JP5748401B2 - Bright pigment ink for slim markers - Google Patents
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- JP5748401B2 JP5748401B2 JP2009238777A JP2009238777A JP5748401B2 JP 5748401 B2 JP5748401 B2 JP 5748401B2 JP 2009238777 A JP2009238777 A JP 2009238777A JP 2009238777 A JP2009238777 A JP 2009238777A JP 5748401 B2 JP5748401 B2 JP 5748401B2
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- 239000000049 pigment Substances 0.000 title claims description 97
- 239000000203 mixture Substances 0.000 claims description 50
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
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- 239000006185 dispersion Substances 0.000 claims description 10
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- 229910052751 metal Inorganic materials 0.000 claims description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims 1
- 239000003550 marker Substances 0.000 description 26
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
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- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本願発明は、高い隠蔽性を持ち、光輝性を備え、使用前すぐに顔料の再分散が容易に行え、かつ、写真プリントの表面に難なく筆記あるいは描画することが出来る顔料マーカーのインク組成に関する。特に携帯に便利な、細身のマーカーに収容される水性顔料マーカーのインク組成に関する。 The present invention relates to an ink composition of a pigment marker that has high concealing properties, has glitter, can be easily redispersed immediately before use, and can be written or drawn on the surface of a photographic print without difficulty. In particular, the present invention relates to an ink composition of an aqueous pigment marker accommodated in a slim marker that is convenient to carry.
一般に、電子写真のプリント表面などの、濃い色に着色された面に筆記あるいは描画を行い、メッセージや表現の追加等を行えるマーカーとして、プリントのインクに影響を及ぼさないことから、水性顔料マーカーが使用されている。また、単に隠蔽性があって、プリント面に影響を及ぼさないだけではなく、目立つ表現を施したいとの要求を受け、光輝性を持つ顔料をインクに添加して、描線に光輝性を持たせたマーカーが実施されている。光輝性の顔料は、金属粉であって比重が非常に重いもので、撹拌が困難であった。また、別の光輝性の顔料としては、平板状の基体を金属酸化物等で覆った、一般にパール顔料と呼称されるものが使用されているが、このような顔料は平板状であるため、一旦容器内にインクが収容されて沈降堆積して層状にハードケーキ化してしまうと、再分散が困難となる。 In general, water-based pigment markers are used as markers that can write or draw on dark colored surfaces such as electrophotographic print surfaces and add messages and expressions, etc., and do not affect print ink. It is used. In addition, it has a concealment property and does not affect the print surface. In response to a demand for a prominent expression, a pigment with glitter is added to the ink to give the line a glitter. Markers have been implemented. The glitter pigment is a metal powder having a very high specific gravity, and stirring is difficult. Further, as another glittering pigment, a flat base covered with a metal oxide or the like, generally called a pearl pigment is used, but such a pigment is flat, Once the ink is stored in the container and settled and formed into a hard cake in layers, redispersion becomes difficult.
平板状の顔料による光輝性付与を選択した場合の沈降対策、即ち易再分散性の付与について、結晶セルロースを添加することによって解決した水性顔料マーカー用インクが開示されている（特許文献１）。ここに開示されているインク組成は、結晶セルロースの他、剪断減粘性付与剤、分散剤、固着性付与樹脂等が添加されており、マーカー用のインクとしては多少高粘度であることが理解される。顔料以外のインクベヒクルが高粘度であることによって平板状顔料の沈降が一定期間は抑制できるものの、例えば１年以上、望ましくは５年以上の長期に亘る静置によって結局は微視的に見て層状の構造物に堆積してしまい、ハードケーキ化してしまうことが容易に予想された。 There has been disclosed an aqueous pigment marker ink that has been solved by adding crystalline cellulose to prevent sedimentation, ie, impart easy redispersibility, when imparting glitter with a flat pigment is selected (Patent Document 1). In addition to crystalline cellulose, the ink composition disclosed herein includes a shear thinning agent, a dispersant, an adhesion-imparting resin, etc., and it is understood that the ink for markers is somewhat high in viscosity. The Although the precipitation of the tabular pigment can be suppressed for a certain period of time due to the high viscosity of the ink vehicle other than the pigment, it is microscopically looked after standing for a long period of, for example, 1 year or longer, preferably 5 years or longer. It was easily expected that it would be deposited on the layered structure and turned into a hard cake.
