JP4822600B2 - Bright water-based ink composition - Google Patents

Description

上記実施例１〜３及び比較例１〜３で作成した各インキ組成物をペン先押し圧式でバルブを解放し、ペン先に流出させる液式のペン（三菱鉛筆株式会社製のユニ・ポスカＰＣ−１Ｍ）の円筒軸筒内にインキ組成物と撹拌用に直径５ｍｍのステンレスボールを同時に充填した後、マーキングペンとして各５本づつ組立、温度50℃の高温槽にペン先方向を上向き９０±５度の角度で２週間放置後、ペンを取り出し、ボールが軸内を上下に移動できる方向に振り、撹拌用ボールが動き出すまでの振り回数を調査した。
【００３８】
【表２】

上記表１及び表２より、実施例１〜３のインキ組成物においては剪断減粘性付与剤及び結晶セルロースの効果によりハードケーキ化が抑制され、ボールの動きは良好であった。比較例１及び２のインキ組成物においてはハードケーキを形成した。比較例３のインキ組成物において剪断減粘性はあるものの、結晶セルロースが存在しないためハードケーキの形成が認められた。
【００３９】
以上の様に本発明に係る光輝性水性インキ組成物は、長期間、静置状態で放置されたとしても、ハードケーキを形成することはない。またインキ組成物の撹拌を容易にすることができるので、色分離を容易に回復せしめ、速やかに顔料と溶媒を均一混合せしめて均一な濃度の筆跡が容易に得られる。更には、撹拌用ボールの個数を最低１個ですむため、製品コスト的にも有利な優れたインキ組成物である。
【００４０】
【発明の効果】
以上、説明したように本発明に係る光輝性水性インキ組成物によれば、結晶セルロースと、剪断減粘性付与剤と、板状粒子顔料と、水とを構成成分として含むので、組成物に平均粒径の大きな光輝性顔料を用いたときに、長期間静置状態で発生しうるハードケーキ化を防止し、容易に顔料を再分散させることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a glittering water-based ink composition, and more specifically, is used by filling a writing instrument such as a marking pen, an applicator, etc. The present invention relates to an ink composition.
[0002]
[Prior art]
Conventionally, plate-like particles such as pearl pigments and aluminum powder pigments have been used as pigments in inks for obtaining glittery handwriting in aqueous ink compositions. These plate-like particle pigments need to be larger than ordinary organic pigments and inorganic pigments in order to reflect light and obtain luster, and the average particle size of the plate-like particle pigments used is at least 5 μm or more. Is needed. When such a plate-like particle pigment having a large average particle diameter is used, the sedimentation rate of the particles is high, and the pigment and the solvent in the ink are not uniform, that is, color separation is likely to occur. Therefore, when filling and using a writing instrument, shake the writing instrument several times just before writing, move a ball or stick for ink stirring installed in advance inside the shaft tube, mix the pigment and solvent by external force, and evenly mix It is necessary to obtain handwriting of density.
[0003]
However, if left unattended for a long period of time, even if the writing instrument is shaken before use, the internal stirring balls and bars cannot be moved, and the pigment is redispersed in the ink composition. It becomes difficult to make it. That is, the precipitate containing the pigment is cured to form a so-called hard cake.
[0004]
[Problems to be solved by the invention]
The present invention has been made in view of the above-mentioned problems and demands in the prior art, and when a bright pigment having a large average particle diameter is used in the composition, it can be formed into a hard cake that can be generated in a stationary state for a long time. It is an object of the present invention to provide a glittering water-based ink composition that can prevent re-dispersion and easily redisperse the pigment.
[0005]
[Means for Solving the Problems]
As a result of diligent research to solve the above problems, the present inventor has suppressed the sedimentation of plate-like particle pigments by adding a mixture of crystalline cellulose and a shear thinning agent into an aqueous solution in which plate-like particle pigments are dispersed. And it has been found that the formation of a hard cake is prevented, and the present invention has been achieved.
