JP6464344B1 - Method for producing printed matter and printed matter - Google Patents
Method for producing printed matter and printed matter Download PDFInfo
- Publication number
- JP6464344B1 JP6464344B1 JP2018042735A JP2018042735A JP6464344B1 JP 6464344 B1 JP6464344 B1 JP 6464344B1 JP 2018042735 A JP2018042735 A JP 2018042735A JP 2018042735 A JP2018042735 A JP 2018042735A JP 6464344 B1 JP6464344 B1 JP 6464344B1
- Authority
- JP
- Japan
- Prior art keywords
- ink
- printed matter
- printing
- lithographic printing
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000008170 walnut oil Substances 0.000 description 1
- 201000008559 xeroderma pigmentosum group F Diseases 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/06—Lithographic printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
- C09D11/105—Alkyd resins
Abstract
【課題】本発明の目的は、印刷・加工適性（着肉性、耐汚れ性）に優れる平版印刷用光輝性インキを用いた、従来よりも光沢度が高く鏡面性を有する印刷物の製造方法、及び、前記印刷物の製造方法により得られる印刷物を提供することにある。【解決手段】平版印刷用光輝性インキを用いた印刷物の製造方法であって、前記平版印刷用光輝性インキが、平均厚さが１５〜１００ｎｍ、かつ、平均粒子径が１〜３０μｍである金属顔料（Ａ）と、バインダー樹脂とを含み、基材上に前記平版印刷用光輝性インキを印刷する工程（ｉ）と、印刷物を４０〜１３０℃かつ１０〜５００ｋｇｆ／ｃｍ2の条件で加熱加圧処理する工程（ｉｉ）とを、この順に行う、印刷物の製造方法である。【選択図】なしAn object of the present invention is to use a glittering ink for lithographic printing which is excellent in printing / processing suitability (thickness and stain resistance), and a method for producing a printed matter having a higher glossiness and mirror surface than before. And it is providing the printed matter obtained by the manufacturing method of the said printed matter. A method of producing a printed matter using a lithographic printing glitter ink, wherein the lithographic printing glitter ink has an average thickness of 15 to 100 nm and an average particle diameter of 1 to 30 μm. A step (i) of printing the lithographic printing glitter ink on a base material containing a pigment (A) and a binder resin; and heating and pressurizing the printed material under conditions of 40 to 130 ° C. and 10 to 500 kgf / cm 2. This is a printed matter manufacturing method in which the processing step (ii) is performed in this order. [Selection figure] None
Description
本発明は、平版印刷用光輝性インキを用いた印刷物の製造方法、及び前記印刷物の製造方法により得られる印刷物に関する。 The present invention relates to a method for producing a printed matter using a glitter ink for planographic printing, and a printed matter obtained by the method for producing the printed matter.
近年、印刷物の意匠性を向上させることを目的とした、シルバー、ゴールド、ブロンズといった金属光沢を付与した印刷物が、市場のニーズとして高まっている。 In recent years, printed materials with a metallic luster such as silver, gold, and bronze, which are intended to improve the design of printed materials, are increasing as market needs.
これらの印刷物は従来、グラビア、シルクスクリーン、フレキソなどの印刷方式により作成されていた。しかしながら上記の印刷方式は、絵柄の変更に伴う版材の交換に手間がかかることから、少量多品種の印刷物には向いておらず、また印刷速度の点においても問題があった。 These printed materials have been conventionally produced by a printing method such as gravure, silk screen, flexo, or the like. However, the above printing method is not suitable for a small quantity and a large variety of printed materials because it takes time to change the plate material accompanying the change of the pattern, and there is a problem in terms of printing speed.
一方で、印刷速度の速い平版（オフセット）印刷を用いて金属光沢を付与した印刷物を作成する場合、これまでは、予め金属層を蒸着した用紙を使用したり、箔押しやインラインホイラーなどによる後加工を用いたりする必要があった。しかしながら、用紙や後加工による印刷物の製造方法は、特殊な装置を印刷機に設置する必要がある、専用糊を使用するため基材を選ぶ、繊細な絵柄や小さい文字の形成が困難であるなど、基材汎用性、生産面、コスト面での負荷が大きかった。特に上記の後加工方法は、必要とする絵柄以上の大きさに箔を当て、必要な絵柄分だけ型抜きするもので、小さな絵柄に使用する際には無駄が多くなってしまっていた。 On the other hand, when creating printed materials with a metallic luster using lithographic (offset) printing with a high printing speed, until now, post-processing by using a metal layer pre-deposited, foil stamping, inline wheeler, etc. It was necessary to use. However, paper and post-processed printed material manufacturing methods require special equipment to be installed in the printing press, select a base material to use special glue, and difficult to form delicate pictures and small letters. The load on substrate versatility, production, and cost was great. In particular, the post-processing method described above involves applying foil to a size larger than the required pattern and punching out only the required pattern, which has been wasteful when used for small patterns.
上記問題の解決のため、金属光沢を付与するための平版印刷用光輝性インキも検討・開発されてきたが、従来品は、上記グラビア、シルクスクリーン、フレキソなどの印刷方式により作成された印刷物に比べ、光沢度が著しく劣っている現状であった。 In order to solve the above-mentioned problems, lithographic inks for lithographic printing to impart metallic luster have been studied and developed. However, conventional products are printed materials created by printing methods such as gravure, silk screen, and flexo. Compared with the present situation, the glossiness is extremely inferior.
その理由として、平版印刷用光輝性インキは、光輝性のみならず、平版印刷方式特有の、着肉性や乳化適性などにも留意して素材選定する必要があることが挙げられる。例えば、任意のアルミニウム顔料を用いただけでは、印刷適性に優れていたとしても鏡面性が発現しない恐れが高い。 The reason is that the lithographic ink for lithographic printing needs to be selected in consideration of not only the radiance but also the inking property and emulsification suitability specific to the lithographic printing method. For example, if only an aluminum pigment is used, there is a high possibility that the specularity will not be exhibited even if the printability is excellent.
また、平版印刷では殆どの場合、用紙基材に印刷される。一般に用紙基材は、グラビア、シルクスクリーン、フレキソなどの印刷方式で使用されるフィルム基材と異なり、表面が粗い。その場合、基材表面の粗さの影響を受け光沢度が変化するため、用紙基材に対しても鏡面性を有する印刷物を得るためには、フィルム基材への印刷物と同等以上に印刷物の表面を平滑にすることが要求される。 In lithographic printing, in most cases, printing is performed on a paper substrate. In general, a paper substrate has a rough surface unlike a film substrate used in a printing method such as gravure, silk screen, or flexo. In that case, the glossiness changes under the influence of the roughness of the surface of the base material. Therefore, in order to obtain a printed material having a mirror surface even for the paper base material, the printed material should be equal to or better than the printed material on the film base material. A smooth surface is required.
フィルム基材へ印刷する場合、たとえ印刷表面が平滑でなくても、平滑である基材側から見ることで、光沢度を高く見せることが可能である。しかしながら不透明である用紙基材ではそれができないため、印刷層自体を十分平滑にしなければならない。 When printing on a film substrate, even if the printing surface is not smooth, it is possible to make the gloss look high by looking from the smooth substrate side. However, since this is not possible with a paper substrate that is opaque, the printed layer itself must be sufficiently smooth.
これまでに検討されている平版印刷用光輝性インキの例として、特許文献１にはアルミニウム顔料を用いたオフセット印刷用のペースト状金属粉印刷インキについて記載されている。しかしながら、印刷適性も優れた平版印刷用光輝性インキを得、更には高い光沢性、鏡面性を有する印刷物を得るための方策に関しては記載がない。 As an example of glittering ink for lithographic printing that has been studied so far, Patent Document 1 describes a paste-like metal powder printing ink for offset printing using an aluminum pigment. However, there is no description about a method for obtaining a brilliant ink for lithographic printing excellent in printability and further obtaining a printed matter having high glossiness and specularity.
