JP6889568B2 - Ink composition and image forming method using it - Google Patents
Ink composition and image forming method using it Download PDFInfo
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- JP6889568B2 JP6889568B2 JP2017026917A JP2017026917A JP6889568B2 JP 6889568 B2 JP6889568 B2 JP 6889568B2 JP 2017026917 A JP2017026917 A JP 2017026917A JP 2017026917 A JP2017026917 A JP 2017026917A JP 6889568 B2 JP6889568 B2 JP 6889568B2
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- water
- mass
- acid
- ink composition
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- 238000000034 method Methods 0.000 title claims description 37
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- 239000002270 dispersing agent Substances 0.000 claims description 82
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- 150000003839 salts Chemical class 0.000 claims description 31
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Description
本発明は、インクジェット印刷に適した金属光沢性インキ組成物及びそれを用いた画像形成方法に関する。 The present invention relates to a metallic luster ink composition suitable for inkjet printing and an image forming method using the same.
近年、インクジェット印刷方式は、簡便性などの点から、業務用から家庭用まで幅広く普及している。インクジェット印刷では、シアン、マゼンタ、イエローの三原色を利用して鮮明なカラー画像の印刷が可能であるが、装飾的な効果を発現する目的などにより、金属光沢を有する印刷も要求されている。従来から、金属光沢顔料としては、アルミニウム、金又は銀粒子などの金属粒子を含有するインキが開発されているが、金属粒子は、比重が大きいため、インキ中での分散安定性に劣り、凝集や沈降を生じ易い。特に、インクジェット印刷方式では、ノズルヘッドからインキの微小滴を吹き付けて画像を形成する方式であるため、ノズルの目詰まりや、分散安定性の低下が画像品質に影響する。そのため、インキ組成物の安定性は特に重要となる。 In recent years, the inkjet printing method has become widespread from commercial use to home use in terms of convenience and the like. In inkjet printing, it is possible to print a clear color image using the three primary colors of cyan, magenta, and yellow, but printing having a metallic luster is also required for the purpose of exhibiting a decorative effect. Conventionally, inks containing metal particles such as aluminum, gold, or silver particles have been developed as metallic luster pigments. However, since metal particles have a large specific gravity, they are inferior in dispersion stability in ink and aggregate. And sedimentation are likely to occur. In particular, in the inkjet printing method, since a fine droplet of ink is sprayed from the nozzle head to form an image, clogging of the nozzle and deterioration of dispersion stability affect the image quality. Therefore, the stability of the ink composition is particularly important.
特開2003−306625号公報(特許文献1)には、インクジェット印刷方式に適したインキ組成物として、水又は水溶性有機溶媒中に金や銀などの金属ナノ粒子を含む金属コロイドを分散させたインキ組成物が開示されている。この文献には、セルロース樹脂、水溶性アクリル樹脂などの結着樹脂を0.1〜3重量%の割合で添加してもよいことが記載されている。しかし、このインキ組成物では、金属コロイド粒子の分散安定性が低く、凝集粒子が沈殿し易い。 According to Japanese Patent Application Laid-Open No. 2003-306625 (Patent Document 1), a metal colloid containing metal nanoparticles such as gold and silver is dispersed in water or a water-soluble organic solvent as an ink composition suitable for an inkjet printing method. The ink composition is disclosed. This document describes that a binder resin such as a cellulose resin or a water-soluble acrylic resin may be added at a ratio of 0.1 to 3% by weight. However, in this ink composition, the dispersion stability of the metal colloidal particles is low, and the agglomerated particles are likely to precipitate.
特開2009−227736号公報(特許文献2)には、金属ナノ粒子(A1)と分散剤(A2)とで形成された金属コロイド粒子(A);及び溶媒(B)を含み、前記分散剤(A2)がカルボキシル基を有する有機化合物(a)及び高分子分散剤(b)を含むインクジェット印刷用インキ組成物が記載されている。この文献には、バインダー樹脂(ポリビニルアルコール、ポリエチレングリコールなどの親水性高分子など)などの添加剤を添加してもよいことも記載されている。この文献のインキ組成物は、分散安定性に優れており、インクジェット方式で画像を形成するのに適している。しかし、被記録媒体の種類によっては、画像の耐擦過性(擦りに対する堅牢性)が十分でない場合がある。 Japanese Unexamined Patent Publication No. 2009-227736 (Patent Document 2) contains metal colloidal particles (A) formed of metal nanoparticles (A1) and a dispersant (A2); and a solvent (B). An ink composition for inkjet printing containing an organic compound (a) in which (A2) has a carboxyl group and a polymer dispersant (b) is described. This document also describes that additives such as binder resins (polyvinyl alcohol, hydrophilic polymers such as polyethylene glycol, etc.) may be added. The ink composition of this document has excellent dispersion stability and is suitable for forming an image by an inkjet method. However, depending on the type of recording medium, the scratch resistance (fastness to rubbing) of the image may not be sufficient.
特開2012−41378号公報(特許文献3)には、銀粒子と、0.02〜1.5質量%のワックス粒子と、水とを含み、前記ワックス粒子が、前記銀粒子の平均粒径D1[nm]に対して所定の平均粒径D2[nm]を有するインク組成物が記載され、特開2012−57050号公報(特許文献4)には、銀粒子と、水と、アルコール(炭素数1〜10のモノオール又はジオール)とを含むインク組成物が記載され、特開2012−82284号公報(特許文献5)には、銀粒子と、0.05〜3質量%のシリコーン系オイルと、水とを含むインク組成物が記載されている。これらのインク組成物は、金属光沢を有し、耐擦性に優れた画像を形成できる。しかし、これらのインク組成物は、画像を形成する被膜自体の強度が低いためか、耐摩耗性又は耐擦過性が未だ十分ではない。 Japanese Unexamined Patent Publication No. 2012-41378 (Patent Document 3) contains silver particles, 0.02 to 1.5% by mass of wax particles, and water, and the wax particles are the average particle size of the silver particles. An ink composition having a predetermined average particle size D2 [nm] with respect to D1 [nm] is described, and Japanese Patent Application Laid-Open No. 2012-57050 (Patent Document 4) describes silver particles, water, alcohol (carbon). An ink composition containing (numbers 1 to 10 of monool or diol) is described, and Japanese Patent Application Laid-Open No. 2012-82284 (Patent Document 5) describes silver particles and 0.05 to 3% by mass of silicone-based oil. And an ink composition containing water are described. These ink compositions have a metallic luster and can form an image having excellent abrasion resistance. However, these ink compositions are still not sufficiently wear-resistant or scratch-resistant, probably because the strength of the film itself forming the image is low.
特開2012−101491号公報(特許文献6)には、被記録媒体の被記録面に対して、銀粒子と定着樹脂とを含む第1のインク組成物を吐出して下地層を形成し、この下地層に対して、銀粒子を含み、定着樹脂を含まない第2のインク組成物を吐出して上層を形成するインクジェット記録方法において、前記第1のインク組成物の総質量に対して、定着樹脂を1〜10質量%(好ましくは2〜7質量%)の濃度で含有させることが記載されている。この文献には、銀粒子の平均粒子径が1〜100nmであることが記載され、銀粒子の高分子分散剤として、ゼラチン、メチルセルロース、カルボキシメチルセルロースなどの天然高分子;ポリビニルアルコール、ポリビニルピロリドン、アクリル系樹脂などの合成高分子が記載されている。また、結着樹脂として、種々の樹脂及びゴムが例示され、水系ウレタン樹脂エマルションが好ましいと記載されている。しかし、金属光沢及び耐擦性を高めるためには、下地層と上層とを形成する必要がある。しかも、下地層で耐擦性を高めているため、上層自体の耐擦性を高めることが困難である。 In Japanese Patent Application Laid-Open No. 2012-101491 (Patent Document 6), a first ink composition containing silver particles and a fixing resin is ejected onto a recording surface of a recording medium to form a base layer. In an inkjet recording method in which a second ink composition containing silver particles and not containing a fixing resin is ejected onto the base layer to form an upper layer, the total mass of the first ink composition is increased. It is described that the fixing resin is contained in a concentration of 1 to 10% by mass (preferably 2 to 7% by mass). This document describes that the average particle size of silver particles is 1 to 100 nm, and as a polymer dispersant for silver particles, natural polymers such as gelatin, methyl cellulose, and carboxymethyl cellulose; polyvinyl alcohol, polyvinylpyrrolidone, and acrylic. Synthetic polymers such as based resins are described. Further, various resins and rubbers are exemplified as the binder resin, and it is described that an aqueous urethane resin emulsion is preferable. However, in order to enhance metallic luster and abrasion resistance, it is necessary to form a base layer and an upper layer. Moreover, since the base layer enhances the abrasion resistance, it is difficult to enhance the abrasion resistance of the upper layer itself.
さらに、これらのインキ組成物では、例えば、表面が平滑な光沢紙に形成した画像部を、布で激しく擦ると画像部が剥がれる場合がある。さらに、光沢紙の種類(インク受容層の成分)によっては、軽く擦っても画像部が剥がれる場合がある。そのため、光沢紙の種類に拘わらず、耐擦過性の高い印字部又は画像部を形成可能なインキ組成物が要求されている。 Further, in these ink compositions, for example, when an image portion formed on glossy paper having a smooth surface is violently rubbed with a cloth, the image portion may be peeled off. Further, depending on the type of glossy paper (component of the ink receiving layer), the image portion may be peeled off even if it is lightly rubbed. Therefore, there is a demand for an ink composition capable of forming a printed portion or an image portion having high scratch resistance regardless of the type of glossy paper.
従って、本発明の目的は、インクジェット方式などの印刷方式を利用して、被印刷体に、金属光沢及び耐擦過性に優れた印字部(文字など)や画像を形成するのに有用なインキ組成物(又はインク組成物)及びそれを用いた画像形成方法を提供することにある。 Therefore, an object of the present invention is an ink composition useful for forming a printed portion (characters, etc.) and an image having excellent metallic luster and scratch resistance on a printed object by using a printing method such as an inkjet method. It is an object of the present invention (or an ink composition) and an image forming method using the same.
本発明の他の目的は、長期間に亘り安定して印字又は印刷可能なインキ組成物及びそれを用いた画像形成方法を提供することにある。 Another object of the present invention is to provide an ink composition that can be stably printed or printed over a long period of time and an image forming method using the same.
本発明のさらに他の目的は、インキ受容層を有する光沢紙の種類が異なっていても、高い耐擦過性の印字部又は画像部を強固に密着できるインキ組成物及びそれを用いた画像形成方法を提供することにある。 Still another object of the present invention is an ink composition capable of firmly adhering a printed portion or an image portion having high scratch resistance even if the type of glossy paper having an ink receiving layer is different, and an image forming method using the same. Is to provide.
本発明者らは、前記課題を達成するため鋭意検討した結果、銀ナノ粒子と、カルボキシル基又はその塩を有する分散剤と、水性溶媒とを含むインキ組成物において、被膜形成能を有する水溶性又は水分散性高分子を少量添加すると、インクジェット方式により、光沢紙に対しても、密着性が高く、高い銀鏡面光沢及び耐擦過性の印字部又は画像部を形成できることを見いだし、本発明を完成した。 As a result of diligent studies to achieve the above problems, the present inventors have made a water-soluble film-forming ability in an ink composition containing silver nanoparticles, a dispersant having a carboxyl group or a salt thereof, and an aqueous solvent. Alternatively, it has been found that when a small amount of a water-dispersible polymer is added, a printed portion or an image portion having high adhesion, high silver mirror surface gloss and scratch resistance can be formed even on glossy paper by an inkjet method. completed.
すなわち、本発明は、銀ナノ粒子(a)と、カルボキシル基又はその塩を有する分散剤(b)と、水性溶媒(c)とを含み、インクジェット方式で被印刷体に印字又は印刷するためのインキ組成物又はインク組成物(例えば、インクジェット印刷用インキ組成物)に関し、固形分換算(又は不揮発分換算)で、銀ナノ粒子(a)100質量部に対して、被膜形成能を有する水溶性又は水分散性高分子(d)を1〜30質量部の割合で含んでいる。 That is, the present invention contains silver nanoparticles (a), a dispersant (b) having a carboxyl group or a salt thereof, and an aqueous solvent (c), and is used for printing or printing on an object to be printed by an inkjet method. With respect to an ink composition or an ink composition (for example, an ink composition for inkjet printing), water-soluble having a film-forming ability with respect to 100 parts by mass of silver nanoparticles (a) in terms of solid content (or non-volatile content). Alternatively, the water-dispersible polymer (d) is contained in a proportion of 1 to 30 parts by mass.
また、分散剤(b)は、固形分換算(又は不揮発分換算)で、銀ナノ粒子(a)100質量部に対して、1〜20質量部の割合で含有させてもよい。水溶性又は水分散性高分子(d)は、固形分換算(又は不揮発分換算)で、銀ナノ粒子(a)100質量部に対して、2〜25質量部(例えば、2.5〜10質量部)の割合で含有させてもよい。 Further, the dispersant (b) may be contained in a ratio of 1 to 20 parts by mass with respect to 100 parts by mass of the silver nanoparticles (a) in terms of solid content (or non-volatile content). The water-soluble or water-dispersible polymer (d) has 2 to 25 parts by mass (for example, 2.5 to 10 parts by mass) with respect to 100 parts by mass of the silver nanoparticles (a) in terms of solid content (or non-volatile content). It may be contained in a ratio of (part by mass).
前記分散剤(b)は、カルボキシル基又はその塩を有する有機化合物(b1)及び/又はカルボキシル基又はその塩を有する高分子分散剤(b2)を含んでいてもよく、カルボキシル基又はその塩を有する有機化合物(例えば、C14−34縮合多環式脂肪族ヒドロキシカルボン酸又はその塩)(b1)と、カルボキシル基又はその塩を有する高分子分散剤(例えば、酸価5mgKOH/g以上の高分子分散剤又はその塩)(b2)とを前者/後者(質量比)=85/15〜10/90(例えば、70/30〜20/80)の割合で含んでいてもよい。 The dispersant (b) may contain an organic compound (b1) having a carboxyl group or a salt thereof and / or a polymer dispersant having a carboxyl group or a salt thereof (b2). An organic compound having (for example, C 14-34 condensed polycyclic aliphatic hydroxycarboxylic acid or a salt thereof) (b1) and a polymer dispersant having a carboxyl group or a salt thereof (for example, an acid value of 5 mgKOH / g or more) The molecular dispersant or a salt thereof) (b2) may be contained in a ratio of the former / the latter (mass ratio) = 85/15 to 10/90 (for example, 70/30 to 20/80).