また、光輝性顔料を含むインクに、更にパール顔料を入れて視認性を向上させ、増粘性多糖類の水溶液を用いてこれら顔料の沈降を防止して、使い勝手を良好にしたとされる水性インクの配合組成が開示されている（特許文献２）。このインキ組成物の好ましい粘度範囲は５００〜１５０００ｍＰａ・ｓｅｃ．（摂氏２０度における、ずり速度１．９２ｓｅｃ．−１）となっており、顔料の沈降は、ある期間防止できるとしても、マーカー用のインクとしては不向きな範囲となっている。また、この文献において光輝性顔料と称している比較的大きな平均粒子径（４０μｍ程度）の平板状顔料と、パール顔料と称している比較的小さな粒子径（５〜４０μｍの範囲）の平板状顔料とを加えているが、比較的小さな粒子径の平板状顔料の添加量の方が多く、これら平板状顔料が沈降堆積した際の構造は、密な構造となることが予想され、この組成において再分散には困難があることは容易に予想できる。 In addition, a pearl pigment is further added to the ink containing the glitter pigment to improve the visibility, and an aqueous solution of a thickening polysaccharide is used to prevent the precipitation of these pigments. Is disclosed (Patent Document 2). The preferred viscosity range of this ink composition is 500 to 15000 mPa · sec. (Shear rate at 20 degrees Celsius is 1.92 sec. −1 ), and even though the sedimentation of the pigment can be prevented for a certain period, it is in a range unsuitable as a marker ink. Further, a flat pigment having a relatively large average particle size (about 40 μm) referred to as a luster pigment in this document, and a flat pigment having a relatively small particle size (range from 5 to 40 μm) referred to as a pearl pigment. However, the amount of the tabular pigment having a relatively small particle diameter is larger, and the structure when these tabular pigments are deposited is expected to be a dense structure. It can be easily predicted that there will be difficulties in redispersion.
ところで近年、本出願人により、酸化チタン等の比重の大きな顔料を含むインク組成物を収容し、筆記あるいは描画に供する細身のマーカーが工業的に実施されている（特許文献３、４）。このような細身のマーカーの機構においては、顔料分が沈降してしまった場合に再分散を行う撹拌子の大きさに自ずと制限が生まれるため、通常の顔料よりも強固なハードケーキを形成する可能性のある平板状顔料を含むインクを収容すれば、顔料分の再分散には、更なる困難性が存在することが容易に予想された。言うまでもないが、このような筆記具は、細い描線が描けるペン芯で滞りなくインクが流出することが要求され、上記したような大きな平板状顔料を含み高粘度のインク組成では、目詰まりの懸念が拭い去れず、高粘度の液体では流出することができない。 By the way, in recent years, a thin marker that contains an ink composition containing a pigment having a large specific gravity such as titanium oxide and is used for writing or drawing has been industrially implemented by the present applicant (Patent Documents 3 and 4). In such a thin marker mechanism, the size of the stirrer that re-disperses when the pigment content settles is naturally limited, so it is possible to form a hard cake that is stronger than ordinary pigments It was easily anticipated that there would be additional difficulties in redispersing the pigment if an ink containing a sizable flat pigment was accommodated. Needless to say, such a writing instrument is required to allow the ink to flow out without a stagnation with a pen core that can draw a thin line, and there is a concern about clogging with a high viscosity ink composition containing a large flat pigment as described above. It cannot be wiped off and cannot flow out with a highly viscous liquid.
しかしながら、このような筆記具の使用者の要求としては、携帯できる程度の細身の筆記具に光輝性の強い水性インクを収容し、プリントした電子写真の表面に、細い描線を滞りなく描くことのできることにあるため、これらの事項を全て満足するインク組成物について検討すべきものであると本発明者等は認識をした。 However, as a user of such a writing instrument, a thin writing instrument that is portable enough to contain water-based ink with high brilliancy can be used to smoothly draw thin lines on the surface of printed electrophotography. Therefore, the present inventors have recognized that an ink composition that satisfies all of these matters should be studied.
本願発明者等は、上記の課題を解決するため、鋭意研究を行った結果、平均粒子径の異なる２種類の光輝性の平板状顔料を必要量添加し、描線の隠蔽性、及び、視認性について遜色ない程度としたうえで、結晶セルロースも添加した水性インクを組成し、平均粒子径の大きな第１の平板状顔料の添加量に満たない量を、平均粒子径のより小さな第２の平板状顔料の添加量とすることによって、内径１５ｍｍ未満のインク収容部を持ち、小さな撹拌子を備えた細身のマーカーに収容されたとしても、筆記を開始する前の撹拌によって素早く再分散を行えることを見出し、本発明を完成させたものである。 The inventors of the present application have conducted intensive research to solve the above-mentioned problems, and as a result, required amounts of two types of glittering flat pigments having different average particle diameters were added, and the concealment and visibility of drawn lines were added. A water-based ink containing crystalline cellulose was added to the same level, and an amount less than the addition amount of the first tabular pigment having a large average particle size was added to the second flat plate having a smaller average particle size. By adding the amount of pigment, it can be quickly redispersed by agitation before starting writing, even if it has an ink container with an inner diameter of less than 15 mm and is contained in a thin marker with a small stirring bar. And the present invention has been completed.
