記録液では、いずれも、記録ヘッドの吐
出口部分において、空気との接触による記録液中水分の
蒸発に伴い樹脂微粒子の造膜が開始され、目詰まりが発
生するため、記録液を安定して吐出することは不可能で
あった。また、これらの記録液は、記録紙織維への毛細
管現象による記録液の滲みを完全に防ぐことはできず、
高画質画像を提供することは不可能であった。さらに、
これらの記録液は、記録紙内部への浸透を完全に防ぐこ
とができず、高濃度画像化と高画質化に限界があった。
また、耐水性についても同様に限界があった。さらに、
上記従来開示の記録液を、吐出口での目詰まりを回避す
るために、水で希釈すると、希釈前と比べて、同一体積
の液滴中に含まれる樹脂微粒子の含有量、即ち、画像形
成に寄与する樹脂固形分含有量が減少し、画像濃度が著
しく低下し、高画質な画像を提供することが不可能であ
った。即ち、従来開示の記録液では、樹脂微粒子の高含
有量化(樹脂固形分の高含有量化)による高画像濃度で
高画質の画像を提供することと吐出口での目詰まりを回
避することとの両立は不可能であった。However, in any of the recording liquids disclosed in the above publications, resin fine particles are generated at the discharge port of the recording head due to evaporation of moisture in the recording liquid due to contact with air. Since film formation was started and clogging occurred, it was impossible to stably discharge the recording liquid. In addition, these recording liquids cannot completely prevent the bleeding of the recording liquid due to the capillary phenomenon on the recording paper textile,
It was impossible to provide high quality images. further,
These recording liquids cannot completely prevent permeation into the recording paper, and there is a limit to high density image formation and high image quality.
Also, there was a similar limitation in water resistance. further,
When the recording liquid of the conventional disclosure is diluted with water in order to avoid clogging at the discharge port, the content of the resin fine particles contained in the liquid droplets of the same volume as before the dilution, that is, image formation The content of resin solids that contributes to the reduction in image density decreases, the image density significantly decreases, and it is impossible to provide high-quality images. That is, in the recording liquid disclosed in the related art, it is possible to provide a high-quality image with a high image density by increasing the content of resin fine particles (increase in the content of resin solids) and to avoid clogging at the discharge port. Balancing was impossible.
【0005】本発明は上記課題を解決するためになされ
たものであり、本発明の目的は、高い画像濃度を有し、
記録紙上での滲みや浸透のない耐水性に優れた画像を提
供することが可能で、且つ吐出安定性に優れた記録液を
提供することにある。また、本発明の他の目的は、該記
録液を用いた画像記録方法を提供することにある。The present invention has been made to solve the above problems, and an object of the present invention is to provide a high image density,
An object of the present invention is to provide a recording liquid capable of providing an image having excellent water resistance without bleeding or penetration on a recording paper and having excellent ejection stability. Another object of the present invention is to provide an image recording method using the recording liquid.
【0006】[0006]
【課題を解決するための手段】上記の目的を達成可能な
本発明の記録液は、着色剤、水及び3種類以上の樹脂微
粒子を含有することを特徴とする。The recording liquid of the present invention, which can achieve the above object, is characterized by containing a colorant, water and three or more kinds of resin fine particles.
【0007】また、本発明は、記録液の液滴を記録ヘッ
ドから吐出させて記録体上に記録を行う画像記録方法に
おいて、上記の記録液を用いることを特徴とする。Further, the present invention is characterized in that the above-mentioned recording liquid is used in an image recording method for recording on a recording medium by discharging droplets of the recording liquid from a recording head.
【0008】以上のような記録液が、樹脂微粒子の高含
有量化(樹脂固形分の高含有量化)による高画像濃度の
達成と記録ヘッドの吐出口での目詰まり回避との両立を
可能にする理由は、必ずしも明確ではないが、以下のよ
うに推論する。The above-described recording liquid makes it possible to achieve both high image density by increasing the content of resin fine particles (increase in the content of resin solids) and avoiding clogging at the ejection openings of the recording head. The reason is not always clear, but it is inferred as follows.
【0009】記録液中に3種類以上の異なる樹脂微粒子
が含まれると、記録液中で、ある樹脂微粒子の周囲(最
近接配位位置)にこの樹脂微粒子と同種の樹脂微粒子が
存在する確率が3分の1以下に減少する。これにより同
種樹脂微粒子同士の接近及び衝突確率が減少し、同種樹
脂微粒子同士の接近から衝突、融着を経て、造膜に至る
一連のプロセスが阻害され(配位効果)、目詰まりが防
止される。When three or more kinds of different resin fine particles are contained in the recording liquid, there is a probability that the same kind of resin fine particles as this resin fine particle exist around a certain resin fine particle (closest coordinate position) in the recording liquid. It is reduced to less than one third. This reduces the probability of similar resin particles approaching and colliding with each other, and prevents a series of processes from approaching similar resin particles through collision and fusion to film formation (coordination effect), thereby preventing clogging. You.
【0010】また、記録液中に同種樹脂微粒子のみが存
在する場合より、異種樹脂微粒子が存在する場合の方が
粒子間引力が働きにくくなる(反発力が働き易くなる)
ので、互いに樹脂微粒子の接近が妨げられ、樹脂微粒子
同士の衝突確率が減少し(粒子間反発力効果)、このた
め上記と同様樹脂微粒子同士の接近から衝突、融着を経
て、造膜に至る一連のプロセスが阻害され(配位効
果)、目詰まりが防止される。[0010] Further, in the case where different kinds of resin fine particles are present in the recording liquid, the attractive force between the particles is less likely to be exerted than in the case where only the same kind of resin fine particles is present (the repulsive force is more likely to be exerted).
Therefore, the approach of the resin fine particles is hindered from each other, and the probability of collision between the resin fine particles is reduced (the effect of interparticle repulsion). A series of processes is inhibited (coordination effect) and clogging is prevented.
【0011】さらに、目詰まり防止に関しては、同種微
粒子間の粒径及び形状等の差より異種微粒子間の粒径及
び形状等の差の方が大きいと考えられ、ある樹脂微粒子
の周囲に、この樹脂微粒子の粒径、形状等と大きく異な
る粒径、形状等を有する異種の樹脂微粒子が存在するこ
とによって、同程度の粒径、形状等を有する微粒子のみ
が存在する場合と比べて、同種、異種の樹脂微粒子同士
の接近が妨害され(幾何構造効果)、上記と同様に目詰
まりが防止されるとも考えられる。Further, with respect to the prevention of clogging, it is considered that the difference in particle size and shape between different kinds of fine particles is larger than the difference in particle size and shape between fine particles of the same kind. By the presence of different types of resin fine particles having a particle size, shape, etc., significantly different from the particle size, shape, etc. of the resin fine particles, compared to the case where only fine particles having a similar particle size, shape, etc. are present, the same type, It is considered that the approach between different kinds of resin fine particles is hindered (geometric structure effect), and clogging is prevented in the same manner as described above.
【0012】本発明において、上記総合効果により樹脂
微粒子同士の接近が顕著に抑制されるので、該記録液中
に含まれる樹脂微粒子の総合含有率を上げることがで
き、ひいては一滴の液滴中の樹脂微粒子の含有量を増や
すことができ、高画像濃度の画像を形成することが可能
になる。In the present invention, the approach of the resin fine particles to each other is remarkably suppressed by the above-described overall effect, so that the total content of the resin fine particles contained in the recording liquid can be increased, and, consequently, the ratio of one droplet in one droplet can be increased. The content of the resin fine particles can be increased, and an image having a high image density can be formed.
【0013】そして、これら3種類以上の樹脂微粒子の
膜化が並行して進行し、紙等の記録体上での記録液の滲
みや浸透が防止され、樹脂とその中に閉じ込められた着
色剤とからなる、高画像濃度で且つ高い耐水性の画像を
記録体上に形成することが可能になる。The film formation of these three or more types of resin fine particles proceeds in parallel, preventing bleeding or permeation of a recording liquid on a recording medium such as paper, and forming a resin and a colorant confined therein. Thus, an image having high image density and high water resistance can be formed on a recording medium.
【0014】[0014]
【発明の実施の形態】以下、本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
【0015】本発明の記録液は、水、着色剤、及び3種
類以上の樹脂微粒子を含有する。本発明に用いる樹脂微
粒子としては、非架橋性樹脂微粒子、自己架橋性樹脂微
粒子、及び架橋剤の作用により架橋する樹脂微粒子を使
用することができ、具体的には、フッ素系樹脂微粒子、
ポリエステル系樹脂微粒子、酢酸ビニル系樹脂微粒子、
塩化ビニル系樹脂微粒子、スチレン−ブタジェン重合体
系樹脂微粒子、ポリウレタン系樹脂系樹脂微粒子、ポリ
スチレン系樹脂微粒子、酢酸ビニル−アクリル共重合体
系樹脂微粒子、酢酸ビニル−アクリルアミド共重合体系
樹脂微粒子、エチレン−酢酸ビニル共重合体樹脂、エポ
キシ樹脂系樹脂微粒子、ポリアミド樹脂系樹脂微粒子、
シリコーン系樹脂微粒子、アクリル系樹脂微粒子及びア
クリルシリコン系樹脂微粒子等の樹脂微粒子を用いるこ
とができる。本発明において、自己架橋性の樹脂とは、
架橋剤の作用ではなく、該樹脂の主鎖及び/又は側鎖に
組み込まれた官能基の反応性により、架橋する樹脂をい
う。The recording liquid of the present invention contains water, a colorant, and three or more types of fine resin particles. As the resin fine particles used in the present invention, non-crosslinkable resin fine particles, self-crosslinkable resin fine particles, and resin fine particles that can be crosslinked by the action of a crosslinking agent can be used.
Polyester resin fine particles, vinyl acetate resin fine particles,
Vinyl chloride resin fine particles, styrene-butadiene polymer resin fine particles, polyurethane resin resin fine particles, polystyrene resin fine particles, vinyl acetate-acryl copolymer resin fine particles, vinyl acetate-acrylamide copolymer resin fine particles, ethylene-vinyl acetate Copolymer resin, epoxy resin-based resin fine particles, polyamide resin-based resin fine particles,
Resin fine particles such as silicone resin fine particles, acrylic resin fine particles, and acrylic silicone resin fine particles can be used. In the present invention, the self-crosslinkable resin is
It refers to a resin that crosslinks not by the action of a crosslinking agent but by the reactivity of a functional group incorporated in the main chain and / or side chain of the resin.
【0016】本発明では、各樹脂による膜形成プロセス
に時間的な差を生じさせると共に組成的な相違により膜
を形成しにくくさせ、これにより目詰まり、即ち、記録
ヘッド吐出口部での膜形成を防止するという観点から、
記録液中に含まれる3種類以上の樹脂微粒子のうち、少
なくとも1種類が非架橋性の樹脂微粒子であることが好
ましい。また、列挙された非架橋性の樹脂微粒子の中で
は、造膜性(画像形成性)に優れ、且つ高撥水性、高耐
水性、高耐候性を備えて、高耐水性で高画像濃度の画像
形成に有用であることから、フッ素系樹脂微粒子が好ま
しい。フッ素系樹脂微粒子としては、フルオロオレフィ
ン単位を有するフッ素系樹脂微粒子が好ましく、中で
も、フルオロオレフィン単位及びビニルエーテル単位か
ら構成されるフッ素含有ビニルエーテル系樹脂微粒子が
特に好ましい。According to the present invention, a time difference is caused in a film forming process by each resin, and it is difficult to form a film due to a difference in composition, thereby causing clogging, that is, film formation at a recording head discharge port. From the perspective of preventing
It is preferable that at least one of the three or more types of resin fine particles contained in the recording liquid is a non-crosslinkable resin fine particle. In addition, among the non-crosslinkable resin fine particles listed above, they have excellent film forming properties (image forming properties), and have high water repellency, high water resistance, and high weather resistance, and have high water resistance and high image density. Fluorine-based resin fine particles are preferred because they are useful for image formation. As the fluorine-based resin fine particles, fluorine-based resin fine particles having a fluoroolefin unit are preferable, and among them, fluorine-containing vinyl ether-based resin fine particles composed of a fluoroolefin unit and a vinyl ether unit are particularly preferable.
【0017】ここでフルオロオレフィン単位の例は、−
CF2 CF2 −、−CF2 CF(CF3 )−、−CF2
CFCl−等が挙げられる。一方、ビニルエーテル単位
の例は、以下のようなものを挙げることができる。Here, an example of the fluoroolefin unit is-
CF 2 CF 2 -, - CF 2 CF (CF 3) -, - CF 2
CFCl- and the like. On the other hand, examples of the vinyl ether unit include the following.
【0018】[0018]
【化1】 Embedded image
【0019】フルオロオレフィン単位及びビニルエーテ
ル単位から構成されるフッ素含有ビニルエーテル系樹脂
微粒子としては、上記フルオロオレフィン単位とビニル
エーテル単位が交互に組み合わされた交互共重合体が好
ましい。As the fluorine-containing vinyl ether resin fine particles composed of a fluoroolefin unit and a vinyl ether unit, an alternating copolymer in which the above-mentioned fluoroolefin unit and vinyl ether unit are alternately combined is preferable.