また特許文献２〜３には、光輝性顔料を含有する印刷インキをオフセット印刷し、その上部にクリアー層を設けた印刷物に関する記載がある。しかしながら、実際に記載されている印刷機は、版材に樹脂凸版を使用した方式であり、水と油の反発を利用し画像形成を行う平版印刷方式とは異なる。また特許文献２〜３には、平版印刷用として使用する樹脂、植物油、溶剤などの記載はあるものの、具体的な種類、添加量は明記されておらず、使用する材料次第では、印刷時に汚れによる印刷不良を起こしたり、光沢性が発現しなかったりする恐れがある。更に上記文献では、上記クリアー層によって光輝性を向上させているものの、光輝性顔料を含有する印刷インキ層が凸凹であると、前記印刷インキ層表面で反射光が乱反射を起こし、光沢性の発現が不十分となる。 Patent Documents 2 to 3 describe a printed matter in which a printing ink containing a bright pigment is offset printed and a clear layer is provided thereon. However, the printing machine actually described is a method using a resin relief plate as a plate material, and is different from a lithographic printing method in which image formation is performed by utilizing repulsion of water and oil. In addition, Patent Documents 2 to 3 describe resins, vegetable oils, solvents, and the like used for lithographic printing, but specific types and addition amounts are not specified, and depending on the materials used, stains may occur during printing. There is a risk that printing failure may occur due to or that glossiness does not appear. Furthermore, in the above-mentioned document, although the glitter is improved by the clear layer, if the printing ink layer containing the glitter pigment is uneven, the reflected light causes irregular reflection on the surface of the printing ink layer, thereby exhibiting gloss. Is insufficient.
その他、特許文献４には、フレキソ印刷でパールインキを印刷したのち、非光輝性インキをオフセット方式により印刷した印刷物が開示されている。しかしながら特許文献４にも記載されているように、前記パールインキによる印刷層は表面が凸凹になっているため、光の乱反射により、光沢度に劣る印刷物になってしまう。また上記の通り、特許文献４で具体的に開示されたパールインキは平版印刷用ではないため、光輝性インキを平版印刷方式で使用し、しかもその印刷適性を向上させる手法に関しては記載がない。 In addition, Patent Document 4 discloses a printed matter obtained by printing a pearl ink by flexographic printing and then printing a non-brilliant ink by an offset method. However, as described in Patent Document 4, since the surface of the printed layer made of the pearl ink has an uneven surface, the printed matter is inferior in glossiness due to irregular reflection of light. Further, as described above, since the pearl ink specifically disclosed in Patent Document 4 is not intended for lithographic printing, there is no description regarding a technique for using glitter ink and improving its printing suitability.
本発明は、上記課題を解決すべくなされたものであって、その目的は、印刷・加工適性（着肉性、耐汚れ性）に優れる平版印刷用光輝性インキを用いた、従来よりも光沢度が高く鏡面性を有する印刷物の製造方法、及び、前記印刷物の製造方法により得られる印刷物を提供することにある。 The present invention has been made in order to solve the above-mentioned problems, and its purpose is to use glossy ink for lithographic printing, which is excellent in printing and processing suitability (thickness and stain resistance), and more glossy than before. The object is to provide a method for producing a printed matter having a high degree of specularity and a printed matter obtained by the method for producing a printed matter.
本発明者らが鋭意研究した結果、特定の形状を有する金属顔料（Ａ）を含む平版印刷用光輝性インキを用い、かつ、前記光輝性インキを印刷した後に、特定の条件で加熱加圧処理を施すことで、上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies by the present inventors, a lithographic printing glitter ink containing a metal pigment (A) having a specific shape was used, and after printing the glitter ink, heating and pressurizing treatment was performed under specific conditions. As a result, it was found that the above-mentioned object can be achieved, and the present invention has been completed.
即ち本発明は、平版印刷用光輝性インキを用いた印刷物の製造方法であって、前記平版印刷用光輝性インキが、平均厚さが１５〜１００ｎｍ、かつ、平均粒子径が１〜３０μｍである金属顔料（Ａ）と、バインダー樹脂とを含み、
前記バインダー樹脂が、アルキッド樹脂及び／または石油樹脂を、インキ全量に対して５〜９０質量％含み、
前記アルキッド樹脂の重量平均分子量が、１，０００〜１５０，０００であり、
前記石油樹脂の重量平均分子量が、５００〜５，０００であり、
基材上に前記平版印刷用光輝性インキを印刷する工程（ｉ）と、
印刷物を４０〜１３０℃かつ１０〜５００ｋｇｆ／ｃｍ2の条件で加熱加圧処理する工
程（ｉｉ）とを、この順に行う、印刷物の製造方法に関するものである。
That is, the present invention is a method for producing a printed matter using a lithographic printing glitter ink, wherein the lithographic printing glitter ink has an average thickness of 15 to 100 nm and an average particle diameter of 1 to 30 μm. Including a metal pigment (A) and a binder resin,
The binder resin contains alkyd resin and / or petroleum resin in an amount of 5 to 90% by mass based on the total amount of ink,
The alkyd resin has a weight average molecular weight of 1,000 to 150,000,
The petroleum resin has a weight average molecular weight of 500 to 5,000,
A step (i) of printing the lithographic printing glitter ink on a substrate;
The present invention relates to a method for producing a printed material, in which the step (ii) of heating and pressing the printed material under conditions of 40 to 130 ° C. and 10 to 500 kgf / cm 2 is performed in this order.
更に本発明は、前記バインダー樹脂が、アルキッド樹脂及び／または石油樹脂を、バインダー樹脂全量中２０〜１００質量％含む、上記印刷物の製造方法に関するものである。 Furthermore, this invention relates to the manufacturing method of the said printed matter in which the said binder resin contains 20-100 mass% of alkyd resin and / or petroleum resin in binder resin whole quantity.
更に本発明は、前記金属顔料（Ａ）が、アルミニウム顔料を含む、上記印刷物の製造方法に関するものである。 Furthermore, this invention relates to the manufacturing method of the said printed matter in which the said metal pigment (A) contains an aluminum pigment.
更に本発明は、前記工程（ｉｉ）の後に、更に、平版印刷用非光輝性インキを印刷する工程（ｉｉｉ）を行う、上記印刷物の製造方法に関するものである。 Furthermore, this invention relates to the manufacturing method of the said printed matter which performs the process (iii) of printing the brilliant ink for lithographic printing after the said process (ii).
更に本発明は、前記工程（ｉ）と前記工程（ｉｉ）との間で、更に、平版印刷用非光輝性インキを印刷する工程（ｉｉｉ）を行う、上記印刷物の製造方法に関するものである。 Furthermore, this invention relates to the manufacturing method of the said printed matter which performs the process (iii) which further prints the non-brilliant ink for lithographic printing between the said process (i) and the said process (ii).
本発明によって、印刷・加工適性（着肉性、耐汚れ性）に優れる平版印刷用光輝性インキを用いた、従来よりも光沢度が高く鏡面性を有する印刷物の製造方法、及び、前記印刷物の製造方法により得られる印刷物を提供することが可能となった。 According to the present invention, there is provided a method for producing a printed matter having a glossiness higher than that in the past and having a specularity using a glittering ink for lithographic printing, which is excellent in printing and processing suitability (inking properties and stain resistance), and It has become possible to provide printed matter obtained by the manufacturing method.