すなわち、本発明は、次の（１）〜（７）に存する。
（１）内径１０ｍｍを下回る有底筒状のインク収容容器と、前記インク収容容器内にインク撹拌子が封入され、前記インク収容容器の開放された開口部前方にインク流出口のスリット幅が１ｍｍを下回る筆記用尖端を持つ筆記具に収容される水性インク組成物であって、分散用樹脂と、ガラスフレークに金属で被覆したパール顔料である第１の平板状の顔料と、前記第１の平板状の顔料の平均粒子径に満たない平均粒子径を持ちマイカ表面に金属酸化物の被覆を施したパール顔料である第２の平板状の顔料が、前記第１の平板状の顔料の添加量に満たない添加量であって、更に結晶性セルロースを０．５重量％以上、２重量％未満を含む水性インク組成物。
（２）前記結晶性セルロースが分散されて含まれていることを特徴とする上記（１）に記載の水性インク組成物。
（３）前記粒子径の異なる２種以上の平板状の顔料成分の合計が５重量％以上、２０重量％以下である上記（１）に記載の水性インク組成物。
（４）前記第１及び第２の平板状の顔料の外、更に、色材を含む上記（１）に記載の水性インク組成物。
（５）前記色材が、顔料と、分散樹脂と、水、又は、水及びアルコールからなる分散液である上記（４）に記載の水性インク組成物。
（６）前記色材が、染料又は顔料と、樹脂エマルジョンと、水とを少なくとも含む分散液である前記（４）に記載の水性インク組成物。
（７）摂氏温度２５度において、ずり速度３．８３ｓｅｃ．−１の時の粘度が８０ｍＰａ・ｓｅｃ．以上２００ｍＰａ・ｓｅｃ．以下、かつ、ずり速度３８．３ｓｅｃ．−１の時の粘度が１５ｍＰａ・ｓｅｃ．以上６０ｍＰａ・ｓｅｃ．以下である上記（１）〜（６）の何れか一つに記載の水性インク組成物。
That is, this invention exists in following (1)-( 7 ).
( 1 ) A bottomed cylindrical ink container having an inner diameter of less than 10 mm, an ink stirrer is enclosed in the ink container, and the slit width of the ink outlet is 1 mm in front of the opened opening of the ink container. Water-based ink composition housed in a writing instrument having a writing tip less than 1, a dispersion resin, a first flat pigment that is a pearl pigment coated with metal on glass flakes, and the first flat plate second flat plate-like pigment average particle size of less than the average particle diameter shaped for pigment lifting Chi mica surface is a pearl pigment which has been subjected to coating of metal oxide, the addition of the first flat plate-like pigment A water-based ink composition containing less than 0.5% by weight of crystalline cellulose and less than 2% by weight, with an addition amount less than the amount.
(2) an aqueous ink composition according to (1) above, wherein the crystalline cellulose is characterized in that it contains dispersed.
(3) the sum of two or more plate-like pigment components with different particle size of 5 wt% or more, the water-based ink composition according to SL above 20 wt% or less (1).
(4) the first and second outer plate-like pigment, further, the aqueous ink composition according to the above (1) containing a coloring material.
(5) the coloring material, a pigment, a dispersing resin, water, or an aqueous ink composition described above is a dispersion consisting of water and an alcohol SL (4).
( 6 ) The water-based ink composition according to ( 4), wherein the color material is a dispersion liquid containing at least a dye or pigment, a resin emulsion, and water.
( 7 ) At a temperature of 25 degrees Celsius, the shear rate is 3.83 sec. -1 viscosity is 80 mPa · sec. 200 mPa · sec. In the following, the shear rate is 38.3 sec. -1 viscosity is 15 mPa · sec. 60 mPa · sec. Less is (1) above - water-based ink composition according to any one of (6).
本願発明によれば、内径１５ｍｍ未満あるいは内径１０ｍｍ未満のインク収容部を持ち、小さな撹拌子を備えた細身のマーカーに収容されることとなっても、描線の隠蔽性、及び、視認性が向上し、かつ、筆記を開始する前の撹拌によって素早く再分散を行えるマーカー用水性インク組成物が得られる。 According to the present invention, even if the ink container has an inner diameter of less than 15 mm or less than 10 mm, and is accommodated in a thin marker with a small stirrer, the concealment and visibility of the drawn line are improved. And the aqueous ink composition for markers which can be rapidly re-dispersed by stirring before starting writing is obtained.
以下に、本発明の実施形態を詳しく説明する。
本発明の水性インク組成物は、比較的粒子径の大きな第１の平板状の顔料と、比較的粒子径の小さな第２の平板状の顔料と、結晶セルロースとを含み、前記第２の平板状の顔料の添加量を前記第１の平板状の顔料の添加量以下としたことを特徴とするものである。
図１は、本発明の水性インク組成物における平板状の顔料分沈降堆積の模式図、図２は前記した特許文献２に記載されたインク組成物における平板状の顔料分沈降堆積の模式図である。
Hereinafter, embodiments of the present invention will be described in detail.
The aqueous ink composition of the present invention includes a first flat pigment having a relatively large particle diameter, a second flat pigment having a relatively small particle diameter, and crystalline cellulose, and the second flat plate. The amount of the pigment in the form of a pigment is not more than the amount of the pigment in the first plate-like pigment.