【0020】本発明の記録液は、3種類以上の樹脂微粒
子を含有すればよく、これにより樹脂固形分高含有量化
による高画像濃度化、高画質化と目詰まり回避との両立
を十分に達成し得るが、4種類以上の樹脂微粒子を含有
することにより、前述した最近接配位位置に同種樹脂微
粒子の存在する確率が一層低下し(配位効果の促進)、
また粒子間引力が一層働きにくくなる等のため、目詰ま
りの発生がより効果的に防止される。記録液に含まれる
樹脂微粒子の種類の上限値は特にないが、各樹脂微粒子
の形状、大きさが一定で、且つその形状を球形と仮定し
た場合、粒子を最密充填した時の最近接粒子数(配位
数)、即ち、ある粒子と接触状態で存在する粒子の数は
12となる。従って、樹脂微粒子の種類の上限の最適値
は12と考えられ、さらに確率的な振れの幅を考慮すれ
ば、樹脂微粒子の種類の上限は18種類(12種類+6
種類)とすることが好ましい。以上より、本発明におけ
る記録液中に含有される樹脂微粒子の種類は、配位効果
による同種樹脂微粒子同士の接近及び衝突確率減少の観
点からは、好ましくは3種類以上18種類以下であり、
より好ましくは4種類以上12種類以下である。なお、
本発明では、樹脂を構成するモノマーが同じであって
も、変性の仕方等の違いにより樹脂微粒子又はその分散
液の特性、即ち、最低成膜温度、ガラス転位点、イオン
性、pH、重量平均分子量及び平均粒子径等のいずれか
1つ以上が異なれば別の種類の樹脂微粒子と考える。The recording liquid of the present invention only needs to contain three or more types of resin fine particles, thereby sufficiently achieving high image density by increasing the resin solid content, and simultaneously achieving high image quality and avoiding clogging. However, by containing four or more types of resin fine particles, the probability of the presence of the same type of resin fine particles at the closest coordination position described above is further reduced (promoting the coordination effect),
Further, since the attraction between particles becomes more difficult, clogging can be prevented more effectively. Although there is no particular upper limit for the type of resin fine particles contained in the recording liquid, the shape and size of each resin fine particle are constant, and assuming that the shape is spherical, the closest particles when the particles are closest packed are used. The number (coordination number), that is, the number of particles existing in contact with a certain particle is 12. Therefore, the optimum value of the upper limit of the type of the resin fine particles is considered to be 12, and the upper limit of the type of the resin fine particles is 18 types (12 types + 6) in consideration of the stochastic fluctuation width.
Type). From the above, the types of the resin fine particles contained in the recording liquid in the present invention are preferably 3 or more and 18 or less from the viewpoint of approaching the same type of resin fine particles and reducing the collision probability due to the coordination effect.
More preferably, the number is 4 or more and 12 or less. In addition,
In the present invention, even if the monomers constituting the resin are the same, the characteristics of the resin fine particles or a dispersion thereof, that is, the minimum film forming temperature, the glass transition point, the ionicity, the pH, the weight average, depend on the method of modification and the like. If at least one of the molecular weight and the average particle diameter is different, it is considered to be another type of resin fine particles.
【0021】本発明に用いる各脂微粒子の平均粒子径
は、0.01μm以上5μm以下であることが好ましい
が、0.05μm以上3μm以下であることがより好ま
しい。樹脂微粒子の平均粒子径が0.01μm未満だと
造膜性が悪く、また5μmを超えると光学濃度(画像濃
度)が低下する。The average particle diameter of each fat fine particle used in the present invention is preferably 0.01 μm or more and 5 μm or less, more preferably 0.05 μm or more and 3 μm or less. If the average particle diameter of the resin fine particles is less than 0.01 μm, the film-forming property is poor, and if it exceeds 5 μm, the optical density (image density) decreases.
【0022】また、本発明において、樹脂微粒子の合計
含有率(樹脂微粒子固形分の合計含有率)は、記録液の
全量に対して10〜95重量%であることが好ましく、
15〜90重量%の範囲であることがより好ましく、2
0〜80重量%の範囲であることがさらに好ましい。樹
脂微粒子の合計含有率が10重量%未満になると画像の
光学濃度が低くなり、また95重量%を超えると吐出安
定性が低下する懸念がある。また、記録液に含まれる各
樹脂微粒子の含有割合は、所望の特性を最大限に実現す
るため適宜に選択されるが、n種類(n:3以上の正の
整数)の樹脂微粒子を混合した場合、記録液中の樹脂微
粒子の固形分量の全合計をW重量部とすると、記録液中
のそれぞれの樹脂微粒子の固形分量は2W/n重量部か
ら0.1W/n重量部までの範囲にあることが好まし
い。この範囲より多くても少なくても、複数の異種樹脂
微粒子の共存による目詰まり防止効果が低下する場合が
ある。また、記録液中に含まれる樹脂微粒子の内、非架
橋性の樹脂微粒子の含有割合は、その一種類につき上記
と同様に2W/n重量部から0.1W/n重量部までの
範囲にあることが好ましいが、さらに、2W/n重量部
から0.3W/n重量部までの範囲にあることがより好
ましい。該含有割合が2W/n重量部より多くなると上
記のように複数の異種樹脂微粒子の共存による目詰まり
防止効果が低下し、0.3W/n重量部より少なくなる
と目詰まり防止効果の低下とともに耐水性などが低下す
る懸念がある。In the present invention, the total content of the resin fine particles (the total content of solid resin fine particles) is preferably 10 to 95% by weight based on the total amount of the recording liquid.
More preferably, it is in the range of 15 to 90% by weight.
More preferably, it is in the range of 0 to 80% by weight. If the total content of the resin fine particles is less than 10% by weight, the optical density of the image will be low, and if it exceeds 95% by weight, there is a concern that the ejection stability may be reduced. Further, the content ratio of each resin fine particle contained in the recording liquid is appropriately selected in order to realize desired characteristics to the maximum, but n kinds (n: a positive integer of 3 or more) of resin fine particles are mixed. In this case, assuming that the total amount of the solid content of the resin fine particles in the recording liquid is W parts by weight, the solid content of each resin fine particle in the recording liquid ranges from 2 W / n parts by weight to 0.1 W / n parts by weight. Preferably, there is. If the amount is more or less than this range, the effect of preventing clogging due to the coexistence of a plurality of different resin fine particles may be reduced. In addition, the content ratio of the non-crosslinkable resin fine particles in the resin fine particles contained in the recording liquid is in the range of 2 W / n parts by weight to 0.1 W / n parts by weight for one kind thereof in the same manner as described above. It is more preferred, but more preferably in the range from 2 W / n parts by weight to 0.3 W / n parts by weight. When the content is more than 2 W / n parts by weight, the effect of preventing clogging due to the coexistence of a plurality of different types of resin fine particles is reduced as described above. When the content is less than 0.3 W / n parts by weight, the effect of preventing clogging is reduced and water resistance is reduced. There is a concern that the properties will decrease.
【0023】本発明において、着色剤としては、主溶媒
である水との親和性がよいもの、均一分散性が良好なも
のが使用でき、具体的には、顔料、水溶性染料、分散染
料が用いられる。In the present invention, as the coloring agent, those having good affinity for water as a main solvent and those having good uniform dispersibility can be used. Specifically, pigments, water-soluble dyes and disperse dyes can be used. Used.
【0024】本発明に用いることのできる顔料として
は、有機顔料、無機顔料等が挙げられ、例えば、白黒用
としては、ファーネスブラック、チャンネルブラック等
のカーボンブラック(C.I.ピグメントッブラック
7)類、アニリンブラック(C.I.ピグメントブラッ
ク1)等の有機顔料が挙げられる。さらに、カラー用と
しては、C.I.ピグメントイエロー1、3、12、1
3、14、17、24、34、35、37、42、5
3、55、81、83、95、97、98、100、1
01、104、108、109、110、117、12
0、138、153、C.I.ピグメントバイオレット
1、3、5:1、16、19、23、38、C.I.ピ
グメントッブルー1、2、15、15:1、15:2、
15:3、15:4、15:6、16等の顔料がある。
記録液中に含まれる顔料の含有率は、1〜50重量%が
好ましいが、1.5〜40重量%がより好ましい。これ
らの顔料をより均一に分散するためには、場合によって
ボールミル等で分散処理してもよい。Examples of the pigment which can be used in the present invention include organic pigments and inorganic pigments. For example, carbon blacks such as furnace black and channel black (C.I. And organic pigments such as aniline black (CI pigment black 1). Further, for color, C.I. I. Pigment Yellow 1, 3, 12, 1
3, 14, 17, 24, 34, 35, 37, 42, 5,
3, 55, 81, 83, 95, 97, 98, 100, 1,
01, 104, 108, 109, 110, 117, 12
0, 138, 153, C.I. I. Pigment Violet 1, 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2,
There are pigments such as 15: 3, 15: 4, 15: 6, 16 and the like.
The content of the pigment contained in the recording liquid is preferably from 1 to 50% by weight, more preferably from 1.5 to 40% by weight. In order to disperse these pigments more evenly, dispersion treatment may be performed by a ball mill or the like in some cases.
【0025】本発明に用いることのできる水溶性染料と
しては、直接染料、酸性染料等が挙げられ、例えば、
C.I.ダイレクトブラック9、17、19、22、3
2、51、56、62、69、77、80、91、9
4、97、108、112、113、114、117、
118、121、122、125、132、146、1
54、166、168、173、199、C.I.ダイ
レクトバイオレット7、9、47、48、51、66、
90、93、94、95、98、100、101、C.
I.ダイレクトイエロー8、9、11、12、27、2
8、29、33、35、39、41、44、50、5
3、58、59、68、86、87、93、95、9
6、98、100、106、108、109、110、
130、132、144、161、163、C.I.ダ
イレクトブルー1、10、15、22、25、55、6
7、68、71、76、77、78、80、84、8
6、87、90、98、106、201、202、24
4、251、280、C.I.アシッドブラック7、2
4、29、48、C.I.アシッドバイオレット5、3
4、43、47、48、90、103、C.I.アシッ
ドイエロー17、19、23、25、39、40、4
4、49、50、61、110、174、218、C.
I.アシッドブルー9、25、40、41、62、7
2、76、80、106、112、120、205、2
30、271、280等が挙げられるが、これらに限定
されない。記録液中に含まれるこれらの染料の含有率
は、染料の種類、溶媒成分の種類、記録液に対して要求
されている特性等に依存して決定されるが、一般には、
0.2〜40重量%、好ましくは0.5〜30重量%の
範囲が良い。Examples of the water-soluble dye that can be used in the present invention include direct dyes and acid dyes.
C. I. Direct Black 9, 17, 19, 22, 3
2, 51, 56, 62, 69, 77, 80, 91, 9
4, 97, 108, 112, 113, 114, 117,
118, 121, 122, 125, 132, 146, 1
54, 166, 168, 173, 199, C.I. I. Direct violet 7, 9, 47, 48, 51, 66,
90, 93, 94, 95, 98, 100, 101, C.I.
I. Direct Yellow 8, 9, 11, 12, 27, 2
8, 29, 33, 35, 39, 41, 44, 50, 5,
3, 58, 59, 68, 86, 87, 93, 95, 9
6, 98, 100, 106, 108, 109, 110,
130, 132, 144, 161, 163, C.I. I. Direct Blue 1, 10, 15, 22, 25, 55, 6
7, 68, 71, 76, 77, 78, 80, 84, 8
6, 87, 90, 98, 106, 201, 202, 24
4, 251, 280, C.I. I. Acid Black 7, 2
4, 29, 48, C.I. I. Acid Violet 5, 3
4, 43, 47, 48, 90, 103, C.I. I. Acid Yellow 17, 19, 23, 25, 39, 40, 4
4, 49, 50, 61, 110, 174, 218, C.I.
I. Acid Blue 9, 25, 40, 41, 62, 7
2, 76, 80, 106, 112, 120, 205, 2,
30, 271 and 280, but are not limited to these. The content of these dyes contained in the recording liquid is determined depending on the type of dye, the type of solvent component, the properties required for the recording liquid, and the like.
The range is from 0.2 to 40% by weight, preferably from 0.5 to 30% by weight.
【0026】本発明に用いる水には、イオン交換水、超
純水、蒸留水、限外濾過水を使用することが好ましい。As the water used in the present invention, it is preferable to use ion-exchanged water, ultrapure water, distilled water and ultrafiltration water.
【0027】その他、必要に応じて、リン酸二水素カリ
ウム、リン酸二水素ナトリウム等のpH調節剤、防カ
ビ、防腐、防錆等の目的で安息香酸、ジクロフェン、ヘ
キサクロロフェン、ソルビン酸等を記録液に添加しても
よい。さらに必要に応じて、エチレングリコール、グリ
セリン等の各種一般添加剤を記録液に加えてもよい。本
発明の記録液は、記録液の液滴をヘツドから吐出させて
紙等の記録体上に記録を行なう画像記録方法に使用する
ことができる。In addition, if necessary, a pH adjuster such as potassium dihydrogen phosphate and sodium dihydrogen phosphate, and benzoic acid, diclofen, hexachlorophene, sorbic acid and the like for the purpose of fungicide, preservation, rust prevention and the like. It may be added to the recording liquid. If necessary, various general additives such as ethylene glycol and glycerin may be added to the recording liquid. The recording liquid of the present invention can be used for an image recording method in which droplets of the recording liquid are ejected from a head to perform recording on a recording medium such as paper.
【0028】また、本発明の記録液はインクジェット記
録のみならず、静電吸引方式の画像記録、筆記具等に適
宜使用可能である。The recording liquid of the present invention can be used not only for ink jet recording but also for electrostatic suction type image recording and writing implements.
