JP4507528B2 - Compound pigment base and compound pigment - Google Patents
Compound pigment base and compound pigment Download PDFInfo
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Description
本発明は、複合化顔料原体および複合化顔料に関する。より詳しくは、保存安定性、分散性に優れたインクジェット記録用インクに用いられる複合化顔料の原体および複合化顔料に関する。 The present invention relates to a composite pigment base and a composite pigment. More specifically, the present invention relates to a composite pigment base and a composite pigment used in an ink jet recording ink having excellent storage stability and dispersibility.
インクジェット記録方法は、微細なノズルヘッドからインク液滴を吐出して、文字や図形を紙などの記録媒体の表面に記録する方法である。インクジェット記録方法としては電歪素子を用いて電気信号を機械信号に変換し、ノズルヘッド部分に貯えたインク液滴を断続的に吐出して記録媒体表面に文字や記号を記録する方法や、あるいはノズルヘッドの吐出部分に近い一部でインク液の一部を急速に加熱して泡を発生させ、その泡による体積膨張でインク液滴を断続的に吐出して、記録媒体表面に文字や記号を記録する方法などが実用化されている。 The ink jet recording method is a method of recording characters and figures on the surface of a recording medium such as paper by discharging ink droplets from a fine nozzle head. As an ink jet recording method, an electric signal is converted into a mechanical signal using an electrostrictive element, and ink droplets stored in the nozzle head portion are intermittently ejected to record characters and symbols on the surface of the recording medium, or A part of the ink liquid is rapidly heated at a part near the ejection part of the nozzle head to generate bubbles, and ink droplets are intermittently ejected by the volume expansion caused by the bubbles, and characters and symbols are printed on the surface of the recording medium. A method for recording the image has been put into practical use.
インクジェット記録用インクとして、最近では、顔料を水中に分散させた水系顔料インクが提供されている。これは、顔料を用いたインクの方が、水溶性染料を用いたインクに比べて、得られる印刷画像の耐水性や耐光性に優れるという特徴を有するからである。このような水系顔料インクにおいては、界面活性剤や高分子分散剤等の分散剤を用いて顔料を水性分散媒中に分散させることが一般的に行われている。しかしながら、このような場合、顔料表面に吸着しただけの分散剤は、脱離と吸着を繰り返す事で、分散状態を低下させる場合が認められる。 Recently, water-based pigment inks in which pigments are dispersed in water have been provided as inks for inkjet recording. This is because the ink using the pigment has the characteristics that the obtained printed image is superior in water resistance and light resistance as compared with the ink using the water-soluble dye. In such a water-based pigment ink, it is generally performed to disperse a pigment in an aqueous dispersion medium using a dispersant such as a surfactant or a polymer dispersant. However, in such a case, it is recognized that the dispersing agent only adsorbed on the pigment surface may lower the dispersion state by repeating desorption and adsorption.
インクジェット記録用インクに含まれる顔料の分散性を向上させる目的で、着色剤粒子がポリマーで被覆されたマイクロカプセル化顔料を使用する技術が知られている。例えば、特定の繰返し単位を含む高分子アゾ開始剤及びビニル系重合性分散剤の存在下で、前記高分子アゾ開始剤が活性化しない条件下で、非水溶性着色剤を分散させ、続いて、得られた分散液において、前記高分子アゾ開始剤を活性化させて前記ビニル系重合性分散剤を重合させることにより得られるマイクロカプセル化着色剤を含むマイクロカプセル化着色剤分散液及び水性インク組成物が開示されている（例えば、特許文献１参照。）。 For the purpose of improving the dispersibility of the pigment contained in the ink for ink jet recording, a technique using a microencapsulated pigment in which colorant particles are coated with a polymer is known. For example, in the presence of a polymeric azo initiator containing a specific repeating unit and a vinyl polymerizable dispersant, the water-insoluble colorant is dispersed under conditions where the polymeric azo initiator is not activated, In the obtained dispersion, a microencapsulated colorant dispersion and a water-based ink containing a microencapsulated colorant obtained by activating the polymer azo initiator to polymerize the vinyl polymerizable dispersant The composition is disclosed (for example, refer patent document 1).
また、上記インクジェット記録用インクにて、銀色等の金属色を持つ、アルミニウム等の金属からなる顔料（以下、金属顔料とも称す）が用いられることもある。
しかし、金属顔料は表面不均一による低光沢性であること、また、水分などとの接触を避け不活性ガス雰囲気下での保存が必要であるなど、使用の面で制約があった。さらに、水との反応性も高く、長期保存では水素発生やゲル化等による品質劣化が発生するなど保存性に問題があった。
In the inkjet recording ink, a pigment made of a metal such as aluminum having a metal color such as silver (hereinafter also referred to as a metal pigment) may be used.