FIG. 1 is a schematic diagram of the flat pigment content sedimentation deposition in the aqueous ink composition of the present invention, and FIG. 2 is a schematic diagram of the flat pigment content sedimentation deposition in the ink composition described in Patent Document 2 described above. is there.
本発明に用いる平板状の顔料としては、光輝性の平板状顔料であって、ガラスフレークを金属等で被覆したもの、雲母等の表面を金属又は金属化合物等で被覆した所謂パール顔料等、強い光輝性を持ち、安定性の高いものであれば何でも利用できる。一般的に入手容易であれば尚良い。
本願発明の水性インク組成物は、極細の筆記描線を描くことのできるマーカー用であるため、細い流路を持つ筆記尖端を通って、このインク組成物が漏出しなければならない。そうすると、これらの平板状の顔料の平均粒子径は、１３０μｍ以下であることが好ましく、５μｍ以上５０μｍ以下であることがより好ましい。言うまでもなく、１３０μｍを超える場合には、細い流路の筆記先端等で目詰まりしやすくなる。また、５μｍ未満では筆記描線においてくっきりした光輝性を得難くなる。これらの粒子径の測定はレーザー散乱による測定（Ｎ４による摂氏２５度の水溶媒中での測定）の他、光学顕微鏡又は電子顕微鏡により、一定面積の視野中の粒子を計数することによっても算出することができる。
The flat pigment used in the present invention is a glittering flat pigment, such as a glass flake coated with a metal or the like, a so-called pearl pigment whose surface such as mica is coated with a metal or a metal compound, or the like. Anything can be used as long as it has glitter and high stability. Generally, it is better if it is easily available.
Since the water-based ink composition of the present invention is for a marker capable of drawing an extremely fine writing line, the ink composition must leak through a writing tip having a narrow flow path. Then, the average particle diameter of these flat pigments is preferably 130 μm or less, and more preferably 5 μm or more and 50 μm or less. Needless to say, when the thickness exceeds 130 μm, clogging is likely to occur at the writing tip of a narrow channel. On the other hand, when the thickness is less than 5 μm, it is difficult to obtain a clear glitter in the writing line. These particle diameters are calculated not only by laser scattering (measurement in an aqueous solvent at 25 degrees Celsius by N4) but also by counting particles in a field of view of a certain area with an optical microscope or an electron microscope. be able to.
本願発明の水性インク組成物においては、２種類の異なる粒子径を持つ光輝性を有する平板状顔料、即ち、比較的大きな平均粒子径の第１の平板状顔料、比較的小さな平均粒子径の第２の平板状顔料と、に分けて添加することとしている。
１種類の平板状顔料のみの添加の場合、この顔料が層状に沈降堆積することによって、通常の顔料分よりも強固なハードケーキを形成することとなり、再撹拌が困難となることが容易に想像される。ここで、平板状顔料を２種類添加した場合、同じか極近い平均粒子径を持つもの同士の２種類である場合は、前記した１種類の場合同様、層状に沈降堆積してしまうことが予想される。
また、２種類の異なる粒子径を持つ光輝性を有する平板状顔料を添加、即ち、比較的大きな平均粒子径の第１の平板状顔料、比較的小さな平均粒子径の第２の平板状顔料と、に分けて添加した場合でも、前記第２の平板状顔料を前記第１の平板状顔料の添加量を超えて添加したときには、図２のモデル図に示すように、第１の平板状顔料の周囲は、緻密な第２の平板状顔料が層状に堆積して、結局は層状の沈降堆積物となることが予想される。
In the water-based ink composition of the present invention, a tabular pigment having glitter having two different particle sizes, that is, a first tabular pigment having a relatively large average particle size, and a first pigment having a relatively small average particle size. The two tabular pigments are added separately.
In the case of adding only one type of flat pigment, it is easily imagined that re-stirring becomes difficult because this pigment precipitates and deposits in layers, forming a hard cake stronger than the usual pigment content. Is done. Here, when two types of tabular pigments are added, in the case of two types having the same or very close average particle diameter, it is expected that they will settle and deposit in a layered manner as in the case of the one type described above. Is done.
Further, a tabular pigment having a glittering property having two different particle sizes is added, that is, a first tabular pigment having a relatively large average particle size, a second tabular pigment having a relatively small average particle size, and When the second tabular pigment is added in an amount exceeding the amount of the first tabular pigment, the first tabular pigment is added as shown in the model diagram of FIG. It is expected that a dense second flat pigment is deposited in the form of a layer, and eventually becomes a layered sediment.