【0029】[0029]
【実施例】以下、本発明を実施例に基づいて詳細に説明
する。 (実施例1)記録液は以下のようにして作成した。水系
銅フタロシアニン系顔料(ピグメントブルー15:3)
分散液(固形分=35%)22重量部と、水及びフルオ
ロオレフィンとビニルエーテルの乳化重合により作製さ
れた含フッ素ビニルエーテル系樹脂微粒子(平均粒子
径:0.15μm)を含む樹脂分散液(固形分=50
%、旭硝子社製、商品名:FE−3000)21重量部
と、水及びシリコン変性アクリル樹脂微粒子(平均粒子
径:0.1〜0.2μm)を含む樹脂分散液(固形分=
45%、三洋化成工業社製、商品名:G−45)23重
量部と、水及び側鎖にカルボキシル基が付加された変性
ポリエステル樹脂微粒子(平均粒子径:0.1〜0.2
μm)を含む樹脂分散液(固形分=30%、高松油脂社
製、商品名:A−215G)34重量部とを添加し、撹
拌して均一に混合させた。その後、この混合液を孔径1
0μmのメンブランフィルターにてろ過して、ゴミ及び
粗大粒子を除去し、記録液中顔料(着色剤)濃度{=顔
料固形分×100/記録液(液体)全量}が8重量%、
固形分中顔料(着色剤)濃度{=顔料固形分×100/
(顔料固形分+樹脂微粒子固形分合計)}が20重量
%、記録液中樹脂微粒子全固形分濃度{=樹脂微粒子固
形分合計×100/記録液全量}が31重量%の記録液
を得た。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. (Example 1) A recording liquid was prepared as follows. Water-based copper phthalocyanine pigment (Pigment Blue 15: 3)
A resin dispersion (solid content: 22 parts by weight of a dispersion (solid content = 35%)) and fluorine-containing vinyl ether-based resin fine particles (average particle size: 0.15 μm) produced by emulsion polymerization of water, a fluoroolefin, and vinyl ether = 50
%, Manufactured by Asahi Glass Co., Ltd., trade name: FE-3000), a resin dispersion liquid containing 21 parts by weight of water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm) (solid content =
45%, manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: G-45) 23 parts by weight, water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2)
of resin dispersion (solid content = 30%, manufactured by Takamatsu Oil & Fat Co., Ltd., trade name: A-215G) was added, and the mixture was stirred and uniformly mixed. Thereafter, the mixed solution was added with a pore size of 1
The particles were filtered through a 0 μm membrane filter to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid {= pigment solid content × 100 / the total amount of the recording liquid (liquid)} was 8% by weight.
Pigment (colorant) concentration in solid content = pigment solid content x 100 /
(Pigment solid content + Resin fine particle solid content) = 20% by weight, total concentration of resin fine particle total solid content in the recording liquid == Total resin fine particle solid content × 100 / Total amount of recording liquid} = 31% by weight. .
【0030】このようにして作製した記録液をバーコー
ターを用いて、複写機用普通紙上に塗布し、室温にて乾
燥させることにより、普通紙上に塗布乾燥膜からなるベ
タ画像を得た。そして、得られた画像の光学濃度を画像
表面側から測定した。その結果、画像面積1cm2 当た
り0.9mgという少量の記録液量で塗布したベタ画像
の光学濃度は1.4という高い値であった。The recording liquid thus prepared was applied to plain paper for copying machines using a bar coater and dried at room temperature to obtain a solid image consisting of a coating and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm 2 of image area was as high as 1.4.
【0031】また、この普通紙上のベタ画像の縦断面を
光学顕微鏡により観察したところ、ベタ画像は普通紙の
上に主として形成されていて、記録液の普通紙中への浸
透はほとんど認められなかった。When the longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and almost no permeation of the recording liquid into the plain paper was recognized. Was.
【0032】一方、記録ヘッド吐出口での記録液の目詰
まり性の評価を次のように行った。内径15mmの注射
器の先に内径180μmの標準注射針(岩下エンジニア
リング製)をセットし、この注射器の中に記録液を10
ml吸入した。次いで、注射器の上部を密閉し注射針か
らの記録液の滴下を停止させた状態にして、放置した。
所定時間経過後、上部を開放し、記録液が継続して注射
針から滴下可能かどうかを調べた。この操作を、放置の
所定時間を少しずつ延長しながら繰り返し、注射針から
記録液が滴下可能であった最長放置時間を目詰まり発生
までの余裕時間とした。このようにして測定した本方式
での記録液の目詰まり発生までの余裕時間は50秒と長
いものであった。On the other hand, the clogging property of the recording liquid at the discharge port of the recording head was evaluated as follows. A standard syringe needle (manufactured by Iwashita Engineering) having an inner diameter of 180 μm was set at the tip of a syringe having an inner diameter of 15 mm, and 10 μl of the recording liquid was placed in the syringe.
ml was inhaled. Next, the upper part of the syringe was closed, and dripping of the recording liquid from the injection needle was stopped, and the syringe was left.
After a lapse of a predetermined time, the upper portion was opened, and it was examined whether the recording liquid could be continuously dropped from the injection needle. This operation was repeated while gradually increasing the predetermined time of leaving, and the longest leaving time during which the recording liquid could be dropped from the injection needle was defined as a margin time until the occurrence of clogging. The margin time until the clogging of the recording liquid in this method measured in this way was as long as 50 seconds.
【0033】次に、市販のインクジェットプリンターを
用いて、この記録液の普通紙上への印字テストを実施し
た。その結果、水で希釈しない記録液の原液を安定に吐
出することができた。このようにして印字されたサンプ
ルの印字ドットを拡大ルーペ及び光学顕微鏡により観察
したところ、ドット周辺部での滲みのない鮮明なドット
であることがわかった。Next, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.
【0034】さらに、上記バーコーターによるベタ画像
及びプリンターによる印字サンプルに水をこぼし、耐水
性を評価した。その結果、水による画像の滲み、着色剤
の広かりは認められず、本実施例に係る記録液が耐水性
の高いものであることがわかった。 (実施例2)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)22重量部
と、水及びフルオロオレフィンとビニルエーテルの乳化
重合により作製された含フッ素ビニルエーテル系樹脂微
粒子(平均粒子径:0.15μm)を含む樹脂分散液
(固形分=50%、旭硝子社製、商品名:FE−300
0)20重量部と、水及び変性スチレン−ブタジエン共
重合体樹脂微粒子(平均粒子径:0.19μm)を含む
樹脂分散液(固形分=48.5%、住化エイビーエス・
ラテックス社製、商品名:SN−335)20重量部
と、水及び側鎖にカルボキシル基が付加された変性ポリ
エステル樹脂微粒子(平均粒子径:0.1〜0.2μ
m)を含む樹脂分散液(固形分=25%、高松油脂社
製、商品名:A−115G、pH及びガラス転位点がA
−215Gと異なる)39重量部とを添加し、撹拌して
均一に混合させた。その後、この混合液を孔径10μm
のメンブランフィルターにてろ過して、ゴミ及び粗大粒
子を除去し、記録液中顔料(着色剤)濃度が7重量%、
固形分中顔料(着色剤)濃度が20重量%、記録液中樹
脂微粒子全固形分濃度が29重量%の記録液を得た。Further, water was spilled on the solid image by the bar coater and the print sample by the printer, and the water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 2) 22 parts by weight of an aqueous copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, a fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) A resin dispersion containing 20 parts by weight of water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) (solid content = 48.5%, Sumika ABS.
Latex Co., Ltd., trade name: SN-335) 20 parts by weight, water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm)
m) (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-115G, pH and glass transition point are A
(Different from -215G) was added and stirred to mix uniformly. Thereafter, the mixed solution was added with a pore size of 10 μm.
To remove dirt and coarse particles, the pigment (colorant) concentration in the recording liquid is 7% by weight,
A recording liquid having a pigment (colorant) concentration in the solid content of 20% by weight and a total solid content of the resin fine particles in the recording liquid of 29% by weight was obtained.
【0035】このようにして作製した記録液をバーコー
ターを用いて、複写機用普通紙上に塗布し、室温にて乾
燥させることにより、普通紙上に塗布乾燥膜からなるベ
タ画像を得た。そして、得られた画像の光学濃度を画像
表面側から測定した。その結果、画像面積1cm2 当た
り0.9mgという少量の記録液量で塗布したベタ画像
の光学濃度は1.4という高い値であった。The recording liquid thus prepared was coated on plain paper for a copying machine using a bar coater and dried at room temperature to obtain a solid image consisting of a coated and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm 2 of image area was as high as 1.4.
【0036】また、この普通紙上のベタ画像の縦断面を
光学顕微鏡により観察したところ、ベタ画像は普通紙の
上に主として形成されていて、記録液の普通紙中への浸
透はほとんど認められなかった。When the longitudinal section of the solid image on the plain paper was observed by an optical microscope, the solid image was mainly formed on the plain paper, and the recording liquid hardly penetrated into the plain paper. Was.
【0037】次に、実施例1と同様の方式にて、記録ヘ
ッド吐出口での記録液の目詰まり性を評価した。その結
果、本方式での記録液の目詰まり発生までの余裕時間は
50秒と長いものであった。Next, the clogging of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 50 seconds.
【0038】さらに、市販のインクジェットプリンター
を用いて、この記録液の普通紙上への印字テストを実施
した。その結果、水で希釈しない記録液の原液を安定に
吐出することができた。このようにして印字されたサン
プルの印字ドットを拡大ルーペ及び光学顕微鏡により観
察したところ、ドット周辺部での滲みのない鮮明なドッ
トであることがわかった。Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.
【0039】引き続いて、上記バーコーターによるベタ
画像及びプリンターによる印字サンプルに水をこぼし、
耐水性を評価した。その結果、水による画像の滲み、着
色剤の広かりは認められず、本実施例に係る記録液が耐
水性の高いものであることがわかった。 (実施例3)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)23重量部
と、水及びフルオロオレフィンとビニルエーテルの乳化
重合により作製された含フッ素ビニルエーテル系樹脂微
粒子(平均粒子径:0.15μm)を含む樹脂分散液
(固形分=50%、旭硝子社製、商品名:FE−300
0)16重量部と、水及びシリコン変性アクリル樹脂微
粒子(平均粒子径:0.1〜0.2μm)を含む樹脂分
散液(固形分=45%、三洋化成工業社製、商品名:G
−45)18重量部と、水及び側鎖にカルボキシル基が
付加された変性ポリエステル樹脂微粒子(平均粒子径:
0.1〜0.2μm)を含む樹脂分散液(固形分=30
%、高松油脂社製、商品名:A−215G)27重量部
と、水及び変性スチレン−ブタジエン共重合体樹脂微粒
子(平均粒子径:0.19μm)を含む樹脂分散液(固
形分=48.5%、住化エイビーエス・ラテックス社
製、商品名:SN−335)17重量部とを添加し、撹
拌して均一に混合させた。その後、この混合液を孔径1
0μmのメンブランフィルターにてろ過して、ゴミ及び
粗大粒子を除去し、記録液中顔料(着色剤)濃度が8重
量%、固形分中顔料(着色剤)濃度が20重量%、記録
液中樹脂微粒子全固形分濃度が32重量%の記録液を得
た。Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 3) 23 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) A resin dispersion containing 16 parts by weight of water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm) (solid content = 45%, manufactured by Sanyo Chemical Industries, trade name: G)
-45) 18 parts by weight of water and a modified polyester resin fine particle having a carboxyl group added to a side chain (average particle size:
0.1-0.2 μm) (solid content = 30)
%, Manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G), and a resin dispersion liquid containing 27 parts by weight of water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) (solid content = 48.%). 5%, 17 parts by weight of Sumika ABS Latex Co., Ltd., trade name: SN-335) were added thereto, and the mixture was stirred and uniformly mixed. Thereafter, the mixed solution was added with a pore size of 1
The particles were filtered through a 0 μm membrane filter to remove dust and coarse particles. The pigment (colorant) concentration in the recording liquid was 8% by weight, the pigment (colorant) concentration in the solid content was 20% by weight, and the resin in the recording liquid was A recording liquid having a total solid content of fine particles of 32% by weight was obtained.
【0040】このようにして作製した記録液をバーコー
ターを用いて、複写機用普通紙上に塗布し、室温にて乾
燥させることにより、普通紙上に塗布乾燥膜からなるベ
タ画像を得た。そして、得られた画像の光学濃度を画像
表面側から測定した。その結果、画像面積1cm2 当た
り0.9mgという少量の記録液量で塗布したベタ画像
の光学濃度は1.6という高い値であった。The recording liquid thus prepared was applied to plain paper for copying machines using a bar coater and dried at room temperature to obtain a solid image consisting of a coating and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm 2 of image area was as high as 1.6.
【0041】また、この普通紙上のベタ画像の縦断面を
光学顕微鏡により観察したところ、ベタ画像は普通紙の
上に主として形成されていて、記録液の普通紙中への浸
透はほとんど認められなかった。When the longitudinal section of the solid image on the plain paper was observed by an optical microscope, the solid image was mainly formed on the plain paper, and almost no permeation of the recording liquid into the plain paper was recognized. Was.
【0042】次に、実施例1と同様の方式にて、記録ヘ
ッド吐出口での記録液の目詰まり性を評価した。その結
果、本方式での記録液の目詰まり発生までの余裕時間は
100秒と長いものであった。Next, the clogging property of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 100 seconds.
【0043】さらに、市販のインクジェットプリンター
を用いて、この記録液の普通紙上への印字テストを実施
した。その結果、水で希釈しない記録液の原液を安定に
吐出することができた。このようにして印字されたサン
プルの印字ドットを拡大ルーペ及び光学顕微鏡により観
察したところ、ドット周辺部での滲みのない鮮明なドッ
トであることがわかった。Further, a printing test of this recording liquid on plain paper was carried out using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.