以下に、本発明の印刷物の製造方法、及び、前記印刷物の製造方法により得られる印刷物について、好ましい形態を上げながら詳細に説明する。 Hereinafter, the method for producing a printed matter of the present invention and the printed matter obtained by the method for producing a printed matter will be described in detail with increasing preferred forms.
＜１．平版印刷用光輝性インキ＞
まず、本発明における平版印刷用光輝性インキ（以下、単に「光輝性インキ」ともいう）について説明する。
本発明における光輝性インキは、平均厚さが１５〜１００ｎｍ、かつ、平均粒子径が１〜３０μｍである金属顔料（Ａ）と、バインダー樹脂とを含む。
<1. Bright ink for lithographic printing>
First, the brilliant ink for lithographic printing in the present invention (hereinafter also simply referred to as “brilliant ink”) will be described.
The glitter ink in the present invention contains a metal pigment (A) having an average thickness of 15 to 100 nm and an average particle diameter of 1 to 30 μm, and a binder resin.
上記の通り、本発明における金属顔料（Ａ）の平均厚さは、１５〜１００ｎｍであり、好ましくは１５〜８０ｎｍ、特に好ましくは１５〜５０ｎｍである。平均厚さを１５ｎｍ以上とすることで、ブロッキングや後胴残りなどがない、印刷適性に優れたインキとなるうえ、基材への密着性も向上する。また、基材の影響、例えば紙繊維による凸凹の影響を受けにくくなり、後述する加熱加圧処理を施すことで、光沢度の高い、鏡面の様な輝きを有する印刷物が得られる。一方、平均厚さを１００ｎｍ以下とすると、金属顔料（Ａ）が基材上で配向した際、前記金属顔料（Ａ）同士が重なった部分の段差が十分小さくなることで、均一的な配向が実現でき、光沢度の著しい向上や、鏡面の様な輝きを有する印刷物を得ることができる。また、後述する加熱加圧処理を施した際の汚れ、例えば、プレス板へのインキ付着なども防止できる。 As above-mentioned, the average thickness of the metal pigment (A) in this invention is 15-100 nm, Preferably it is 15-80 nm, Most preferably, it is 15-50 nm. By setting the average thickness to 15 nm or more, the ink is excellent in printability with no blocking or rear cylinder residue, and adhesion to the substrate is also improved. Moreover, it becomes difficult to receive the influence of a base material, for example, the unevenness | corrugation by paper fiber, and the printed matter which has the glossiness like a mirror surface with high glossiness is obtained by performing the heat-pressing process mentioned later. On the other hand, when the average thickness is 100 nm or less, when the metal pigment (A) is oriented on the substrate, the level difference in the portion where the metal pigments (A) overlap is sufficiently small, so that uniform orientation is achieved. It can be realized, and a printed matter having a remarkable improvement in glossiness and a mirror-like shine can be obtained. Moreover, the stain | pollution | contamination at the time of performing the heating-pressing process mentioned later, for example, ink adhesion to a press board, etc. can be prevented.
更に、本発明における金属顔料（Ａ）は、平均粒子径が１〜３０μｍであり、より好ましくは３〜２０μｍであり、更に好ましくは５〜１５μｍである。平均粒子径を１μｍ以上とすることで、基材上で前記金属顔料（Ａ）が配向した際に粒子感が出ることがなくなり、光の乱反射を防ぎ光沢度が向上する。一方、３０μｍ以下とすることで、基材上での金属顔料（Ａ）の重なりが好適なものとなり、光の乱反射を防ぐことができる。また、印刷物の着肉不良を防ぐことができる。 Furthermore, the metal pigment (A) in the present invention has an average particle diameter of 1 to 30 μm, more preferably 3 to 20 μm, and further preferably 5 to 15 μm. By setting the average particle diameter to 1 μm or more, no particle feeling is produced when the metal pigment (A) is oriented on the base material, and irregular reflection of light is prevented and glossiness is improved. On the other hand, by setting it as 30 micrometers or less, the overlap of the metal pigment (A) on a base material becomes suitable, and the irregular reflection of light can be prevented. In addition, it is possible to prevent imperfection of printed matter.
上記のように、平均厚さが１５〜１００ｎｍ、かつ、平均粒子径が１〜３０μｍである金属顔料（Ａ）を用いることで、前記金属顔料（Ａ）が、光輝性インキによって形成される印刷層表面で均一かつ平滑に配向すると考えられる。その結果、後述する加熱加圧処理の際に、軟化・溶解したバインダー樹脂が、加熱加圧処理装置に付着することを抑制することができる。 As described above, by using the metal pigment (A) having an average thickness of 15 to 100 nm and an average particle diameter of 1 to 30 μm, the metal pigment (A) is formed by glittering ink. It is considered that the layer surface is oriented uniformly and smoothly. As a result, the softened / dissolved binder resin can be prevented from adhering to the heat / pressure treatment apparatus during the heat / pressure treatment described below.
なお、金属顔料（Ａ）の平均厚さや平均粒子径は、走査型電子顕微鏡によって測定することができる。具体的には、平均厚さは、走査型電子顕微鏡写真（例えば、倍率３０，０００倍にて撮影した写真を利用する。なお写真は必要に応じて複数枚用いて良い。また、倍率、加速電圧、測定距離などは画像により厚さを測定できる範囲で変更しても良い。）から、顔料の厚みが確認できる部分を１００か所抽出し、それぞれで顔料の厚さを測定したのち、その値を平均することで求める。また平均粒子径は、走査型電子顕微鏡写真（例えば、倍率５０００倍にて撮影した写真を利用する。なお写真は必要に応じて複数枚用いて良い。また、倍率、加速電圧、測定距離などは画像により粒子径を測定できる範囲で変更しても良い。）から、粒子径が確認できる粒子を１００個抽出し、それぞれで顔料の粒子径（計測した粒子の面積に相当する円の直径）を測定したのち、その値を平均することで求める。 In addition, the average thickness and average particle diameter of a metal pigment (A) can be measured with a scanning electron microscope. Specifically, for the average thickness, a scanning electron micrograph (for example, a photograph taken at a magnification of 30,000 is used. A plurality of photographs may be used as necessary. The voltage, measurement distance, etc. may be changed within the range where the thickness can be measured by an image.) From 100 portions where the pigment thickness can be confirmed are extracted, and after measuring the pigment thickness, Calculate by averaging the values. The average particle diameter is a scanning electron micrograph (for example, a photograph taken at a magnification of 5000 times. A plurality of photographs may be used if necessary. Further, magnification, acceleration voltage, measurement distance, etc. From the image, the particle diameter can be changed within a range that can be measured.) From 100 particles, the particle diameter of which can be confirmed is extracted, and the particle diameter of the pigment (the diameter of the circle corresponding to the measured particle area) is extracted for each particle. After measurement, the value is obtained by averaging.
本発明における金属顔料（Ａ）としては、上記平均厚さ及び平均粒子径を有しているものであれば、従来既知の金属顔料を任意に使用できる。なお本発明における「金属顔料」とは、単金属材料や合金材料を主として（５０質量％以上）含む顔料を表し、具体的な材質として、アルミニウム、銅、亜鉛、鉄、銀などの単金属材料や、真鍮、青銅、ステンレスなどの合金材料が例示できる。また、顔料の表面が、無機物（金属酸化物、マイカ、ガラスなど）、有機物（着色顔料、界面活性剤、樹脂など）、シランカップリング剤などで処理されていてもよいし、顔料が金属層を含む積層体となっていてもよい。更に、２種類以上の金属顔料（Ａ）を併用してもよい。
本発明では、後述する加熱加圧処理を施すことで光沢度の高い印刷物が得られることや、印刷適性に優れた光輝性インキが得られることから、金属顔料（Ａ）がアルミニウム顔料であることが好ましい。
As the metal pigment (A) in the present invention, a conventionally known metal pigment can be arbitrarily used as long as it has the above average thickness and average particle diameter. The “metal pigment” in the present invention represents a pigment mainly containing a single metal material or an alloy material (50% by mass or more), and specific materials such as single metal materials such as aluminum, copper, zinc, iron, and silver. Examples thereof include alloy materials such as brass, bronze, and stainless steel. The surface of the pigment may be treated with an inorganic substance (metal oxide, mica, glass, etc.), an organic substance (colored pigment, surfactant, resin, etc.), a silane coupling agent, etc. It may be a laminated body containing. Further, two or more kinds of metal pigments (A) may be used in combination.