前記分散剤(b)と、水溶性又は水分散性高分子(d)との割合は、固形分換算(又は不揮発分換算)で、前者/後者(質量比)=30/70〜90/10程度であってもよい。 The ratio of the dispersant (b) to the water-soluble or water-dispersible polymer (d) is in terms of solid content (or non-volatile content), and the former / latter (mass ratio) = 30/70 to 90/10. It may be about.
水溶性又は水分散性高分子(d)の濃度は、組成物全体に対して、0.05〜0.75質量%(例えば、0.05〜0.7質量%)程度であってもよい。また、水性溶媒(c)は、水と、水溶性アルコール、水溶性多価アルコール及びピロリドン類から選択された少なくとも一種の有機溶媒とを含んでいてもよい。 The concentration of the water-soluble or water-dispersible polymer (d) may be about 0.05 to 0.75% by mass (for example, 0.05 to 0.7% by mass) with respect to the entire composition. .. Further, the aqueous solvent (c) may contain water and at least one organic solvent selected from water-soluble alcohols, water-soluble polyhydric alcohols and pyrrolidones.
前記被印刷体は、インキ受容層を有する光沢紙であってもよい。このような光沢紙であっても、印字部又は画像を高い密着性で形成できる。 The printed matter may be glossy paper having an ink receiving layer. Even with such glossy paper, a printed portion or an image can be formed with high adhesion.
本発明は、インキ組成物(又はインク組成物)をインクジェット方式で印字又は印刷し、印字部又は画像を形成する方法も包含する。この方法では、被印刷体(例えば、インキ受容層を有する光沢紙)に、前記インキ組成物をインクジェット方式で印字又は印刷し、画像を形成できる。 The present invention also includes a method of printing or printing an ink composition (or an ink composition) by an inkjet method to form a printed portion or an image. In this method, the ink composition can be printed or printed on an object to be printed (for example, glossy paper having an ink receiving layer) by an inkjet method to form an image.
本発明では、銀ナノ粒子を分散するための分散剤と水溶性又は水分散性高分子とを含むため、水溶性又は水分散性高分子の使用量が少なくても、インクジェット方式などの印刷方式によって、被印刷体に、高い耐擦過性を有し、鏡面の銀光沢の印字部(文字など)や画像を形成できる。また、分散剤及び水溶性又は水分散性高分子の使用量が少なくても、分散安定性が高く、目詰まりを起こすことなく、長期間に亘り安定して印字又は印刷可能である。特に、インキ受容層を有する光沢紙の種類が異なっていても、高い耐擦過性の印字部又は画像部を強固に密着させて形成できる。 Since the present invention contains a dispersant for dispersing silver nanoparticles and a water-soluble or water-dispersible polymer, even if the amount of the water-soluble or water-dispersible polymer used is small, a printing method such as an inkjet method can be used. As a result, the printed material has high scratch resistance, and a mirror-finished silver-gloss printed portion (characters, etc.) or an image can be formed. Further, even if the amount of the dispersant and the water-soluble or water-dispersible polymer used is small, the dispersion stability is high, and printing or printing can be performed stably for a long period of time without causing clogging. In particular, even if the type of glossy paper having the ink receiving layer is different, the printed portion or the image portion having high scratch resistance can be formed in close contact with each other.
[インキ組成物]
本発明のインキ組成物(又はインク組成物)は、銀ナノ粒子(a)と、この銀ナノ粒子(a)を分散させるためのカルボキシル基又はその塩を有する分散剤(b)と、分散媒としての水性溶媒(c)と、被膜形成能を有する水溶性又は水分散性高分子(d)とを含んでいる。
[Ink composition]
The ink composition (or ink composition) of the present invention comprises silver nanoparticles (a), a dispersant (b) having a carboxyl group or a salt thereof for dispersing the silver nanoparticles (a), and a dispersion medium. (C) and a water-soluble or water-dispersible polymer (d) having a film-forming ability.
[銀ナノ粒子(a)]
銀ナノ粒子(a)の平均粒子径(平均一次粒子径)は、ナノメーターサイズであり、例えば、1〜100nm(例えば、2〜80nm)、好ましくは3〜70nm(例えば、4〜50nm)、さらに好ましくは5〜40nm(例えば、10〜30nm)程度であってもよい。銀ナノ粒子(a)は粗大粒子をほとんど含んでおらず、前記銀ナノ粒子(a)の最大一次粒子径は、例えば、200nm以下、好ましくは150nm以下、さらに好ましくは100nm以下である。さらに、銀ナノ粒子(a)において、一次粒子径が100nm以上の粒子の割合は、質量基準で、例えば、10質量%以下(例えば、0〜8質量%程度)、好ましくは5質量%以下(例えば、0.01〜3質量%程度)、さらに好ましくは1質量%以下(例えば、0.02〜0.5質量%程度)であってもよい。
[Silver nanoparticles (a)]
The average particle size (average primary particle size) of the silver nanoparticles (a) is nanometer size, for example, 1 to 100 nm (for example, 2 to 80 nm), preferably 3 to 70 nm (for example, 4 to 50 nm). More preferably, it may be about 5 to 40 nm (for example, 10 to 30 nm). The silver nanoparticles (a) contain almost no coarse particles, and the maximum primary particle size of the silver nanoparticles (a) is, for example, 200 nm or less, preferably 150 nm or less, and more preferably 100 nm or less. Further, in the silver nanoparticles (a), the proportion of particles having a primary particle diameter of 100 nm or more is, for example, 10% by mass or less (for example, about 0 to 8% by mass), preferably 5% by mass or less (for example, about 0 to 8% by mass) on a mass basis. For example, it may be about 0.01 to 3% by mass), more preferably 1% by mass or less (for example, about 0.02 to 0.5% by mass).
銀ナノ粒子(a)は、分散剤(b)に対する配位性が高いためか、分散剤(b)と組み合わせることにより、銀ナノ粒子(a)の分散安定性を高めることができる。 Because the silver nanoparticles (a) have a high coordinating property with respect to the dispersant (b), the dispersion stability of the silver nanoparticles (a) can be enhanced by combining with the dispersant (b).
なお、必要であれば、銀ナノ粒子(a)は、他の金属ナノ粒子を含んでいてもよい。このような金属ナノ粒子としては、例えば、周期表第8族金属(鉄、ニッケル、コバルト、ルテニウム、ロジウム、パラジウム、レニウム、イリジウム、白金など)、周期表第1B族金属(銅、金など)、周期表第3B族金属(アルミニウム、ガリウム、インジウムなど)及び周期表第4B族金属(ゲルマニウム、スズ、鉛など)などであってもよい。なお、金属(金属原子)は、分散剤(b)に対する配位性の高い金属、例えば、周期表第8族金属、周期表第1B族金属などである場合が多い。 If necessary, the silver nanoparticles (a) may contain other metal nanoparticles. Examples of such metal nanoparticles include metal of Group 8 of the periodic table (iron, nickel, cobalt, ruthenium, rhodium, palladium, renium, iridium, platinum, etc.) and metal of Group 1B of the periodic table (copper, gold, etc.). , Group 3B metal of the periodic table (aluminum, gallium, indium, etc.) and metal of Group 4B of the periodic table (germanium, tin, lead, etc.). The metal (metal atom) is often a metal having a high coordination property with respect to the dispersant (b), for example, a metal of Group 8 of the periodic table, a metal of Group 1B of the periodic table, or the like.
[分散剤(b)]
分散剤(又は保護コロイド)(b)は、カルボキシル基又はその塩を有しており、カルボキシル基を有する有機化合物(b1)及び/又はカルボキシル基を有する高分子分散剤(b2)を含んでいてもよい。分散剤(b)は非揮発性分散剤である場合が多い。
[Dispersant (b)]
The dispersant (or protective colloid) (b) has a carboxyl group or a salt thereof, and contains an organic compound (b1) having a carboxyl group and / or a polymer dispersant (b2) having a carboxyl group. May be good. The dispersant (b) is often a non-volatile dispersant.
有機化合物(b1)のカルボキシル基の数は、1分子中に、1以上、例えば、1〜10、好ましくは1〜5、さらに好ましくは1〜3程度であってもよい。 The number of carboxyl groups of the organic compound (b1) may be 1 or more, for example, 1 to 10, preferably 1 to 5, and more preferably 1 to 3 in one molecule.
また、有機化合物(b1)は、カルボキシル基以外の官能基(又は銀ナノ粒子に対する配位性基など)を有していてもよい。このような官能基(又は配位性基)としては、例えば、ハロゲン原子(フッ素原子、塩素原子、臭素原子、ヨウ素原子など)、アミノ基、ジアルキルアミノ基、イミノ基(−NH−)、窒素含有ヘテロ環基(ピリジル基、モルホリニル基などの5〜8員窒素ヘテロ基、カルバゾール基などの5〜8員窒素ヘテロ基を含む縮合環基)、アミド基(−CON<)、シアノ基、ニトロ基など]、ヒドロキシル基、アルコキシ基(例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などのC1−6アルコキシ基)、ホルミル基、カルボニル基(−CO−)、エステル基(−COO−)、酸素含有ヘテロ環基(テトラヒドロピラニル基などの5〜8員酸素含有ヘテロ環基など)、チオ基、チオール基、チオカルボニル基(−SO−)、アルキルチオ基(メチルチオ基、エチルチオ基などのC1−4アルキルチオ基など)、スルホ基、スルファモイル基、スルフィニル基(−SO2−)などの他、これらの塩を形成した基(アンモニウム塩基など)などが挙げられる。有機化合物(b1)は、これらの官能基を、単独で又は2種以上(同種又は異種の複数の官能基)組み合わせて有していてもよい。有機化合物(b1)は、カルボキシル基と塩を形成可能な塩基性基(アミノ基、置換アミノ基、イミノ基、アンモニウム塩基など)を有していないのが好ましい。 Further, the organic compound (b1) may have a functional group (or a coordinating group with respect to silver nanoparticles) other than the carboxyl group. Examples of such a functional group (or coordinating group) include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an amino group, a dialkylamino group, an imino group (-NH-), and nitrogen. Containing heterocyclic group (fused ring group containing 5-8 member nitrogen hetero group such as pyridyl group and morpholinyl group, 5-8 member nitrogen hetero group such as carbazole group), amide group (-CON <), cyano group, nitro Groups, etc.], hydroxyl groups, alkoxy groups (eg, C 1-6 alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group), formyl group, carbonyl group (-CO-), ester group (-COO-). ), Oxygen-containing heterocyclic group (5- to 8-membered oxygen-containing heterocyclic group such as tetrahydropyranyl group), thio group, thiol group, thiocarbonyl group (-SO-), alkylthio group (methylthio group, ethylthio group, etc.) C 1-4 alkylthio group, etc.), sulfo group, sulfamoyl group, sulfinyl group (-SO 2- ), etc., and groups forming these salts (ammonium base, etc.) can be mentioned. The organic compound (b1) may have these functional groups alone or in combination of two or more (multiple functional groups of the same type or different types). The organic compound (b1) preferably does not have a basic group (amino group, substituted amino group, imino group, ammonium base, etc.) capable of forming a salt with a carboxyl group.
代表的な有機化合物(b1)には、カルボン酸、例えば、モノカルボン酸、ポリカルボン酸、ヒドロキシカルボン酸(又はオキシカルボン酸)などが挙げられる。 Representative organic compounds (b1) include carboxylic acids such as monocarboxylic acids, polycarboxylic acids, hydroxycarboxylic acids (or oxycarboxylic acids) and the like.
モノカルボン酸としては、例えば、脂肪族モノカルボン酸[飽和モノカルボン酸(例えば、ギ酸、酢酸、プロピオン酸、酪酸、カプリル酸、カプロン酸、ヘキサン酸、カプリン酸、ラウリン酸、ミリスチン酸、シクロヘキサンカルボン酸、ステロイド核を有するカルボン酸(デヒドロコール酸、コラン酸、アロコラン酸などの胆汁酸)などのC1−34脂肪族モノカルボン酸、好ましくはC2−30脂肪族モノカルボン酸など)、不飽和モノカルボン酸(例えば、オレイン酸、エルカ酸、リノール酸、アビエチン酸などのC4−34不飽和脂肪族モノカルボン酸、好ましくはC10−30不飽和脂肪族モノカルボン酸)]、芳香族モノカルボン酸(安息香酸、ナフトエ酸などのC7−12芳香族モノカルボン酸など)などが挙げられる。 Examples of the monocarboxylic acid include aliphatic monocarboxylic acids [saturated monocarboxylic acids (eg, formic acid, acetic acid, propionic acid, butyric acid, capric acid, caproic acid, hexanoic acid, capric acid, lauric acid, myristic acid, cyclohexanecarboxylic acid). C 1-34 aliphatic monocarboxylic acids such as acids, carboxylic acids with steroid nuclei (biliary acids such as dehydrocholic acid, colic acid, arochoric acid) , preferably C 2-30 aliphatic monocarboxylic acids, etc. Saturated monocarboxylic acids (eg, C 4-34 unsaturated aliphatic monocarboxylic acids such as oleic acid, erucic acid, linoleic acid, avietic acid, preferably C 10-30 unsaturated aliphatic monocarboxylic acids)], aromatics Examples thereof include monocarboxylic acids (C7-12 aromatic monocarboxylic acids such as benzoic acid and naphthoic acid).
ポリカルボン酸としては、例えば、脂肪族ポリカルボン酸[例えば、飽和ポリカルボン酸(例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、アゼライン酸、セバシン酸、シクロヘキサンジカルボン酸などのC2−14脂肪族飽和ポリカルボン酸、好ましくはC2−10脂肪族飽和ポリカルボン酸など)、不飽和ポリカルボン酸(例えば、マレイン酸、フマル酸、イタコン酸、ソルビン酸、テトラヒドロフタル酸などのC4−14脂肪族不飽和ポリカルボン酸、好ましくはC4−10脂肪族不飽和ポリカルボン酸など)など]、芳香族ポリカルボン酸(例えば、フタル酸、トリメリット酸などのC8−12芳香族ポリカルボン酸など)などが挙げられる。 Examples of the polycarboxylic acid include aliphatic polycarboxylic acids [for example, C such as saturated polycarboxylic acids (eg, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid). 2-14 aliphatic saturated polycarboxylic acids, preferably C 2-10 aliphatic saturated polycarboxylic acids, unsaturated polycarboxylic acids (eg, maleic acid, fumaric acid, itaconic acid, sorbic acid, tetrahydrophthalic acid, etc.) C 4-14 aliphatic unsaturated polycarboxylic acids, preferably C 4-10 aliphatic unsaturated polycarboxylic acids, etc.], aromatic polycarboxylic acids (eg, C 8-12 such as phthalic acid, trimellitic acid, etc.) Aromatic polycarboxylic acids, etc.) and the like.