[0006]
The present invention is a glitter comprising a crystalline cellulose and a shear thinning agent, a pearl pigment, an aluminum powder pigment, a plate-like particle pigment made of a metal or metal oxide coated glass flake, an aluminum coated polyester film, and water. A water-based ink composition and a writing instrument using the same are summarized.
[0007]
That is, the glittering water-based ink composition according to the present invention comprises the constitutions or means described in the following (1) to (4), and solves the above problems.
(1) 0.5 to 10% by mass of one or more crystalline celluloses selected from the following group A,
0.05 to 1.5 mass% of one or more kinds of shear thinning agents selected from the following group B,
1.0 to 15% by mass of one or more plate-like particle pigments selected from the following group C ;
A glittering water-based ink composition for marking pens, comprising water as a constituent component.
Group A: Natural cellulose after delignification of fiber selected from wood pulp, refined linter, cotton fiber, hemp fiber, and regenerated cellulose coagulated and regenerated from viscose solution or copper ammonium solution Group B: Guar gum, xanthan gum, locust Natural polysaccharides selected from gum, welan gum, rhamsan gum, karaya gum, tragacanth gum, succinoglucan and their derivatives, and cellulose compounds selected from carboxymethylcellulose, hydroxypropylcellulose and hydroxypropylmethylcellulose and their derivatives
Group C: Pearl pigment, metal or metal oxide-coated glass flake, aluminum-coated polyester film (2) The average particle size of the crystalline cellulose is 6 μm or less. Ink composition.
(3) above Symbol plate-like particle pigments, according to claim 1 or 2 marking pen aqueous glittering ink composition according to, wherein the average particle size of less than 130 .mu.m.
[0008]
( 4 ) A glittering marking pen comprising the glittering water-based ink composition according to any one of claims 1 to 3 and a stirrer therein.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the glittering water-based ink composition according to the present invention will be described in detail. The glittering water-based ink composition according to the present invention is not limited to the following embodiment.
[0010]
The glittering water-based ink composition according to the present invention contains crystalline cellulose, a shear thinning agent, a plate-like particle pigment, and water as constituent components.
[0011]
The addition of the crystalline cellulose used in the present invention and the shear thinning agent imparts a high viscosity to suppress the sedimentation of the plate-like particle pigment and allows the crystalline cellulose to settle when left undisturbed. It penetrates between the plate-like particle pigments, prevents adhesion between the plate-like particle pigments, and prevents so-called hard cake formation. For this reason, when the glittering water-based ink composition according to the present invention is used as a writing instrument or applicator, by shaking the writing instrument or applicator and applying a shear stress, the composition viscosity is reduced and a stirring ball, a stirring bar, etc. The stirring bar can be easily stirred and moved in the composition. Thereby, the plate-like particle pigment can be redispersed in the composition.
[0012]
In the glittering water-based ink composition according to the present invention, when an appropriate amount of the shear thinning agent is added, a measured value η obtained by a rotational viscometer at a temperature of 25 ° C. is expressed by a flow relational expression η = K (rpm) ^y . When expressed, it is desirable that K is a constant that is K ≧ 30 or more, and that y under such conditions falls within the range of −0.8 ≦ y ≦ −0.1 from the relationship of the measured value η. .
[0013]
The K value and the y value are constants for satisfying the flow relational expression determined by the characteristics of the glittering water-based ink composition, and the measured value η and (rpm) at that time are substituted into the flow relational expression. Sought by. The above (rpm) is the number of rotations (rpm) at the time of measurement with a rotational viscometer.
[0014]
When the K value is less than 30, the viscosity of the composition is lowered even in a stationary state regardless of the range of the y value, and the stability upon standing is lowered. Further, when the K value is 30 or more and the y value exceeds −0.1, the shear thinning is reduced, and the high viscosity is maintained even during writing, so that the writing line is drawn. cause.
[0015]
When the K value and the y value in the glittering water-based ink composition according to the present invention are within the above ranges, the stability at the time of standing and the outflow amount of the ink composition at the time of use when writing, etc. It will be optimal. In particular, in the glittering water-based ink composition, it is more desirable that −0.7 ≦ y ≦ −0.2.