However, metal pigments have limitations in terms of use, such as low gloss due to surface unevenness, and need to be stored in an inert gas atmosphere avoiding contact with moisture and the like. Furthermore, the reactivity with water is also high, and there has been a problem in storage stability such as deterioration of quality due to hydrogen generation or gelation during long-term storage.
アルミニウム等の活性の高い金属を用いた顔料（着色剤粒子）は、水系溶媒中で水分と反応しやすく、保存中に水素の発生やゲル化等の問題が生じ、水系溶媒を用いたインクに適用し難く、従来は、通常、非水溶剤系のインクとされていた。
また、従来の金属顔料及び金属顔料を含むインク、塗料等を保存する場合、水との反応性の問題、表面酸化の問題があり、長期保存が不可能であった。
加えて、従来の金属顔料は、通常、粒径が２０〜３０μｍと大きく、そのままでは、インクジェット用インクに使用できなかった。
更に、上記粒径の大きさに加え、その比重の大きさから、分散安定性が悪く、直ぐ沈降する。そのため上記特許文献１のマイクロカプセル化技術を用いても分散安定性を十分改善できなかった。
Pigments (colorant particles) using a highly active metal such as aluminum easily react with moisture in aqueous solvents, causing problems such as generation of hydrogen and gelation during storage. Conventionally, non-aqueous solvent-based inks have been used.
Further, when storing conventional metal pigments and inks, paints, and the like containing metal pigments, there are problems of reactivity with water and surface oxidation, and long-term storage is impossible.
In addition, conventional metal pigments usually have a large particle size of 20 to 30 μm, and as such cannot be used for inkjet inks.
Furthermore, in addition to the size of the above particle size, due to its specific gravity, the dispersion stability is poor and sediments immediately. Therefore, even when the microencapsulation technology of Patent Document 1 is used, the dispersion stability cannot be sufficiently improved.
一方、インクジェット用インクによって得られる画像に金属光沢光輝性装飾等を付与するため、金属蒸着層と樹脂層を有する積層体の破片を含有するインクジェットインクが開示されている（例えば、特許文献２参照。）。しかし、この特許文献２の技術は、水との反応性に対する問題を克服できるものではない。 On the other hand, an ink-jet ink containing a piece of a laminate having a metal vapor-deposited layer and a resin layer is disclosed in order to impart a metallic luster glitter decoration or the like to an image obtained by the ink-jet ink (see, for example, Patent Document 2). .) However, the technique of Patent Document 2 cannot overcome the problem of reactivity with water.
従って、本発明の目的は、上記問題点を解決することであり、保存安定性に優れ、水との反応性の問題もない、金属又は金属化合物を用いた複合化顔料原体を提供することである。
更に、インクジェット用水性インク組成物として、水系での分散安定性を維持することができ、印字品質及び保存安定性に優れるとともに、耐水性、耐光性、及び光沢性にも優れた記録物を得ることのできる複合化顔料を提供することにある。
Accordingly, an object of the present invention is to solve the above-mentioned problems, and to provide a composite pigment base material using a metal or a metal compound, which has excellent storage stability and does not have a problem of reactivity with water. It is.
Furthermore, as a water-based ink composition for inkjet, it is possible to maintain dispersion stability in an aqueous system, and to obtain a recorded matter having excellent printing quality and storage stability, and excellent water resistance, light resistance, and glossiness. It is to provide a composite pigment that can be used.
本発明者は、従来の金属顔料は微粉体状では反応性が高く、保存性、水との反応性に問題があるが、構成を酸化ケイ素層／金属顔料層／酸化ケイ素層の積層構造の複合化顔料とすることにより化学的に安定となり、水との反応性がなく、長期保存性が著しく向上し、更に、インクジェット用水性インク組成物としても品質が優れることを見いだし、本発明に到達したものである。 The present inventor has found that conventional metal pigments are highly reactive in the form of fine powder, and have problems with storage stability and reactivity with water, but the structure is a laminated structure of silicon oxide layer / metal pigment layer / silicon oxide layer. The composite pigment is chemically stable, has no reactivity with water, has a significantly improved long-term storage stability, and has been found to be excellent in quality as a water-based ink composition for inkjet. It is what.