ヒドロキシカルボン酸としては、ヒドロキシモノカルボン酸[脂肪族ヒドロキシモノカルボン酸(例えば、グリコール酸、乳酸、オキシ酪酸、グリセリン酸、6−ヒドロキシヘキサン酸、ステロイド核を有するヒドロキシカルボン酸(コール酸、デオキシコール酸、ケノデオキシコール酸、12−オキソケノデオキシコール酸、グリココール酸、リトコール酸、ヒオデオキシコール酸、ウルソデオキシコール酸、アポコール酸、タウロコール酸、ピオコール酸、ピトコール酸などの胆汁酸)などのC2−50脂肪族ヒドロキシモノカルボン酸、好ましくはC2−34脂肪族ヒドロキシモノカルボン酸、さらに好ましくはC2−30脂肪族ヒドロキシモノカルボン酸など)、芳香族ヒドロキシモノカルボン酸(サリチル酸、オキシ安息香酸、没食子酸などのC7−12芳香族ヒドロキシモノカルボン酸など)など]、ヒドロキシポリカルボン酸[脂肪族ヒドロキシポリカルボン酸(例えば、タルトロン酸、酒石酸、クエン酸、リンゴ酸などのC2−10脂肪族ヒドロキシポリカルボン酸など)など]などが挙げられる。 As the hydroxycarboxylic acid, hydroxymonocarboxylic acid [aliphatic hydroxymonocarboxylic acid (for example, glycolic acid, lactic acid, oxybutyric acid, glyceric acid, 6-hydroxyhexanoic acid, hydroxycarboxylic acid having a steroid nucleus (colic acid, deoxychol) C 2-50 such as acids, kenodeoxycholic acid, 12-oxokenodeoxycholic acid, glycocholic acid, lithocylic acid, hyodeoxycholic acid, ursodeoxycholic acid, apocolic acid, taurocholic acid, pyolic acid, pyricic acid and other bile acids) Aliphatic hydroxymonocarboxylic acid, preferably C 2-34 aliphatic hydroxymonocarboxylic acid, more preferably C 2-30 aliphatic hydroxymonocarboxylic acid, aromatic hydroxymonocarboxylic acid (salicylic acid, oxybenzoic acid, gallic acid) C 7-12 aromatic hydroxymonocarboxylic acids such as acids, etc.], hydroxypolycarboxylic acids [C 2-10 aliphatic acids such as aliphatic hydroxypolycarboxylic acids (eg, tartronic acid, tartaric acid, citric acid, malic acid, etc.) (Hydroxypolycarboxylic acid, etc.)] and the like.
なお、これらのカルボン酸(有機化合物(b1))において、少なくとも一部のカルボキシル基は、塩(例えば、トリエチルアミンとの塩などの第三級アミン塩、アンモニウム塩、ナトリウム塩などのアルカリ金属塩などの塩基性化合物との塩)を形成していてもよく、無水物、水和物などであってもよい。なお、カルボン酸のカルボキシル基が、塩を形成していない遊離のカルボン酸であってもよい。 In these carboxylic acids (organic compound (b1)), at least a part of the carboxyl group is a salt (for example, a tertiary amine salt such as a salt with triethylamine, an alkali metal salt such as an ammonium salt or a sodium salt, etc. It may form a salt with a basic compound of the above, and may be an anhydride, a hydrate, or the like. The carboxyl group of the carboxylic acid may be a free carboxylic acid that does not form a salt.
有機化合物(b1)は、単独で又は2種以上組み合わせてもよい。 The organic compound (b1) may be used alone or in combination of two or more.
これらの有機化合物(b1)のうち、脂肪族ヒドロキシカルボン酸(脂肪族ヒドロキシモノカルボン酸および脂肪族ヒドロキシポリカルボン酸)などのヒドロキシカルボン酸が好ましく、脂肪族ヒドロキシカルボン酸の中でも、さらに、脂環族ヒドロキシカルボン酸(又は脂環族骨格を有するヒドロキシカルボン酸、例えば、胆汁酸(コール酸など)などのC6−34脂環族ヒドロキシカルボン酸、好ましくはC10−34脂環族ヒドロキシカルボン酸、さらに好ましくはC16−30脂環族ヒドロキシカルボン酸)が好ましい。 Among these organic compounds (b1), hydroxycarboxylic acids such as aliphatic hydroxycarboxylic acids (aliphatic hydroxymonocarboxylic acid and aliphatic hydroxypolycarboxylic acid) are preferable, and among the aliphatic hydroxycarboxylic acids, an alicyclic is further formed. Group hydroxycarboxylic acid (or hydroxycarboxylic acid having an alicyclic skeleton, eg, C 6-34 alicyclic hydroxycarboxylic acid such as bile acid (such as cholic acid), preferably C 10-34 alicyclic hydroxycarboxylic acid , More preferably C 16-30 alicyclic hydroxycarboxylic acid).
また、ステロイド核を有するヒドロキシカルボン酸及びカルボン酸、例えば、ヒドロキシ基及びカルボキシル基を有する胆汁酸(コール酸など)などの多環式脂肪族ヒドロキシカルボン酸(例えば、縮合多環式脂肪族ヒドロキシカルボン酸、好ましくはC10−34縮合多環式脂肪族ヒドロキシカルボン酸、さらに好ましくはC14−34縮合多環式脂肪族ヒドロキシカルボン酸、特にC18−30縮合多環式脂肪族ヒドロキシカルボン酸)、カルボキシル基を有する胆汁酸(デヒドロコール酸、コラン酸など)などの多環式脂肪族カルボン酸(例えば、縮合多環式脂肪族カルボン酸、好ましくはC10−34縮合多環式脂肪族カルボン酸、さらに好ましくはC14−34縮合多環式脂肪族ヒドロキシカルボン酸、特にC18−30縮合多環式脂肪族カルボン酸)などの多環式脂肪族カルボン酸(例えば、C10−50縮合多環式脂肪族カルボン酸、好ましくはC12−40縮合多環式脂肪族カルボン酸、さらに好ましくはC14−34縮合多環式脂肪族カルボン酸、特にC18−30縮合多環式脂肪族カルボン酸)は、嵩高い構造を有しており、銀ナノ粒子の凝集を抑制する効果が大きいためか好ましい。 Also, hydroxycarboxylic acids and carboxylic acids with steroid nuclei, such as polycyclic aliphatic hydroxycarboxylic acids (eg, condensed polycyclic aliphatic hydroxycarboxylic acids) such as bile acids with hydroxy and carboxyl groups (such as cholic acid). Acids, preferably C 10-34 fused polycyclic aliphatic hydroxycarboxylic acids, more preferably C 14-34 condensed polycyclic aliphatic hydroxycarboxylic acids, especially C 18-30 condensed polycyclic aliphatic hydroxycarboxylic acids. , Polycyclic aliphatic carboxylic acids (eg, fused polycyclic aliphatic carboxylic acids, preferably C 10-34 condensed polycyclic aliphatic carboxylic acids) such as bile acids having a carboxyl group (dehydrocholic acid, colanic acid, etc.) Polycyclic aliphatic carboxylic acids such as acids, more preferably C 14-34 fused polycyclic aliphatic hydroxycarboxylic acids, especially C 18-30 condensed polycyclic aliphatic carboxylic acids (eg, C 10-50 condensation). Polycyclic aliphatic carboxylic acid, preferably C 12-40 fused polycyclic aliphatic carboxylic acid, more preferably C 14-34 condensed polycyclic aliphatic carboxylic acid, especially C 18-30 condensed polycyclic aliphatic carboxylic acid. Carboxylic acid) has a bulky structure and is preferable because it has a large effect of suppressing aggregation of silver nanoparticles.
なお、有機化合物(b1)の分子量は、例えば、1000以下(例えば、46〜900程度)、好ましくは800以下(例えば、50〜700程度)、さらに好ましくは600以下(例えば、100〜500程度)であってもよい。 The molecular weight of the organic compound (b1) is, for example, 1000 or less (for example, about 46 to 900), preferably 800 or less (for example, about 50 to 700), and more preferably 600 or less (for example, about 100 to 500). May be.
また、有機化合物(b1)のpKa値は、例えば、1以上(例えば、1〜10程度)、好ましくは2以上(例えば、2〜8程度)であってもよい。 Further, the pKa value of the organic compound (b1) may be, for example, 1 or more (for example, about 1 to 10), preferably 2 or more (for example, about 2 to 8).
(b2)高分子分散剤
高分子分散剤(又は高分子型分散剤)(b2)は、少なくともカルボキシル基を有し、銀ナノ粒子(a)を分散可能であればよく、銀ナノ粒子(a)を被覆して保護コロイドを形成してもよい。高分子分散剤(又は高分子型分散剤)(b2)としては、両親媒性の高分子分散剤(又はオリゴマー型分散剤)を好適に使用できる。
(B2) Polymer Dispersant The polymer dispersant (or polymer type dispersant) (b2) may have at least a carboxyl group and can disperse the silver nanoparticles (a), and the silver nanoparticles (a) may be dispersed. ) May be coated to form a protective colloid. As the polymer dispersant (or polymer-type dispersant) (b2), an amphipathic polymer dispersant (or oligomer-type dispersant) can be preferably used.
高分子分散剤としては、通常、塗料、インキ分野などで着色剤の分散に用いられている高分子分散剤が例示できる。代表的な高分子分散剤(両親媒性の高分子分散剤)としては、親水性モノマーで形成された親水性ユニット(又は親水性ブロック)を含む水溶性又は水分散性樹脂が含まれる。 Examples of the polymer dispersant include polymer dispersants usually used for dispersing colorants in the fields of paints and inks. Typical polymer dispersants (amphipathic polymer dispersants) include water-soluble or water-dispersible resins containing hydrophilic units (or hydrophilic blocks) formed of hydrophilic monomers.
前記親水性モノマーとしては、例えば、カルボキシル基又は酸無水物基含有単量体((メタ)アクリル酸、マレイン酸、無水マレイン酸などの不飽和多価カルボン酸又はその酸無水物など)、スルホ基を有する単量体(スチレンスルホン酸など)、ヒドロキシル基含有単量体(2−ヒドロキシエチル(メタ)アクリレートなどのヒドロキシアルキル(メタ)アクリレート、ビニルフェノールなど)などの付加重合性モノマー;エチレンオキシドなどの縮合重合性モノマーなどが例示できる。前記縮合重合性モノマーは、ヒドロキシル基などの活性水素(例えば、前記ヒドロキシル基)との反応により、親水性ユニット(又はブロック)を形成していてもよい。親水性モノマーは、単独で又は2種以上組み合わせて親水性ユニット(又はブロック)を形成していてもよい。好ましい親水性モノマーは、(メタ)アクリル酸、マレイン酸、無水マレイン酸、エチレンオキシドなどであってもよい。 Examples of the hydrophilic monomer include a carboxyl group or acid anhydride group-containing monomer (unsaturated polyvalent carboxylic acid such as (meth) acrylic acid, maleic acid, and maleic anhydride, or an acid anhydride thereof), and a sulfo. Add-polymerizable monomers such as group-containing monomers (styrene sulfonic acid, etc.), hydroxyl group-containing monomers (hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, vinylphenol, etc.); ethylene oxide, etc. Examples thereof include the condensation polymerizable monomer of. The condensation polymerizable monomer may form a hydrophilic unit (or block) by reacting with an active hydrogen such as a hydroxyl group (for example, the hydroxyl group). The hydrophilic monomers may form a hydrophilic unit (or block) alone or in combination of two or more. Preferred hydrophilic monomers may be (meth) acrylic acid, maleic acid, maleic anhydride, ethylene oxide and the like.
なお、高分子分散剤(b2)は、少なくともカルボキシル基又は酸無水物基を有していればよく、前記親水性モノマーの官能基、例えば、酸基(スルホ基)、ヒドロキシル基を有していてもよい。これらの官能基は、単独で又は2種以上組み合わせて高分子分散剤(b2)に導入してもよい。 The polymer dispersant (b2) may have at least a carboxyl group or an acid anhydride group, and has a functional group of the hydrophilic monomer, for example, an acid group (sulfo group) or a hydroxyl group. You may. These functional groups may be introduced into the polymer dispersant (b2) alone or in combination of two or more.
高分子分散剤は、少なくとも親水性ユニット(又は親水性ブロック)を含んでいてもよく、親水性モノマーの単独又は共重合体(例えば、ポリアクリル酸又はその塩など)であってもよく、親水性モノマーと疎水性モノマーとのコポリマーであってもよい。疎水性モノマー(非イオン性モノマー)としては、(メタ)アクリル酸エステル[(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ステアリルなどの(メタ)アクリル酸C1−20アルキル、(メタ)アクリル酸シクロヘキシルなどの(メタ)アクリル酸シクロアルキル、(メタ)アクリル酸フェニルなどの(メタ)アクリル酸アリール、(メタ)アクリル酸ベンジル、(メタ)アクリル酸2−フェニルエチルなどの(メタ)アクリル酸アラルキルなど]などの(メタ)アクリル系モノマー;スチレン、α−メチルスチレン、ビニルトルエンなどのスチレン系モノマー;α−C2−20オレフィン(エチレン、プロピレン、1−ブテン、イソブチレン、1−ヘキセン、1−オクテン、1−ドデセンなど)などのオレフィン系モノマー;酢酸ビニル、酪酸ビニルなどのカルボン酸ビニルエステル系モノマーなどの付加重合性モノマー:プロピレンオキシドなどのC3−6アルキレンオキサイドなどの縮合重合性モノマーが挙げられる。疎水性モノマーは、単独で又は2種以上組み合わせて疎水性ユニットを構成していてもよい。 The polymer dispersant may contain at least a hydrophilic unit (or a hydrophilic block), may be a hydrophilic monomer alone or a copolymer (eg, polyacrylic acid or a salt thereof), and may be hydrophilic. It may be a copolymer of a sex monomer and a hydrophobic monomer. Examples of the hydrophobic monomer (nonionic monomer) include (meth) acrylic acid ester [(meth) methyl acrylate, (meth) ethyl acrylate, (meth) n-butyl acrylate, and (meth) 2-ethylhexyl acrylate. , (Meta) lauryl acrylate, (meth) stearyl acrylate and the like (meth) acrylate C 1-20 alkyl, (meth) cyclohexyl acrylate and the like (meth) acrylate cycloalkyl, (meth) acrylate phenyl and the like (Meta) acrylic acid monomers such as (meth) acrylic acid aryl, (meth) acrylic acid benzyl, (meth) acrylic acid 2-phenylethyl, etc. (meth) acrylic acid aralkyl, etc .; styrene, α-methylstyrene, Styrene-based monomers such as vinyl toluene; olefin-based monomers such as α-C 2-20 olefins (ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-octene, 1-dodecene, etc.); vinyl acetate, vinyl butyrate, etc. Additive-polymerizable monomers such as carboxylic acid vinyl ester-based monomers such as: Condensation-polymerizable monomers such as C 3-6 alkylene oxide such as propylene oxide can be mentioned. The hydrophobic monomers may be used alone or in combination of two or more to form a hydrophobic unit.