[0016]
The crystalline cellulose used in the glittering water-based ink composition according to the present invention is solidified from, for example, natural cellulose after delignification of wood pulp, refined linter, cotton fiber, hemp fiber, or viscose solution or copper ammonium solution. mention may be made of the reproduced playback cellulose vinegar, than those which are commercially available, there is Avicel TG series, PH series (manufactured by Asahi Kasei Co., Ltd.), and the like. The particle size of the crystalline cellulose is not particularly limited. However, when a particle having a large particle size is used, the viscosity of the ink is increased and the writing quality of the writing instrument is lowered. Therefore, the average particle size is 6 μm or less. It is desirable to use powder. The addition amount of the crystalline cellulose is 0.5 to 10% by mass with respect to the ink composition . Further, it is preferable to increase or decrease in accordance with the amount of the plate-like particle pigment to be used, and to use it at 1 to 5% by mass.
[0017]
As the shear thinning agent used in the glittering water-based ink composition according to the present invention, a substance that is soluble or easily dispersible in water is effective. For example, guar gum, xanthan gum, locust gum, welan gum, and lamb gum gum Natural polysaccharides such as karaya gum, tragacanth gum and succinoglucan and derivatives thereof, and cellulose compounds such as carboxymethylcellulose, hydroxypropylcellulose and hydroxypropylmethylcellulose and derivatives thereof are used . These can be used alone or in combination. Other shear thinning agents include inorganic fine particles, crosslinkable acrylic acid polymers, etc., but since they have a matting effect and a decrease in shear thinning, they are preferably used in ink compositions that require glitter. Absent. The addition amount of the shear thinning agent is preferably 10 to 30% by mass with respect to the amount of crystalline cellulose used, and 0.05 to 1.5% by mass with respect to the total amount of the ink composition. you.
[0018]
Further, the shear thinning agent may be used by coating (external addition) on the surface of crystalline cellulose. Examples of such a material comprising a surface-treated crystalline cellulose and a shear thinning agent include Avicel RC series (manufactured by Asahi Kasei Co., Ltd.). Since such an additive is more uniformly dispersed when added to water, it is effective in expressing the action.
[0019]
The plate-like particles pigment used in the aqueous glittering ink composition of the present invention, pearl pigments, metallic or metal oxide coated glass flakes, can be cited aluminum coating polyester film and the like, these pigments in handwriting Thus, the light can be reflected and the glitter can be imparted to the ink composition.
[0020]
The pearl pigment includes a natural product such as fish scale foil and a synthetic product such as a product obtained by coating the surface of natural mica with a metal oxide and a product obtained by coating the surface of synthetic mica with a metal oxide. In general, the latter is often used in terms of availability, safety, and stability. Pearl pigments exhibit various color tones depending on the type of metal oxide coated on the mica surface and the coating thickness. Commercially available pearl pigments include Iriodin 100 (particle diameter 10-60 μm, silver), Iriodin 151 (particle diameter 1-110 μm, silver), Iriodin 153 (particle diameter 20-100 μm, silver), Iriodin 201 (particle diameter) 5 to 25 μm, gold), Iriodin 217 (particle diameter 10 to 60 μm, bronze), Iriodin 289 (particle diameter 10 to 125 μm, blue), Iriodin 504 (particle diameter 10 to 60 μm, wine red color), Iriodin 530 (particles) Diameter 10 to 125 μm, copper color) (made by Merck Japan Ltd.).