In the present invention, a printed matter having a high glossiness can be obtained by applying a heat and pressure treatment described later, and a glittering ink having excellent printability can be obtained. Therefore, the metal pigment (A) is an aluminum pigment. Is preferred.
なおアルミニウム顔料には複数の製造方法があり、本発明ではそのどちらで製造されたものであっても利用できる。例えば粉砕法は、アルミニウム塊（インゴット）を溶融した後、フレークまたは固形状で取り出し、必要に応じて表面処理を加えた後、溶剤中でミル粉砕して、粒径、厚さ及び表面状態を整形する手法である。なお本発明では、金属顔料（Ａ）として、ミルから取り出したままの（溶剤中に分散された）形態のもの（アルミニウムペースト）を利用してもよい。 In addition, there are a plurality of production methods for aluminum pigments, and any of those produced in the present invention can be used. For example, in the pulverization method, an aluminum lump (ingot) is melted and then taken out as flakes or solids, and after surface treatment as necessary, milled in a solvent to determine the particle size, thickness and surface condition. It is a technique of shaping. In the present invention, as the metal pigment (A), a metal pigment (A) that has been removed from the mill (dispersed in a solvent) (aluminum paste) may be used.
また蒸着法は、フィルム上に剥離層を均一に塗り、更にその上にアルミニウム層を薄く展開したのち、剥離層を溶かすことで、偏平状となったアルミニウム顔料を採取する。そして得られたアルミニウム顔料に対し、撹拌処理、超音波処理、噴霧処理などによって、形状を整える手法である。 In the vapor deposition method, a release layer is uniformly coated on a film, and an aluminum layer is further thinly spread on the film. Then, the release layer is melted to collect a flat aluminum pigment. And it is the method of adjusting the shape with respect to the obtained aluminum pigment by stirring treatment, ultrasonic treatment, spraying treatment or the like.
本発明における金属顔料（Ａ）としてアルミニウム顔料を用いる場合、平均厚さが１５〜１００ｎｍ、かつ、平均粒子径が１〜３０μｍの範囲内であれば、上記どちらの製法で製造されたものを用いてもよいが、蒸着法で精製されたアルミニウム顔料の方が、顔料膜厚が均一なために印刷した際の印刷物表面においても均一の薄膜を形成しやすく、印刷物の光沢度や印刷適性に優れるため、好ましく選択される。 When an aluminum pigment is used as the metal pigment (A) in the present invention, the one manufactured by either of the above-described methods is used as long as the average thickness is 15 to 100 nm and the average particle diameter is in the range of 1 to 30 μm. However, aluminum pigment purified by vapor deposition method is more uniform in pigment film thickness, so it is easier to form a uniform thin film on the printed surface, and it has better gloss and printability. Therefore, it is preferably selected.
一方で金属顔料（Ａ）には、印刷層内での分散状態による分類があり、具体的にはリーフィングタイプやノンリーフィングタイプが知られている。これらは例えば、金属顔料（Ａ）の表面処理によって制御でき、具体的には金属顔料（Ａ）に対し、特開２００３−１２９６４号公報記載の処理や、ステアリン酸などの高級脂肪酸による表面処理を施すことで、リーフィングタイプとなる。リーフィングタイプの金属顔料（Ａ）は、印刷層表面に浮き出て平行配列するものであり、光沢性を発現しやすい。一方、ノンリーフィングタイプの金属顔料（Ａ）は、印刷層内に均一に分散されており、浸透乾燥型、ヒートセット型などの乾燥方式をとるインキに対して用いることで、好適に光沢性を発現できる。 On the other hand, the metal pigment (A) is classified according to the dispersion state in the printing layer, and specifically, leafing type and non-leafing type are known. These can be controlled, for example, by the surface treatment of the metal pigment (A). Specifically, the metal pigment (A) is subjected to the treatment described in JP-A-2003-12964 or a surface treatment with a higher fatty acid such as stearic acid. By applying, it becomes a leafing type. The leafing type metal pigment (A) floats on the surface of the printing layer and is arranged in parallel, and easily exhibits gloss. On the other hand, the non-leafing type metal pigment (A) is uniformly dispersed in the printing layer, and is suitably used for inks having a drying method such as a osmotic drying type or a heat set type, so that the glossiness is suitably improved. It can be expressed.
本発明における金属顔料（Ａ）は、上記いずれのタイプも使用可能であるが、リーフィングタイプの方が、印刷物の光沢度が高く、また加熱加圧処理の際に、バインダー樹脂の、加熱加圧処理装置への付着を防止する効果が高いことから好ましい。 Any of the above types can be used as the metal pigment (A) in the present invention, but the leafing type has higher gloss of the printed matter, and the heat and pressure of the binder resin during the heat and pressure treatment. It is preferable because the effect of preventing adhesion to the processing apparatus is high.
本発明における金属顔料（Ａ）の添加量は、インキ全量中に３〜２０質量％であることが好ましく、より好ましくは３．５〜１５質量％、更に好ましくは４〜１０質量％である。金属顔料（Ａ）の添加量を３質量％以上とすることで、画像を均一に覆うに十分な量となり、白抜けなどの画像欠陥のない印刷物となる。また、下地の影響を受けなくなるため、白味を帯びることなく、光沢性に優れる印刷物が得られる。一方、２０質量％以下とすることで、印刷後の基材上で金属顔料（Ａ）同士が過度に重なることがなく、均一で乱反射を起こしにくい印刷表面が得られ、結果として光沢度が向上し、鏡面の様な輝きを有する印刷物が得られる。またパイリングや地汚れがない、印刷適性に優れたインキとなる。 The addition amount of the metal pigment (A) in the present invention is preferably 3 to 20% by mass, more preferably 3.5 to 15% by mass, and further preferably 4 to 10% by mass in the total amount of the ink. By making the addition amount of the metal pigment (A) 3% by mass or more, it becomes an amount sufficient to uniformly cover the image, and a printed matter without image defects such as white spots is obtained. In addition, since it is not affected by the background, a printed matter having excellent glossiness can be obtained without being white. On the other hand, when the content is 20% by mass or less, the metal pigments (A) do not excessively overlap each other on the substrate after printing, and a printing surface that is uniform and hardly causes irregular reflection can be obtained. As a result, the glossiness is improved. Thus, a printed matter having a mirror-like shine can be obtained. In addition, the ink is excellent in printability and free from piling and background stains.