即ち、本発明は、下記構成により達成される。
（１）シート状基材面に、樹脂層と顔料層とが順次積層された構造からなり、前記樹脂層が、ポリビニルアルコール、ポリエチレングリコール、ポリアクリル酸、ポリアクリルアミド又はセルロース誘導体からなる樹脂の水溶液を前記基材に塗布して乾燥させたものであり、前記顔料層が、酸化ケイ素層、金属又は金属化合物層、酸化ケイ素層が順次積層された構造を有する複合化顔料原体。
（２）前記顔料層の厚みが１００〜５００ｎｍである前記（１）記載の複合化顔料原体。
（３）前記酸化ケイ素層が、ゾル−ゲル法によってシリコンアルコキシド又はその重合体から形成された前記（１）記載の複合化顔料原体。
（４）前記金属又は金属化合物層が、真空蒸着、イオンプレーティング又はスパッタリング法により形成された前記（１）記載の複合化顔料原体。
（５）前記シート状基材が、ポリエチレンテレフタレート又はその共重合体である前記（１）記載の複合化顔料原体。
（６）前記樹脂層と顔料層との順次積層構造を複数有する前記（１）記載の複合化顔料原体。
（７）複数の顔料層の積層構造の全体の厚みが５０００ｎｍ以下である前記（６）記載の複合化顔料原体。
That is, the present invention is achieved by the following configuration.
(1) An aqueous solution of a resin having a structure in which a resin layer and a pigment layer are sequentially laminated on a sheet-like substrate surface, and the resin layer is made of polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, or a cellulose derivative. A composite pigment base material, wherein the pigment layer has a structure in which a silicon oxide layer, a metal or metal compound layer, and a silicon oxide layer are sequentially laminated.
(2) The composite pigment base material according to (1), wherein the pigment layer has a thickness of 100 to 500 nm.
( 3 ) The composite pigment base material according to (1), wherein the silicon oxide layer is formed from silicon alkoxide or a polymer thereof by a sol-gel method.
( 4 ) The composite pigment base material according to (1), wherein the metal or metal compound layer is formed by vacuum deposition, ion plating, or sputtering.
( 5 ) The composite pigment raw material according to (1), wherein the sheet-like substrate is polyethylene terephthalate or a copolymer thereof.
( 6 ) The composite pigment base material according to (1), wherein the composite pigment base material has a plurality of sequentially laminated structures of the resin layer and the pigment layer.
( 7 ) The composite pigment base material according to ( 6 ), wherein the total thickness of the multilayer structure of the plurality of pigment layers is 5000 nm or less.
（８）前記（１）記載の複合化顔料原体の前記顔料層を、前記樹脂層を境界として前記シート状基材より剥離し、粉砕した複合化顔料。
（９）前記剥離が、前記複合化顔料原体を液体中に浸漬することによりなされた前記（８）記載の複合化顔料。
（１０）前記粉砕が超音波処理によりなされた前記（８）記載の複合化顔料。
（１１）前記（１）記載の複合化顔料原体を液体中に浸漬しながら超音波処理したことにより得られた複合化顔料。
（１２）前記液体が水系である前記（９）又は（１１）記載の複合化顔料。
（１３） 前記（８）〜（１２）の何れか一項に記載の複合顔料を用いた塗布液。
( 8 ) A composite pigment obtained by peeling and pulverizing the pigment layer of the composite pigment base material according to (1) from the sheet-like base material with the resin layer as a boundary.
(9) The separation, composite pigment of which the said composite pigment base material was made by immersion in a liquid (8) described.
( 10 ) The composite pigment according to ( 8 ), wherein the pulverization is performed by ultrasonic treatment.
( 11 ) A composite pigment obtained by sonicating the composite pigment base described in (1) above in a liquid.
( 12 ) The composite pigment according to ( 9 ) or ( 11 ), wherein the liquid is aqueous.
(13) A coating solution using the composite pigment according to any one of (8) to (12).
本発明によれば、従来の技術では得ることができなかった保存安定性に優れ、水との反応性の問題もない、金属又は金属化合物を用いた複合化顔料原体を得ることができる。
つまり、本発明の複合化顔料原体は金属顔料層が酸化ケイ素層に囲まれた積層構造体であるため、酸素及び水に対する影響が低減される。
また本発明の複合化顔料原体は、例えば、液体中に浸漬しながら超音波処理することにより、平均粒径が３μｍ程度の複合化顔料を得ることができる。
According to the present invention, it is possible to obtain a composite pigment base material using a metal or a metal compound, which has excellent storage stability that could not be obtained by conventional techniques and does not have a problem of reactivity with water.
That is, since the composite pigment base material of the present invention is a laminated structure in which the metal pigment layer is surrounded by the silicon oxide layer, the influence on oxygen and water is reduced.
Moreover, the composite pigment base material of the present invention can be obtained, for example, by subjecting it to ultrasonic treatment while being immersed in a liquid to obtain a composite pigment having an average particle size of about 3 μm.
また、インクジェット用水性インク組成物として、上記酸化ケイ素は比重が小さいこと及び樹脂層のポリビニルアルコール等が保護コロイドとなり、水系での分散安定性を向上することができ、また、記録媒体（紙等）との接着性も良くなり、印字品質及び保存安定性に優れるとともに、速乾性を有し、しかも、耐水性、耐光性、及び光沢性にも優れた記録物を得ることのできる複合化顔料を提供することができる。
加えて、本発明の複合化顔料原体は、ロール状にて保存することで、空気中の酸素、水分との接触をより抑えることが可能となり、従来の金属顔料では困難であった１年を超える長期保存が可能となっている。
In addition, as a water-based ink composition for inkjet, the silicon oxide has a small specific gravity and polyvinyl alcohol or the like of the resin layer serves as a protective colloid, and can improve dispersion stability in an aqueous system. ), Improved print quality and storage stability, quick drying, and excellent water resistance, light resistance, and glossiness. Can be provided.