【0044】引き続いて、上記バーコーターによるベタ
画像及びプリンターによる印字サンプルに水をこぼし、
耐水性を評価した。その結果、水による画像の滲み、着
色剤の広かりは認められず、本実施例に係る記録液が耐
水性の高いものであることがわかった。 (実施例4)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)20重量部
と、水及びフルオロオレフィンとビニルエーテルの乳化
重合により作製された含フッ素ビニルエーテル系樹脂微
粒子(平均粒子径:0.15μm)を含む樹脂分散液
(固形分=50%、旭硝子社製、商品名:FE−300
0)14重量部と、水及び変性スチレン−ブタジエン共
重合体樹脂微粒子(平均粒子径:0.19μm)を含む
樹脂分散液(固形分=48.5%、住化エイビーエス・
ラテックス社製、商品名:SN−335)15重量部
と、水及び側鎖にカルボキシル基が付加された変性ポリ
エステル樹脂微粒子(平均粒子径:0.1〜0.2μ
m)を含む樹脂分散液(固形分=30%、高松油脂社
製、商品名:A−215G)23重量部と、水及び側鎖
にカルボキシル基が付加された変性ポリエステル樹脂微
粒子(平均粒子径:0.1〜0.2μm)を含む樹脂分
散液(固形分=25%、高松油脂社製、商品名:A−1
15G)28重量部とを添加し、撹拌して均一に混合さ
せた。その後、この混合液を孔径10μmのメンブラン
フィルターにてろ過して、ゴミ及び粗大粒子を除去し、
記録液中顔料(着色剤)濃度が7重量%、固形分中顔料
(着色剤)濃度が20重量%、記録液中樹脂微粒子全固
形分濃度が28重量%の記録液を得た。Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Example 4 20 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) A resin dispersion containing 14 parts by weight of water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) (solid content = 48.5%, Sumika ABS.
Latex Co., Ltd., product name: SN-335) 15 parts by weight, water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm)
m), 23 parts by weight of solid dispersion (solid content = 30%, manufactured by Takamatsu Oil & Fat Co., Ltd., trade name: A-215G), and modified polyester resin fine particles having carboxyl groups added to water and side chains (average particle diameter) : 0.1 to 0.2 µm) (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-1)
15G) 28 parts by weight were added, and the mixture was stirred and uniformly mixed. Thereafter, the mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles,
A recording liquid was obtained in which the concentration of the pigment (colorant) in the recording liquid was 7% by weight, the concentration of the pigment (colorant) in the solid content was 20% by weight, and the total solid content of the resin fine particles in the recording liquid was 28% by weight.
【0045】このようにして作製した記録液をバーコー
ターを用いて、複写機用普通紙上に塗布し、室温にて乾
燥させることにより、普通紙上に塗布乾燥膜からなるベ
タ画像を得た。そして、得られた画像の光学濃度を画像
表面側から測定した。その結果、画像面積1cm2 当た
り0.9mgという少量の記録液量で塗布したベタ画像
の光学濃度は1.5という高い値であった。The recording liquid thus prepared was coated on plain paper for copying machines using a bar coater and dried at room temperature to obtain a solid image consisting of a coating and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm 2 of image area was as high as 1.5.
【0046】また、この普通紙上のベタ画像の縦断面を
光学顕微鏡により観察したところ、ベタ画像は普通紙の
上に主として形成されていて、記録液の普通紙中への浸
透はほとんど認められなかった。When the longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and the recording liquid hardly penetrated into the plain paper. Was.
【0047】次に、実施例1と同様の方式にて、記録ヘ
ッド吐出口での記録液の目詰まり性を評価した。その結
果、本方式での記録液の目詰まり発生までの余裕時間は
105秒と長いものであった。Next, the clogging property of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 105 seconds.
【0048】さらに、市販のインクジェットプリンター
を用いて、この記録液の普通紙上への印字テストを実施
した。その結果、水で希釈しない記録液の原液を安定に
吐出することができた。このようにして印字されたサン
プルの印字ドットを拡大ルーペ及び光学顕微鏡により観
察したところ、ドット周辺部での滲みのない鮮明なドッ
トであることがわかった。Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.
【0049】引き続いて、上記バーコーターによるベタ
画像及びプリンターによる印字サンプルに水をこぼし、
耐水性を評価した。その結果、水による画像の滲み、着
色剤の広かりは認められず、本実施例に係る記録液が耐
水性の高いものであることがわかった。 (実施例5)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)20重量部
と、水及びシリコン変性アクリル樹脂微粒子(平均粒子
径:0.1〜0.2μm)を含む樹脂分散液(固形分=
45%、三洋化成工業社製、商品名:G−45)15重
量部と、水及び変性スチレン−ブタジエン共重合体樹脂
微粒子(平均粒子径:0.19μm)を含む樹脂分散液
(固形分=48.5%、住化エイビーエス・ラテックス
社製、商品名:SN−335)14重量部と、水及び側
鎖にカルボキシル基が付加された変性ポリエステル樹脂
微粒子(平均粒子径:0.1〜0.2μm)を含む樹脂
分散液(固形分=30%、高松油脂社製、商品名:A−
215G)23重量部と、水及び側鎖にカルボキシル基
が付加された変性ポリエステル樹脂微粒子(平均粒子
径:0.1〜0.2μm)を含む樹脂分散液(固形分=
25%、高松油脂社製、商品名:A−115G)28重
量部とを添加し、撹拌して均一に混合させた。その後、
この混合液を孔径10μmのメンブランフィルターにて
ろ過して、ゴミ及び粗大粒子を除去し、記録液中顔料
(着色剤)濃度が7重量%、固形分中顔料(着色剤)濃
度が20重量%、記録液中樹脂微粒子全固形分濃度が2
8重量%の記録液を得た。Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Example 5 20 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), water and silicon-modified acrylic resin fine particles (average particle diameter: 0.1 to 0.2 μm) ) (Solid content =
Resin dispersion liquid containing 15 parts by weight of 45% (manufactured by Sanyo Chemical Industries, Ltd., trade name: G-45), water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) (solid content = 48.5%, manufactured by Sumika ABS Latex Co., Ltd., trade name: SN-335), 14 parts by weight, and modified polyester resin fine particles having carboxyl groups added to water and side chains (average particle diameter: 0.1 to 0) .2 μm) (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-
215G) A resin dispersion (solid content = 23 parts by weight) containing modified polyester resin fine particles (average particle diameter: 0.1 to 0.2 μm) having carboxyl groups added to water and side chains.
25% by weight, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-115G) and mixed with stirring. afterwards,
The mixed solution was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles. The concentration of the pigment (colorant) in the recording liquid was 7% by weight, and the concentration of the pigment (colorant) in the solid content was 20% by weight. The total solid content of the resin fine particles in the recording liquid is 2
8% by weight of the recording liquid was obtained.
【0050】このようにして作製した記録液をバーコー
ターを用いて、複写機用普通紙上に塗布し、室温にて乾
燥させることにより、普通紙上に塗布乾燥膜からなるベ
タ画像を得た。そして、得られた画像の光学濃度を画像
表面側から測定した。その結果、画像面積1cm2 当た
り0.9mgという少量の記録液量で塗布したベタ画像
の光学濃度は1.4という高い値であった。The recording liquid thus prepared was coated on plain paper for copying machines using a bar coater and dried at room temperature to obtain a solid image consisting of a coated and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm 2 of image area was as high as 1.4.
【0051】また、この普通紙上のベタ画像の縦断面を
光学顕微鏡により観察したところ、ベタ画像は普通紙の
上に主として形成されていて、記録液の普通紙中への浸
透はほとんど認められなかった。When a longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and the recording liquid hardly penetrated into the plain paper. Was.
【0052】次に、実施例1と同様の方式にて、記録ヘ
ッド吐出口での記録液の目詰まり性を評価した。その結
果、本方式での記録液の目詰まり発生までの余裕時間は
90秒と長いものであった。Next, the clogging property of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 90 seconds.
【0053】さらに、市販のインクジェットプリンター
を用いて、この記録液の普通紙上への印字テストを実施
した。その結果、水で希釈しない記録液の原液を安定に
吐出することができた。このようにして印字されたサン
プルの印字ドットを拡大ルーペ及び光学顕微鏡により観
察したところ、ドット周辺部での滲みのない鮮明なドッ
トであることがわかった。Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.
【0054】引き続いて、上記バーコーターによるベタ
画像及びプリンターによる印字サンプルに水をこぼし、
耐水性を評価した。その結果、水による画像の滲み、着
色剤の広かりは認められず、本実施例に係る記録液が耐
水性の高いものであることがわかった。 (実施例6)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)21重量部
と、水及びフルオロオレフィンとビニルエーテルの乳化
重合により作製された含フッ素ビニルエーテル系樹脂微
粒子(平均粒子径:0.15μm)を含む樹脂分散液
(固形分=50%、旭硝子社製、商品名:FE−300
0)12重量部と、水及びシリコン変性アクリル樹脂微
粒子(平均粒子径:0.1〜0.2μm)を含む樹脂分
散液(固形分=45%、三洋化成工業社製、商品名:G
−45)13重量部と、水及び側鎖にカルボキシル基が
付加された変性ポリエステル樹脂微粒子(平均粒子径:
0.1〜0.2μm)を含む樹脂分散液(固形分=30
%、高松油脂社製、商品名:A−215G)19重量部
と、水及び側鎖にカルボキシル基が付加された変性ポリ
エステル樹脂微粒子(平均粒子径:0.1〜0.2μ
m)を含む樹脂分散液(固形分=25%、高松油脂社
製、商品名:A−115G)23重量部と、水及び変性
スチレン−ブタジエン共重合体樹脂微粒子(平均粒子
径:0.19μm)を含む樹脂分散液(固形分=48.
5%、住化エイビーエス・ラテックス社製、商品名:S
N−335)12重量部とを添加し、撹拌して均一に混
合させた。その後、この混合液を孔径10μmのメンブ
ランフィルターにてろ過して、ゴミ及び粗大粒子を除去
し、記録液中顔料(着色剤)濃度が7重量%、固形分中
顔料(着色剤)濃度が20重量%、記録液中樹脂微粒子
全固形分濃度が29重量%の記録液を得た。Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 6) 21 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and fluorine-containing vinyl ether resin fine particles produced by emulsion polymerization of water, a fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) A resin dispersion (solid content = 45%, manufactured by Sanyo Chemical Industries, Ltd., containing 12 parts by weight, water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm), trade name: G)
-45) 13 parts by weight and water and a modified polyester resin fine particle having a carboxyl group added to a side chain (average particle diameter:
0.1-0.2 μm) (solid content = 30)
%, Manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G) and 19 parts by weight of water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm)
m), 23 parts by weight of a resin dispersion (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-115G), water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) ) (Solid content = 48.
5%, manufactured by Sumika ABS Latex, trade name: S
N-335), 12 parts by weight, and stirred to mix uniformly. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid was 7% by weight, and the pigment (colorant) concentration in the solid content was 20%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 29% by weight was obtained.
【0055】このようにして作製した記録液をバーコー
ターを用いて、複写機用普通紙上に塗布し、室温にて乾
燥させることにより、普通紙上に塗布乾燥膜からなるベ
タ画像を得た。そして、得られた画像の光学濃度を画像
表面側から測定した。その結果、画像面積1cm2 当た
り0.9mgという少量の記録液量で塗布したベタ画像
の光学濃度は1.6という高い値であった。The recording liquid thus prepared was coated on plain paper for a copying machine using a bar coater, and dried at room temperature to obtain a solid image consisting of a coated and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm 2 of image area was as high as 1.6.
【0056】また、この普通紙上のベタ画像の縦断面を
光学顕微鏡により観察したところ、ベタ画像は普通紙の
上に主として形成されていて、記録液の普通紙中への浸
透はほとんど認められなかった。When the longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and almost no permeation of the recording liquid into the plain paper was recognized. Was.
【0057】次に、実施例1と同様の方式にて、記録ヘ
ッド吐出口での記録液の目詰まり性を評価した。その結
果、本方式での記録液の目詰まり発生までの余裕時間は
135秒と長いものであった。Next, the clogging property of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 135 seconds.
【0058】さらに、市販のインクジェットプリンター
を用いて、この記録液の普通紙上への印字テストを実施
した。その結果、水で希釈しない記録液の原液を安定に
吐出することができた。このようにして印字されたサン
プルの印字ドットを拡大ルーペ及び光学顕微鏡により観
察したところ、ドット周辺部での滲みのない鮮明なドッ
トであることがわかった。Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.
【0059】引き続いて、上記バーコーターによるベタ
画像及びプリンターによる印字サンプルに水をこぼし、
耐水性を評価した。その結果、水による画像の滲み、着
色剤の広かりは認められず、本実施例に係る記録液が耐
水性の高いものであることがわかった。 (実施例7)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)21重量部
と、水及びフルオロオレフィンとビニルエーテルの乳化
重合により作製された含フッ素ビニルエーテル系樹脂微
粒子(平均粒子径:0.15μm)を含む樹脂分散液
(固形分=50%、旭硝子社製、商品名:FE−300
0)10重量部と、水及びシリコン変性アクリル樹脂微
粒子(平均粒子径:0.1〜0.2μm)を含む樹脂分
散液(固形分=45%、三洋化成工業社製、商品名:G
−45)11重量部と、水及び側鎖にカルボキシル基が
付加された変性ポリエステル樹脂微粒子(平均粒子径:
0.1〜0.2μm)を含む樹脂分散液(固形分=30
%、高松油脂社製、商品名:A−215G)16重量部
と、水及び側鎖にカルボキシル基が付加された変性ポリ
エステル樹脂微粒子(平均粒子径:0.1〜0.2μ
m)を含む樹脂分散液(固形分=25%、高松油脂社
製、商品名:A−115G)19重量部と、水及び変性
スチレン−ブタジエン共重合体樹脂微粒子(平均粒子
径:0.19μm)を含む樹脂分散液(固形分=48.
5%、住化エイビーエス・ラテックス社製、商品名:S
N−335)10重量部と、水及びメトキシシリル基を
有するアクリルシリコン樹脂微粒子(平均粒子径=0.