本発明における平版印刷用光輝性インキはバインダー樹脂を含む。中でも、前記バインダー樹脂として、アルキッド樹脂及び石油樹脂から選ばれる少なくとも１種の樹脂を、バインダー樹脂全量中２０〜１００質量％含むことが好ましく、４０〜１００質量％含むことがより好ましく、６０〜９５質量％含むことが特に好ましい。バインダー樹脂として上記の樹脂を用い、かつ、上記で述べた金属顔料（Ａ）と併用することで、平版印刷適性を保持しながら、従来よりも光沢度が高く、鏡面性を有する印刷物を得ることができる。その理由は定かではないが、例えば以下の理由が考えられる。すなわち、アルキッド樹脂や石油樹脂は、構造中に極性基を含み、この極性基が金属顔料（Ａ）の表面に吸着することで、互いの凝集を防ぎ、インキ中でも均一に分散されると考える。また均一に分散されることで、インキの粘弾性が平版印刷に好適なものとなり、印刷時のトラブルも抑制できると考えられる。
更には、アルキッド樹脂や石油樹脂は、分子構造上立体障害が少ないため、印刷後のインキ層内において、金属顔料（Ａ）の配向を阻害することがない。その結果、金属顔料（Ａ）が偏ることなく均一に配向することで、凸凹のない印刷物となり、後述する加熱加圧処理を施すことで、優れた光沢性や鏡面性が発現すると考えられる。加えて、アルキッド樹脂や石油樹脂は、平版印刷に必要な乳化適性、ローラー転移性、粘弾性をインキに付与できるとともに、軟化温度などの熱的特性の点で、本発明の加熱加圧処理によって鏡面性に優れた印刷物が得られる点からも好適である。一般に、軟化温度が低いバインダー樹脂に対して加熱加圧処理を施すと、それら樹脂が加熱加圧処理装置に付着する可能性があるが、本発明では、上記の通り、特定の形状を有する金属顔料（Ａ）によって、その防止を図っている。
The glittering ink for lithographic printing in the present invention contains a binder resin. Among them, the binder resin preferably contains at least one resin selected from alkyd resins and petroleum resins, in an amount of 20 to 100% by mass, more preferably 40 to 100% by mass, and more preferably 60 to 95%, based on the total amount of the binder resin. It is particularly preferable to contain it in mass%. By using the above-mentioned resin as a binder resin and using it in combination with the metal pigment (A) described above, a printed matter having a higher gloss and mirror surface than conventional ones can be obtained while maintaining lithographic printing suitability. Can do. Although the reason is not certain, for example, the following reasons can be considered. That is, alkyd resins and petroleum resins contain polar groups in the structure, and the polar groups are adsorbed on the surface of the metal pigment (A), thereby preventing mutual aggregation and being dispersed evenly in the ink. Further, by being uniformly dispersed, it is considered that the viscoelasticity of the ink is suitable for lithographic printing, and troubles during printing can be suppressed.
Furthermore, since the alkyd resin and petroleum resin have few steric hindrances in terms of molecular structure, the orientation of the metal pigment (A) is not hindered in the ink layer after printing. As a result, the metal pigment (A) is uniformly oriented without being biased, so that a printed matter having no unevenness is obtained, and it is considered that excellent glossiness and specularity are exhibited by performing the heating and pressing treatment described later. In addition, the alkyd resin and petroleum resin can impart emulsification suitability, roller transferability and viscoelasticity necessary for lithographic printing to the ink, and in terms of thermal characteristics such as softening temperature, the heat and pressure treatment of the present invention can be used. This is also preferable from the viewpoint of obtaining a printed material having excellent specularity. In general, when heat and pressure treatment is performed on a binder resin having a low softening temperature, the resin may adhere to the heat and pressure treatment apparatus. In the present invention, as described above, a metal having a specific shape is used. The pigment (A) is used to prevent this.
なお、本発明における光輝性インキに含まれる、アルキッド樹脂及び／または石油樹脂の量は、インキ全量に対して５〜９０質量％であることが好ましく、１５〜８７．５質量％であることがより好ましく、２５〜８５質量％であることがより好ましい。 The amount of the alkyd resin and / or petroleum resin contained in the glitter ink in the present invention is preferably 5 to 90% by mass, and preferably 15 to 87.5% by mass with respect to the total amount of the ink. More preferably, it is more preferably 25 to 85% by mass.
本発明における平版印刷用光輝性インキにアルキッド樹脂を用いる場合、その重量平均分子量は１，０００〜１５０，０００であることが好ましく、より好ましくは１，０００〜３０，０００であり、更に好ましくは１，０００〜１０，０００である。重量平均分子量が１，０００以上であれば、インキに粘度をつけることができ、印刷時に汚れにくくなることから、粘度を付与し印刷適性を向上させるための増粘剤の添加を抑制できる。一般に、増粘剤を過剰添加すると、印刷紙面上の入射光と反射光の間で屈折を起こし易くなり光沢が低下する原因となるため、本発明では、重量平均分子量を１，０００以上とすることが好適である。また、１５０，０００以下とすることで、金属顔料（Ａ）の配向阻害が起こらず、鏡面的な輝きが発現するとともに、印刷面のザラツキが防止できる。 When an alkyd resin is used for the glittering ink for lithographic printing in the present invention, the weight average molecular weight is preferably 1,000 to 150,000, more preferably 1,000 to 30,000, still more preferably. 1,000 to 10,000. If the weight average molecular weight is 1,000 or more, the ink can be given a viscosity, and it becomes difficult to get smeared during printing. Therefore, the addition of a thickener for imparting viscosity and improving printability can be suppressed. In general, excessive addition of a thickening agent tends to cause refraction between incident light and reflected light on the printing paper surface and causes a reduction in gloss. In the present invention, the weight average molecular weight is 1,000 or more. Is preferred. Moreover, by setting it as 150,000 or less, the orientation inhibition of a metal pigment (A) does not occur, mirror-like brightness is expressed, and the printing surface can be prevented from being rough.
一方、本発明における平版印刷用光輝性インキに石油樹脂を用いる場合、上記アルキッド樹脂の場合と同様の理由により、その重量平均分子量は５００〜５，０００であることが好ましく、より好ましくは８００〜３，０００であり、更に好ましくは８００〜２，０００である。なお、アルキッド樹脂と好適な重量平均分子量範囲が異なるのは、分子構造の違いにより反応性が異なるためである。 On the other hand, when a petroleum resin is used for the lithographic printing glitter ink in the present invention, the weight average molecular weight is preferably 500 to 5,000, more preferably 800 to 5,000 for the same reason as in the case of the alkyd resin. It is 3,000, More preferably, it is 800-2,000. The reason why the preferred weight average molecular weight range is different from that of the alkyd resin is that the reactivity is different depending on the molecular structure.
なお、上記重量平均分子量は、公知の方法、例えばゲルパーメーションクロマトグラフィー（ＧＰＣ）法によって測定できる。 In addition, the said weight average molecular weight can be measured by a well-known method, for example, a gel permeation chromatography (GPC) method.
本発明では、アルキッド樹脂または石油樹脂を単独で用いても良いし、両者を併用しても良い。中でも、金属顔料（Ａ）の分散安定性と配向のしやすさの点から、少なくともアルキッド樹脂を含むことがより好ましい。その場合、本発明において使用されるアルキッド樹脂の添加量は、インキ全量中３０〜９０質量％であることが好ましく、より好ましくは４０〜８５質量％であり、更に好ましくは５０〜８０質量％である。添加量が３０質量％以上であれば、金属顔料（Ａ）の配向を阻害する材料や光を乱反射する材料の添加量が抑えられ、光沢度の低下を防止できる。また９０質量％以下であれば、顔料比率の低下による光沢度や濃度の低下、インキの軟調化及び過乳化を引き起こすことがなくなり、また印刷適性も保持したインキを得ることができる。 In the present invention, the alkyd resin or petroleum resin may be used alone, or both may be used in combination. Among these, it is more preferable to include at least an alkyd resin from the viewpoint of dispersion stability of the metal pigment (A) and ease of orientation. In that case, the addition amount of the alkyd resin used in the present invention is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and further preferably 50 to 80% by mass in the total amount of the ink. is there. When the addition amount is 30% by mass or more, the addition amount of a material that inhibits the orientation of the metal pigment (A) or a material that diffuses light is suppressed, and a decrease in glossiness can be prevented. On the other hand, if it is 90% by mass or less, it is possible to obtain an ink that does not cause a decrease in glossiness and density due to a decrease in the pigment ratio, causes softening and overemulsification of the ink, and retains printability.