In addition, by storing the composite pigment base material of the present invention in a roll shape, it becomes possible to further suppress contact with oxygen and moisture in the air, which has been difficult for conventional metal pigments for one year. Long-term storage exceeding 1 is possible.
本発明の複合化顔料原体は、金属顔料層が酸化ケイ素層に囲まれた積層構造体であるため、酸素及び水に対する影響を低減でき、従来の技術では得ることができなかった保存安定性に優れ、水との反応性の問題もない、金属複合化顔料原体を提供することができる。
また、前記複合化顔料原体から剥離した本発明の複合化顔料は、インクジェット用水性インク組成物として、金属顔料層が酸化ケイ素層により、保護されているため、水との反応性を防止でき、比重が小さく、水系の溶剤中でも使用可能であり、また、樹脂層が保護コロイドの役割を有し、水系での分散安定性を向上することができ、更に、記録媒体（紙等）との接着性も良くなり、印字品質及び保存安定性に優れるとともに、速乾性を有し、しかも、耐水性、耐光性、及び光沢性にも優れた記録物を得ることのできる複合化顔料を提供するという効果を奏する。
Since the composite pigment base material of the present invention is a laminated structure in which the metal pigment layer is surrounded by the silicon oxide layer, the influence on oxygen and water can be reduced, and the storage stability that could not be obtained by the conventional technology It is possible to provide a metal composite pigment base material which is excellent in water resistance and has no problem of reactivity with water.
In addition, the composite pigment of the present invention peeled from the composite pigment base can prevent reactivity with water because the metal pigment layer is protected by a silicon oxide layer as an ink-jet aqueous ink composition. The specific gravity is small, it can be used even in aqueous solvents, and the resin layer has a role of protective colloid, can improve dispersion stability in aqueous systems, and can be used with a recording medium (such as paper). Provided is a composite pigment having improved adhesion, excellent print quality and storage stability, quick drying, and capable of obtaining a recorded product with excellent water resistance, light resistance and gloss. There is an effect.
以下、本発明の複合化顔料原体および複合化顔料について詳細に説明する。
本発明の複合化顔料原体は、シート状基材面の片面又は両面に、樹脂層と顔料層とが順次積層された構造からなり、前記顔料層が、酸化ケイ素層、金属又は金属化合物層、酸化ケイ素層が順次積層された構造であり、本発明の複合化顔料は前記複合化顔料原体の顔料層を、前記樹脂層を境界として前記シート状基材より剥離し、粉砕した顔料である。
即ち、本発明の複合化顔料は金属又は金属化合物顔料であるが、従来の金属顔料の欠点、特に保存性を改良し、また、インクジェット用水性インク組成物としても優れた適性、特に分散安定性を付与するために、金属顔料を酸化ケイ素層／金属又は金属化合物層／酸化ケイ素層が順次積層された積層板状構造としたことを特徴とする。
以下、本発明の複合化顔料原体および複合化顔料を構成する各層の構成成分、層の形成方法及び処理方法等について説明する。
Hereinafter, the composite pigment base material and the composite pigment of the present invention will be described in detail.
The composite pigment base material of the present invention has a structure in which a resin layer and a pigment layer are sequentially laminated on one side or both sides of a sheet-like substrate surface, and the pigment layer is a silicon oxide layer, a metal or metal compound layer. The composite pigment of the present invention is a pigment obtained by separating the pigment layer of the composite pigment base material from the sheet-like base material with the resin layer as a boundary and pulverizing it. is there.
That is, although the composite pigment of the present invention is a metal or metal compound pigment, it improves the drawbacks of conventional metal pigments, particularly storage stability, and is also excellent as an aqueous ink composition for inkjet, particularly dispersion stability. Therefore, the metal pigment has a laminated plate-like structure in which a silicon oxide layer / metal or a metal compound layer / silicon oxide layer is sequentially laminated.
Hereinafter, the component of each layer constituting the composite pigment base material and the composite pigment of the present invention, a method for forming the layer, a treatment method, and the like will be described.
〔顔料層〕
本発明の複合化顔料原体の積層板状構造中の顔料層について説明する。
本発明の顔料層は、酸化ケイ素層、金属又は金属化合物層、酸化ケイ素層が順次積層された構造である。
顔料層の厚さは、１００〜５００ｎｍの範囲が好ましい。１００ｎｍ未満では、機械的強度が不足であり、５００ｎｍを超えると強度が高くなりすぎるため粉砕・分散が困難になる。
(Pigment layer)
The pigment layer in the laminated plate-like structure of the composite pigment base material of the present invention will be described.