1〜0.2μm)を含む樹脂分散液(固形分=35%、
三洋化成工業社製、商品名:SW−135)14重量部
とを添加し、撹拌して均一に混合させた。その後、この
混合液を孔径10μmのメンブランフィルターにてろ過
して、ゴミ及び粗大粒子を除去し、記録液中顔料(着色
剤)濃度が7重量%、固形分中顔料(着色剤)濃度が2
0重量%、記録液中樹脂微粒子全固形分濃度が29重量
%の記録液を得た。Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 7) 21 parts by weight of a water-based copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, a fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) A resin dispersion containing 10 parts by weight, water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm) (solid content = 45%, manufactured by Sanyo Chemical Industries, Ltd., trade name: G)
-45) 11 parts by weight of water and a modified polyester resin fine particle having a carboxyl group added to a side chain (average particle diameter:
0.1-0.2 μm) (solid content = 30)
%, Manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G) and 16 parts by weight of water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm)
m), 19 parts by weight of a resin dispersion (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-115G), and water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) ) (Solid content = 48.
5%, manufactured by Sumika ABS Latex, trade name: S
N-335) 10 parts by weight of acrylic silicon resin fine particles having water and a methoxysilyl group (average particle diameter = 0.
1 to 0.2 μm) (solid content = 35%,
14 parts by weight (manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: SW-135) were added, and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid was 7% by weight, and the pigment (colorant) concentration in the solid content was 2%.
A recording liquid having a concentration of 0% by weight and a total solid content of fine resin particles in the recording liquid of 29% by weight was obtained.
【0060】このようにして作製した記録液をバーコー
ターを用いて、複写機用普通紙上に塗布し、室温にて乾
燥させることにより、普通紙上に塗布乾燥膜からなるベ
タ画像を得た。そして、得られた画像の光学濃度を画像
表面側から測定した。その結果、画像面積1cm2 当た
り0.9mgという少量の記録液量で塗布したベタ画像
の光学濃度は1.6という高い値であった。The recording liquid thus prepared was coated on plain paper for copying machines using a bar coater and dried at room temperature to obtain a solid image consisting of a coated and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm 2 of image area was as high as 1.6.
【0061】また、この普通紙上のベタ画像の縦断面を
光学顕微鏡により観察したところ、ベタ画像は普通紙の
上に主として形成されていて、記録液の普通紙中への浸
透はほとんど認められなかった。When the longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and almost no permeation of the recording liquid into the plain paper was observed. Was.
【0062】次に、実施例1と同様の方式にて、記録ヘ
ッド吐出口での記録液の目詰まり性を評価した。その結
果、本方式での記録液の目詰まり発生までの余裕時間は
170秒と長いものであった。Next, the clogging of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 170 seconds.
【0063】さらに、市販のインクジェットプリンター
を用いて、この記録液の普通紙上への印字テストを実施
した。その結果、水で希釈しない記録液の原液を安定に
吐出することができた。このようにして印字されたサン
プルの印字ドットを拡大ルーペ及び光学顕微鏡により観
察したところ、ドット周辺部での滲みのない鮮明なドッ
トであることがわかった。Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.
【0064】引き続いて、上記バーコーターによるベタ
画像及びプリンターによる印字サンプルに水をこぼし、
耐水性を評価した。その結果、水による画像の滲み、着
色剤の広かりは認められず、本実施例に係る記録液が耐
水性の高いものであることがわかった。 (実施例8)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)20重量部
と、水及びフルオロオレフィンとビニルエーテルの乳化
重合により作製された含フッ素ビニルエーテル系樹脂微
粒子(平均粒子径:0.15μm)を含む樹脂分散液
(固形分=50%、旭硝子社製、商品名:FE−300
0)7重量部と、水及びシリコン変性アクリル樹脂微粒
子(平均粒子径:0.1〜0.2μm)を含む樹脂分散
液(固形分=45%、三洋化成工業社製、商品名:G−
45)8重量部と、水及び側鎖にカルボキシル基が付加
された変性ポリエステル樹脂微粒子(平均粒子径:0.
1〜0.2μm)を含む樹脂分散液(固形分=30%、
高松油脂社製、商品名:A−215G)12重量部と、
水及び側鎖にカルボキシル基が付加された変性ポリエス
テル樹脂微粒子(平均粒子径:0.1〜0.2μm)を
含む樹脂分散液(固形分=25%、高松油脂社製、商品
名:A−115G)14重量部と、水及び側鎖にカルボ
キシル基が付加された変性ポリエステル樹脂微粒子(平
均粒子径:0.1〜0.2μm)を含む樹脂分散液(固
形分=30%、高松油脂社製、商品名:A−515G、
A−215G及びA−115GとはpH及びガラス転位
点が異なる)12重量部と、水及び変性スチレン−ブタ
ジエン共重合体樹脂微粒子(平均粒子径:0.19μ
m)を含む樹脂分散液(固形分=48.5%、住化エイ
ビーエス・ラテックス社製、商品名:SN−335)7
重量部と、水及びアクリル酸エステル−シリコーン共重
合体樹脂微粒子(平均粒子径:0.16μm)を含む樹
脂分散液(固形分=38.8%、昭和高分子社製、商品
名:ROY−6312)9重量部と、水及びメトキシシ
リル基を有するアクリルシリコン樹脂微粒子(平均粒子
径=0.1〜0.2μm)を含む樹脂分散液(固形分=
35%、三洋化成工業社製、商品名:SW−135)1
0重量部とを添加し、撹拌して均一に混合させた。その
後、この混合液を孔径10μmのメンブランフィルター
にてろ過して、ゴミ及び粗大粒子を除去し、記録液中顔
料(着色剤)濃度が7重量%、固形分中顔料(着色剤)
濃度が20重量%、記録液中樹脂微粒子全固形分濃度が
28重量%の記録液を得た。Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Example 8 20 parts by weight of a water-based copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, a fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) A resin dispersion containing 7 parts by weight of water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm) (solid content = 45%, manufactured by Sanyo Chemical Industries, trade name: G-
45) 8 parts by weight and water and a modified polyester resin fine particle having a carboxyl group added to a side chain (average particle diameter: 0.
1 to 0.2 μm) (solid content = 30%,
Takamatsu Yushi Co., Ltd., trade name: A-215G) 12 parts by weight,
Resin dispersion (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-) containing water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm) 115G) A resin dispersion (solid content = 30%, Takamatsu Yushi Co., Ltd.) containing 14 parts by weight and water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm) Product name: A-515G,
12 parts by weight of A-215G and A-115G having different pH and glass transition point) and water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm)
m)) (solid content = 48.5%, manufactured by Sumika ABS Latex, trade name: SN-335) 7
Resin dispersion containing 3 parts by weight of water and acrylic acid ester-silicone copolymer resin fine particles (average particle diameter: 0.16 μm) (solid content = 38.8%, manufactured by Showa Polymer Co., Ltd., trade name: ROY-) 6312) A resin dispersion liquid containing 9 parts by weight of water and acrylsilicone resin fine particles having a methoxysilyl group (average particle diameter = 0.1 to 0.2 μm) (solid content =
35%, manufactured by Sanyo Chemical Industries, trade name: SW-135) 1
And 0 parts by weight, and stirred to mix uniformly. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, the concentration of the pigment (colorant) in the recording liquid was 7% by weight, and the pigment (colorant) in the solid content.
A recording liquid having a concentration of 20% by weight and a total solid content of resin fine particles in the recording liquid of 28% by weight was obtained.
【0065】このようにして作製した記録液をバーコー
ターを用いて、複写機用普通紙上に塗布し、室温にて乾
燥させることにより、普通紙上に塗布乾燥膜からなるベ
タ画像を得た。そして、得られた画像の光学濃度を画像
表面側から測定した。その結果、画像面積1cm2 当た
り0.9mgという少量の記録液量で塗布したベタ画像
の光学濃度は1.6という高い値であった。The recording liquid thus prepared was applied to plain paper for copying machines using a bar coater and dried at room temperature to obtain a solid image consisting of a coating and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm 2 of image area was as high as 1.6.
【0066】また、この普通紙上のベタ画像の縦断面を
光学顕微鏡により観察したところ、ベタ画像は普通紙の
上に主として形成されていて、記録液の普通紙中への浸
透はほとんど認められなかった。When the longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and the recording liquid hardly penetrated into the plain paper. Was.
【0067】次に、実施例1と同様の方式にて、記録ヘ
ッド吐出口での記録液の目詰まり性を評価した。その結
果、本方式での記録液の目詰まり発生までの余裕時間は
195秒と長いものであった。Next, the clogging property of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 195 seconds.
【0068】さらに、市販のインクジェットプリンター
を用いて、この記録液の普通紙上への印字テストを実施
した。その結果、水で希釈しない記録液の原液を安定に
吐出することができた。このようにして印字されたサン
プルの印字ドットを拡大ルーペ及び光学顕微鏡により観
察したところ、ドット周辺部での滲みのない鮮明なドッ
トであることがわかった。Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.
【0069】引き続いて、上記バーコーターによるベタ
画像及びプリンターによる印字サンプルに水をこぼし、
耐水性を評価した。その結果、水による画像の滲み、着
色剤の広かりは認められず、本実施例に係る記録液が耐
水性の高いものであることがわかった。 (実施例9)フタロシアニン系染料(アシッドブルー
9)水溶液(固形分=10%)48重量部に水及びフル
オロオレフィンとビニルエーテルの乳化重合により作製
された含フッ素ビニルエーテル系樹脂微粒子(平均粒子
径:0.15μm)を含む樹脂分散液(固形分=50
%、旭硝子社製、商品名:FE−3000)6重量部
と、水及びシリコン変性アクリル樹脂微粒子(平均粒子
径:0.1〜0.2μm)を含む樹脂分散液(固形分=
45%、三洋化成工業社製、商品名:G−45)7重量
部と、水及び側鎖にカルボキシル基が付加された変性ポ
リエステル樹脂微粒子(平均粒子径:0.1〜0.2μ
m)を含む樹脂分散液(固形分=30%、高松油脂社
製、商品名:A−215G)11重量部と、水及び側鎖
にカルボキシル基が付加された変性ポリエステル樹脂微
粒子(平均粒子径:0.1〜0.2μm)を含む樹脂分
散液(固形分=25%、高松油脂社製、商品名:A−1
15G)13重量部と、水及び変性スチレン−ブタジエ
ン共重合体樹脂微粒子(平均粒子径:0.19μm)を
含む樹脂分散液(固形分=48.5%、住化エイビーエ
ス・ラテックス社製、商品名:SN−335)7重量部
と、水及びメトキシシリル基を有するアクリルシリコン
樹脂微粒子(平均粒子径=0.1〜0.2μm)を含む
樹脂分散液(固形分=35%、三洋化成工業社製、商品
名:SW−135)9重量部とを添加し、撹拌して均一
に混合させた。その後、この混合液を孔径10μmのメ
ンブランフィルターにてろ過して、ゴミ及び粗大粒子を
除去し、記録液中染料(着色剤)濃度が5重量%、固形
分中染料(着色剤)濃度が20重量%、記録液中樹脂微
粒子全固形分濃度が19重量%の記録液を得た。Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Example 9 Fluorine-containing vinyl ether-based resin fine particles (average particle diameter: 0) prepared by emulsion polymerization of water, a fluoroolefin and vinyl ether in 48 parts by weight of an aqueous solution of phthalocyanine dye (acid blue 9) (solid content = 10%) .15 μm) (solid content = 50)
%, Manufactured by Asahi Glass Co., Ltd., trade name: FE-3000), a resin dispersion containing 6 parts by weight of water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm) (solid content =
45%, manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: G-45) 7 parts by weight, water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm)
m), 11 parts by weight of a resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G), and modified polyester resin fine particles having a carboxyl group added to water and side chains (average particle diameter) : 0.1 to 0.2 µm) (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-1)
15G) A resin dispersion containing 13 parts by weight of water and modified styrene-butadiene copolymer resin fine particles (average particle size: 0.19 μm) (solid content = 48.5%, manufactured by Sumika ABS Latex Co., Ltd.) Name: SN-335) A resin dispersion (solid content: 35%, Sanyo Chemical Industries, Ltd.) containing 7 parts by weight of water and acrylsilicone resin fine particles having a methoxysilyl group (average particle size = 0.1 to 0.2 μm) (Product name: SW-135) (9 parts by weight), and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore diameter of 10 μm to remove dust and coarse particles, and the dye (colorant) concentration in the recording liquid was 5% by weight, and the dye (colorant) concentration in the solid content was 20%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 19% by weight was obtained.
【0070】このようにして作製した記録液をバーコー
ターを用いて、複写機用普通紙上に塗布し、室温にて乾
燥させることにより、普通紙上に塗布乾燥膜からなるベ
タ画像を得た。そして、得られた画像の光学濃度を画像
表面側から測定した。その結果、画像面積1cm2 当た
り0.9mgという少量の記録液量で塗布したベタ画像
の光学濃度は1.4という高い値であった。The recording liquid thus prepared was applied to plain paper for copying machines using a bar coater, and dried at room temperature to obtain a solid image consisting of a coated and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm 2 of image area was as high as 1.4.
【0071】また、この普通紙上のベタ画像の縦断面を
光学顕微鏡により観察したところ、ベタ画像は普通紙の
上に主として形成されていて、記録液の普通紙中への浸
透はほとんど認められなかった。When a longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and the recording liquid hardly penetrated into the plain paper. Was.
【0072】次に、実施例1と同様の方式にて、記録ヘ
ッド吐出口での記録液の目詰まり性を評価した。その結
果、本方式での記録液の目詰まり発生までの余裕時間は
180秒と長いものであった。Next, the clogging property of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 180 seconds.
【0073】さらに、市販のインクジェットプリンター
を用いて、この記録液の普通紙上への印字テストを実施
した。その結果、水で希釈しない記録液の原液を安定に
吐出することができた。このようにして印字されたサン
プルの印字ドットを拡大ルーペ及び光学顕微鏡により観
察したところ、ドット周辺部での滲みのない鮮明なドッ
トであることがわかった。Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.