ここで、前記比較的小さな平均粒子径の第２の平板状顔料を前記第１の平板状顔料の添加量以下の量を添加した場合には、図１のモデル図に示すように、第１の平板状顔料同士の間に隙間を持たせて沈降堆積するものと想像される。このため、本願発明の水性インク組成物は、前記第２の平板状顔料による、描線の隠蔽性、視認性及び光輝性の補強を犠牲にしても、強固なハードケーキ化を防止するために、前記第２の平板状顔料の添加量を、前記第１の平板状顔料の添加量に満たない量とし、弱い撹拌手段でも再撹拌が可能な沈降堆積物となるように配慮したものである。これら粒子径の異なる２種以上の平板状の顔料成分の合計の添加量は、５重量％以上２０重量％以下であって、５重量％未満の添加量では、描線の光輝性発現が小さく認識に難があり、２０重量％を超える添加では、目詰まりし、筆記不能となり易くなる。 Here, when the second tabular pigment having a relatively small average particle diameter is added in an amount equal to or less than the addition amount of the first tabular pigment, as shown in the model diagram of FIG. It is assumed that sedimentation occurs with a gap between the flat pigments. For this reason, the water-based ink composition of the present invention prevents the formation of a strong hard cake even at the sacrifice of the concealment of drawn lines, visibility, and glitter by the second flat pigment, The amount of the second tabular pigment added is less than the amount of the first tabular pigment added so that a sediment that can be re-stirred even with weak stirring means is taken into consideration. The total addition amount of these two or more types of tabular pigment components having different particle diameters is 5% by weight or more and 20% by weight or less. Addition exceeding 20% by weight tends to clog and make writing impossible.
光輝性を持つ平板状顔料としては、ガラスフレークに金属等で被覆した、メタシャイン２０４０ＰＳ（平均粒子径４０μｍ）、２０２０ＰＳ（平均粒子径２５μｍ）、５０９０ＮＳ（平均粒子径９０μｍ）、５０９０ＲＣ（平均粒子径９０μｍ）（以上、日本板硝子株式会社製）等、マイカ表面に金属酸化物等の被覆を施した、イリオジン１００（粒子径１０〜６０μｍ、銀色）、イリオジン１５１（粒子径１〜１１０μｍ、銀色）、イリオジン１５３（粒子径２０〜１００μｍ、銀色）、イリオジン２０１（粒子径５〜２５μｍ、金色）、イリオジン２１７（粒子径１０〜６０μｍ、赤銅色）、イリオジン２８９（粒子径１０〜１２５μｍ、青色）、イリオジン５０４（粒子径１０〜６０μｍ、ワインレッド色）、イリオジン５３０（粒子径１０〜１２５μｍ、銅色）（以上、メルクジャパン株式会社製）等パール顔料等が挙げられる。 As the flat pigment having glitter, metashine 2040PS (average particle size 40 μm), 2020PS (average particle size 25 μm), 5090 NS (average particle size 90 μm), 5090RC (average particle size) coated with metal or the like on glass flakes. 90 μm) (above, manufactured by Nippon Sheet Glass Co., Ltd.), etc. Miri surface coated with a metal oxide or the like, Iriodin 100 (particle diameter 10-60 μm, silver), Iriodin 151 (particle diameter 1-110 μm, silver), Iriodin 153 (particle diameter 20 to 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 size 10-60 μm, wine red color), Iriodin 530 (particle size 10 Pearl pigments such as 125 μm, copper color (made by Merck Japan Ltd.).
本願発明の水性インク組成物で用いる結晶セルロースは、剪断減粘性付与剤として用いられ、短期的な沈降堆積物のハードケーキ化を防止するものである。短期的には、溶媒を増粘させることによって顔料の沈降速度を遅くする効果を発揮し、顔料粒子同士の間に入り込んでハードケーキ化を防止するので、本願発明の課題克服のためには欠かせない添加物である。しかしながら、この結晶セルロースの添加のみによる対策では、長期的には、沈降堆積物がハードケーキ化する傾向に歯止めをかけることが出来ない。 The crystalline cellulose used in the aqueous ink composition of the present invention is used as a shear thinning agent, and prevents short-term sedimentary deposits from forming a hard cake. In the short term, the effect of slowing the sedimentation rate of the pigment by increasing the viscosity of the solvent is exerted, and since it enters between the pigment particles to prevent hard cake formation, it is essential for overcoming the problems of the present invention. It is an additive that does not. However, this measure only by adding crystalline cellulose cannot prevent the tendency of the sediment to form a hard cake in the long term.
好ましい結晶セルロースは、例えば、木材パルプ、精製リンター、綿繊維、麻繊維等の脱リグニン後の天然セルロース、またはビスコース溶液や銅アンモニウム溶液から凝固再生された再生セルロース等を挙げることができ、市販されているものでは、アビセルＴＧシリーズ、ＰＨシリーズ、セオラスＲＣシリーズ（旭化成株式会社製）等がある。なお、結晶セルロースの粒径は特に限定するものではないが、粒径が大きいものを使用した場合、インキの粘度が上昇し、筆記具の書き味の低下を引き起こすため、平均粒径は６μｍ以下の粉体を分散させて使用することが望ましい。前記結晶セルロースの添加量はインキ組成物に対して０．５〜５重量％が好ましい。 Preferred crystalline cellulose includes, for example, natural cellulose after delignification of wood pulp, refined linter, cotton fiber, hemp fiber, etc., or regenerated cellulose coagulated and regenerated from viscose solution or copper ammonium solution. Among them, there are Avicel TG series, PH series, Theolas RC series (manufactured by Asahi Kasei Corporation) 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 the powder in a dispersed state. The addition amount of the crystalline cellulose is preferably 0.5 to 5% by weight with respect to the ink composition.