The pigment layer of the present invention has a structure in which a silicon oxide layer, a metal or metal compound layer, and a silicon oxide layer are sequentially laminated.
The thickness of the pigment layer is preferably in the range of 100 to 500 nm. If it is less than 100 nm, the mechanical strength is insufficient, and if it exceeds 500 nm, the strength becomes too high, so that pulverization / dispersion becomes difficult.
先ず、顔料層中の金属又は金属化合物層は、金属光沢を有する等の機能を有するものであれば特に限定されるものではないが、アルミニウム、銀、金、ニッケル、クロム、錫、亜鉛、インジウム、チタン等が使用され、これらの単体金属、金属化合物又はこれらの合金およびそれら混合物の少なくとも一種が使用される。
金属又は金属化合物層は、真空蒸着、イオンプレーティング又はスパッタリング法による形成が好ましい。これらの金属又は金属化合物層の厚さは、特に限定されないが、３０〜１５０ｎｍの範囲が好ましい。３０ｎｍ未満では反射性、光輝性に劣り、金属顔料としての性能が低くなり、１５０ｎｍを超えると見かけ比重が増加し、複合化顔料の分散安定性が低下する。金属又は金属化合物層の不必要な増大は、粒子の重量増加を招くだけであり、これより大きい膜厚であっても、反射性、光輝性はあまり変化しない。
First, the metal or metal compound layer in the pigment layer is not particularly limited as long as it has a function such as having a metallic luster, but aluminum, silver, gold, nickel, chromium, tin, zinc, indium Titanium or the like is used, and at least one of these simple metals, metal compounds, alloys thereof and mixtures thereof is used.
The metal or metal compound layer is preferably formed by vacuum deposition, ion plating or sputtering. The thickness of these metal or metal compound layers is not particularly limited, but is preferably in the range of 30 to 150 nm. If it is less than 30 nm, it is inferior in reflectivity and glitter, and the performance as a metal pigment is lowered. If it exceeds 150 nm, the apparent specific gravity increases, and the dispersion stability of the composite pigment decreases. Unnecessary increase of the metal or metal compound layer only increases the weight of the particles, and even if the film thickness is larger than this, the reflectivity and glitter are not changed so much.
顔料層中の酸化ケイ素層は、酸化ケイ素を含有する層であれば特に限定されるものではないが、ゾル−ゲル法によってシリコンアルコキシド又はその重合体から形成されることが好ましい。
上記シリコンアルコキシド又はその重合体を溶解したアルコール溶液を塗布し、加熱焼成することにより、酸化ケイ素層を形成する。
酸化ケイ素層の塗布は、一般的に用いられるグラビア塗布、ロール塗布、ブレード塗布、エクストルージョン塗布、ディップ塗布、スピンコート等により形成される。塗布・乾燥後、必要であれば、カレンダー処理により、表面の平滑化を行う。
The silicon oxide layer in the pigment layer is not particularly limited as long as it is a layer containing silicon oxide, but is preferably formed from silicon alkoxide or a polymer thereof by a sol-gel method.
The silicon oxide layer is formed by applying an alcohol solution in which the silicon alkoxide or a polymer thereof is dissolved and baking it.
The silicon oxide layer is applied by commonly used gravure coating, roll coating, blade coating, extrusion coating, dip coating, spin coating, or the like. After coating and drying, the surface is smoothed by calendaring if necessary.
酸化ケイ素層の厚さは、特に限定されないが、５０〜１５０ｎｍの範囲が好ましい。５０ｎｍ未満では機械的強度が不足であり、１５０ｎｍを超えると強度が高くなり過ぎるため粉砕・分散が困難となり、また金属又は金属化合物層との界面で剥離してしまう場合がある。 Although the thickness of a silicon oxide layer is not specifically limited, The range of 50-150 nm is preferable. If it is less than 50 nm, the mechanical strength is insufficient, and if it exceeds 150 nm, the strength becomes too high, so that pulverization / dispersion becomes difficult, and peeling may occur at the interface with the metal or metal compound layer.
〔樹脂層〕
本発明における樹脂層は、前記顔料層のアンダーコート層であるが、シート状基材面との剥離性を向上させるための剥離性層である。従って、樹脂としては、親水性樹脂であれば特に限定されるものではないが、例えばポリビニルアルコール、ポリエチレングリコール、ポリアクリル酸、ポリアクリルアミドまたはセルロース誘導体が好ましい。
上記親水性樹脂一種または二種以上の混合物の水溶液を塗布し、乾燥等を施した層が形成される。塗布液には粘度調節剤等の添加剤を含有させることができる。
樹脂層の塗布は、上記酸化ケイ素層の塗布と同様に形成される。
[Resin layer]
The resin layer in the present invention is an undercoat layer of the pigment layer, but is a peelable layer for improving the peelability from the sheet-like substrate surface. Accordingly, the resin is not particularly limited as long as it is a hydrophilic resin. For example, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, or a cellulose derivative is preferable.