【0074】引き続いて、上記バーコーターによるベタ
画像及びプリンターによる印字サンプルに水をこぼし、
耐水性を評価した。その結果、水による画像の滲み、着
色剤の広かりは認められず、本実施例に係る記録液が耐
水性の高いものであることがわかった。 (比較例1)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)26重量部
と、水及びフルオロオレフィンとビニルエーテルの乳化
重合により作製された含フッ素ビニルエーテル系樹脂微
粒子(平均粒子径:0.15μm)を含む樹脂分散液
(固形分=50%、旭硝子社製、商品名:FE−300
0)74重量部を添加し、撹拌して均一に混合させた。
その後、この混合液を孔径10μmのメンブランフィル
ターにてろ過して、ゴミ及び粗大粒子を除去し、記録液
中顔料(着色剤)濃度が9重量%、固形分中顔料(着色
剤)濃度が20重量%、記録液中樹脂微粒子全固形分濃
度が37重量%の記録液を得た。Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Comparative Example 1 26 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and fluorine-containing vinyl ether resin fine particles produced by emulsion polymerization of water, a fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) 74 parts by weight were added and stirred to mix uniformly.
Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles. The concentration of the pigment (colorant) in the recording liquid was 9% by weight, and the concentration of the pigment (colorant) in the solid content was 20%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 37% by weight was obtained.
【0075】このようにして作製した記録液について、
実施例1〜9と同様に、光学濃度測定、目詰まり発生ま
での余裕時間測定、及び市販インクジェットプリンター
による普通紙上への印字テストを実施した。その結果、
画像面積1cm2 当たり0.9mgという少量の記録液
量で塗布したベタ画像の光学濃度は1.4であったが、
目詰まり発生までの余裕時間は8秒と短いものであっ
た。また、市販のインクジェットプリンターを用いて印
字テストを実施した結果、目詰まりが発生し、水で希釈
しない記録液の原液を安定に吐出することはできなかっ
た。With respect to the recording liquid thus prepared,
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was 1.4,
The margin time until clogging was as short as 8 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.
【0076】また、この記録液を蒸留水で4倍に希釈
(記録液:水=1:3)したところ、市販のインクジェ
ットプリンターで吐出可能になったが、画像面積1cm
2 当たり0.9mgという少量の記録液量で塗布したベ
タ画像の光学濃度は0.4と低いものであった。 (比較例2)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)24重量部
と、水及びシリコン変性アクリル樹脂微粒子(平均粒子
径:0.1〜0.2μm)を含む樹脂分散液(固形分=
45%、三洋化成工業社製、商品名:G−45)76重
量部を添加し、撹拌して均一に混合させた。その後、こ
の混合液を孔径10μmのメンブランフィルターにてろ
過して、ゴミ及び粗大粒子を除去し、記録液中顔料(着
色剤)濃度が9重量%、固形分中顔料(着色剤)濃度が
20重量%、記録液中樹脂微粒子全固形分濃度が34重
量%の記録液を得た。When this recording liquid was diluted four times with distilled water (recording liquid: water = 1: 3), the recording liquid could be ejected by a commercially available ink jet printer.
The optical density of a solid image coated with a small amount of recording liquid of 0.9 mg per 2 was as low as 0.4. (Comparative Example 2) 24 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), water and silicon-modified acrylic resin fine particles (average particle diameter: 0.1 to 0.2 µm) ) (Solid content =
76% by weight of 45% (manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: G-45) was added, and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles. The concentration of the pigment (colorant) in the recording liquid was 9% by weight, and the concentration of the pigment (colorant) in the solid content was 20%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 34% by weight was obtained.
【0077】このようにして作製した記録液について、
実施例1〜9と同様に、光学濃度測定、目詰まり発生ま
での余裕時間測定、及び市販インクジェットプリンター
による普通紙上への印字テストを実施した。その結果、
画像面積1cm2 当たり0.9mgという少量の記録液
量で塗布したベタ画像の光学濃度は1.3であり、ま
た、目詰まり発生までの余裕時間は10秒と短いもので
あった。また、市販のインクジェットプリンターを用い
て印字テストを実施した結果、目詰まりが発生し、水で
希釈しない記録液の原液を安定に吐出することはできな
かった。With respect to the recording liquid thus prepared,
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was 1.3, and the margin time until the occurrence of clogging was as short as 10 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.
【0078】また、この記録液を蒸留水で4倍に希釈し
たところ、市販のインクジェットプリンターで吐出可能
になったが、画像面積1cm2 当たり0.9mgという
少量の記録液量で塗布したベタ画像の光学濃度は0.4
と低いものであった。 (比較例3)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)18重量部
と、水及び側鎖にカルボキシル基が付加された変性ポリ
エステル樹脂微粒子(平均粒子径:0.1〜0.2μ
m)を含む樹脂分散液(固形分=30%、高松油脂社
製、商品名:A−215G)82重量部を添加し、撹拌
して均一に混合させた。その後、この混合液を孔径10
μmのメンブランフィルターにてろ過して、ゴミ及び粗
大粒子を除去し、記録液中顔料(着色剤)濃度が6重量
%、固形分中顔料(着色剤)濃度が20重量%、記録液
中樹脂微粒子全固形分濃度が25重量%の記録液を得
た。When this recording liquid was diluted four times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 3) 18 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and modified polyester resin fine particles having a carboxyl group added to water and side chains (average particle diameter) : 0.1-0.2μ
82 parts by weight of a resin dispersion containing m) (solid content = 30%, manufactured by Takamatsu Oil & Fat Co., Ltd., trade name: A-215G) was added, and the mixture was stirred and uniformly mixed. Thereafter, the mixed solution was added with a pore size of 10
The particles were filtered through a μm membrane filter to remove dust and coarse particles. The pigment (colorant) concentration in the recording liquid was 6% by weight, the pigment (colorant) concentration in the solid content was 20% by weight, and the resin in the recording liquid was A recording liquid having a total solid content of fine particles of 25% by weight was obtained.
【0079】このようにして作製した記録液について、
実施例1〜9と同様に、光学濃度測定、目詰まり発生ま
での余裕時間測定、及び市販インクジェットプリンター
による普通紙上への印字テストを実施した。その結果、
画像面積1cm2 当たり0.9mgという少量の記録液
量で塗布したベタ画像の光学濃度は1.2であり、ま
た、目詰まり発生までの余裕時間は10秒と短いもので
あった。また、市販のインクジェットプリンターを用い
て印字テストを実施した結果、目詰まりが発生し、水で
希釈しない記録液の原液を安定に吐出することはできな
かった。With respect to the recording liquid thus prepared,
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of the solid image applied with a small recording liquid amount of 0.9 mg per 1 cm 2 of the image area was 1.2, and the margin time until the occurrence of clogging was as short as 10 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.
【0080】また、この記録液を蒸留水で4倍に希釈し
たところ、市販のインクジェットプリンターで吐出可能
になったが、画像面積1cm2 当たり0.9mgという
少量の記録液量で塗布したベタ画像の光学濃度は0.4
と低いものであった。 (比較例4)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)26重量部
と、水及び変性スチレン−ブタジエン共重合体樹脂微粒
子(平均粒子径:0.19μm)を含む樹脂分散液(固
形分=48.5%、住化エイビーエス・ラテックス社
製、商品名:SN−335)74重量部を添加し、撹拌
して均一に混合させた。その後、この混合液を孔径10
μmのメンブランフィルターにてろ過して、ゴミ及び粗
大粒子を除去し、記録液中顔料(着色剤)濃度が9重量
%、固形分中顔料(着色剤)濃度が20重量%、記録液
中樹脂微粒子全固形分濃度が36重量%の記録液を得
た。When this recording liquid was diluted four times with distilled water, it could be ejected with a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 4) 26 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) ) Was added thereto (solid content = 48.5%, manufactured by Sumika ABS Latex Co., Ltd., trade name: SN-335), and the mixture was stirred and uniformly mixed. Thereafter, the mixed solution was added with a pore size of 10
The particles were filtered through a μm membrane filter to remove dust and coarse particles. The pigment (colorant) concentration in the recording liquid was 9% by weight, the pigment (colorant) concentration in the solid content was 20% by weight, and the resin in the recording liquid was A recording liquid having a total solid content of fine particles of 36% by weight was obtained.
【0081】このようにして作製した記録液について、
実施例1〜9と同様に、光学濃度測定、目詰まり発生ま
での余裕時間測定、及び市販インクジェットプリンター
による普通紙上への印字テストを実施した。その結果、
画像面積1cm2 当たり0.9mgという少量の記録液
量で塗布したベタ画像の光学濃度は1.4であったが、
目詰まり発生までの余裕時間は8秒と短いものであっ
た。また、市販のインクジェットプリンターを用いて印
字テストを実施した結果、目詰まりが発生し、水で希釈
しない記録液の原液を安定に吐出することはできなかっ
た。With respect to the recording liquid thus prepared,
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was 1.4,
The margin time until clogging was as short as 8 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.
【0082】また、この記録液を蒸留水で4倍に希釈し
たところ、市販のインクジェットプリンターで吐出可能
になったが、画像面積1cm2 当たり0.9mgという
少量の記録液量で塗布したベタ画像の光学濃度は0.4
と低いものであった。 (比較例5)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)15重量部
と、水及び側鎖にカルボキシル基が付加された変性ポリ
エステル樹脂微粒子(平均粒子径:0.1〜0.2μ
m)を含む樹脂分散液(固形分=25%、高松油脂社
製、商品名:A−115G)85重量部を添加し、撹拌
して均一に混合させた。その後、この混合液を孔径10
μmのメンブランフィルターにてろ過して、ゴミ及び粗
大粒子を除去し、記録液中顔料(着色剤)濃度が5重量
%、固形分中顔料(着色剤)濃度が20重量%、記録液
中樹脂微粒子全固形分濃度が21重量%の記録液を得
た。When this recording liquid was diluted 4 times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 5) 15 parts by weight of an aqueous copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and modified polyester resin fine particles having a carboxyl group added to water and side chains (average particle diameter) : 0.1-0.2μ
m) was added (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-115G) (85 parts by weight), and the mixture was stirred and uniformly mixed. Thereafter, the mixed solution was added with a pore size of 10
The particles were filtered through a μm membrane filter to remove dust and coarse particles. The pigment (colorant) concentration in the recording liquid was 5% by weight, the pigment (colorant) concentration in the solid content was 20% by weight, and the resin in the recording liquid was A recording liquid having a total solid content of fine particles of 21% by weight was obtained.
【0083】このようにして作製した記録液について、
実施例1〜9と同様に、光学濃度測定、目詰まり発生ま
での余裕時間測定、及び市販インクジェットプリンター
による普通紙上への印字テストを実施した。その結果、
画像面積1cm2 当たり0.9mgという少量の記録液
量で塗布したベタ画像の光学濃度は1.2であり、ま
た、目詰まり発生までの余裕時間は10秒と短いもので
あった。また、市販のインクジェットプリンターを用い
て印字テストを実施した結果、目詰まりが発生し、水で
希釈しない記録液の原液を安定に吐出することはできな
かった。The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of the solid image applied with a small recording liquid amount of 0.9 mg per 1 cm 2 of the image area was 1.2, and the margin time until the occurrence of clogging was as short as 10 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.
【0084】また、この記録液を蒸留水で4倍に希釈し
たところ、市販のインクジェットプリンターで吐出可能
になったが、画像面積1cm2 当たり0.9mgという
少量の記録液量で塗布したベタ画像の光学濃度は0.4
と低いものであった。 (比較例6)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)20重量部
と、水及びメトキシシリル基を有するアクリルシリコン
樹脂微粒子(平均粒子径=0.1〜0.2μm)を含む
樹脂分散液(固形分=35%、三洋化成工業社製、商品
名:SW−135)80重量部を添加し、撹拌して均一
に混合させた。その後、この混合液を孔径10μmのメ
ンブランフィルターにてろ過して、ゴミ及び粗大粒子を
除去し、記録液中顔料(着色剤)濃度が7重量%、固形
分中顔料(着色剤)濃度が20重量%、記録液中樹脂微
粒子全固形分濃度が28重量%の記録液を得た。When this recording liquid was diluted four times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 6) 20 parts by weight of an aqueous copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), and acrylic silicon resin fine particles having water and a methoxysilyl group (average particle size = 0.1) 80 parts by weight of a resin dispersion (solid content = 35%, manufactured by Sanyo Chemical Industries, Ltd., trade name: SW-135) was added thereto, and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid was 7% by weight, and the pigment (colorant) concentration in the solid content was 20%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 28% by weight was obtained.
【0085】このようにして作製した記録液について、
実施例1〜9と同様に、光学濃度測定、目詰まり発生ま
での余裕時間測定、及び市販インクジェットプリンター
による普通紙上への印字テストを実施した。その結果、
画像面積1cm2 当たり0.9mgという少量の記録液
量で塗布したベタ画像の光学濃度は1.4であったが、
目詰まり発生までの余裕時間は7秒と短いものであっ
た。また、市販のインクジェットプリンターを用いて印
字テストを実施した結果、目詰まりが発生し、水で希釈
しない記録液の原液を安定に吐出することはできなかっ
た。The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was 1.4,
The margin time before the occurrence of clogging was as short as 7 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.
【0086】また、この記録液を蒸留水で4倍に希釈し
たところ、市販のインクジェットプリンターで吐出可能
になったが、画像面積1cm2 当たり0.9mgという
少量の記録液量で塗布したベタ画像の光学濃度は0.5
と低いものであった。 (比較例7)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)21重量部
と、水及びフルオロオレフィンとビニルエーテルの乳化
重合により作製された含フッ素ビニルエーテル系樹脂微
粒子(平均粒子径:0.15μm)を含む樹脂分散液
(固形分=50%、旭硝子社製、商品名:FE−300
0)30重量部と、水及び側鎖にカルボキシル基が付加
された変性ポリエステル樹脂微粒子(平均粒子径:0.