またアルキッド樹脂を含む場合、インキ中の全樹脂量に対する配合量は５０〜１００質量％であることが好ましく、７５〜１００質量％であることが特に好ましい。配向性の高いアルキッド樹脂の配合量を５０質量％以上とすることで、金属顔料（Ａ）に対する配向を好適なものとすることができ、結果として鏡面的な輝きの発現や、印刷面のザラツキ低減が可能となる。 Moreover, when an alkyd resin is included, it is preferable that the compounding quantity with respect to the total resin amount in ink is 50-100 mass%, and it is especially preferable that it is 75-100 mass%. By adjusting the blending amount of the highly oriented alkyd resin to 50% by mass or more, the orientation with respect to the metal pigment (A) can be made suitable. As a result, the appearance of specular brightness and the roughness of the printed surface can be achieved. Reduction is possible.
本発明における平版印刷用光輝性インキは、上記以外の樹脂も含むことができ、例えばロジン変性フェノール樹脂を併用することができる。その際、ロジン変性フェノール樹脂の重量平均分子量は５，０００〜２００，０００であることが好ましい。５，０００以上とすることで、粘弾性付与の効果が大きく、画像欠陥や印刷適性の悪化を防止でき、２００，０００以下とすることで金属顔料（Ａ）の配向を阻害することなく、光沢度が高く鏡面性を有する画像が得られる。 The glittering ink for lithographic printing in the present invention can also contain a resin other than those described above, for example, a rosin-modified phenol resin can be used in combination. At that time, the weight average molecular weight of the rosin-modified phenol resin is preferably 5,000 to 200,000. By setting it to 5,000 or more, the effect of imparting viscoelasticity is great, image defects and printability can be prevented from being deteriorated, and by setting it to 200,000 or less, the gloss of the metallic pigment (A) is not hindered. An image having a high degree of specularity can be obtained.
なお、本発明における光輝性インキに含まれる、バインダー樹脂の総量は、インキ全量に対して３０〜９０質量％であることが好ましく、４０〜８５質量％であることがより好ましい。 In addition, it is preferable that it is 30-90 mass% with respect to the ink whole quantity, and, as for the total amount of binder resin contained in the glitter ink in this invention, it is more preferable that it is 40-85 mass%.
本発明における光輝性インキに用いられる溶剤は従来既知のものを任意に用いることができるが、上記バインダー樹脂との相溶性やインキの粘弾性、乾燥性を好適なものとする観点から、植物油、重合植物油、脂肪酸エステル、及び非芳香族系石油溶剤から選ばれる少なくとも１種類を含むことが好ましい。なおこれらの材料は、単独で用いても良いし、２種以上を併用しても良い。 As the solvent used in the glitter ink in the present invention, any conventionally known solvent can be arbitrarily used. From the viewpoint of making the compatibility with the binder resin, the viscoelasticity of the ink, and the drying property suitable, vegetable oil, It preferably contains at least one selected from polymerized vegetable oils, fatty acid esters, and non-aromatic petroleum solvents. In addition, these materials may be used independently and may use 2 or more types together.
なお上記「植物油」とは、グリセリンと脂肪酸とのエステル化反応物であるトリグリセライド、エステル交換反応により生成されたモノグリセライド、ジグリセライドを表す。なお、前記脂肪酸は飽和脂肪酸でも不飽和脂肪酸でも良い。 The “vegetable oil” refers to triglyceride which is an esterification reaction product of glycerin and fatty acid, monoglyceride and diglyceride produced by transesterification. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid.
本発明における植物油として代表的なものは、アサ実油、アマニ油、エノ油、オイチシカ油、オリーブ油、カカオ油、カノーラ油、カポック油、カヤ油、カラシ油、キョウニン油、キリ油、ククイ油、クルミ油、ケシ油、ゴマ油、サフラワー油、ダイコン種油、大豆油、大風子油、ツバキ油、トウモロコシ油、トール油、ナタネ油、ニガー油、ヌカ油、パーム油、ヒマシ油、ヒマワリ油、ブドウ種子油、ヘントウ油、松種子油、綿実油、ヤシ油、落花生油、脱水ヒマシ油などが挙げられる。特に大豆油、ヤシ油、アマニ油、ナタネ油、キリ油が好ましい。 Typical vegetable oils in the present invention are: Asa seed oil, flaxseed oil, eno oil, psyllium oil, olive oil, cacao oil, canola oil, kapok oil, kaya oil, mustard oil, kyounin oil, kiri oil, kukui oil, Walnut oil, poppy oil, sesame oil, safflower oil, radish seed oil, soybean oil, daikon oil, camellia oil, corn oil, tall oil, rapeseed oil, niger oil, nuka oil, palm oil, castor oil, sunflower oil, Examples include grape seed oil, gentian oil, pine seed oil, cottonseed oil, coconut oil, peanut oil, and dehydrated castor oil. Particularly preferred are soybean oil, coconut oil, linseed oil, rapeseed oil and tung oil.
本発明において使用される「重合植物油」とは、例えば上記に列挙した１種類以上の植物油を、酸素を吹き込みながら加熱・攪拌し、重合することにより得られる。ただし、このときの重合反応は熱重合でもよく、酸化重合が必須であるわけではない。重合植物油の製造に用いる植物油としては特に、大豆油、ヤシ油、アマニ油、ナタネ油、キリ油が好ましい。 The “polymerized vegetable oil” used in the present invention is obtained, for example, by polymerizing one or more of the above-listed vegetable oils while heating and stirring while blowing oxygen. However, the polymerization reaction at this time may be thermal polymerization, and oxidative polymerization is not essential. As the vegetable oil used for the production of the polymerized vegetable oil, soybean oil, coconut oil, linseed oil, rapeseed oil and tung oil are particularly preferable.
本発明において使用される「脂肪酸エステル」の例としては、上記に列挙した１種類以上の植物油、例えば大豆油、綿実油、アマニ油、サフラワー油、トール油、脱水ヒマシ油、カノーラ油、ナタネ油などから製造される植物油エステルが挙げられる。その他の例としては脂肪酸モノアルキルエステル化合物が挙げられる。このうちモノエステルを構成する脂肪酸としては炭素数１６〜２０の飽和または不飽和脂肪酸が好ましく、ステアリン酸、イソステアリン酸、ヒドロキシステアリン酸、オレイン酸、リノール酸、リノレン酸、エレオステアリン酸などが例示できる。また脂肪酸モノアルキルエステル化合物を構成する、アルコール由来のアルキル基としては炭素数１〜１０のものが好ましく、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、２−エチルヘキシル基などが例示できる。これらアルコールは、単独で、または２種以上を組み合わせて使用できる。 Examples of “fatty acid esters” used in the present invention include one or more of the vegetable oils listed above, such as soybean oil, cottonseed oil, linseed oil, safflower oil, tall oil, dehydrated castor oil, canola oil, rapeseed oil. Vegetable oil esters produced from the above. Other examples include fatty acid monoalkyl ester compounds. Of these, the fatty acid constituting the monoester is preferably a saturated or unsaturated fatty acid having 16 to 20 carbon atoms such as stearic acid, isostearic acid, hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, etc. it can. Further, the alcohol-derived alkyl group constituting the fatty acid monoalkyl ester compound is preferably one having 1 to 10 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, Examples include 2-ethylhexyl group. These alcohols can be used alone or in combination of two or more.