A layer is formed by applying an aqueous solution of one or more of the above hydrophilic resins and drying. The coating solution can contain additives such as a viscosity modifier.
The resin layer is applied in the same manner as the silicon oxide layer.
樹脂層の厚さは、特に限定されないが、０．５〜５０μｍが好ましく、より好ましくは１〜１０μｍである。０．５μｍ未満では分散樹脂としての量が不足し、５０μｍを超えるとロール化した場合、酸化ケイ素層との界面で剥離し易いものとなってしまう。 Although the thickness of a resin layer is not specifically limited, 0.5-50 micrometers is preferable, More preferably, it is 1-10 micrometers. If it is less than 0.5 μm, the amount as a dispersion resin is insufficient, and if it exceeds 50 μm, when it is rolled, it tends to peel off at the interface with the silicon oxide layer.
本発明の複合化顔料原体としては、前記樹脂層と顔料層との順次積層構造を複数有する層構成も可能である。その際、複数の顔料層の積層構造の全体の厚み、即ち、シート状基材とその直上の樹脂層を除いた、顔料層−樹脂層−顔料層・・・樹脂層−顔料層の厚みは５０００ｎｍ以下であることが好ましい。５０００ｎｍ以下であると、複合化顔料原体をロール状に丸めた場合でも、ひび割れ、剥離を生じ難く、保存性に優れる。また、顔料化した場合も、光輝性に優れており好ましいものである。
また、シート状基材面の両面に、樹脂層と顔料層とが順次積層された構造も挙げられるが、これらに限定されるものではない。
The composite pigment base material of the present invention may have a layer structure having a plurality of sequential laminated structures of the resin layer and the pigment layer. At that time, the total thickness of the laminated structure of a plurality of pigment layers, that is, the thickness of the pigment layer-resin layer-pigment layer ... resin layer-pigment layer, excluding the sheet-like substrate and the resin layer immediately above it, It is preferable that it is 5000 nm or less. When it is 5000 nm or less, even when the composite pigment base material is rolled up, it is difficult to cause cracking and peeling and is excellent in storage stability. In addition, when pigmented, it is excellent in glitter and preferable.
Moreover, although the structure where the resin layer and the pigment layer were laminated | stacked in order on both surfaces of the sheet-like base material surface is mentioned, it is not limited to these.
〔シート状基材〕
本発明の複合化顔料原体に使用されるシート状基材としては、特に限定されないが、ポリテトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート，ポリエチレンナフタレート等のポリエステルフイルム、66ナイロン、６ナイロン等のポリアミドフイルム、ポリカーボネートフイルム、トリアセテートフイルム、ポリイミドフイルム等の離型性フイルムが挙げられる。
好ましいシート状基材としては、ポリエチレンテレフタレートまたはその共重合体である。
これらのシート状基材の厚さは、特に限定されないが、１０〜１５０μｍが好ましい。１０μｍ以上であれば、工程等で取り扱い性に問題がなく、１５０μｍ以下であれば、柔軟性に富み、ロール化、剥離等に問題がない。
[Sheet substrate]
Although it does not specifically limit as a sheet-like base material used for the composite pigment raw material of this invention, Polyester film, such as polytetrafluoroethylene, polyethylene, a polypropylene, a polyethylene terephthalate, a polyethylene naphthalate, 66 nylon, 6 nylon, etc. And releasable films such as polyamide film, polycarbonate film, triacetate film and polyimide film.
A preferable sheet-like substrate is polyethylene terephthalate or a copolymer thereof.
Although the thickness of these sheet-like base materials is not specifically limited, 10-150 micrometers is preferable. If it is 10 μm or more, there is no problem in handleability in the process or the like, and if it is 150 μm or less, it is rich in flexibility and there is no problem in roll formation, peeling and the like.
〔複合化顔料の剥離処理〕
本発明の複合化顔料は、前記複合化顔料原体の顔料層を、樹脂層を境界として前記シート状基材より剥離し、粉砕し微細化して得ることができる。
複合化顔料の剥離処理法としては、特に限定されないが、前記複合化顔料原体を液体中に浸漬することによりなされる方法、また液体中に浸漬すると同時に超音波処理を行い、剥離処理と剥離した複合化顔料の粉砕処理を行う方法が好ましい。さらに前記液体は水系が好ましい。
本発明の複合化顔料は、金属顔料層が酸化ケイ素層により、保護されているため、水系の溶剤中でも使用可能であり、また、樹脂層が保護コロイドの役割を有し、水中での分散処理を行うだけで安定な水系分散液を得ることが可能である。また該樹脂層により、本発明の複合化顔料をインク組成物に用いた際に、該樹脂層は紙等の記録媒体に対する接着性を付与する機能も担う。
[Removal treatment of composite pigment]
The composite pigment of the present invention can be obtained by peeling the pigment layer of the composite pigment base material from the sheet-like base material with the resin layer as a boundary, pulverizing and refining.