[0022]
The metal-coated glass flakes are obtained by coating silver flakes on the glass surface with electroless plating on the glass flakes, and the metal oxide-coated glass flakes are obtained by coating titanium dioxide with the liquid phase method on the surface of the glass flakes. . By changing the thickness of the titanium oxide film, colors such as silver, yellow, red, blue, and green can be obtained. Commercially available metal or metal oxide coated glass flakes include Metashine 2040PS (average particle size 40 μm), 2020PS (average particle size 25 μm), 5090 NS (average particle size 90 μm), 5090RC (average particle size 90 μm) (and above) Manufactured by Nippon Sheet Glass Co., Ltd.). In particular, when a metal or metal oxide coated glass flake is used as a plate-like particle pigment, it is easier to form a hard cake than the pearl pigment. However, in the glittering water-based ink composition according to the present invention, the crystalline cellulose and the shear reduction are used. By using a viscosity-imparting agent, the precipitation of the pigment is suppressed, and the plate-like particle pigments that have settled enter each other to sufficiently prevent the formation of a hard cake.
[0023]
The aluminum-coated polyester film can be obtained by vacuum-depositing aluminum on one side of a polyester film, and then applying a color coating on both sides and then finely cutting it to obtain a desired color. Commercially available aluminum coating polyester films include Crystal Color X-20 (average particle size 100 μm, manufactured by Dia Kogyo Co., Ltd.).
[0024]
The plate-like particle pigments can be used alone or in combination of two or more in accordance with the desired hue and light luminance. Moreover, the usage-amount of the said plate-shaped particle pigment is 1.0-20 mass% with respect to the composition whole quantity . Moreover , it is desirable to use in the range of 5.0-15 mass% preferably.
[0025]
Moreover, as for the magnitude | size of the plate-shaped particle pigment used for the glittering water-based ink composition which concerns on this invention, it is desirable that the average particle diameter is less than 130 micrometers. If the average particle diameter of the plate-like particle pigment is 130 μm or more, when the ink composition is filled as a writing instrument such as a marking pen or an applicator, a pen core manufactured by a fibrous extrusion used in the writing instrument In many cases, the writing becomes impossible or the pigment accumulates in the gaps during the writing to block the ink outflow holes and the writing becomes impossible.
[0026]
In the glittering water-based ink composition according to the present invention, water is added as a main component, and is added so that the viscosity of the composition satisfies the above range of η = K (rpm) ^y .
[0027]
In the glittering water-based ink composition according to the present invention, various materials used in conventional water-based ink compositions can be used in addition to the above components. For example, a water-soluble dye or a water-dispersed pigment can be added to obtain various hues of handwriting. In order to obtain fixing properties, various water-soluble resins and resin emulsions are added, water-soluble organic solvents such as ethylene glycol and glycerin are used to prevent ink drying at the nib and to prevent low-temperature freezing, and urea. A moisturizing agent such as a compound can be added, and further, a preservative such as benzothiazoline can be added. In addition, a wet penetrant such as a surfactant can be added for the purpose of improving the wettability to the writing surface. Regardless of which is used, it is desirable to select a material that matches the purpose, a material that interacts with the content components and has no abnormality in physical properties, or a material that does not have a defect as an ink, and adds a necessary amount.
[0028]
The glitter writing instrument according to the present invention contains the glitter water-based ink composition and a stirrer therein.
[0029]
The stirrer may be anything that can stir the ink composition inside when the main body is shaken several times just before writing. For example, with a stirring ball, a bar, etc. is there. The number of such stirrers is not limited to one, but when the glittering water-based ink composition according to the present invention is used, the ink composition is extremely easily stirred, and can be reduced as much as possible. For this reason, the manufacturing cost of a writing instrument can be made cheap.
[0030]
In general, the plate-like particle pigment used in the glittering water-based ink composition according to the present invention has a thin thickness and a large plane area, and when the pigment settles, the tatami-layer structure in which the pigments face each other and stack. In such a structure, the contact area between the pigments is large and the contact resistance is also large. Further, the dispersing agent adsorbed on the plate-like particle pigment is intricately entangled to further amplify the adhesion between the pigment particles. As a result, the tatami-layer structure is hardened, and some external force is applied. It becomes difficult to immediately separate and collapse.