コポリマー(例えば、親水性モノマーと疎水性モノマーとのコポリマー)の高分子分散剤は、ランダムコポリマー、交互共重合体、ブロックコポリマー(例えば、親水性モノマーで構成された親水性ブロックと、疎水性モノマーで構成された疎水性ブロックとで構成されたコポリマー)、くし型コポリマー(又はくし型グラフトコポリマー)などであってもよい。前記ブロックコポリマーの構造は、特に限定されず、ジブロック構造、トリブロック構造(ABA型、BAB型)などであってもよい。また、前記くし型コポリマーにおいて、主鎖は、前記親水性ブロック又は前記疎水性ブロックで形成してもよく、親水性ブロックおよび疎水性ブロックで形成してもよい。 Polymer dispersants for copolymers (eg, copolymers of hydrophilic and hydrophobic monomers) include random copolymers, alternating copolymers, block copolymers (eg, hydrophilic blocks composed of hydrophilic monomers, and hydrophobic monomers. It may be a copolymer composed of a hydrophobic block composed of, a comb-type copolymer (or a comb-type graft copolymer), or the like. The structure of the block copolymer is not particularly limited, and may be a diblock structure, a triblock structure (ABA type, BAB type), or the like. Further, in the comb-shaped copolymer, the main chain may be formed of the hydrophilic block or the hydrophobic block, or may be formed of the hydrophilic block and the hydrophobic block.
なお、前記のように、親水性ユニットは、親水性ブロック(ポリエチレンオキシドなど)で形成することもできる。親水性ブロック(ポリアルキレンオキシドなど)と疎水性ブロック(ポリオレフィンブロックなど)とは、エステル結合、アミド結合、エーテル結合、ウレタン結合などの連結基を介して結合していてもよい。これらの結合は、例えば、疎水性ブロック(ポリオレフィンなど)を変性剤[不飽和カルボン酸又はその無水物((無水)マレイン酸など)、ラクタム又はアミノカルボン酸、ヒドロキシルアミン、ジアミンなど]で変性した後、親水性ブロックを導入することにより形成してもよい。また、ヒドロキシル基やカルボキシル基などの親水性基を有するモノマー(前記ヒドロキシアルキル(メタ)アクリレートなど)から得られるポリマーと、前記縮合系の親水性モノマー(エチレンオキシドなど)とを反応(又は結合)させることにより、くし型コポリマー(主鎖が疎水性ブロックで構成されたくし型コポリマー)を形成してもよい。 As described above, the hydrophilic unit can also be formed of a hydrophilic block (polyethylene oxide or the like). The hydrophilic block (polyalkylene oxide or the like) and the hydrophobic block (polyolefin block or the like) may be bonded via a linking group such as an ester bond, an amide bond, an ether bond, or a urethane bond. These bonds are, for example, a hydrophobic block (such as polyolefin) modified with a denaturant [unsaturated carboxylic acid or an anhydride thereof (such as (maleic anhydride) maleic acid), lactam or aminocarboxylic acid, hydroxylamine, diamine, etc.]. Later, it may be formed by introducing a hydrophilic block. Further, the polymer obtained from a monomer having a hydrophilic group such as a hydroxyl group or a carboxyl group (such as the hydroxyalkyl (meth) acrylate) is reacted (or bonded) with the hydrophilic monomer of the condensation system (such as ethylene oxide). Thereby, a comb-shaped copolymer (a comb-shaped copolymer in which the main chain is composed of a hydrophobic block) may be formed.
さらに、共重合成分として、親水性の非イオン性モノマーを使用することにより、親水性と疎水性とのバランスを調整してもよい。このような成分としては、2−(2−メトキシエトキシ)エチル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート(例えば、数平均分子量200〜1000程度)などのエチレンオキシユニットを有するモノマー又はオリゴマーなどを例示できる。また、親水性基(カルボキシル基など)を変性(例えば、エステル化)することにより親水性と疎水性とのバランスを調整してもよい。 Further, the balance between hydrophilicity and hydrophobicity may be adjusted by using a hydrophilic nonionic monomer as the copolymerization component. Examples of such a component include a monomer or oligomer having an ethyleneoxy unit such as 2- (2-methoxyethoxy) ethyl (meth) acrylate and polyethylene glycol mono (meth) acrylate (for example, having a number average molecular weight of about 200 to 1000). Can be exemplified. Further, the balance between hydrophilicity and hydrophobicity may be adjusted by modifying (for example, esterifying) a hydrophilic group (carboxyl group or the like).
カルボキシル基を有する高分子分散剤(b2)において、少なくとも一部のカルボキシル基は、塩(アミンとの塩、金属塩など)を形成していてもよいが、カルボキシル基などの酸基が塩を形成していない高分子分散剤[すなわち、遊離のカルボキシル基を有する高分子分散剤]を好適に使用できる。 In the polymer dispersant (b2) having a carboxyl group, at least a part of the carboxyl groups may form a salt (salt with amine, metal salt, etc.), but an acid group such as a carboxyl group forms a salt. A polymer dispersant that has not been formed [that is, a polymer dispersant having a free carboxyl group] can be preferably used.
カルボキシル基を有する高分子分散剤(b2)の酸価は、例えば、1mgKOH/g以上(例えば、2〜100mgKOH/g程度)、好ましくは3mgKOH/g以上(例えば、4〜90mgKOH/g程度)、さらに好ましくは5mgKOH/g以上(例えば、6〜80mgKOH/g程度)、特に7mgKOH/g以上(例えば、8〜70mgKOH/g程度)であってもよく、通常、3〜50mgKOH/g(例えば、5〜30mgKOH/g)程度であってもよい。なお、このような高分子分散剤(b2)において、アミン価は0(又はほぼ0)であってもよい。 The acid value of the polymer dispersant (b2) having a carboxyl group is, for example, 1 mgKOH / g or more (for example, about 2 to 100 mgKOH / g), preferably 3 mgKOH / g or more (for example, about 4 to 90 mgKOH / g). More preferably, it may be 5 mgKOH / g or more (for example, about 6 to 80 mgKOH / g), particularly 7 mgKOH / g or more (for example, about 8 to 70 mgKOH / g), and usually 3 to 50 mgKOH / g (for example, 5). It may be about ~ 30 mgKOH / g). In such a polymer dispersant (b2), the amine value may be 0 (or almost 0).
なお、高分子分散剤において、官能基の位置は、特に限定されず、主鎖であってもよく、側鎖であってもよく、主鎖および側鎖に位置していてもよい。このような官能基は、例えば、親水性モノマー又は親水性ユニット由来の官能基(例えば、(メタ)アクリル酸、無水マレイン酸、エチレンオキサイドなどの共重合により導入された官能基)であってもよい。 In the polymer dispersant, the position of the functional group is not particularly limited, and may be a main chain, a side chain, or may be located in the main chain and the side chain. Such a functional group may be, for example, a hydrophilic monomer or a functional group derived from a hydrophilic unit (for example, a functional group introduced by copolymerization of (meth) acrylic acid, maleic anhydride, ethylene oxide, etc.). Good.
高分子分散剤(b2)は単独で又は2種以上組み合わせて使用してもよい。 The polymer dispersant (b2) may be used alone or in combination of two or more.
なお、高分子分散剤として、特開2004−207558号公報などに記載の高分子分散剤(高分子量顔料分散剤)を使用してもよい。また、高分子分散剤は、合成してもよく、市販品を用いてもよい。以下に、市販の高分子分散剤(又は少なくとも両親媒性の分散剤で構成された分散剤)を具体的に例示すると、ソルスパース13240、ソルスパース13940、ソルスパース32550、ソルスパース31845、ソルスパース24000、ソルスパース26000、ソルスパース27000、ソルスパース28000、ソルスパース41090などのソルスパースシリーズ[アビシア(株)製];ディスパービック160、ディスパービック161、ディスパービック162、ディスパービック163、ディスパービック164、ディスパービック166、ディスパービック170、ディスパービック180、ディスパービック182、ディスパービック184、ディスパービック190、ディスパービック191、ディスパービック192、ディスパービック193、ディスパービック194、ディスパービック2001、ディスパービック2050などのディスパービックシリーズ[ビックケミー(株)製];EFKA−46、EFKA−47、EFKA−48、EFKA−49、EFKA−1501、EFKA−1502、EFKA−4540、EFKA−4550、ポリマー100、ポリマー120、ポリマー150、ポリマー400、ポリマー401、ポリマー402、ポリマー403、ポリマー450、ポリマー451、ポリマー452、ポリマー453[EFKAケミカル(株)製];アジスパーPB711、アジスパーPAl11、アジスパーPB811、アジスパーPB821、アジスパーPW911などのアジスパーシリーズ[味の素(株)製];フローレンDOPA−158、フローレンDOPA−22、フローレンDOPA−17、フローレンTG−700、フローレンTG−720W、フローレン−730W、フローレン−740W、フローレン−745Wなどのフローレンシリーズ[共栄社化学(株)製];ジョンクリル678、ジョンクリル679、ジョンクリル62などのジョンクリルシリーズ[ジョンソンポリマー(株)製]などが挙げられる。代表的な高分子分散剤には、ディスパービック190、ディスパービック194などが挙げられる。 As the polymer dispersant, the polymer dispersant (high molecular weight pigment dispersant) described in JP-A-2004-207558 may be used. Further, the polymer dispersant may be synthesized or a commercially available product may be used. Specific examples of commercially available polymer dispersants (or dispersants composed of at least an amphoteric dispersants) are as follows: Solspurus 13240, Solsperse 13940, Solsperse 32550, Solsperse 31845, Solsperse 24000, Solsperse 26000, Solsperse series such as Solsperse 27000, Solsperse 28000, Solsperse 41090 [manufactured by Abyssia Co., Ltd.]; Big 180, Disperbic 182, Disperbic 184, Disperbic 190, Disperbic 191, Disperbic 192, Disperbic 193, Disparbic 194, Disperbic 2001, Disperbic 2050, etc. Dispervic series [manufactured by BIC Chemie Co., Ltd.] EFKA-46, EFKA-47, EFKA-48, EFKA-49, EFKA-1501, EFKA-1502, EFKA-4540, EFKA-4550, Polymer 100, Polymer 120, Polymer 150, Polymer 400, Polymer 401, Polymer 402 , Polymer 403, Polymer 450, Polymer 451, Polymer 452, Polymer 453 [manufactured by EFKA Chemical Co., Ltd.]; Polymer series such as Floren DOPA-158, Floren DOPA-22, Floren DOPA-17, Floren TG-700, Floren TG-720W, Floren-730W, Floren-740W, Floren-745W [manufactured by Kyoeisha Chemical Co., Ltd.]; John Krill series [manufactured by Johnson Polymer Co., Ltd.] such as John Krill 678, John Krill 679, and John Krill 62 can be mentioned. Typical polymer dispersants include Disperbic 190, Disperbic 194 and the like.
高分子分散剤(b2)の数平均分子量は、例えば、1500〜100000、好ましくは2000〜80000(例えば、2000〜60000)、さらに好ましくは3000〜50000(例えば、5000〜30000)程度であってもよく、7000〜20000程度であってもよい。 The number average molecular weight of the polymer dispersant (b2) may be, for example, 1500 to 100,000, preferably 2000 to 80,000 (for example, 2000 to 60000), and more preferably 3000 to 50000 (for example, 5000 to 30000). It may be about 7,000 to 20,000.
有機化合物(b1)と高分子分散剤(b2)との割合は、固形分換算(又は不揮発分換算)で、前者/後者(質量比)=99/1〜1/99(例えば、95/5〜5/95)、好ましくは85/15〜10/90(例えば、75/25〜15/85)、さらに好ましくは70/30〜20/80(例えば、60/40〜25/75)、特に55/45〜30/70(例えば、50/50〜35/65)程度であってもよい。 The ratio of the organic compound (b1) to the polymer dispersant (b2) is in terms of solid content (or non-volatile content), and the former / latter (mass ratio) = 99/1 to 1/99 (for example, 95/5). ~ 5/95), preferably 85/15 to 10/90 (eg, 75/25 to 15/85), more preferably 70/30 to 20/80 (eg, 60/40 to 25/75), in particular. It may be about 55/45 to 30/70 (for example, 50/50 to 35/65).
分散剤(b)(有機化合物(b1)および高分子分散剤(b2)の総量)の割合は、銀ナノ粒子(a)100質量部に対して、例えば、0.1〜100質量部(例えば、1〜80質量部)、好ましくは2〜60質量部(例えば、3〜50質量部)程度の広い範囲から選択でき、通常、1〜30質量部(例えば、1〜20質量部)、好ましくは5〜20質量部(例えば、7〜17質量部)、さらに好ましくは10〜15質量部程度であってもよい。本発明では、比較的少量の分散剤であっても、粗大粒子が少なく、分散安定性の高い銀ナノ粒子とすることができる。 The ratio of the dispersant (b) (total amount of the organic compound (b1) and the polymer dispersant (b2)) is, for example, 0.1 to 100 parts by mass (for example) with respect to 100 parts by mass of the silver nanoparticles (a). , 1 to 80 parts by mass), preferably from a wide range of about 2 to 60 parts by mass (for example, 3 to 50 parts by mass), and usually 1 to 30 parts by mass (for example, 1 to 20 parts by mass), preferably. May be 5 to 20 parts by mass (for example, 7 to 17 parts by mass), more preferably about 10 to 15 parts by mass. In the present invention, even with a relatively small amount of dispersant, silver nanoparticles having few coarse particles and high dispersion stability can be obtained.
なお、有機化合物(b1)の割合は、例えば、銀ナノ粒子(a)100質量部に対して、例えば、0.05〜50質量部(例えば、0.5〜30質量部)程度の範囲から選択でき、通常、1〜15質量部(例えば、2〜10質量部)、好ましくは2.5〜7.5質量部(例えば、3〜6質量部)程度であってもよい。 The ratio of the organic compound (b1) is, for example, from a range of about 0.05 to 50 parts by mass (for example, 0.5 to 30 parts by mass) with respect to 100 parts by mass of the silver nanoparticles (a). It can be selected and may be usually about 1 to 15 parts by mass (for example, 2 to 10 parts by mass), preferably about 2.5 to 7.5 parts by mass (for example, 3 to 6 parts by mass).