ところで、ここまでは本願発明のインク組成物が細身のマーカー（例えばインク収容容器が直径１５ｍｍ未満のマーカー）に収容された場合のことであるが、極めて細身のマーカー（例えばインク収容容器が直径１０ｍｍ未満のマーカー）である場合には、前記した対応策では不足であり、平板状顔料の再撹拌について、撹拌子が更に小さくなってしまうこともあり、好ましくない。この場合、不思議なことに前記結晶セルロースの量を減らすことによって、平板状顔料の再撹拌の問題が改善することが分かった。この場合には、前記結晶セルロースの添加量は０．５重量％以上２重量％未満であることが望ましい。 By the way, heretofore, the ink composition of the present invention is contained in a thin marker (for example, a marker whose ink container is less than 15 mm in diameter), but an extremely thin marker (for example, an ink container is 10 mm in diameter). If it is less than the marker, the above-mentioned countermeasure is insufficient, and the stirrer may be further reduced with respect to the re-stirring of the flat pigment, which is not preferable. In this case, it has been found that the problem of re-stirring the tabular pigment is improved by reducing the amount of the crystalline cellulose. In this case, the addition amount of the crystalline cellulose is desirably 0.5% by weight or more and less than 2% by weight.
本願発明に係る光輝性の水性インキ組成物にあっては、上記成分の他に、従来の水性インキ組成物に使用される種々の材料を使用することができる。例えば、筆跡の様々な色相を得るために、水溶性の染料や水分散した顔料を添加することができる。また定着性を得るために、各種水溶性の樹脂、樹脂エマルジョンなどを添加したり、ペン先のインキ乾燥防止や、低温凍結防止のためのエチレングリコール、グリセリン等のような水溶性有機溶剤、尿素化合物のような保湿剤を添加したり、更にはベンゾチアゾリン等の防腐剤を添加することができる。その他に筆記面への濡れ性を向上させる目的から界面活性剤等の湿潤浸透剤を添加することができる。いずれを使用するにしても、目的と合致したものや、内容成分と相互作用し物性に異常がでないもの、インキとしての不具合がでないものを選択し、必要量を添加することが望ましい。 In the glittering water-based ink composition according to the present invention, in addition to the above components, various materials used in conventional water-based ink compositions can be used. 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.
次に、光輝性の水性インク組成物の配合、並びに、その光輝性の水性インク組成物を収容するマーカーとの組み合わせの実施例及び比較例により本願発明を更に説明するが、本発明はこれら実施例により限定されるものではない。 Next, the present invention will be further explained by examples and comparative examples of the combination of the glittering water-based ink composition and the combination with the marker containing the glittering water-based ink composition. It is not limited by the examples.
〔インク配合参考例〕
ジョンクリル６１Ｊ（＊１） ２５．０重量％
メタシャインＭＥ２０４０ＰＳ（＊２） ８．０重量％
イリオジン１１１（＊３） ２．０重量％
セオラスＲＣ８１Ｎ液（＊４） ６０．０重量％
青色顔料分散液（＊５） ２．５重量％
イオン交換水 ２．５重量％
＊１、α−メチルスチレンアクリル酸共重合体水溶液（固形分３０重量％）
＊２、ガラスフレークを酸化チタンで被覆したもの（平均粒子径４０μｍ）
＊３、マイカ表面を酸化チタンで被覆したもの（平均粒子径１５μｍ以下）
＊４、セオラスＲＣ８１Ｎを４重量％水に分散した液
＊５、青色顔料１０重量％を水に分散した液
これらの各成分を逐次投入し、摂氏温度２５度において、ずり速度３．８３ｓｅｃ．−１の時の粘度が１３０ｍＰａ・ｓｅｃ．前後、かつ、ずり速度３８．３ｓｅｃ．−１の時の粘度が４０ｍＰａ・ｓｅｃ．前後の光輝性を持つ青色インク組成物を得た。
[Ink formulation reference example]
Jonkrill 61J (* 1) 25.0% by weight
Metashine ME2040PS (* 2) 8.0% by weight
Iriodin 111 (* 3) 2.0% by weight
Theolas RC81N solution (* 4) 60.0% by weight
Blue pigment dispersion (* 5) 2.5% by weight
Ion exchange water 2.5% by weight
* 1, α-methylstyrene acrylic acid copolymer aqueous solution (solid content 30% by weight)
* 2. Glass flakes coated with titanium oxide (average particle size 40 μm)
* 3, Mica surface coated with titanium oxide (average particle size of 15 μm or less)
* 4, liquid obtained by dispersing 4% by weight of Ceorus RC81N in water * 5, liquid obtained by dispersing 10% by weight of blue pigment in water, each of these components was sequentially added, and a shear rate of 3.83 sec. -1 viscosity is 130 mPa · sec. Before and after, and the shear rate is 38.3 sec. -1 viscosity is 40 mPa · sec. A blue ink composition having front and rear glitter was obtained.