The release treatment method of the composite pigment is not particularly limited, but is a method in which the composite pigment raw material is immersed in a liquid, or ultrasonic treatment is performed at the same time as the immersion in the liquid. A method of pulverizing the composite pigment thus obtained is preferred. Further, the liquid is preferably an aqueous system.
The composite pigment of the present invention can be used in an aqueous solvent because the metal pigment layer is protected by the silicon oxide layer, and the resin layer has a role of a protective colloid, and is dispersed in water. It is possible to obtain a stable aqueous dispersion only by performing the step. In addition, when the composite pigment of the present invention is used in an ink composition, the resin layer also has a function of imparting adhesiveness to a recording medium such as paper.
以下に本発明を実施例によって更に具体的に説明するが、勿論本発明の範囲は、これらによって限定されるものではない。 The present invention will be described more specifically with reference to the following examples. However, the scope of the present invention is not limited to these examples.
〔実施例１〕
＜基材シートの調製＞
膜厚１００μｍのＰＥＴフィルム上に、下記組成の塗工液をスピンコート法によって塗布・乾燥し、樹脂層を形成した。
[Example 1]
<Preparation of base sheet>
On a PET film having a thickness of 100 μm, a coating liquid having the following composition was applied and dried by a spin coating method to form a resin layer.
（樹脂層塗工液）
ＰＶＡ（ポリビニルアルコール、平均分子量１０，０００、けん化度８０％）
３．３ｗｔ％
グリセリン １．７ｗｔ％
イオン交換水 残量
(Resin layer coating solution)
PVA (polyvinyl alcohol, average molecular weight 10,000, saponification degree 80%)
3.3 wt%
Glycerol 1.7wt%
Ion exchange water
（樹脂層塗工条件）
コート条件：５００ｒｐｍで５秒間回転させた後、２０００ｒｐｍで３０秒間回転させる
乾燥条件 ：１００℃、５分間
この条件にて形成した樹脂層の厚さは１０μｍであった。
(Resin layer coating conditions)
Coating condition: Rotated at 500 rpm for 5 seconds, then rotated at 2000 rpm for 30 seconds Drying condition: 100 ° C., 5 minutes The thickness of the resin layer formed under these conditions was 10 μm.
＜酸化ケイ素層の形成＞
上記方法にて処理したＰＥＴフィルム上に、下記組成の塗工液をスピンコート法によって塗布・焼成し、酸化ケイ素層を形成した。
<Formation of silicon oxide layer>
On the PET film treated by the above method, a coating liquid having the following composition was applied and baked by a spin coating method to form a silicon oxide layer.
（酸化ケイ素層塗工液）
ＨＡＳ−６（コルコート株式会社製） １０ ｗｔ％
エタノール ４２．５ｗｔ％
２−エトキシエタノール ４７．５ｗｔ％
(Silicon oxide layer coating solution)
HAS-6 (manufactured by Colcoat Co., Ltd.) 10 wt%
Ethanol 42.5wt%
2-Ethoxyethanol 47.5wt%
（酸化ケイ素層塗工条件）
コート条件：５００ｒｐｍで５秒間回転させた後、２０００ｒｐｍで３０秒間回転させる
焼成条件 ：１４０℃、５分間
この条件にて形成した酸化ケイ素層の厚さは７０ｎｍであった。
(Silicon oxide layer coating conditions)
Coating condition: Rotated at 500 rpm for 5 seconds, then rotated at 2000 rpm for 30 seconds Firing condition: 140 ° C., 5 minutes The thickness of the silicon oxide layer formed under these conditions was 70 nm.
＜アルミニウム層の形成＞
下記の装置を用いて、上記の酸化ケイ素層上に、膜厚７０ｎｍのアルミニウム蒸着層を形成した。
装置：（株）真空デバイス、ＶＥ−１０１０形真空蒸着装置
<Formation of aluminum layer>
An aluminum vapor deposition layer having a film thickness of 70 nm was formed on the silicon oxide layer using the following apparatus.
Apparatus: Vacuum device, VE-1010 type vacuum evaporation system
＜酸化ケイ素層の形成＞
前記方法と同様に、上記のアルミニウム層上に、酸化ケイ素層を形成した。形成した酸化ケイ素層の厚さは７０ｎｍであった。
<Formation of silicon oxide layer>
Similar to the above method, a silicon oxide layer was formed on the aluminum layer. The thickness of the formed silicon oxide layer was 70 nm.