1〜0.2μm)を含む樹脂分散液(固形分=30%、
高松油脂社製、商品名:A−215G)49重量部とを
添加し、撹拌して均一に混合させた。その後、この混合
液を孔径10μmのメンブランフィルターにてろ過し
て、ゴミ及び粗大粒子を除去し、記録液中顔料(着色
剤)濃度が7重量%、固形分中顔料(着色剤)濃度が2
0重量%、記録液中樹脂微粒子全固形分濃度が30重量
%の記録液を得た。When this recording liquid was diluted 4 times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was obtained. Has an optical density of 0.5
Was low. (Comparative Example 7) 21 parts by weight of a water-based copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, a fluoroolefin, and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) 30 parts by weight of water and a modified polyester resin fine particle having a carboxyl group added to the side chain (average particle diameter: 0.1%).
1 to 0.2 μm) (solid content = 30%,
49 parts by weight of Takamatsu Yushi Co., Ltd., trade name: A-215G), and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid was 7% by weight, and the pigment (colorant) concentration in the solid content was 2%.
A recording liquid having a concentration of 0% by weight and a total solid content of fine resin particles in the recording liquid of 30% by weight was obtained.
【0087】このようにして作製した記録液について、
実施例1〜9と同様に、光学濃度測定、目詰まり発生ま
での余裕時間測定、及び市販インクジェットプリンター
による普通紙上への印字テストを実施した。その結果、
画像面積1cm2 当たり0.9mgという少量の記録液
量で塗布したベタ画像の光学濃度は1.4であったが、
目詰まり発生までの余裕時間は20秒と短いものであっ
た。また、市販のインクジェットプリンターを用いて印
字テストを実施した結果、目詰まりが発生し、水で希釈
しない記録液の原液を安定に吐出することはできなかっ
た。The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was 1.4,
The margin time before the occurrence of clogging was as short as 20 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.
【0088】また、この記録液を蒸留水で4倍に希釈し
たところ、市販のインクジェットプリンターで吐出可能
になったが、画像面積1cm2 当たり0.9mgという
少量の記録液量で塗布したベタ画像の光学濃度は0.4
と低いものであった。 (比較例8)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)19重量部
と、水及びフルオロオレフィンとビニルエーテルの乳化
重合により作製された含フッ素ビニルエーテル系樹脂微
粒子(平均粒子径:0.15μm)を含む樹脂分散液
(固形分=50%、旭硝子社製、商品名:FE−300
0)30重量部と、水及び側鎖にカルボキシル基が付加
された変性ポリエステル樹脂微粒子(平均粒子径:0.
1〜0.2μm)を含む樹脂分散液(固形分=25%、
高松油脂社製、商品名:A−115G)54重量部とを
添加し、撹拌して均一に混合させた。その後、この混合
液を孔径10μmのメンブランフィルターにてろ過し
て、ゴミ及び粗大粒子を除去し、記録液中顔料(着色
剤)濃度が7重量%、固形分中顔料(着色剤)濃度が2
0重量%、記録液中樹脂微粒子全固形分濃度が27重量
%の記録液を得た。When this recording liquid was diluted 4 times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 8) 19 parts by weight of a water-based copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, a fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) 30 parts by weight of water and a modified polyester resin fine particle having a carboxyl group added to the side chain (average particle diameter: 0.1%).
1 to 0.2 μm) (solid content = 25%,
54 parts by weight of Takamatsu Yushi Co., Ltd., trade name: A-115G), and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid was 7% by weight, and the pigment (colorant) concentration in the solid content was 2%.
A recording liquid having a concentration of 0% by weight and a total solid content of fine resin particles in the recording liquid of 27% by weight was obtained.
【0089】このようにして作製した記録液について、
実施例1〜9と同様に、光学濃度測定、目詰まり発生ま
での余裕時間測定、及び市販インクジェットプリンター
による普通紙上への印字テストを実施した。その結果、
画像面積1cm2 当たり0.9mgという少量の記録液
量で塗布したベタ画像の光学濃度は1.4であったが、
目詰まり発生までの余裕時間は20秒と短いものであっ
た。また、市販のインクジェットプリンターを用いて印
字テストを実施した結果、目詰まりが発生し、水で希釈
しない記録液の原液を安定に吐出することはできなかっ
た。The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was 1.4,
The margin time before the occurrence of clogging was as short as 20 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.
【0090】また、この記録液を蒸留水で4倍に希釈し
たところ、市販のインクジェットプリンターで吐出可能
になったが、画像面積1cm2 当たり0.9mgという
少量の記録液量で塗布したベタ画像の光学濃度は0.4
と低いものであった。 (比較例9)水系銅フタロシアニン系顔料(ピグメント
ブルー15:3)分散液(固形分=35%)21重量部
と、水及び変性スチレン−ブタジエン共重合体樹脂微粒
子(平均粒子径:0.19μm)を含む樹脂分散液(固
形分=48.5%、住化エイビーエス・ラテックス社
製、商品名:SN−335)30重量部と、水及び側鎖
にカルボキシル基が付加された変性ポリエステル樹脂微
粒子(平均粒子径:0.1〜0.2μm)を含む樹脂分
散液(固形分=30%、高松油脂社製、商品名:A−2
15G)49重量部とを添加し、撹拌して均一に混合さ
せた。その後、この混合液を孔径10μmのメンブラン
フィルターにてろ過して、ゴミ及び粗大粒子を除去し、
記録液中顔料(着色剤)濃度が7重量%、固形分中顔料
(着色剤)濃度が20重量%、記録液中樹脂微粒子全固
形分濃度が29重量%の記録液を得た。When this recording liquid was diluted 4 times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 9) 21 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 µm) 30 parts by weight of a resin dispersion (solid content = 48.5%, manufactured by Sumika ABS Latex Co., Ltd., trade name: SN-335), and modified polyester resin fine particles having a carboxyl group added to water and a side chain. (Average particle diameter: 0.1 to 0.2 μm) Resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-2)
15G) 49 parts by weight, and stirred to mix uniformly. Thereafter, the mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles,
A recording liquid was obtained in which the concentration of the pigment (colorant) in the recording liquid was 7% by weight, the concentration of the pigment (colorant) in the solid content was 20% by weight, and the total solid content of the resin fine particles in the recording liquid was 29% by weight.
【0091】このようにして作製した記録液について、
実施例1〜9と同様に、光学濃度測定、目詰まり発生ま
での余裕時間測定、及び市販インクジェットプリンター
による普通紙上への印字テストを実施した。その結果、
画像面積1cm2 当たり0.9mgという少量の記録液
量で塗布したベタ画像の光学濃度は1.4であったが、
目詰まり発生までの余裕時間は18秒と短いものであっ
た。また、市販のインクジェットプリンターを用いて印
字テストを実施した結果、目詰まりが発生し、水で希釈
しない記録液の原液を安定に吐出することはできなかっ
た。The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was 1.4,
The margin time before the occurrence of clogging was as short as 18 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.
【0092】また、この記録液を蒸留水で4倍に希釈し
たところ、市販のインクジェットプリンターで吐出可能
になったが、画像面積1cm2 当たり0.9mgという
少量の記録液量で塗布したベタ画像の光学濃度は0.4
と低いものであった。 (比較例10)水系銅フタロシアニン系顔料(ピグメン
トブルー15:3)分散液(固形分=35%)19重量
部と、水及び側鎖にカルボキシル基が付加された変性ポ
リエステル樹脂微粒子(平均粒子径:0.1〜0.2μ
m)を含む樹脂分散液(固形分=30%、高松油脂社
製、商品名:A−215G)30重量部と、水及び側鎖
にカルボキシル基が付加された変性ポリエステル樹脂微
粒子(平均粒子径:0.1〜0.2μm)を含む樹脂分
散液(固形分=25%、高松油脂社製、商品名:A−1
15G)54重量部とを添加し、撹拌して均一に混合さ
せた。その後、この混合液を孔径10μmのメンブラン
フィルターにてろ過して、ゴミ及び粗大粒子を除去し、
記録液中顔料(着色剤)濃度が7重量%、固形分中顔料
(着色剤)濃度が20重量%、記録液中樹脂微粒子全固
形分濃度が27重量%の記録液を得た。When this recording liquid was diluted 4 times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 10) 19 parts by weight of a water-based copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and modified polyester resin fine particles having a carboxyl group added to water and a side chain (average particle diameter) : 0.1-0.2μ
m), 30 parts by weight of a resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G), and modified polyester resin fine particles having a carboxyl group added to water and side chains (average particle diameter) : 0.1 to 0.2 µm) (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-1)
15G) 54 parts by weight were added, and the mixture was stirred and uniformly mixed. Thereafter, the mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles,
A recording liquid was obtained in which the concentration of the pigment (colorant) in the recording liquid was 7% by weight, the concentration of the pigment (colorant) in the solid content was 20% by weight, and the total solid concentration of the resin fine particles in the recording liquid was 27% by weight.
【0093】このようにして作製した記録液について、
実施例1〜9と同様に、光学濃度測定、目詰まり発生ま
での余裕時間測定、及び市販インクジェットプリンター
による普通紙上への印字テストを実施した。その結果、
画像面積1cm2 当たり0.9mgという少量の記録液
量で塗布したベタ画像の光学濃度は1.3であり、ま
た、目詰まり発生までの余裕時間は20秒と短いもので
あった。また、市販のインクジェットプリンターを用い
て印字テストを実施した結果、目詰まりが発生し、水で
希釈しない記録液の原液を安定に吐出することはできな
かった。The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image coated with a small amount of recording liquid of 0.9 mg per 1 cm 2 of image area was 1.3, and the margin time until clogging was as short as 20 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.
【0094】また、この記録液を蒸留水で4倍に希釈し
たところ、市販のインクジェットプリンターで吐出可能
になったが、画像面積1cm2 当たり0.9mgという
少量の記録液量で塗布したベタ画像の光学濃度は0.3
と低いものであった。 (比較例11)フタロシアニン系染料(アシッドブルー
9)水溶液(固形分=10%)56重量部に水及びフル
オロオレフィンとビニルエーテルの乳化重合により作製
された含フッ素ビニルエーテル系樹脂微粒子(平均粒子
径:0.15μm)を含む樹脂分散液(固形分=50
%、旭硝子社製、商品名:FE−3000)44重量部
を添加し、撹拌して均一に混合させた。その後、この混
合液を孔径10μmのメンブランフィルターにてろ過し
て、ゴミ及び粗大粒子を除去し、記録液中染料(着色
剤)濃度が6重量%、固形分中染料(着色剤)濃度が2
0重量%、記録液中樹脂微粒子全固形分濃度が22重量
%の記録液を得た。When this recording liquid was diluted four times with distilled water, it could be ejected with a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was obtained. Has an optical density of 0.3
Was low. (Comparative Example 11) Fluorinated vinyl ether-based resin fine particles (average particle diameter: 0) prepared by emulsion polymerization of water and a fluoroolefin with vinyl ether were added to 56 parts by weight of an aqueous solution of phthalocyanine dye (acid blue 9) (solid content = 10%). .15 μm) (solid content = 50)
%, Manufactured by Asahi Glass Co., Ltd., trade name: FE-3000) (44 parts by weight) was added, and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles. The dye (colorant) concentration in the recording liquid was 6% by weight, and the dye (colorant) concentration in the solid content was 2%.
A recording liquid having a concentration of 0% by weight and a total solid content of the resin fine particles in the recording liquid of 22% by weight was obtained.
【0095】このようにして作製した記録液について、
実施例1〜9と同様に、光学濃度測定、目詰まり発生ま
での余裕時間測定、及び市販インクジェットプリンター
による普通紙上への印字テストを実施した。その結果、
画像面積1cm2 当たり0.9mgという少量の記録液
量で塗布したベタ画像の光学濃度は1.4であったが、
目詰まり発生までの余裕時間は10秒と短いものであっ
た。また、市販のインクジェットプリンターを用いて印
字テストを実施した結果、目詰まりが発生し、水で希釈
しない記録液の原液を安定に吐出することはできなかっ
た。The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was 1.4,
The margin time until the occurrence of clogging was as short as 10 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.
【0096】また、この記録液を蒸留水で4倍に希釈し
たところ、市販のインクジェットプリンターで吐出可能
になったが、画像面積1cm2 当たり0.9mgという
少量の記録液量で塗布したベタ画像の光学濃度は0.3
と低いものであった。 (比較例12)フタロシアニン系染料(アシッドブルー
9)水溶液(固形分=10%)48重量部に水及びフル
オロオレフィンとビニルエーテルの乳化重合により作製
された含フッ素ビニルエーテル系樹脂微粒子(平均粒子
径:0.15μm)を含む樹脂分散液(固形分=50
%、旭硝子社製、商品名:FE−3000)19重量部
と、水及び側鎖にカルボキシル基が付加された変性ポリ
エステル樹脂微粒子(平均粒子径:0.1〜0.2μ
m)を含む樹脂分散液(固形分=30%、高松油脂社
製、商品名:A−215G)32重量部とを添加し、撹
拌して均一に混合させた。その後、この混合液を孔径1
0μmのメンブランフィルターにてろ過して、ゴミ及び
粗大粒子を除去し、記録液中染料(着色剤)濃度が5重
量%、固形分中染料(着色剤)濃度が20重量%、記録
液中樹脂微粒子全固形分濃度が19重量%の記録液を得
た。When this recording liquid was diluted 4 times with distilled water, it could be ejected with a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was obtained. Has an optical density of 0.3
Was low. (Comparative Example 12) Fluorinated vinyl ether-based resin fine particles (average particle diameter: 0) prepared by emulsion polymerization of water and a fluoroolefin with vinyl ether were added to 48 parts by weight of an aqueous solution of phthalocyanine dye (acid blue 9) (solid content = 10%). .15 μm) (solid content = 50)
%, Manufactured by Asahi Glass Co., Ltd., trade name: FE-3000) and 19 parts by weight of water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm)
m)) and 32 parts by weight of a resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G), and the mixture was stirred and uniformly mixed. Thereafter, the mixed solution was added with a pore size of 1
The particles are filtered through a 0 μm membrane filter to remove dust and coarse particles. The dye (colorant) concentration in the recording liquid is 5% by weight, the dye (colorant) concentration in the solid content is 20% by weight, and the resin in the recording liquid is A recording liquid having a total solid content of fine particles of 19% by weight was obtained.