〔インク配合実施例〕
ジョンクリル６１Ｊ（＊１） ２５．０重量％
メタシャインＭＥ２０４０ＰＳ（＊２） ８．０重量％
イリオジン１１１（＊３） ２．０重量％
セオラスＲＣ８１Ｎ液（＊４） ４７．０重量％
青色顔料分散液（＊５） ２．１重量％
黄色顔料分散液（＊６） ０．９重量％
イオン交換水 １５．０重量％
＊６、黄色顔料１０重量％を水に分散した液
これらの各成分を逐次投入し、摂氏温度２５度において、ずり速度３．８３ｓｅｃ．−１の時の粘度が１２０ｍＰａ・ｓｅｃ．前後、かつ、ずり速度３８．３ｓｅｃ．−１の時の粘度が３５ｍＰａ・ｓｅｃ．前後の光輝性を持つ緑色インク組成物を得た。
[ Examples of ink formulation ]
Jonkrill 61J (* 1) 25.0% by weight
Metashine ME2040PS (* 2) 8.0% by weight
Iriodin 111 (* 3) 2.0% by weight
Theolas RC81N solution (* 4) 47.0% by weight
Blue pigment dispersion (* 5) 2.1% by weight
Yellow pigment dispersion (* 6) 0.9% by weight
Ion-exchanged water 15.0% by weight
* 6 A liquid in which 10% by weight of a yellow pigment is dispersed in water. Each of these components was added in succession, and a shear rate of 3.83 sec. At a temperature of 25 degrees Celsius. -1 viscosity is 120 mPa · sec. Before and after, and the shear rate is 38.3 sec. -1 viscosity is 35 mPa · sec. A green ink composition having front and rear glitter was obtained.
〔インク比較例〕
ジョンクリル６１Ｊ（＊１） ６．７重量％
メタシャインＭＥ２０４０ＰＳ（＊２） ４．０重量％
イリオジン７２２５（＊７） １０．０重量％
セオラスＲＣ８１Ｎ液（＊４） ６０．０重量％
イオン交換水 １９．３重量％
＊７、赤系パール顔料（粒子径５〜４０μｍ）
これらの各成分を逐次投入し、摂氏温度２５度において、ずり速度３．８３ｓｅｃ．−１の時の粘度が１５０ｍＰａ・ｓｅｃ．前後、かつ、ずり速度３８．３ｓｅｃ．−１の時の粘度が４０ｍＰａ・ｓｅｃ．前後の光輝性を持つ赤色インク組成物を得た。
[Ink comparison example]
Jonkrill 61J (* 1) 6.7% by weight
Metashine ME2040PS (* 2) 4.0% by weight
Iriodin 7225 (* 7) 10.0% by weight
Theolas RC81N solution (* 4) 60.0% by weight
Ion-exchanged water 19.3% by weight
* 7 Red pearl pigment (particle size 5-40μm)
Each of these components was added sequentially, and at a temperature of 25 degrees Celsius, the shear rate was 3.83 sec. -1 viscosity is 150 mPa · sec. Before and after, and the shear rate is 38.3 sec. -1 viscosity is 40 mPa · sec. A red ink composition having front and rear glitter was obtained.
〔マーカー容器１〕
筆記尖端のペン芯流路のスリット幅０．１５ｍｍ以下、かつ、インク収容容器外径１５．３ｍｍ×長さ１２２．０ｍｍのバルブ式マーカー（三菱鉛筆株式会社製ＰＣ３ＭＬのペン体）。
[Marker container 1]
A valve-type marker (a pen body of PC3ML manufactured by Mitsubishi Pencil Co., Ltd.) having a slit width of 0.15 mm or less of the pen core channel at the writing tip and an outer diameter of the ink container of 15.3 mm × length of 122.0 mm.
〔マーカー容器２〕
筆記尖端のペン芯流路のスリット幅０．１３ｍｍ以下、かつ、インク収容容器外径１０．３ｍｍ×長さ１３２ｍｍのバルブ式マーカー（三菱鉛筆株式会社製ＰＣ１ＭＤのペン体）。
[Marker container 2]
A valve-type marker (a pen body of PC1MD manufactured by Mitsubishi Pencil Co., Ltd.) having a slit width of 0.13 mm or less of the pen core channel at the writing tip and an outer diameter of the ink container of 10.3 mm × 132 mm in length.