＜保存安定性＞
上記方法にて形成した酸化ケイ素−アルミニウム−酸化ケイ素の積層体を有するＰＥＴフィルム（顔料原体）の保存性を調査する為に、上記顔料原体を４インチ径の紙管に巻き取り、大気中、常温・常圧の環境にて１年間静置した。その結果、１年間経過後でも、顔料原体には酸化・腐食による表面光沢の低下等は認められないものであった。また、静置後の顔料原体を以下に示す顔料化工程により塗布液とした場合にも、ＰＭ／ＭＣ写真用紙上に滴下して得られた塗膜の金属光沢は、１年間の保存を行っていない顔料原体と同一の金属光沢を示した。
<Storage stability>
In order to investigate the preservability of a PET film (pigment base) having a silicon oxide-aluminum-silicon oxide laminate formed by the above method, the pigment base is wound around a 4-inch diameter paper tube, and the atmosphere The sample was allowed to stand for 1 year at room temperature and pressure. As a result, even after one year, the pigment base material did not show a decrease in surface gloss due to oxidation or corrosion. In addition, even when the pigment raw material after standing is used as a coating solution by the pigmentation process shown below, the metallic luster of the coating film obtained by dripping on the PM / MC photographic paper can be stored for one year. It showed the same metallic luster as the untreated pigment base.
＜剥離処理及び顔料化工程＞
上記方法にて形成した、樹脂層−酸化ケイ素−アルミニウム−酸化ケイ素の積層体を有するＰＥＴフィルムをイオン交換水中、超音波分散機を用いて剥離・微細化・分散処理を同時に行い複合化アルミニウム顔料分散液を作製した。
<Peeling treatment and pigmentation process>
A composite aluminum pigment formed by the above-described method, and simultaneously removing, refining and dispersing a PET film having a resin layer-silicon oxide-aluminum-silicon oxide laminate in ion-exchanged water using an ultrasonic disperser. A dispersion was prepared.
上記分散液を遠心分離機を用いて、下記の条件下で遠心分離を行い、顔料を沈降させて分離した。その後、常温にて自然乾燥し、複合化アルミニウム顔料を得た。 The dispersion was centrifuged using a centrifuge under the following conditions to precipitate the pigment and separate it. Thereafter, it was naturally dried at room temperature to obtain a composite aluminum pigment.
遠心条件：１００００ｒｐｍ×３０ｍｉｎ Centrifugal conditions: 10000 rpm x 30 min
なお、上記で得られた複合化アルミニウム顔料を下記組成の通り、２０ｗｔ％の塗布液とし、ＰＭ／ＭＣ写真用紙（セイコーエプソン製、型番ＫＡ４２０ＭＳＨ）上に滴下したところ、銀色光沢を有する塗膜が得られる事を確認した。 The composite aluminum pigment obtained above was applied as a 20 wt% coating solution as described below, and dropped onto PM / MC photographic paper (manufactured by Seiko Epson, model number KA420MSH). It was confirmed that it was obtained.
＜複合化アルミニウム顔料塗布液＞
複合化アルミニウム顔料 ２０．０ｗｔ％
ＰＶＡ（ポリビニルアルコール、平均分子量１０，０００、けん化度８０％）
５．０ｗｔ％
エタノール １０．０ｗｔ％
グリセリン １０．０ｗｔ％
イオン交換水 残量
<Composite aluminum pigment coating solution>
Composite aluminum pigment 20.0wt%
PVA (polyvinyl alcohol, average molecular weight 10,000, saponification degree 80%)
5.0wt%
Ethanol 10.0wt%
Glycerin 10.0wt%
Ion exchange water
上記塗布液を常温、常圧化で６ヶ月保存した後でも、水素の発生や塗布液のゲル化といった現象は認められず、沈降した顔料は数分間攪拌する事で再分散可能であった。そして前回同様ＰＭ／ＭＣ写真用紙（セイコーエプソン製、型番ＫＡ４２０ＭＳＨ）上に滴下したところ、銀色光沢を有する塗膜が得られる事を確認した。 Even after the coating solution was stored at room temperature and normal pressure for 6 months, no hydrogen generation or gelation of the coating solution was observed, and the precipitated pigment could be redispersed by stirring for several minutes. And when it was dripped on PM / MC photographic paper (the Seiko Epson make, model number KA420MSH) like last time, it was confirmed that the coating film which has silver gloss is obtained.
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| JP2002528639A (en) * | 1998-10-23 | 2002-09-03 | アベリー・デニソン・コーポレイション | Metal flake production method |
| JP2001026801A (en) * | 1999-07-16 | 2001-01-30 | Oike Ind Co Ltd | Metal foil powder, and its production |
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