[0031]
On the other hand, in the glittering water-based ink composition according to the present invention, the crystalline cellulose penetrates between the plate-like particle pigments, prevents the opportunity for the plate-like particle pigments to directly contact each other, and is added together. It also prevents the dispersing agent from being intertwined in a complicated manner. In addition, the use of a shear thinning agent increases the viscosity of the ink composition during stationary storage, thereby suppressing the precipitation of the plate-like particle pigment, making it easier for crystalline cellulose to enter the plate-like particle pigment. The combined effects of the above prevent the formation of a hard cake of the glittering water-based ink composition according to the present invention.
[0032]
【Example】
Hereinafter, preferable examples of the glittering water-based ink composition according to the present invention are shown below. The present invention is not limited to the following examples.
Example 1
<Composition composition>
・ Pearl pigment (Iriodine 151, particle size 1-110 μm, silver, Merck Japan, Inc.) 12 parts by mass Dispersing resin (J-62, styrene-acrylic acid copolymer ammonium salt, Johnson Polymer Co., Ltd.) 5 mass Part / adhesion imparting resin (acrylic emulsion AE362, manufactured by Nippon Synthetic Rubber Co., Ltd.) 5 parts by mass / drying-preventing water-soluble organic solvent (glycerin) 5 parts by mass / crystalline cellulose material (Avicel PH-M06, average particle size 6 μm Asahi Kasei Co., Ltd.) 1.8 parts by mass, shear thinning agent (xanthan gum) 0.2 parts by mass, preservative (Proxel GXL, 1,2-benzisothiazolin-3-one, manufactured by ICI Japan Co., Ltd.) 0. 2 parts by mass / water 70.6 parts by mass The above components were mixed by stirring to prepare a water-based ink composition having white silver glitter.
[0033]
(Example 2)
<Composition composition>
・ Metal-coated glass flake (Metashine 2040PS, average particle size 40 μm, silver, manufactured by Nippon Sheet Glass Co., Ltd.) 8 parts by mass ・ Dispersing resin (J-61J, styrene-acrylic acid copolymer ammonium salt, manufactured by Johnson Polymer Co., Ltd.) 5 parts by mass / fixing property-imparting resin (Boncoat 5410 acrylic-styrene copolymer emulsion, manufactured by Dainippon Ink & Chemicals, Inc.) 3 parts by mass / drying-preventing water-soluble organic solvent (glycerin) 5 parts by mass / shear thinning agent coating Crystalline cellulose material (Avicel RC-N81, manufactured by Asahi Kasei Co., Ltd.) 2 parts by mass, preservative (Proxel GXL, 1,2-benzisothiazolin-3-one, manufactured by ICI Japan Co., Ltd.) 0.2 parts by mass, water 74 .8 parts by mass The above ingredients were mixed with stirring to prepare a water-based ink composition having silver glitter.
[0034]
(Example 3)
<Composition composition>
・ Aluminum-coated polyester film (Crystal color X-20, average particle size 100 μm, iris color, manufactured by Dia Kogyo Co., Ltd.) 5 parts by mass ・ Dispersing resin (J-61J, ammonium salt of styrene-acrylic acid copolymer, Johnson polymer stock) (Made by company) 5 parts by mass / adhesiveness imparting resin (Boncoat 5410 acrylic-styrene copolymer emulsion, manufactured by Dainippon Ink & Chemicals) 3 parts by mass / drying-preventing water-soluble organic solvent (glycerin) 5 parts by mass / crystalline cellulose Material (Avicel PH-M06, average particle size 6 μm, manufactured by Asahi Kasei Co., Ltd.) 0.8 part by mass, shear thinning agent (carboxymethylcellulose sodium) 0.2 part by mass, preservative (Proxel GXL, 1,2-benzo Isothiazolin-3-one, manufactured by ICI Japan Ltd.) 0.2 parts by mass Min resin emulsion (Polyfix PM-107, Showa Kobunshi resistance, Ltd.) 5 parts by mass of water 74.8 parts by mass The above components were mixed and stirred to prepare an aqueous ink composition having an iris color glitter.