本発明における「非芳香族系石油溶剤」としては、パラフィン系、ナフテン系、及びこれらの混合溶剤が挙げられる。非芳香族系石油溶剤の市販品の例として、ＪＸＴＧエネルギー社製ＡＦソルベント４号、５号、６号、７号などがある。なお、混入している芳香族炭化水素の含有量が、前記非芳香族系石油溶剤全量中１質量％以下であることが好ましい。また本発明で非芳香族系石油溶剤を用いる場合、そのアニリン点は６０〜１３０℃であることが好ましい。アニリン点を１３０℃以下とすることで、インキ中のバインダー樹脂の溶解性に優れ、インキの流動性を十分確保できるため、レベリングが向上し鏡面性や光沢に優れる印刷物が得られる。また、６０℃以上とすることで、乾燥時にインキ層からの溶剤の離脱性が良化し、乾燥性に優れたインキとなる。なお本発明におけるアニリン点は、例えばＪＩＳ Ｋ ２２５６記載の方法により測定できる。 Examples of the “non-aromatic petroleum solvent” in the present invention include paraffinic, naphthenic, and mixed solvents thereof. Examples of commercially available non-aromatic petroleum solvents include AF Solvent Nos. 4, 5, 6, and 7 manufactured by JXTG Energy. In addition, it is preferable that content of the aromatic hydrocarbon mixed is 1 mass% or less in the said non-aromatic petroleum solvent whole quantity. Moreover, when using a non-aromatic petroleum solvent by this invention, it is preferable that the aniline point is 60-130 degreeC. By setting the aniline point to 130 ° C. or less, the binder resin in the ink is excellent in solubility and the fluidity of the ink can be sufficiently secured, so that the leveling is improved and a printed matter having excellent specularity and gloss can be obtained. Moreover, by setting it as 60 degreeC or more, the detachment | desorption property of the solvent from an ink layer improves at the time of drying, and it becomes the ink excellent in drying property. In addition, the aniline point in this invention can be measured by the method of JISK2256, for example.
また本発明における平版印刷用光輝性インキは、エーテル類を併用することもできる。代表的なものは、ジ−ｎ−オクチルエーテル、ジノニルエーテル、ジへプチルエーテル、ジヘキシルエーテル、ジデシルエーテル、ノニルへキシルエーテル、ノニルヘプチルエーテル、ノニルオクチルエーテルなどが挙げられる。 Further, the glittering ink for lithographic printing in the present invention can be used in combination with ethers. Typical examples include di-n-octyl ether, dinonyl ether, diheptyl ether, dihexyl ether, didecyl ether, nonyl hexyl ether, nonyl heptyl ether, nonyl octyl ether and the like.
更に本発明における平版印刷用光輝性インキには、必要に応じて金属ドライヤーを添加することができる。金属ドライヤーとしては、マンガン、コバルト、ニッケル、亜鉛錯体などが挙げられる。 Furthermore, a metallic dryer can be added to the glittering ink for lithographic printing according to the present invention, if necessary. Examples of the metal dryer include manganese, cobalt, nickel, and zinc complex.
更に本発明における平版印刷用光輝性インキには、必要に応じて増粘剤を添加することができる。増粘剤としては、カルボン酸系共重合体、特開２０１３−２１３１１２記載のゲル状脂肪酸グリセリド、及びイソブテン、ノルマルブテンからなる長鎖状炭化水素共重合体などが挙げられる。 Furthermore, a thickener can be added to the glittering ink for lithographic printing according to the present invention, if necessary. Examples of the thickener include carboxylic acid copolymers, gel fatty acid glycerides described in JP2013-213112, and long-chain hydrocarbon copolymers composed of isobutene and normal butene.
その他、本発明における平版印刷用光輝性インキには、必要に応じてゲル化剤、顔料分散剤、酸化防止剤、耐擦過剤、裏移り防止剤、非イオン系界面活性剤、多価アルコールなどの添加剤を適宜使用することができる。 In addition, the glittering ink for lithographic printing according to the present invention includes a gelling agent, a pigment dispersant, an antioxidant, an anti-scratch agent, an anti-set-off agent, a nonionic surfactant, a polyhydric alcohol, etc. These additives can be used as appropriate.
＜２．平版印刷用非光輝性インキ＞
続いて、後述する平版印刷用非光輝性インキを印刷する工程（ｉｉｉ）にて使用する、平版印刷用非光輝性インキ（以下、単に「非光輝性インキ」ともいう）について説明する。
<2. Non-brilliant ink for lithographic printing>
Subsequently, a non-brilliant ink for lithographic printing (hereinafter also simply referred to as “non-brilliant ink”) used in the step (iii) of printing a non-brilliant ink for lithographic printing described later will be described.
なお、上記光輝性インキと非光輝性インキとは、インキ中の金属顔料の量によって区別される。具体的には、本発明における光輝性インキとは、金属顔料の量が、インキ中の全着色剤中５０質量％以上であるものであり、非光輝性インキとは、金属顔料の含有量が、インキ中の全着色剤中５０質量％未満であるものである。なお、非光輝性インキ中の、金属顔料の含有量は、インキ中の全着色剤に対して３０質量％以下であることが好ましく、１０質量％以下であることがより好ましく、５質量％以下であることが特に好ましく、２質量%以下であることが極めて好ましい。 Note that the glitter ink and the non-luster ink are distinguished by the amount of the metal pigment in the ink. Specifically, the glitter ink in the present invention is one in which the amount of the metal pigment is 50% by mass or more in the total colorant in the ink, and the non-brilliant ink has a content of the metal pigment. The total colorant in the ink is less than 50% by mass. In addition, the content of the metal pigment in the non-brilliant ink is preferably 30% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less with respect to the total colorant in the ink. Particularly preferred is 2% by mass or less.
本発明における非光輝性インキは、着色剤として顔料を含むことが好ましい。顔料として、従来既知の有機顔料、及び／または無機顔料を任意に使用することができる。また前記顔料として、体質顔料を含んでもよい。本発明における顔料の配合量（ただし前記顔料の配合量に、体質顔料の配合量は含まない）は、本発明の効果を阻害することなく、印刷物の発色性や鮮明性を確保できる量とすることが好ましい。具体的には、非光輝性インキ全量に対し、１０〜４０質量％とすることが好ましく、１５〜３５質量％とすることが特に好ましい。 The non-brilliant ink in the present invention preferably contains a pigment as a colorant. Conventionally known organic pigments and / or inorganic pigments can be arbitrarily used as the pigment. Further, as the pigment, an extender pigment may be included. The blending amount of the pigment in the present invention (however, the blending amount of the pigment does not include the blending amount of the extender pigment) is an amount that can ensure the color developability and sharpness of the printed matter without impairing the effects of the present invention. It is preferable. Specifically, it is preferable to set it as 10-40 mass% with respect to non-brilliant ink whole quantity, and it is especially preferable to set it as 15-35 mass%.
本発明における非光輝性インキは、バインダー樹脂として、ロジン変性フェノール樹脂、アルキッド樹脂、及び石油樹脂から選ばれる少なくとも１種の樹脂を含むことが好ましい。なお、上記３種類の樹脂のいずれかを単独で用いても良いし、併用しても良い。特に本発明では、顔料の分散安定性や、印刷物の鏡面性を阻害しない点から、少なくともロジン変性フェノール樹脂を含むことが好ましい。非光輝性インキに含まれるバインダー樹脂の含有量は、前記非光輝性インキ全量に対し、１５〜３０質量％であることが好ましく、より好ましくは２０〜２５質量％である。 The non-brilliant ink in the present invention preferably contains at least one resin selected from rosin-modified phenolic resins, alkyd resins, and petroleum resins as a binder resin. In addition, any of the above three types of resins may be used alone or in combination. In particular, in the present invention, it is preferable to include at least a rosin-modified phenol resin from the viewpoint of not inhibiting the dispersion stability of the pigment and the specularity of the printed matter. The content of the binder resin contained in the non-brilliant ink is preferably 15 to 30% by mass, and more preferably 20 to 25% by mass with respect to the total amount of the non-brilliant ink.