また、高分子分散剤(b2)の割合は、例えば、銀ナノ粒子(a)100質量部に対して、例えば、0.1〜60質量部(例えば、1〜50質量部)程度の範囲から選択でき、通常、2〜30質量部(例えば、2.5〜20質量部)、さらに好ましくは3〜15質量部(例えば、5〜10質量部)程度であってもよい。 The ratio of the polymer dispersant (b2) is, for example, from a range of about 0.1 to 60 parts by mass (for example, 1 to 50 parts by mass) with respect to 100 parts by mass of the silver nanoparticles (a). It can be selected and may be usually about 2 to 30 parts by mass (for example, 2.5 to 20 parts by mass), more preferably about 3 to 15 parts by mass (for example, 5 to 10 parts by mass).
なお、本発明では、必要であれば、他の分散剤を含んでいてもよく、他の分散剤は、無機化合物であってもよいが、通常、有機化合物である。他の分散剤としては、例えば、アルカノール類(ヘキサノール、オクタノール、デカノール、ドデカノール、オクタデカノールなどのC6−20アルカンモノオール)、アルデヒド類(カプリルアルデヒド、ラウリルアルデヒド、パルミトアルデヒドなどのC6−20脂肪族アルデヒド)、高級脂肪酸又はその塩、スルホン酸類(例えば、アルカンスルホン酸、ベンゼンスルホン酸、トルエンスルホン酸などのアレーンスルホン酸など)が挙げられる。これらの他の分散剤は、単独で又は2種以上組み合わせてもよい。 In the present invention, if necessary, another dispersant may be contained, and the other dispersant may be an inorganic compound, but is usually an organic compound. Other dispersants include, for example, alkanols (C 6-20 alkanemonools such as hexanol, octanol, decanol, dodecanol, octadecanol ) and aldehydes (C 6 such as caprylaldehyde, laurylaldehyde, palmitaldehyde). -20 aliphatic aldehydes), higher fatty acids or salts thereof, sulfonic acids (eg, alkane sulfonic acids, benzene sulfonic acids, arene sulfonic acids such as toluene sulfonic acids, etc.). These other dispersants may be used alone or in combination of two or more.
他の分散剤の割合は、前記分散剤(b)100質量部に対して、例えば、0.1〜100質量部、好ましくは0.5〜50質量部、さらに好ましくは1〜30質量部程度であってもよい。 The ratio of the other dispersant is, for example, 0.1 to 100 parts by mass, preferably 0.5 to 50 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the dispersant (b). It may be.
[水性溶媒(c)]
水性溶媒(c)は、水単独であってもよく、水と、水溶性有機溶媒とを含んでいてもよい。水溶性溶媒としては、例えば、アルコール類(メタノール、エタノール、プロパノール、イソプロパノールなどのC1−4アルカノールなど)、多価アルコール類(エチレングリコール、プロピレングリコールなどのアルカンジオール、グリセリン、トリメチロールプロパンなどのアルカントリオール、ペンタエリスリトールなどのアルカンテトラオールなど)、アミド類(ホルムアミド、アセトアミドなどのアシルアミド類、N−メチルホルムアミド、N−メチルアセトアミド,N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミドなどのモノ又はジC1−4アシルアミド類など)、ピロリドン類(2−ピロリドン、3−ピロリドン、N−メチル−2−ピロリドン、N−メチル−3−ピロリドンなど)、ケトン類(アセトンなど)、エーテル類(ジオキサン、テトラヒドロフランなど)、有機カルボン酸類(酢酸など)、セロソルブ類(メチルセロソルブ、エチルセロソルブなどのC1−4アルキルセロソルブ類など)、セロソルブアセテート類(エチルセロソルブアセテートなどのC1−4アルキルセロソルブアセテート類)、カルビトール類(メチルカルビトール、エチルカルビトール、プロピルカルビトール、ブチルカルビトールなどのC1−4アルキルカルビトール類など)、カルビトールアセテート類(メチルカルビトールアセテートなどのC1−4アルキルカルビトールアセテート)、ジメチルスルホキシドなどが例示できる。これらの有機溶媒は、単独で又は二種以上組み合わせて使用できる。
[Aqueous solvent (c)]
The aqueous solvent (c) may be water alone, or may contain water and a water-soluble organic solvent. Examples of the water-soluble solvent include alcohols (such as C 1-4 alkanol such as methanol, ethanol, propanol and isopropanol), polyhydric alcohols (alkanediol such as ethylene glycol and propylene glycol), glycerin and trimethylolpropane and the like. Alkanetriol, alkanetetraol such as pentaerythritol), amides (acylamides such as formamide and acetamido, N-methylformamide, N-methylacetamide, N, N-dimethylformamide, N, N-dimethylacetamide and the like) Or diC 1-4 acylamides, etc.), pyrrolidones (2-pyrrolidone, 3-pyrrolidone, N-methyl-2-pyrrolidone, N-methyl-3-pyrrolidone, etc.), ketones (acetone, etc.), ethers (aceto, etc.) Dioxane, tetrahydrofuran, etc.), organic carboxylic acids (acetic acid, etc.), cellosolves (C 1-4 alkyl cellosolves, such as methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates (C 1-4 alkyl cellosolve acetate, such as ethyl cellosolve acetate) Species), carbitols (C 1-4 alkyl carbitols such as methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, etc.), carbitol acetates (C 1-4 such as methyl carbitol acetate) Alkylcarbitol acetate), dimethylsulfoxide and the like can be exemplified. These organic solvents can be used alone or in combination of two or more.
水溶性有機溶媒は、水溶性アルコール(エタノール、イソプロパノールなど)、水溶性多価アルコール(グリセリンなど)及びピロリドン類(N−メチルピロリドンなど)から選択された少なくとも一種の有機溶媒とを含んでいてもよい。 The water-soluble organic solvent may contain at least one organic solvent selected from water-soluble alcohols (ethanol, isopropanol, etc.), water-soluble polyhydric alcohols (glycerin, etc.) and pyrrolidones (N-methylpyrrolidone, etc.). Good.
前記アルコールの割合は、水100質量部に対して、例えば、1〜30質量部、好ましくは2〜20質量部、さらに好ましくは3〜15質量部(例えば、5〜10質量部)程度であってもよい。前記多価アルコール及びピロリドン類の割合は、それぞれ、水100質量部に対して、例えば、1〜50質量部、好ましくは3〜30質量部、さらに好ましくは5〜25質量部(例えば、10〜20質量部)程度であってもよい。 The ratio of the alcohol is, for example, about 1 to 30 parts by mass, preferably 2 to 20 parts by mass, and more preferably 3 to 15 parts by mass (for example, 5 to 10 parts by mass) with respect to 100 parts by mass of water. You may. The ratio of the polyhydric alcohol and the pyrrolidones is, for example, 1 to 50 parts by mass, preferably 3 to 30 parts by mass, and more preferably 5 to 25 parts by mass (for example, 10 to 10 parts by mass) with respect to 100 parts by mass of water. It may be about 20 parts by mass).
[被膜形成能を有する水溶性又は水分散性高分子(d)]
本発明では、前記成分を含むインキ組成物(又はインク組成物)に被膜形成能を有する水溶性又は水分散性高分子(d)を添加することにより、耐擦過性に優れた印字部又は画像部を形成できる。その理由については明確ではないものの、銀粒子がナノ粒子であり、水溶性又は水分散性高分子(d)が被膜形成能(製膜性)を有するためか、水溶性又は水分散性高分子(d)が少量であっても、強固で密着性の高い印字部又は画像部を形成するものと推測される。
[Water-soluble or water-dispersible polymer having film-forming ability (d)]
In the present invention, by adding a water-soluble or water-dispersible polymer (d) having a film-forming ability to an ink composition (or ink composition) containing the above components, a printed portion or an image having excellent scratch resistance is added. Part can be formed. Although the reason is not clear, it is probably because the silver particles are nanoparticles and the water-soluble or water-dispersible polymer (d) has a film-forming ability (film-forming property), or the water-soluble or water-dispersible polymer. Even if the amount of (d) is small, it is presumed that a strong and highly adhesive printed portion or image portion is formed.
水溶性又は水分散性高分子には、水溶性樹脂の他、樹脂エマルジョンも含まれる。水溶性又は水分散性高分子は、前記高分子分散剤(b2)とは異なる種類の高分子が使用される。水溶性又は水分散性樹脂には、例えば、スチレン系樹脂(スチレン−(メタ)アクリル酸共重合体;スチレン−(メタ)アクリル酸メチル−(メタ)アクリル酸共重合体などのスチレン−(メタ)アクリル酸アルキルエステル−(メタ)アクリル酸共重合体;スチレン−無水マレイン酸共重合体;スチレン−スチレンスルホン酸共重合体など)、アクリル系樹脂(メタクリル酸メチル−(メタ)アクリル酸共重合体、メタクリル酸メチル−アクリル酸アルキルエステル−(メタ)アクリル酸共重合体などの(メタ)アクリル酸アルキルエステル−(メタ)アクリル酸共重合体、(メタ)アクリル酸アルキルエステル−スチレン−(メタ)アクリル酸共重合体、ポリアクリルアミドなど)、ポリ酢酸ビニル樹脂、エチレン−酢酸ビニル共重合樹脂、塩化ビニル−酢酸ビニル共重合樹脂、ポリエチレンイミン、ビニルアルコール系樹脂(ポリビニルアルコール、エチレン−ビニルアルコール共重合体など)、ビニルピロリドン系樹脂(ポリビニルピロリドン、ビニルピロリドン−酢酸ビニル共重合体など)、ポリエチレングリコール系樹脂(ポリエチレングリコール、ポリエチレングリコール−ポリプロピレングリコールブロック共重合体など)、水溶性ウレタン樹脂、水溶性アクリルウレタン樹脂、水溶性エポキシ樹脂、水溶性ポリエステル系樹脂、水溶性ポリアミド樹脂、天然高分子(ゼラチン、アラビアゴム、トラガントゴム、デキストリン、アルギン酸など)、セルロースエーテル類(メチルセルロースなどのアルキルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロースなどのヒドロキシアルキルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロースなどのヒドロキシアルキル−アルキルセルロース、カルボキシメチルセルロースなど)、ポリエチレンスルホン酸塩、ナフタレンスルホン酸のホルマリン縮合物などが含まれる。これらの水溶性又は水分散性樹脂は単独で又は二種以上組み合わせて使用できる。 The water-soluble or water-dispersible polymer includes a resin emulsion as well as a water-soluble resin. As the water-soluble or water-dispersible polymer, a polymer of a type different from that of the polymer dispersant (b2) is used. Examples of the water-soluble or water-dispersible resin include styrene-based resins (styrene- (meth) acrylate copolymer; styrene- (meth) acrylate copolymer such as styrene-methyl (meth) acrylate- (meth) acrylate copolymer; ) Acrylic acid alkyl ester- (meth) acrylic acid copolymer; styrene-maleic anhydride copolymer; styrene-styrene sulfonic acid copolymer, etc.), acrylic resin (methyl methacrylate- (meth) acrylic acid copolymer) Combined, (meth) acrylic acid alkyl ester such as methyl methacrylate-acrylic acid alkyl ester- (meth) acrylic acid copolymer- (meth) acrylic acid copolymer, (meth) acrylic acid alkyl ester-styrene- (meth) ) Acrylic acid copolymer, polyacrylamide, etc.), Polyvinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, polyethylene imine, vinyl alcohol-based resin (polyvinyl alcohol, ethylene-vinyl alcohol) Polymers, etc.), vinyl pyrrolidone-based resins (polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, etc.), polyethylene glycol-based resins (polyethylene glycol, polyethylene glycol-polypropylene glycol block copolymers, etc.), water-soluble urethane resins, water-soluble Acrylic urethane resin, water-soluble epoxy resin, water-soluble polyester resin, water-soluble polyamide resin, natural polymer (gelatin, Arabic rubber, tragant rubber, dextrin, alginic acid, etc.), cellulose ethers (alkyl cellulose such as methyl cellulose, hydroxyethyl cellulose, etc.) , Hydroxyalkyl cellulose such as hydroxypropyl cellulose, hydroxyalkyl-alkyl cellulose such as hydroxypropyl methyl cellulose, carboxymethyl cellulose, etc.), polyethylene sulfonate, formalin condensate of naphthalene sulfonic acid, and the like. These water-soluble or water-dispersible resins can be used alone or in combination of two or more.
なお、水溶性又は水分散性樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)で測定したとき、ポリスチレン換算で、0.5×104〜100×104、好ましくは0.7×104〜10×104程度であってもよい。なお、一部の高分子(例えば、セルロースエーテル類など)はGPCにより分子量を測定することが困難である場合がある。このような高分子では、重合度が、例えば、100〜100000、好ましくは200〜10000程度であってもよい。 The weight average molecular weight of the water-soluble or water-dispersible resin is 0.5 × 10 4 to 100 × 10 4 , preferably 0.7 × 10 in terms of polystyrene when measured by gel permeation chromatography (GPC). It may be about 4 to 10 × 10 4. It may be difficult to measure the molecular weight of some polymers (for example, cellulose ethers) by GPC. In such a polymer, the degree of polymerization may be, for example, 100 to 100,000, preferably about 200 to 10000.
さらに、カルボキシル基が導入された水溶性又は水分散性樹脂の酸価は、10〜200mgKOH/g、好ましくは30〜150mgKOH/g、さらに好ましくは50〜120mgKOH/g程度であってもよい。また、塩基でカルボキシル基の塩を形成し、樹脂に水溶性又は水分散性を付与してもよい。塩基としては、アミン類(トリエチルアミンなどのトリアルキルアミン、トリエタノールアミン、ジメチルアミノエタノールなどのアルカノールアミン、モルホリンなどの複素環式アミンなど)、水酸化ナトリウムなどのアルカリ金属水酸化物、アルカリ金属炭酸塩などであってもよい。 Further, the acid value of the water-soluble or water-dispersible resin into which the carboxyl group has been introduced may be 10 to 200 mgKOH / g, preferably 30 to 150 mgKOH / g, and more preferably about 50 to 120 mgKOH / g. Further, a salt of a carboxyl group may be formed with a base to impart water solubility or water dispersibility to the resin. Bases include amines (trialkylamines such as triethylamine, alkanolamines such as triethanolamine and dimethylaminoethanol, heterocyclic amines such as morpholin), alkali metal hydroxides such as sodium hydroxide, and alkali metal carbonates. It may be salt or the like.