【0097】このようにして作製した記録液について、
実施例1〜9と同様に、光学濃度測定、目詰まり発生ま
での余裕時間測定、及び市販インクジェットプリンター
による普通紙上への印字テストを実施した。その結果、
画像面積1cm2 当たり0.9mgという少量の記録液
量で塗布したベタ画像の光学濃度は1.4であったが、
目詰まり発生までの余裕時間は22秒と短いものであっ
た。また、市販のインクジェットプリンターを用いて印
字テストを実施した結果、目詰まりが発生し、水で希釈
しない記録液の原液を安定に吐出することはできなかっ
た。The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was 1.4,
The margin time before the occurrence of clogging was as short as 22 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.
【0098】また、この記録液を蒸留水で4倍に希釈し
たところ、市販のインクジェットプリンターで吐出可能
になったが、画像面積1cm2 当たり0.9mgという
少量の記録液量で塗布したベタ画像の光学濃度は0.3
と低いものであった。 (比較例13〜17)水及びフルオロオレフィンとビニ
ルエーテルの乳化重合により作製された含フッ素ビニル
エーテル系樹脂微粒子を含む樹脂分散液の代わりに、そ
れぞれ、比較例2〜6に用いた樹脂分散液を使用したこ
とを除いて、比較例11と同様に記録液を作製し、試験
を行ったところ、1種類の樹脂微粒子のみを用いる組合
せでは、いずれの場合も、高光学濃度と目詰まり防止と
の両立は不可能であった。 (比較例18)水及び側鎖にカルボキシル基が付加され
た変性ポリエステル樹脂微粒子を含む樹脂分散液(高松
油脂社製、商品名:A−215G)の代わりに、水及び
側鎖にカルボキシル基が付加された変性ポリエステル樹
脂微粒子(平均粒子径:0.1〜0.2μm)を含む樹
脂分散液(固形分=25%、高松油脂社製、商品名:A
−115G)を使用したことを除いて、比較例12と同
様に記録液を作製し、試験を行ったところ、高光学濃度
と目詰まり防止との両立は不可能であった。 (比較例19)水及びフルオロオレフィンとビニルエー
テルの乳化重合により作製された含フッ素ビニルエーテ
ル系樹脂微粒子を含む樹脂分散液の代わりに、水及び変
性スチレン−ブタジエン共重合体樹脂微粒子(平均粒子
径:0.19μm)を含む樹脂分散液(固形分=48.
5%、住化エイビーエス・ラテックス社製、商品名:S
N−335)を使用したことを除いて、比較例12と同
様に記録液を作製し、試験を行ったところ、高光学濃度
と目詰まり防止との両立は不可能であった。 (比較例20)水及びフルオロオレフィンとビニルエー
テルの乳化重合により作製された含フッ素ビニルエーテ
ル系樹脂微粒子を含む樹脂分散液の代わりに、水及び側
鎖にカルボキシル基が付加された変性ポリエステル樹脂
微粒子(平均粒子径:0.1〜0.2μm)を含む樹脂
分散液(固形分=30%、高松油脂社製、商品名:A−
215G)を、水及び側鎖にカルボキシル基が付加され
た変性ポリエステル樹脂微粒子を含む樹脂分散液(高松
油脂社製、商品名:A−215G)の代わりに、水及び
側鎖にカルボキシル基が付加された変性ポリエステル樹
脂微粒子(平均粒子径:0.1〜0.2μm)を含む樹
脂分散液(固形分=25%、高松油脂社製、商品名:A
−115G)をそれぞれ使用したことを除いて、比較例
12と同様に記録液を作製し、試験を行ったところ、高
光学濃度と目詰まり防止との両立は不可能であった。When this recording liquid was diluted 4 times with distilled water, it could be ejected with a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm 2 of image area was obtained. Has an optical density of 0.3
Was low. (Comparative Examples 13 to 17) The resin dispersions used in Comparative Examples 2 to 6, respectively, were used instead of the resin dispersions containing the fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water and a fluoroolefin and vinyl ether. A recording liquid was prepared and tested in the same manner as in Comparative Example 11, except that the combination using only one type of resin fine particles was compatible with both high optical density and prevention of clogging. Was impossible. (Comparative Example 18) Instead of a resin dispersion liquid (manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G) containing water and a modified polyester resin fine particle having a carboxyl group added to a side chain, a carboxyl group was added to water and a side chain. Resin dispersion containing added modified polyester resin fine particles (average particle diameter: 0.1 to 0.2 μm) (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A)
A recording liquid was prepared and tested in the same manner as in Comparative Example 12 except that -115G) was used, and it was impossible to achieve both high optical density and prevention of clogging. (Comparative Example 19) Water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0) were used instead of a resin dispersion containing fine particles of a fluorinated vinyl ether resin prepared by emulsion polymerization of water and a fluoroolefin and vinyl ether. .19 μm) (solid content = 48.
5%, manufactured by Sumika ABS Latex, trade name: S
A recording liquid was prepared and tested in the same manner as in Comparative Example 12 except that N-335) was used, and it was impossible to achieve both high optical density and prevention of clogging. (Comparative Example 20) Instead of a resin dispersion containing fine particles of a fluorine-containing vinyl ether resin produced by emulsion polymerization of water and a fluoroolefin and vinyl ether, fine particles of a modified polyester resin having a carboxyl group added to water and a side chain (average) Resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-
215G), instead of water and a resin dispersion containing modified polyester resin fine particles having a carboxyl group added to the side chain (manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G), a carboxyl group is added to water and a side chain. Resin dispersion (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A)
A recording liquid was prepared and tested in the same manner as in Comparative Example 12 except that each of -115G) was used, and it was impossible to achieve both high optical density and prevention of clogging.
【0099】[0099]
【発明の効果】本発明は、3種以上の樹脂微粒子を含有
するので、高い画像濃度を有し、記録紙上での滲みや浸
透のない耐水性に優れた画像を提供することが可能で、
且つ吐出安定性に優れた記録液を提供することができ
る。According to the present invention, since it contains three or more kinds of resin fine particles, it is possible to provide an image having high image density and excellent in water resistance without bleeding or permeation on recording paper.
In addition, a recording liquid having excellent ejection stability can be provided.
【0100】また、本発明は、上記利点を有する画像記
録方法を提供することができる。Further, the present invention can provide an image recording method having the above advantages.
フロントページの続き (72)発明者 諏訪部 恭史 神奈川県足柄上郡中井町境430グリーンテ クなかい 富士ゼロックス株式会社内Continued on the front page (72) Inventor Yasushi Suwabe 430 Green Tech Nakai, Nakai-cho, Ashigarakami-gun, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd.
Claims (15)
を含有することを特徴とする記録液。1. A recording liquid comprising a colorant, water and three or more kinds of resin fine particles.
特徴とする請求項1に記載の記録液。2. The recording liquid according to claim 1, further comprising non-crosslinkable resin fine particles.
脂微粒子であることを特徴とする請求項2に記載の記録
液。3. The recording liquid according to claim 2, wherein the non-crosslinkable resin fine particles are fluorine resin fine particles.
フィン単位を有することを特徴とする請求項3に記載の
記録液。4. The recording liquid according to claim 3, wherein the fluororesin fine particles have a fluoroolefin unit.
0.01μm〜5μmであることを特徴とする請求項
1、2、3及び4のいずれか1項に記載の記録液。5. The recording liquid according to claim 1, wherein the average particle diameter of each of the resin fine particles is 0.01 μm to 5 μm.
5重量%であることを特徴とする請求項1、2、3、4
及び5のいずれか1項に記載の記録液。6. A total content of the fine resin particles is 10 to 9.
5. The composition according to claim 1, wherein the content is 5% by weight.
6. The recording liquid according to any one of claims 5 and 6.
を特徴とする請求項1、2、3、4、5及び6のいずれ
か1項に記載の記録液。7. The recording liquid according to claim 1, wherein the recording liquid contains four or more types of resin fine particles.
る請求項1、2、3、4、5、6及び7のいずれか1項
に記載の記録液。8. The recording liquid according to claim 1, wherein the colorant is a pigment.
ることを特徴とする請求項8に記載の記録液。9. The recording liquid according to claim 8, wherein the content of the pigment is 1 to 50% by weight.
する請求項1、2、3、4、5、6及び7のいずれか1
項に記載の記録液。10. The method according to claim 1, wherein the colorant is a dye.
The recording liquid according to the item.
%であることを特徴とする請求項10に記載の記録液。11. The recording liquid according to claim 10, wherein the content of the dye is 0.2 to 40% by weight.
せて記録体上に記録を行う画像記録方法において、該記
録液として請求項1、2、3、4、5、6、7、8、
9、10及び11のいずれか1項に記載の記録液を用い
ることを特徴とする画像記録方法。12. An image recording method in which a recording liquid is ejected from a recording head to record on a recording medium, wherein the recording liquid is used as the recording liquid. ,
12. An image recording method using the recording liquid according to any one of 9, 10, and 11.
せて記録体上に記録を行う画像記録方法において、該記
録液として、水、着色剤及び4種類以上の樹脂微粒子を
含有する記録液を用いることを特徴とする画像記録方
法。13. An image recording method for discharging a droplet of a recording liquid from a recording head to perform recording on a recording medium, wherein the recording liquid contains water, a colorant, and four or more types of resin fine particles. An image recording method characterized by using:
とする請求項12又は13に記載の画像記録方法。14. The image recording method according to claim 12, wherein the recording medium is plain paper.
せて記録体上に記録を行う画像記録方法において、該記
録液として、水、着色剤及び4種類以上の樹脂微粒子を
含有する記録液を用い、且つ該記録体として普通紙を用
いることを特徴とする画像記録方法。15. An image recording method in which droplets of a recording liquid are ejected from a recording head to record on a recording medium, wherein the recording liquid contains water, a colorant, and four or more types of resin fine particles. And using plain paper as the recording medium.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26530896A JP3319308B2 (en) | 1996-09-12 | 1996-09-12 | Recording liquid and image recording method |
US08/925,391 US6075085A (en) | 1996-09-12 | 1997-09-08 | Recording liquid and image recording method |
US09/497,473 US6398356B1 (en) | 1996-09-12 | 2000-02-04 | Recording liquid and image recording method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26530896A JP3319308B2 (en) | 1996-09-12 | 1996-09-12 | Recording liquid and image recording method |
Publications (2)
Publication Number | Publication Date |
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JPH1088056A true JPH1088056A (en) | 1998-04-07 |
JP3319308B2 JP3319308B2 (en) | 2002-08-26 |
Family
ID=17415400
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Application Number | Title | Priority Date | Filing Date |
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JP26530896A Expired - Fee Related JP3319308B2 (en) | 1996-09-12 | 1996-09-12 | Recording liquid and image recording method |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6740152B1 (en) | 1999-09-10 | 2004-05-25 | Fuji Xerox Co., Ltd. | Recording liquid for ink printers, method of the manufacture thereof, and method of image recording |
JP2005330361A (en) * | 2004-05-19 | 2005-12-02 | Seiko Epson Corp | Ink composition for inkjet recording |
US7097295B1 (en) | 1999-09-10 | 2006-08-29 | Fuji Xerox Co., Ltd. | Recording liquid for ink printers and method for recording images |
JP2008037920A (en) * | 2006-08-02 | 2008-02-21 | Kao Corp | Water-based ink for inkjet recording |
JP2010155442A (en) * | 2009-01-05 | 2010-07-15 | Ricoh Co Ltd | Image forming method using pretreatment liquid, set of pretreatment liquid and inkjet recording ink, cartridge, inkjet recording device, and image formation product |
JP2011057991A (en) * | 2002-09-24 | 2011-03-24 | Seiko Epson Corp | Ink composition for inkjet recording, recording method using the same, and recorded material |
-
1996
- 1996-09-12 JP JP26530896A patent/JP3319308B2/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6740152B1 (en) | 1999-09-10 | 2004-05-25 | Fuji Xerox Co., Ltd. | Recording liquid for ink printers, method of the manufacture thereof, and method of image recording |
US7097295B1 (en) | 1999-09-10 | 2006-08-29 | Fuji Xerox Co., Ltd. | Recording liquid for ink printers and method for recording images |
JP2011057991A (en) * | 2002-09-24 | 2011-03-24 | Seiko Epson Corp | Ink composition for inkjet recording, recording method using the same, and recorded material |
JP2005330361A (en) * | 2004-05-19 | 2005-12-02 | Seiko Epson Corp | Ink composition for inkjet recording |
JP4670259B2 (en) * | 2004-05-19 | 2011-04-13 | セイコーエプソン株式会社 | Ink composition for inkjet recording |
JP2008037920A (en) * | 2006-08-02 | 2008-02-21 | Kao Corp | Water-based ink for inkjet recording |
JP2010155442A (en) * | 2009-01-05 | 2010-07-15 | Ricoh Co Ltd | Image forming method using pretreatment liquid, set of pretreatment liquid and inkjet recording ink, cartridge, inkjet recording device, and image formation product |
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