これらの実施例、比較例のインク組成物をマーカー容器１、２に充填し、所定の撹拌子（直径５ｍｍのステンレス製のボール）２個と共に封入し、以下の評価を行った。 The ink compositions of these Examples and Comparative Examples were filled in the marker containers 1 and 2 and sealed together with two predetermined stirring bars (stainless steel balls having a diameter of 5 mm), and the following evaluation was performed.
〔再分散性の評価〕
それぞれのマーカー容器のペン芯側を上に向けたままで、摂氏５０度の恒温槽内に静置し、１ヶ月後に取り出し、摂氏２５度の環境においてペン体前後方向に震蕩を行い、内部の撹拌子が動く音が聞こえた震蕩の回数を記録した。
[Evaluation of redispersibility]
With the pen core side of each marker container facing upward, leave it in a thermostatic bath at 50 degrees Celsius, remove it one month later, shake it in the longitudinal direction of the pen body in an environment of 25 degrees Celsius, and stir the inside Recorded the number of tremors that the child was able to hear.
〔流出性〕
前記再分散性の評価後に、同じ試料によって筆記した時の様子を観察した。
◎…初筆から難なく描画できた
○…初筆にはカスレが見られた
△…描線には所々カスレが見られる
×…筆記できない
[Leakage]
After evaluation of the redispersibility, the state of writing with the same sample was observed.
◎… I was able to draw without difficulty from the first brush ○… Scratch was seen in the first brush △… Scratch was seen in some strokes ×… Cannot write
〔描線の隠蔽性、光輝性〕
それぞれの試料によって筆記した描線の様子を観察した。
◎…描線は下地を完全に隠蔽し、光輝性も問題ない
△…描線の隠蔽が不十分、または、光輝性に劣る
×…描線の隠蔽が不十分、かつ、光輝性に劣る
[Hiding of drawn lines, brightness]
The state of the drawn line written by each sample was observed.
◎… The drawn line completely hides the groundwork, and there is no problem with the glossiness. Δ… The drawing line is insufficiently concealed or inferior in brightness.
以上のように、本願発明のインク組成物によって、内径１５ｍｍ未満あるいは内径１０ｍｍ未満のインク収容部を持ち、小さな撹拌子を備えた細身のマーカーに収容されることとなっても、描線の隠蔽性、及び、視認性が遜色なく、かつ、筆記を開始する前の撹拌によって素早く再分散を行えるマーカー用水性インク組成物が得られることがわかった。 As described above, even if the ink composition of the present invention has an ink container having an inner diameter of less than 15 mm or less than 10 mm and is accommodated in a thin marker having a small stirrer, the drawn line is concealed. It was also found that a marker-based water-based ink composition can be obtained that is inferior in visibility and can be quickly redispersed by stirring before starting writing.
高い隠蔽性を持ち、光輝性を備え、使用前すぐに顔料の再分散が容易に行え、かつ、写真プリントの表面に難なく筆記あるいは描画することが出来る顔料マーカーのインク組成物が得られる。特に携帯に便利な、細身のマーカーに収容される水性顔料マーカーのインク組成物が得られる It is possible to obtain an ink composition of a pigment marker that has high hiding properties, has glitter, can be easily redispersed immediately before use, and can be easily written or drawn on the surface of a photographic print. A water-based pigment marker ink composition that is housed in a slender marker that is particularly convenient to carry is obtained.
Claims (7)
前記インク収容容器内にインク撹拌子が封入され、
前記インク収容容器の開放された開口部前方に
インク流出口のスリット幅が１ｍｍを下回る筆記用尖端を持つ
筆記具に収容される水性インク組成物であって、
分散用樹脂と、
ガラスフレークに金属で被覆したパール顔料である第１の平板状の顔料と、
前記第１の平板状の顔料の平均粒子径に満たない平均粒子径を持ちマイカ表面に金属酸化物の被覆を施したパール顔料である第２の平板状の顔料が、
前記第１の平板状の顔料の添加量以下の添加量であって、
更に結晶性セルロースを０．５重量％以上、２重量％未満を含む水性インク組成物。 A bottomed cylindrical ink storage container having an inner diameter of less than 10 mm;
An ink stirrer is enclosed in the ink container,
A water-based ink composition housed in a writing instrument having a writing tip with a slit width of an ink outlet being less than 1 mm in front of the opened opening of the ink container,
A dispersion resin;
A first flat pigment which is a pearl pigment coated with metal on glass flakes ;
Second flat plate-like pigment is a pearl pigment which has been subjected to the metal oxide coating to said first plate-like mean average particle size lifting Chi mica surface less than the particle size of the pigment,
The addition amount is less than or equal to the addition amount of the first flat pigment,
An aqueous ink composition further comprising 0.5% by weight or more and less than 2% by weight of crystalline cellulose.
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| JP6324867B2 (en) * | 2014-09-30 | 2018-05-16 | ゼブラ株式会社 | Water-based ink composition for marking pen and direct liquid type marking pen |
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