これらの水溶性又は水分散性高分子のうち、水溶性スチレン系樹脂(スチレン−(メタ)アクリル酸共重合体、スチレン−(メタ)アクリル酸メチル−(メタ)アクリル酸共重合体、スチレン−無水マレイン酸共重合体など)、水溶性アクリル系樹脂((メタ)アクリル酸アルキルエステル−(メタ)アクリル酸共重合体、(メタ)アクリル酸アルキルエステル−スチレン−(メタ)アクリル酸共重合体など)、ビニルアルコール系樹脂(ポリビニルアルコールなど)、ビニルピロリドン系樹脂(ポリビニルピロリドンなど)、天然高分子(ゼラチン、アラビアゴム、デキストリンなど)、セルロースエーテル類(ヒドロキシアルキルセルロース、ヒドロキシアルキル−アルキルセルロース、カルボキシメチルセルロースなど)などを用いる場合が多い。 Among these water-soluble or water-dispersible polymers, water-soluble styrene resins (styrene- (meth) acrylic acid copolymer, styrene-methyl (meth) acrylate- (meth) acrylic acid copolymer, styrene- Maleic anhydride copolymer, etc.), water-soluble acrylic resin ((meth) acrylic acid alkyl ester- (meth) acrylic acid copolymer, (meth) acrylic acid alkyl ester-styrene- (meth) acrylic acid copolymer , Vinyl alcohol-based resin (polyvinyl alcohol, etc.), vinyl pyrrolidone-based resin (polyvinyl pyrrolidone, etc.), natural polymers (gelatin, arabic rubber, dextrin, etc.), cellulose ethers (hydroxyalkyl cellulose, hydroxyalkyl-alkyl cellulose, etc.) Carboxymethyl cellulose, etc.) are often used.
樹脂エマルジョンとしては、例えば、(メタ)アクリル系樹脂エマルジョン(例えば、ポリメタクリル酸メチル樹脂、メタクリル酸メチル−(メタ)アクリル酸アルキルエステル共重合体、メタクリル酸メチル−(メタ)アクリル酸アルキルエステル−(メタ)アクリル酸共重合体などを含むエマルジョン)、スチレン系樹脂エマルジョン(例えば、スチレン−(メタ)アクリル酸共重合樹脂、スチレン−(メタ)アクリル酸アルキルエステル共重合体、スチレン−(メタ)アクリル酸アルキルエステル−(メタ)アクリル酸共重合体系単量体などを含むエマルジョン)、酢酸ビニル系樹脂エマルジョン(例えば、ポリ酢酸ビニル樹脂、エチレン−酢酸ビニル共重合樹脂を含むエマルジョン)アクリル−シリコーン系樹脂エマルジョン、ポリエステル−アクリル系樹脂エマルジョンなどが例示でき、スチレン−ブタジエン共重合体などのゴム粒子のエマルジョンであってもよい。これらの樹脂エマルジョンも単独で又は二種以上組み合わせて使用できる。樹脂エマルジョンの樹脂粒子の平均粒径は、1nm〜1μm程度であってもよく、通常、10〜1000nm、好ましくは20〜800nm、さらに好ましくは30〜500nm程度であってもよい。また、樹脂エマルジョンは、室温(20℃)で造膜性を有している場合が多い。 Examples of the resin emulsion include (meth) acrylic resin emulsions (for example, polymethyl methacrylate resin, methyl methacrylate- (meth) acrylic acid alkyl ester copolymer, methyl methacrylate- (meth) acrylic acid alkyl ester-. (Emulsion containing (meth) acrylic acid copolymer, etc.), styrene resin emulsion (for example, styrene- (meth) acrylic acid copolymer resin, styrene- (meth) acrylic acid alkyl ester copolymer, styrene- (meth) Acrylic acid alkyl ester- (meth) Acrylic acid copolymer system Emulsion containing monomer, etc.), Vinyl acetate resin emulsion (for example, emulsion containing polyvinyl acetate resin, ethylene-vinyl acetate copolymer resin) Acrylic-silicone type Examples thereof include resin emulsions and polyester-acrylic resin emulsions, and may be emulsions of rubber particles such as styrene-butadiene copolymers. These resin emulsions can also be used alone or in combination of two or more. The average particle size of the resin particles of the resin emulsion may be about 1 nm to 1 μm, and is usually 10 to 1000 nm, preferably 20 to 800 nm, and more preferably about 30 to 500 nm. Further, the resin emulsion often has a film-forming property at room temperature (20 ° C.).
これらの樹脂エマルジョンのうち、(メタ)アクリル系樹脂エマルジョン(メタクリル酸メチル−(メタ)アクリル酸アルキルエステル−(メタ)アクリル酸共重合体エマルジョンなど)、スチレン系樹脂エマルジョン(スチレン−(メタ)アクリル酸アルキルエステル−(メタ)アクリル酸共重合体系単量体エマルジョンなど)を用いる場合が多い。 Among these resin emulsions, (meth) acrylic resin emulsion (methyl methacrylate- (meth) acrylic acid alkyl ester- (meth) acrylic acid copolymer emulsion, etc.), styrene resin emulsion (styrene- (meth) acrylic) Acid alkyl ester- (meth) acrylic acid copolymer system monomer emulsion, etc.) is often used.
水溶性又は水分散性高分子(d)の使用量は、固形分換算(又は不揮発分換算)で、銀ナノ粒子(a)100質量部に対して、1〜30質量部(例えば、2〜25質量部)、好ましくは2.5〜20質量部(例えば、3〜15質量部)程度であってもよく、通常、2〜12質量部(例えば、2.5〜10質量部、好ましくは3〜8.5質量部)程度であってもよい。本発明では、水溶性又は水分散性高分子(d)の使用量が少量であっても、高い耐擦過性の印字部又は画像を、光沢紙などの被印刷体に対して高い密着性で形成できる。 The amount of the water-soluble or water-dispersible polymer (d) used is 1 to 30 parts by mass (for example, 2 to 30 parts by mass) with respect to 100 parts by mass of the silver nanoparticles (a) in terms of solid content (or non-volatile content). 25 parts by mass), preferably about 2.5 to 20 parts by mass (for example, 3 to 15 parts by mass), and usually 2 to 12 parts by mass (for example, 2.5 to 10 parts by mass, preferably 2.5 to 10 parts by mass). It may be about 3 to 8.5 parts by mass). In the present invention, even if the amount of the water-soluble or water-dispersible polymer (d) used is small, a highly scratch-resistant printed portion or image can be printed with high adhesion to an object to be printed such as glossy paper. Can be formed.
水溶性又は水分散性高分子(d)の濃度は、組成物全体に対して、0.05〜0.75質量%(例えば、0.05〜0.7質量%)、好ましくは0.07〜0.5質量%(例えば、0.08〜0.4質量%)、さらに好ましくは0.1〜0.3質量%程度であってもよい。 The concentration of the water-soluble or water-dispersible polymer (d) is 0.05 to 0.75% by mass (for example, 0.05 to 0.7% by mass), preferably 0.07, based on the entire composition. It may be about 0.5% by mass (for example, 0.08 to 0.4% by mass), more preferably about 0.1 to 0.3% by mass.
さらに、前記分散剤(b)と、水溶性又は水分散性高分子(d)との割合は、固形分換算で、前者/後者(質量比)=5/95〜95/5程度の範囲から選択でき、例えば、10/90〜95/5(例えば、30/70〜90/10)、好ましくは40/60〜90/10(例えば、50/50〜87/13)、さらに好ましくは55/45〜85/15(例えば、60/40〜80/20)程度であってもよい。本発明では、分散剤(b)に対する水溶性又は水分散性高分子(d)の割合が小さくても、高い耐擦過性を有する印字部又は画像部を高い密着性で形成できる。 Further, the ratio of the dispersant (b) to the water-soluble or water-dispersible polymer (d) is in the range of the former / the latter (mass ratio) = 5/95 to 95/5 in terms of solid content. It can be selected, for example, 10/90 to 95/5 (for example, 30/70 to 90/10), preferably 40/60 to 90/10 (for example, 50/50 to 87/13), and more preferably 55/. It may be about 45 to 85/15 (for example, 60/40 to 80/20). In the present invention, even if the ratio of the water-soluble or water-dispersible polymer (d) to the dispersant (b) is small, a printed portion or an image portion having high scratch resistance can be formed with high adhesion.
前記分散剤(b)及び水溶性又は水分散性高分子(d)の総量は、固形分換算で、銀ナノ粒子(a)100質量部に対して、5〜50質量部(例えば、7〜40質量部)、好ましくは10〜30質量部(例えば、15〜25質量部)程度であってもよく、通常、5〜30質量部(例えば、10〜25質量部、好ましくは15〜20質量部)程度であってもよい。本発明では、分散剤(b)及び水溶性又は水分散性高分子(d)の使用量が少量であっても、光沢紙などの被印刷体に対して高い密着性で、高い耐擦過性の印字部又は画像を形成できる。 The total amount of the dispersant (b) and the water-soluble or water-dispersible polymer (d) is 5 to 50 parts by mass (for example, 7 to 50 parts by mass) with respect to 100 parts by mass of the silver nanoparticles (a) in terms of solid content. 40 parts by mass), preferably about 10 to 30 parts by mass (for example, 15 to 25 parts by mass), and usually 5 to 30 parts by mass (for example, 10 to 25 parts by mass, preferably 15 to 20 parts by mass). Part) may be about. In the present invention, even if the amount of the dispersant (b) and the water-soluble or water-dispersible polymer (d) used is small, the adhesiveness to the printed material such as glossy paper is high and the scratch resistance is high. The printed part or image can be formed.
本発明のインキ組成物(分散液)は、高い分散安定性を有するため、インキ組成物(分散液)中の銀ナノ粒子(a)(金属の質量換算)の濃度は、特に制限されず、0.1〜50質量%程度の範囲から選択でき、例えば、0.5〜30質量%、好ましくは1〜20質量%、さらに好ましくは1.5〜10質量%(例えば、2〜5質量%)程度であってもよい。 Since the ink composition (dispersion liquid) of the present invention has high dispersion stability, the concentration of silver nanoparticles (a) (mass equivalent of metal) in the ink composition (dispersion liquid) is not particularly limited. It can be selected from the range of about 0.1 to 50% by mass, for example, 0.5 to 30% by mass, preferably 1 to 20% by mass, and more preferably 1.5 to 10% by mass (for example, 2 to 5% by mass). ) May be the case.
なお、本発明では、インキ組成物の固形分中の銀ナノ粒子濃度が高くても、高い分散性を維持できるとともに、金属光沢を有する印字部又は画像部を形成できる。インキ組成物(分散液)の固形分全体に対する銀ナノ粒子(a)の濃度は、特に限定されず、10〜90質量%(例えば、25〜88質量%、特に35〜85質量%)程度の広い範囲から選択でき、例えば、50〜90質量%、好ましくは55〜88質量%(例えば、60〜87質量%)、さらに好ましくは65〜87質量%程度であってもよい。 In the present invention, even if the concentration of silver nanoparticles in the solid content of the ink composition is high, high dispersibility can be maintained and a printed portion or image portion having metallic luster can be formed. The concentration of the silver nanoparticles (a) with respect to the total solid content of the ink composition (dispersion liquid) is not particularly limited, and is about 10 to 90% by mass (for example, 25 to 88% by mass, particularly 35 to 85% by mass). It can be selected from a wide range, and may be, for example, 50 to 90% by mass, preferably 55 to 88% by mass (for example, 60 to 87% by mass), and more preferably about 65 to 87% by mass.
なお、インキ組成物(又はインク組成物)は、本発明の効果を損なわない範囲で、慣用の添加剤、例えば、可塑剤(又は造膜助剤)、光沢付与剤、金属腐食防止剤(防錆剤)、安定剤(酸化防止剤、紫外線吸収剤、光安定剤など)、界面活性剤(アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤、特にアニオン性界面活性剤及び/又はノニオン性界面活性剤)、分散安定化剤、増粘剤又は粘度調整剤、保湿剤、チクソトロピー性賦与剤、レベリング剤、浸透剤、消泡剤、pH調整剤、キレート剤、表面張力調整剤、着色剤(染顔料など)、色相改良剤、染料定着剤、殺菌剤、防カビ剤、防腐剤、酸素吸収剤などを含んでいてもよい。なお、界面活性剤は、アセチレングリコール系界面活性剤、ポリシロキサン系界面活性剤、フッ素系界面活性剤などであってもよい。これらの添加剤は、単独で又は二種以上組み合わせて使用できる。 The ink composition (or ink composition) is a conventional additive, for example, a plasticizing agent (or a film-forming auxiliary), a gloss-imparting agent, or a metal corrosion inhibitor (prevention), as long as the effect of the present invention is not impaired. Rust agents), stabilizers (antioxidants, UV absorbers, light stabilizers, etc.), surfactants (anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, especially anions Sexual surfactants and / or nonionic surfactants), dispersion stabilizers, thickeners or viscosity modifiers, moisturizers, thixotropic surfactants, leveling agents, penetrants, antifoaming agents, pH adjusters, chelates. It may contain an agent, a surface tension adjusting agent, a coloring agent (dyeing pigment, etc.), a hue improving agent, a dye fixing agent, a bactericidal agent, an antifungal agent, a preservative, an oxygen absorber, and the like. The surfactant may be an acetylene glycol-based surfactant, a polysiloxane-based surfactant, a fluorine-based surfactant, or the like. These additives can be used alone or in combination of two or more.
インキ組成物の粘度は、インクジェット方式による記録において、液滴を安定に吐出可能であればよく、B型粘度計を用いて、室温(25℃)で測定したとき、例えば、2〜20mPa・s、好ましくは2.5〜15mPa・s(例えば、3〜12mPa・s)、さらに好ましくは3〜10mPa・s(例えば、3〜5mPa・s)程度であってもよい。 The viscosity of the ink composition may be as long as it can stably eject droplets in recording by an inkjet method, and when measured at room temperature (25 ° C.) using a B-type viscometer, for example, 2 to 20 mPa · s. It may be preferably about 2.5 to 15 mPa · s (for example, 3 to 12 mPa · s), and more preferably about 3 to 10 mPa · s (for example, 3 to 5 mPa · s).
[インキ組成物の製造方法]
なお、インキ組成物(又はインク組成物)は、例えば、慣用の方法で調製した銀ナノ粒子(a)を含む分散液に、水溶性又は水分散性高分子(d)を添加することにより調製できる。銀ナノ粒子(a)を含む分散液は、市販品を用いてもよく、前記特許文献2に記載の方法に準じて調製してもよい。より具体的には、前記銀ナノ粒子(a)に対応する金属化合物を、分散剤(b)および還元剤の存在下、溶媒中で還元することにより調製できる。
[Manufacturing method of ink composition]
The ink composition (or ink composition) is prepared, for example, by adding a water-soluble or water-dispersible polymer (d) to a dispersion liquid containing silver nanoparticles (a) prepared by a conventional method. it can. As the dispersion liquid containing the silver nanoparticles (a), a commercially available product may be used, or may be prepared according to the method described in Patent Document 2. More specifically, it can be prepared by reducing the metal compound corresponding to the silver nanoparticles (a) in a solvent in the presence of the dispersant (b) and the reducing agent.