[0035]
(Comparative Example 1)
A water-based ink composition having white silver glitter was prepared in the same manner as the other components except that the crystalline cellulose material and shear thinning agent of Example 1 were replaced with polyvinylpyrrolidone.
(Comparative Example 2)
A water-based ink composition having silver glitter was prepared by replacing the crystalline cellulose material and the shear thinning agent of Example 2 with polyvinyl pyrrolidone in the same manner as the other components.
(Comparative Example 3)
The crystalline cellulose material of Example 3 was replaced with water, and the other components were the same, and a water-based ink composition having iris color glitter was prepared.
[0036]
The K value and the y value were calculated from the measured value η and the number of rotations (rpm) obtained by using each of the ink compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 3 using a rotational viscometer at a temperature of 25 ° C. . The results are shown in Table 1.
[0037]
[Table 1]

Each ink composition prepared in the above Examples 1 to 3 and Comparative Examples 1 to 3 is a pen with a pressure applied by a pen tip, and a liquid pen (Uni Posca PC manufactured by Mitsubishi Pencil Co., Ltd.) is allowed to flow out to the pen tip. -1M) After simultaneously filling an ink composition and a stainless steel ball having a diameter of 5 mm for stirring into a cylindrical shaft cylinder, assembling five each as a marking pen, the pen tip direction upward 90 ± After being left for 2 weeks at an angle of 5 degrees, the pen was removed, the ball was swung in a direction that could move up and down the shaft, and the number of swings until the stirring ball started to move was investigated.
[0038]
[Table 2]

From the above Tables 1 and 2, in the ink compositions of Examples 1 to 3, hard cake formation was suppressed by the effects of the shear thinning agent and crystalline cellulose, and the movement of the balls was good. In the ink compositions of Comparative Examples 1 and 2, a hard cake was formed. In the ink composition of Comparative Example 3, although there was shear thinning, formation of a hard cake was recognized because no crystalline cellulose was present.
[0039]
As described above, the glittering water-based ink composition according to the present invention does not form a hard cake even when left standing for a long time. Further, since the ink composition can be easily stirred, the color separation can be easily recovered, and the pigment and the solvent can be quickly uniformly mixed to easily obtain a handwriting having a uniform concentration. Furthermore, since at least one stirring ball is required, the ink composition is excellent in terms of product cost.
[0040]
【The invention's effect】
As described above, according to the glittering water-based ink composition according to the present invention, since it contains crystalline cellulose, a shear thinning agent, a plate-like particle pigment, and water as constituent components, When a bright pigment having a large particle size is used, it is possible to prevent the formation of a hard cake that can occur in a stationary state for a long period of time and to easily redisperse the pigment.

Claims (4)

0.5 to 10% by mass of one or more crystalline celluloses selected from the following group A,
0.05 to 1.5 mass% of one or more kinds of shear thinning agents selected from the following group B,
1.0 to 15% by mass of one or more plate-like particle pigments selected from the following group C ;
A glittering water-based ink composition for marking pens, comprising water as a constituent component.
Group A: Natural cellulose after delignification of fiber selected from wood pulp, refined linter, cotton fiber, hemp fiber, and regenerated cellulose coagulated and regenerated from viscose solution or copper ammonium solution Group B: Guar gum, xanthan gum, locust Natural polysaccharides selected from gum, welan gum, rhamzan gum, karaya gum, tragacanth gum, succinoglucan and their derivatives, and cellulose compounds selected from carboxymethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose and their derivatives
Group C: Pearl pigment, metal or metal oxide coated glass flake, aluminum coated polyester film 2. The glittering water-based ink composition for marking pens according to claim 1, wherein the crystalline cellulose has an average particle size of 6 [mu] m or less. The glittering water-based ink composition for marking pens according to claim 1 or 2 , wherein the plate-like particle pigment has an average particle diameter of less than 130 µm. A glittering marking pen comprising the glittering water-based ink composition according to any one of claims 1 to 3 and a stirrer therein.