前記銀ナノ粒子(a)に対応する金属化合物としては、ハロゲン化銀、銀塩[銀無機酸塩(硫酸銀、硝酸銀など)、銀有機酸塩(酢酸銀など)など]などを使用する場合が多い。なお、これらの銀化合物は、水溶液などの水性溶媒の溶液の形態で用いてもよい。 When silver halide, silver salt [silver inorganic acid salt (silver sulfate, silver nitrate, etc.), silver organic acid salt (silver acetate, etc.), etc.] is used as the metal compound corresponding to the silver nanoparticles (a). There are many. In addition, these silver compounds may be used in the form of a solution of an aqueous solvent such as an aqueous solution.
還元剤としては、慣用の成分、例えば、水素化ホウ素ナトリウム類(水素化ホウ素ナトリウム、シアノ水素化ホウ素ナトリウム、水素化トリエチルホウ素ナトリウムなど)、水素化アルミニウムリチウム、次亜リン酸又はその塩(ナトリウム塩など)、ボラン類(ジボラン、ジメチルアミンボランなど)、ヒドラジン、ホルマリン、アミン類などが例示できる。これらの還元剤は単独で又は二種以上組み合わせて使用できる。還元剤としてはアミン類を用いる場合が多い。 As the reducing agent, conventional components such as sodium borohydride (sodium borohydride, sodium cyanoborohydride, sodium triethylborohydride, etc.), lithium aluminum hydride, hypophosphite or a salt thereof (sodium) Examples thereof include salts), boranes (diborane, dimethylamineborane, etc.), hydrazine, formarin, amines, and the like. These reducing agents can be used alone or in combination of two or more. Amines are often used as the reducing agent.
アミン類としては、脂肪族アミン類(例えば、プロピルアミン、ブチルアミン、ヘキシルアミン、ジエチルアミン、ジプロピルアミン、ジメチルエチルアミン、ジエチルメチルアミン、トリエチルアミン、エチレンジアミン、N,N,N′,N′−テトラメチルエチレンジアミン、1,3−ジアミノプロパン、N,N,N′,N′−テトラメチル−1,3−ジアミノプロパンなどのアルカンアミン;トリエチレンテトラミン、テトラエチレンペンタミンなどのポリアルキレンポリアミンなど)、脂環式アミン類(例えば、ピペリジン、N−メチルピペリジン、ピペラジン、N,N′−ジメチルピペラジン、ピロリジン、N−メチルピロリジン、モルホリンなど)、芳香族アミン類(例えば、アニリン、N−メチルアニリン、N,N−ジメチルアニリン、トルイジン、アニシジン、フェネチジンなど)、芳香脂肪族アミン類(例えば、ベンジルアミン、N−メチルベンジルアミン、N,N−ジメチルベンジルアミン、フェネチルアミン、キシリレンジアミン、N,N,N′,N′−テトラメチルキシリレンジアミンなどのアラルキルアミン)、アルカノールアミン類[例えば、メチルアミノエタノール、ジメチルアミノエタノール(2−(ジメチルアミノ)エタノール)、エタノールアミン、ジエタノールアミン、トリエタノールアミン、プロパノールアミン、ブタノールアミン、ヘキサノールアミン、ジメチルアミノプロパノールなどのC2−10アルカノールアミン、好ましくはC2−6アルカノールアミン]などが挙げることができる。これらのアミン類のうち、アルカノールアミン類が好ましい。 Examples of amines include aliphatic amines (for example, propylamine, butylamine, hexylamine, diethylamine, dipropylamine, dimethylethylamine, diethylmethylamine, triethylamine, ethylenediamine, N, N, N', N'-tetramethylethylenediamine. Alcanamines such as 1,3-diaminopropane, N, N, N', N'-tetramethyl-1,3-diaminopropane; polyalkylene polyamines such as triethylenetetramine and tetraethylenepentamine), alicyclic Formula amines (eg, piperidine, N-methylpiperidin, piperazine, N, N'-dimethylpiperazin, pyrrolidine, N-methylpyrrolidin, morpholin, etc.), aromatic amines (eg, aniline, N-methylaniline, N, N-dimethylaniline, toluidine, anicidin, phenetidine, etc.), aromatic aliphatic amines (eg, benzylamine, N-methylbenzylamine, N, N-dimethylbenzylamine, phenethylamine, xylylene diamine, N, N, N' Aralkylamines such as N'-tetramethylxylylene diamine), alkanolamines [eg, methylaminoethanol, dimethylaminoethanol (2- (dimethylamino) ethanol), ethanolamine, diethanolamine, triethanolamine, propanolamine, C 2-10 alkanol amines such as butanol amines, hexanol amines and dimethylaminopropanols, preferably C 2-6 alkanol amines] and the like can be mentioned. Of these amines, alkanolamines are preferred.
還元剤の使用量は、金属原子換算で前記銀化合物1当量(又は1モル)に対して、1〜30モル、好ましくは1.5〜15モル、さらに好ましくは2〜10モル程度であってもよく、通常1〜5モル程度であってもよい。 The amount of the reducing agent used is 1 to 30 mol, preferably 1.5 to 15 mol, more preferably 2 to 10 mol, based on 1 equivalent (or 1 mol) of the silver compound in terms of metal atoms. It may be about 1 to 5 mol.
還元反応は、慣用の方法、例えば、攪拌しながら、温度10〜75℃(例えば、15〜50℃、好ましくは20〜35℃)程度で行うことができる。反応系の雰囲気は、空気、不活性ガス(窒素ガスなど)であってもよく、還元性ガス(水素ガスなど)を含む雰囲気であってもよい。 The reduction reaction can be carried out by a conventional method, for example, at a temperature of about 10 to 75 ° C. (for example, 15 to 50 ° C., preferably 20 to 35 ° C.) with stirring. The atmosphere of the reaction system may be air, an inert gas (nitrogen gas or the like), or an atmosphere containing a reducing gas (hydrogen gas or the like).
なお、反応溶媒は、水と前記水溶性有機溶媒との混合溶媒を使用できるが、水単独である場合が多い。なお、必要であれば、反応溶媒の種類などに応じて、酸(塩酸、硫酸、硝酸、リン酸などの無機酸、酢酸などの有機酸)、アルカリ[水酸化ナトリウム、アンモニアなどの無機塩基、アミン類(例えば、アルキルアミン、アルカノールアミンなどの第三級アミン類などの有機塩基)などの塩基類]を用いて、反応系のpHを調整してもよい。 As the reaction solvent, a mixed solvent of water and the water-soluble organic solvent can be used, but in many cases, water alone is used. If necessary, depending on the type of reaction solvent, acids (inorganic acids such as hydrochloric acid, sulfuric acid, nitrate and phosphoric acid, organic acids such as acetic acid) and alkalis [inorganic bases such as sodium hydroxide and ammonia, Bases such as amines (eg, organic bases such as tertiary amines such as alkylamines and alkanolamines)] may be used to adjust the pH of the reaction system.
還元反応の終了後、反応混合液を慣用の方法により、濃縮、濾過、精製してもよく、そのまま分散液として使用してもよい。前記特定の分散剤(b)を使用すると、比較的少量であっても、粗大粒子の少ない銀ナノ粒子を生成できる。 After completion of the reduction reaction, the reaction mixture may be concentrated, filtered, or purified by a conventional method, or may be used as it is as a dispersion. By using the specific dispersant (b), silver nanoparticles having few coarse particles can be produced even in a relatively small amount.
このようにして調製された分散液に、前記水溶性又は水分散性高分子(d)を添加して混合することにより、インキ組成物を調製できる。なお、水溶性有機溶媒(例えば、アルコール類、多価アルコール類及/又はピロリドン類)は、前記分散液に添加する場合が多い。また、分散液には、水を添加して濃度を調整してもよく、前記添加剤などを添加してもよい。 The ink composition can be prepared by adding the water-soluble or water-dispersible polymer (d) to the dispersion liquid prepared in this manner and mixing them. In addition, a water-soluble organic solvent (for example, alcohols, polyhydric alcohols and / or pyrrolidones) is often added to the dispersion liquid. Further, water may be added to the dispersion liquid to adjust the concentration, or the above-mentioned additive or the like may be added to the dispersion liquid.
[印字部又は画像部の形成方法]
本発明のインキ組成物(又はインク組成物)は、インクジェット方式で被印刷体(又は被記録媒体)に印字又は印刷し、印字部又は画像を形成するために有用である。そのため、本発明のインキ組成物は、例えば、インクジェット印刷用インキ組成物ということもできる。前記被印刷体(又は被記録媒体)は、基材と、この基材の少なくとも一方の面に形成されたインキ受容層とを有していてもよい。また、被印刷体は、インク吸収性又は非吸収性であってもよい。
[Method of forming a printing part or an image part]
The ink composition (or ink composition) of the present invention is useful for printing or printing on a printed object (or recording medium) by an inkjet method to form a printed portion or an image. Therefore, the ink composition of the present invention can be said to be, for example, an ink composition for inkjet printing. The printed matter (or recording medium) may have a base material and an ink receiving layer formed on at least one surface of the base material. Further, the printed material may be ink-absorbent or non-absorbent.
基材の種類は、用途に応じて、紙(例えば、上質紙、アート紙、コート紙、キャスト紙、合成紙などの印刷用紙など)、プラスチックフィルム(ポリオレフィン系フィルム、ポリエステル系フィルム、ポリイミド系フィルム(ポリアミドイミドフィルムを含む)など)、金属基板(シリコン基板、アルミニウム基板など)、セラミック(ガラスを含む)基板(ガラス基板、アルミナ基板などのセラミックス基板)などであってもよく、複合基板(繊維基材にフェノール樹脂、エポキシ樹脂などが含浸した含浸基板、例えば、紙−フェノール樹脂基板、ガラス−エポキシ樹脂基板など)であってもよい。基材は、紙である場合が多い。 The type of base material is paper (for example, printing paper such as high-quality paper, art paper, coated paper, cast paper, synthetic paper, etc.), plastic film (polyester film, polyester film, polyimide film, etc.), depending on the application. It may be a metal substrate (including a polyamide imide film), a metal substrate (silicon substrate, an aluminum substrate, etc.), a ceramic (including glass) substrate (a ceramic substrate such as a glass substrate or an alumina substrate), or a composite substrate (fiber). An impregnated substrate in which the base material is impregnated with a phenol resin, an epoxy resin or the like, for example, a paper-phenol resin substrate, a glass-epoxy resin substrate, etc.) may be used. The base material is often paper.
インキ受容層は、通常、顔料(白色顔料)およびバインダー樹脂を含んでおり、白色顔料としては、タルク、クレー(カオリン)、酸化チタン、合成シリカ、コロイダルシリカ、炭酸カルシウム、炭酸マグネシウム、アルミナ、硫酸バリウムなどが例示できる。顔料は、タルク、シリカ、及び/又は酸化チタンを含んでいる場合が多い。 The ink receiving layer usually contains a pigment (white pigment) and a binder resin, and examples of the white pigment include talc, clay (kaolin), titanium oxide, synthetic silica, colloidal silica, calcium carbonate, magnesium carbonate, alumina, and sulfuric acid. Barium and the like can be exemplified. Pigments often contain talc, silica, and / or titanium oxide.
バインダー樹脂としては、例えば、デンプン(変性デンプンを含む)、ビニルアルコール系樹脂(ポリビニルアルコールなど)、ビニルピロリドン系樹脂(ポリビニルピロリドンなど)、スチレン系樹脂(スチレン−ブタジエン樹脂など)、アクリル系樹脂、ポリエステル系樹脂、ウレタン系樹脂などが例示できる。バインダー樹脂は、デンプン及び/又はポリビニルアルコールを含む場合が多い。 Examples of the binder resin include starch (including modified starch), vinyl alcohol-based resin (polyvinyl alcohol, etc.), vinylpyrrolidone-based resin (polyvinylpyrrolidone, etc.), styrene-based resin (styrene-butadiene resin, etc.), acrylic resin, and the like. Examples thereof include polyester-based resins and urethane-based resins. The binder resin often contains starch and / or polyvinyl alcohol.
前記インキ受容層は、ポリエチレンイミン、カチオン化デンプン、カチオン化ポリウレタン樹脂などの耐水化剤を含んでいてもよい。また、受容層は、種々の助剤、例えば、有色顔料又は染料、顔料分散剤、消泡剤、離型剤、浸透剤、滑剤、安定化剤(紫外線吸収剤、酸化防止剤など)、防腐剤、架橋剤などを含んでいてもよい。 The ink receiving layer may contain a water resistant agent such as polyethyleneimine, cationized starch, and cationized polyurethane resin. In addition, the receiving layer contains various auxiliaries such as colored pigments or dyes, pigment dispersants, defoamers, mold release agents, penetrants, lubricants, stabilizers (ultraviolet absorbers, antioxidants, etc.), and antiseptic. It may contain an agent, a cross-linking agent, and the like.
インキ受容層を有する被印刷体は、インクジェット専用紙であってもよい。特に、前記被印刷体(又は被記録媒体)は、光沢紙(例えば、インキ受容層を有する光沢紙)であってもよく、光沢紙としては市販の光沢紙を使用してもよい。光沢紙には、カレンダー加工(スーパカレンダー加工など)が施されていてもよい。本発明では、光沢紙(インキ受容層を有する光沢紙)の種類が異なっていても、高い耐擦過性を有し、金属光沢性(銀光沢性)の印字部又は画像部を高い密着性で形成できる。例えば、布や紙などで印字部又は画像部を激しく擦っても印字部及び画像部が剥離することがない。なお、インキ組成物を被印刷体に印字又は印刷すると、分散剤(又は保護コロイド)及び溶媒は、インク受容層に吸収され、基材表面に銀粒子と水溶性又は水分散性高分子(樹脂成分)とが定着するためか、銀粒子がナノ粒子であるため、少量の水溶性又は水分散性高分子であっても、結着樹脂として有効に機能し、耐擦過性の高い印字部又は画像部を形成できるものと思われる。なお、分散剤のうち高分子分散剤も結着樹脂(樹脂成分)として機能していてもよい。 The printed material having the ink receiving layer may be an inkjet paper. In particular, the printed object (or recording medium) may be glossy paper (for example, glossy paper having an ink receiving layer), and commercially available glossy paper may be used as the glossy paper. The glossy paper may be subjected to calendar processing (super calendar processing, etc.). In the present invention, even if the types of glossy paper (glossy paper having an ink receiving layer) are different, it has high scratch resistance and has high adhesion to a printed portion or an image portion having metallic luster (silver luster). Can be formed. For example, even if the printed portion or the image portion is violently rubbed with a cloth or paper, the printed portion and the image portion do not peel off. When the ink composition is printed or printed on the object to be printed, the dispersant (or protective colloid) and the solvent are absorbed by the ink receiving layer, and silver particles and a water-soluble or water-dispersible polymer (resin) are formed on the surface of the substrate. Because the silver particles are nanoparticles, probably because the components) are fixed, even a small amount of water-soluble or water-dispersible polymer functions effectively as a binder resin, and the printed part has high scratch resistance. It seems that the image part can be formed. Of the dispersants, the polymer dispersant may also function as a binder resin (resin component).
インクジェット方式は、バブルジェット(登録商標)方式(サーマル方式)、ピエゾ(圧電素子)方式のいずれであってもよく、本発明の組成物を水性インキ組成物として用い、インクジェットプロッター、インクジェットプリンター、インクジェットディスペンサーなどのインクジェット印刷方式を利用して印字部又は画像部を形成してもよい。 The inkjet method may be either a bubble jet (registered trademark) method (thermal method) or a piezo (piezoelectric element) method, and the composition of the present invention is used as an aqueous ink composition, and an inkjet plotter, an inkjet printer, or an inkjet is used. A printing portion or an image portion may be formed by using an inkjet printing method such as a dispenser.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
[銀ナノ粒子分散液の調製]
特許文献2の実施例1に準じて銀ナノ粒子を含む分散液を調製した。すなわち、硝酸銀66.8g、カルボキシル基を有する高分子分散剤(ビッグケミー製、「ディスパービック190」、溶媒:水、不揮発成分40%、酸価10mgKOH/g、アミン価0)7.2g、及びコール酸(和光純薬工業(株)製)1.8gを、イオン交換水100gに投入し、激しく撹拌し、懸濁液を得た。この懸濁液に対して、ジメチルアミノエタノール(和光純薬工業(株)製)100gを水温が50℃を超えないように徐々に加えたのち、水温50℃のウォーターバス中で4時間加熱撹拌した。得られた反応液を、ガラスフィルタ(ADVANTEC製GC−90、ポアサイズ0.8マイクロメートル)でろ過し、銀を15質量%含む銀ナノ粒子分散液を得た。この分散液について、透過型電子顕微鏡(日本電子(株)製)で銀ナノ粒子の粒径を確認したところ、一次粒子の個数平均粒子径は約20nmであった。
[Preparation of silver nanoparticle dispersion liquid]
A dispersion containing silver nanoparticles was prepared according to Example 1 of Patent Document 2. That is, 66.8 g of silver nitrate, a polymer dispersant having a carboxyl group (manufactured by Big Chemie, "Disperbic 190", solvent: water, 40% non-volatile component, acid value 10 mgKOH / g, amine value 0) 7.2 g, and cole. 1.8 g of an acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 100 g of ion-exchanged water and stirred vigorously to obtain a suspension. To this suspension, 100 g of dimethylaminoethanol (manufactured by Wako Pure Chemical Industries, Ltd.) is gradually added so that the water temperature does not exceed 50 ° C, and then heated and stirred in a water bath at a water temperature of 50 ° C for 4 hours. did. The obtained reaction solution was filtered through a glass filter (GC-90 manufactured by ADVANTEC, pore size 0.8 micrometer) to obtain a silver nanoparticle dispersion liquid containing 15% by mass of silver. When the particle size of the silver nanoparticles of this dispersion was confirmed with a transmission electron microscope (manufactured by JEOL Ltd.), the average particle size of the number of primary particles was about 20 nm.
[インキ組成物1の調製]
得られた銀ナノ粒子を含む分散液に、表1に示す割合で、グリセリン、N−メチル−2−ピロリドン(NMP)、イソプロパノール(IPA)、イオン交換水、水溶性高分子としてポリビニルアルコール(平均重合度1,500以上、けん化度72〜82モル%、和光純薬工業(株)製)を撹拌混合し、インキ組成物1を調製した。
[Preparation of Ink Composition 1]
Glycerin, N-methyl-2-pyrrolidone (NMP), isopropanol (IPA), ion-exchanged water, and polyvinyl alcohol as a water-soluble polymer (average) were added to the obtained dispersion containing silver nanoparticles in the proportions shown in Table 1. An ink composition 1 was prepared by stirring and mixing a degree of polymerization of 1,500 or more, a degree of saponification of 72 to 82 mol%, and manufactured by Wako Pure Chemical Industries, Ltd.
[インキ組成物2〜10の調製]
表1に示す割合で、添加剤の種類を用いる以外、インキ組成物1と同様にして、インキ組成物2〜10を調製した。なお、水溶性高分子として、インキ組成物2、6、7、9及び10ではインキ組成物1と同様のポリビニルアルコールを用い、インキ組成物3ではゼラチン(和光純薬工業(株)製)を用い、インキ組成物4では水溶性アクリル樹脂(アクリセットARL−453 (株)日本触媒製)を用いた。また、インキ組成物5では、水分散性高分子として、アクリル樹脂エマルション(ユーダブルEF−002 (株)日本触媒製)を用いた。なお、インキ組成物8では水溶性高分子を添加することなく調製した。
[Preparation of Ink Compositions 2 to 10]
Ink compositions 2 to 10 were prepared in the same manner as in ink composition 1 except that the types of additives were used at the ratios shown in Table 1. As the water-soluble polymer, polyvinyl alcohol similar to that of ink composition 1 is used in ink compositions 2, 6, 7, 9 and 10, and gelatin (manufactured by Wako Pure Chemical Industries, Ltd.) is used in ink composition 3. In the ink composition 4, a water-soluble acrylic resin (Acryset ARL-453, manufactured by Nippon Catalyst Co., Ltd.) was used. Further, in the ink composition 5, an acrylic resin emulsion (manufactured by Nippon Shokubai Co., Ltd.) was used as the water-dispersible polymer. The ink composition 8 was prepared without adding a water-soluble polymer.
インキ組成物1〜10の組成を表1に示す。 The compositions of the ink compositions 1 to 10 are shown in Table 1.
なお、水溶性高分子及び水分散性高分子の量は、固形分換算の含有量である。 The amounts of the water-soluble polymer and the water-dispersible polymer are the contents in terms of solid content.
[実施例1]
インキ組成物1を用いて、バブルジェット(登録商標)方式インクジェットプリンター(キヤノン(株)製「PIXUS iP2700」)を用いて印刷した。すなわち、インクジェットプリンターに対応する空のインクジェットカートリッジに、インキ組成物1を注入して、プリンターにセットし、被記録媒体としてのインク受容層を含む光沢紙(キヤノン(株)製プロフェッショナルフォトペーパー)の上に印刷した。
[Example 1]
Printing was performed using the ink composition 1 using a bubble jet (registered trademark) inkjet printer (“PIXUS iP2700” manufactured by Canon Inc.). That is, a glossy paper (Professional Photo Paper manufactured by Canon Inc.) containing an ink receiving layer as a recording medium by injecting the ink composition 1 into an empty inkjet cartridge corresponding to an inkjet printer and setting the ink composition 1 in the printer. Printed on.
[実施例2]
被記録媒体として、キヤノン(株)製写真用紙・光沢 プロ[プラチナグレード]を用いる以外、実施例1と同様にして印刷物を得た。
[Example 2]
A printed matter was obtained in the same manner as in Example 1 except that Canon Co., Ltd. Photo Paper / Glossy Pro [Platinum Grade] was used as the recording medium.
[実施例3]
被記録媒体として、セイコーエプソン(株)製写真用紙 エントリー<光沢>を用いる以外、実施例1と同様にして印刷物を得た。
[Example 3]
A printed matter was obtained in the same manner as in Example 1 except that the photo paper entry <gloss> manufactured by Seiko Epson Corporation was used as the recording medium.
[実施例4]
インキ組成物2を用いる以外、実施例1と同様にして印刷物を得た。
[Example 4]
A printed matter was obtained in the same manner as in Example 1 except that the ink composition 2 was used.
[実施例5]
インキ組成物2を用い、被記録媒体としてキヤノン(株)製写真用紙・光沢 プロ[プラチナグレード]を用いた以外、実施例1と同様にして印刷物を得た。
[Example 5]
A printed matter was obtained in the same manner as in Example 1 except that the ink composition 2 was used and Canon Co., Ltd. Photo Paper / Glossy Pro [Platinum Grade] was used as the recording medium.
[実施例6]
インキ組成物2を用い、被記録媒体としてセイコーエプソン(株)製写真用紙 エントリー<光沢>を用いた以外、実施例1と同様にして印刷物を得た。
[Example 6]
A printed matter was obtained in the same manner as in Example 1 except that the ink composition 2 was used and the photo paper entry <gloss> manufactured by Seiko Epson Corporation was used as the recording medium.
[実施例7〜11]
インキ組成物3(実施例7)、インキ組成物4(実施例8)、インキ組成物5(実施例9)、インキ組成物6(実施例10)及びインキ組成物7(実施例11)を用いた以外、実施例1と同様にして印刷物を得た。
[Examples 7 to 11]
Ink composition 3 (Example 7), ink composition 4 (Example 8), ink composition 5 (Example 9), ink composition 6 (Example 10), and ink composition 7 (Example 11). A printed matter was obtained in the same manner as in Example 1 except that it was used.
[比較例1]
インキ組成物8を用いた以外、実施例1と同様にして印刷物を得た。
[Comparative Example 1]
A printed matter was obtained in the same manner as in Example 1 except that the ink composition 8 was used.
[比較例2]
インキ組成物8を用い、被記録媒体としてキヤノン(株)製写真用紙・光沢 プロ[プラチナグレード]を用いた以外、実施例1と同様にして印刷物を得た。
[Comparative Example 2]
A printed matter was obtained in the same manner as in Example 1 except that the ink composition 8 was used and Canon Co., Ltd. Photo Paper / Glossy Pro [Platinum Grade] was used as the recording medium.
[比較例3]
インキ組成物8を用い、被記録媒体としてセイコーエプソン(株)製写真用紙 エントリー<光沢>を用いた以外、実施例1と同様にして印刷物を得た。
[Comparative Example 3]
A printed matter was obtained in the same manner as in Example 1 except that the ink composition 8 was used and the photo paper entry <gloss> manufactured by Seiko Epson Corporation was used as the recording medium.
[比較例4及び5]
インキ組成物9(比較例4)及びインキ組成物10(比較例5)を用いた以外、実施例1と同様にして印刷物を得た。
[Comparative Examples 4 and 5]
A printed matter was obtained in the same manner as in Example 1 except that the ink composition 9 (Comparative Example 4) and the ink composition 10 (Comparative Example 5) were used.
(印刷物の評価方法)
得られた印刷物について、以下のような特性を評価した。
(Evaluation method for printed matter)
The following characteristics were evaluated for the obtained printed matter.
(1)光沢度
各実施例および比較例で印刷したベタ画像を光沢計(日本電色工業(株)製VG2000)を用い、20°光沢度を測定し、以下の基準に従い評価した。
(1) Glossiness The solid images printed in each Example and Comparative Example were measured for 20 ° glossiness using a gloss meter (VG2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) and evaluated according to the following criteria.
A:光沢度が900以上
B:光沢度が900未満。
A: Glossiness is 900 or more B: Glossiness is less than 900.
(2)耐擦過性
各実施例および比較例で印刷したベタ画像に対し、摩擦摩耗試験機を用い、乾いた木綿で、荷重500g及び10往復する摩擦試験を行なった。そして、摩擦試験後のベタ画像を、以下に示す基準にしたがって画像の耐擦過性を評価した。
(2) Scratch resistance The solid images printed in each Example and Comparative Example were subjected to a friction test with a load of 500 g and 10 reciprocations with dry cotton using a friction and wear tester. Then, the scratch resistance of the solid image after the friction test was evaluated according to the criteria shown below.
耐擦性試験後の印刷物の20°光沢度を測定し、耐擦性試験前後での光沢度の低下率を求め、以下の基準に従い評価した。 The 20 ° glossiness of the printed matter after the scratch resistance test was measured, and the rate of decrease in glossiness before and after the scratch resistance test was determined and evaluated according to the following criteria.
A:光沢度の低下率が10%未満
B:光沢度の低下率が10%以上、50%未満
C:光沢度の低下率が50%以上。
A: Gloss reduction rate is less than 10% B: Gloss reduction rate is 10% or more and less than 50% C: Gloss reduction rate is 50% or more.
これらの評価結果を表2及び表3に示す。 The evaluation results are shown in Tables 2 and 3.
表2及び表3から明らかなように、実施例では、安定に印刷できるとともに、高い金属光沢を有し、かつ耐擦過性の高い画像を形成できた。なお、比較例4では、インクジェットプリンターからのインキ組成物9の吐出性が不安定であり、印刷できなかった。 As is clear from Tables 2 and 3, in the examples, stable printing was possible, and an image having a high metallic luster and high scratch resistance could be formed. In Comparative Example 4, the ejection property of the ink composition 9 from the inkjet printer was unstable, and printing was not possible.
本発明のインキ組成物は、被印刷体(特に、光沢紙)に耐久性の高い印字部や画像部を形成するのに適している。特に、本発明のインキ組成物は、分散安定性が高いため、水性インキとしてインクジェット方式により画像を形成するのに適しているものの、インクジェット方式に限らず、他の印刷方式(例えば、スクリーン印刷方式など)で印字部又は画像部を形成してもよい。 The ink composition of the present invention is suitable for forming a highly durable printing portion or image portion on a printed object (particularly, glossy paper). In particular, since the ink composition of the present invention has high dispersion stability, it is suitable for forming an image by an inkjet method as a water-based ink, but it is not limited to the inkjet method, and other printing methods (for example, a screen printing method). Etc.) may form a print section or an image section.
Claims (7)
前記分散剤(b)が、C14−34縮合多環式脂肪族ヒドロキシカルボン酸又はその塩(b1)と、酸価5mgKOH/g以上の高分子分散剤又はその塩(b2)とを含み、
前記被印刷体が、インキ受容層を有する光沢紙であり、
固形分換算で、銀ナノ粒子(a)100質量部に対して、被膜形成能を有する水溶性又は水分散性高分子(d)を1〜10質量部の割合で含み、かつ
組成物全体に対して、水溶性又は水分散性高分子(d)の濃度が0.05〜0.75質量%であるインキ組成物。 An ink composition containing silver nanoparticles (a), a dispersant (b) having a carboxyl group or a salt thereof, and an aqueous solvent (c) for printing or printing on an object to be printed.
The dispersant (b) contains a C 14-34 condensed polycyclic aliphatic hydroxycarboxylic acid or a salt thereof (b1) and a polymer dispersant having an acid value of 5 mgKOH / g or more or a salt thereof (b2).
The object to be printed is glossy paper having an ink receiving layer .
In solid content conversion, based on silver nanoparticles (a) 100 parts by weight, viewed contains a proportion of 1-10 parts by weight of a water-soluble or water-dispersible polymer (d) having a film forming ability, and
An ink composition in which the concentration of the water-soluble or water-dispersible polymer (d) is 0.05 to 0.75% by mass with respect to the entire composition.
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