本発明における非光輝性インキは、溶剤として従来既知のものを任意に用いることができ、例えば、植物油、重合植物油、脂肪酸エステル、及び非芳香族系石油溶剤から選ばれる少なくとも１種を使用できる。なお好適に使用できる、植物油、重合植物油、脂肪酸エステル、及び非芳香族系石油溶剤の種類や配合量は、上記光輝性インキの場合と同様である。 As the non-brilliant ink in the present invention, conventionally known solvents can be arbitrarily used. For example, at least one selected from vegetable oils, polymerized vegetable oils, fatty acid esters, and non-aromatic petroleum solvents can be used. The types and blending amounts of vegetable oil, polymerized vegetable oil, fatty acid ester, and non-aromatic petroleum solvent that can be suitably used are the same as in the case of the glitter ink.
また、本発明における非光輝性インキは、上記光輝性インキの場合と同様に、必要に応じて金属ドライヤーや増粘剤を使用できる。 In addition, the non-brilliant ink in the present invention can use a metal dryer or a thickener as necessary, as in the case of the glitter ink.
その他、本発明における非光輝性インキは、上記の成分以外にも、既存のゲル化剤、顔料分散剤、乳化剤、乳化抑制剤、酸化防止剤、耐擦過剤、裏移り防止剤、非イオン系界面活性剤、多価アルコールなどの各種添加剤を、適宜用いることができる。その配合量の総量は、非光輝性インキ全量に対して１０質量％以下とすることが好ましい。 In addition, the non-brilliant ink in the present invention includes, in addition to the above components, existing gelling agents, pigment dispersants, emulsifiers, emulsification inhibitors, antioxidants, scratch-resistant agents, anti-set-off agents, nonionic Various additives such as a surfactant and a polyhydric alcohol can be appropriately used. The total amount is preferably 10% by mass or less based on the total amount of the non-brilliant ink.
＜３．平版印刷用光輝性インキを印刷する工程（ｉ）＞
続いて、上記で説明した平版印刷用光輝性インキを印刷する工程（ｉ）（以下、単に「印刷工程（ｉ）」ともいう）について説明する。
印刷工程（ｉ）では、平版（オフセット）印刷により、光輝性インキが後述する基材上に付与される。なお、前記平版印刷で使用される印刷機として、オフセット輪転印刷機とオフセット枚葉印刷機のどちらを使用してもよいが、金属顔料（Ａ）の配向性や、インキの乾燥性の点から、オフセット枚葉印刷機を選択することが好ましい。
<3. Step of printing glitter ink for lithographic printing (i)>
Subsequently, the step (i) for printing the lithographic printing glitter ink described above (hereinafter also simply referred to as “printing step (i)”) will be described.
In the printing step (i), the glitter ink is applied on the substrate described later by lithographic (offset) printing. In addition, as a printing machine used in the lithographic printing, either an offset rotary printing machine or an offset sheet-fed printing machine may be used. From the viewpoint of the orientation of the metal pigment (A) and the drying property of the ink. It is preferable to select an offset sheet-fed printing press.
本発明の印刷物の製造方法では、光輝性インキを基材上に付与した後、前記光輝性インキを乾燥させてから加熱加圧処理する工程（ｉｉ）に移ってもよいし、乾燥させずに加熱加圧処理する工程（ｉｉ）に移ってもよい。 In the method for producing a printed matter of the present invention, after the glitter ink is applied on the substrate, the glitter ink may be dried and then transferred to the step (ii) of heating and pressurizing without drying. You may transfer to the process (ii) which heat-presses.
なお、光輝性インキを乾燥させる方式として、ヒートセット型、酸化重合型、浸透乾燥型のいずれを選択してもよいが、本発明の場合は、経時で徐々に金属顔料（Ａ）をリーフィングさせることで、光輝性に優れた印刷物が得られる観点から、特に酸化重合型の乾燥方式を有する平版印刷において、好適に使用できる。また同様の理由により、酸化重合型の乾燥方式をとる光輝性インキの場合、前記光輝性インキを基材上に付与した後、乾燥させてから加熱加圧処理する工程（ｉｉ）に移る方法が好適に利用できる。 As a method for drying the glitter ink, any of a heat set type, an oxidation polymerization type, and a permeation drying type may be selected. In the present invention, the metal pigment (A) is gradually leafed over time. Thus, from the viewpoint of obtaining a printed matter excellent in glitter, it can be suitably used particularly in lithographic printing having an oxidation polymerization type drying method. For the same reason, in the case of glittering ink that takes an oxidation polymerization type drying method, after applying the glittering ink on a substrate, the method is transferred to a step (ii) of drying and heating and pressurizing. It can be suitably used.
＜４．印刷物を加熱加圧処理する工程（ｉｉ）＞
続いて、上記工程（ｉ）の後に行う、光輝性インキが印刷された印刷物を加熱加圧処理する工程（ｉｉ）（以下、単に「加熱加圧工程（ｉｉ）」ともいう）について説明する。
本発明では、４０〜１３０℃かつ１０〜５００ｋｇｆ／ｃｍ2の条件で加熱加圧処理を行う。上記条件で加熱加圧処理を行うことで、紙面上に無秩序に配向した金属顔料（Ａ）の配向を均一化することが可能となり、光沢度の著しい向上や、鏡面のような輝きを有する印刷物が得られると考えられる。
<4. Process of heat-pressing printed matter (ii)>
Subsequently, the step (ii) (hereinafter also simply referred to as “heating and pressurizing step (ii)”) of heating and pressurizing the printed matter printed with the glitter ink is performed after the step (i).
In the present invention, the heat and pressure treatment is performed under the conditions of 40 to 130 ° C. and 10 to 500 kgf / cm 2 . By performing the heat and pressure treatment under the above-mentioned conditions, it becomes possible to make the orientation of the metal pigment (A) randomly oriented on the paper surface uniform, and the printed matter has a remarkable improvement in glossiness and shine like a mirror surface. Can be obtained.
上記効果をより好適に発現させるとともに、加熱加圧処理を施した際の装置の汚れ、例えば、プレス板へのインキ付着なども防止できる観点から、上記加熱温度は６０〜１３０℃であることが好ましく、８０〜１３０℃であることが特に好ましい。また上記加圧圧力は５０〜５００ｋｇｆ／ｃｍ2であることが好ましく、１００〜５００ｋｇｆ／ｃｍ2であることが特に好ましい。 The heating temperature is preferably 60 to 130 ° C. from the viewpoint of more suitably expressing the above effect and preventing contamination of the apparatus when subjected to heat and pressure treatment, for example, ink adhesion to the press plate. Preferably, it is 80-130 degreeC. Also the applied pressure is preferably from 50~500kgf / cm 2, and particularly preferably 100~500kgf / cm 2.
また、加熱加圧工程（ｉｉ）を行うための装置として、エンドレスプレス機、平プレス機などがあり、本発明ではいずれも好適に使用できるが、必要に応じて印刷装置に組み込むことができ、また連続的に加熱加圧処理を施すことができる、エンドレスプレス機が好適に使用できる。更に、上記印刷工程（ｉ）で使用する印刷機と、上記装置と、必要に応じてインキの乾燥に使用する乾燥機とを直列に接続し、前記印刷工程（ｉ）と加熱加圧工程（ｉｉ）とをインラインで実施してもよいし、オフラインで、両工程を別個に実施してもよい。なお、酸化重合型の乾燥方式をとる光輝性インキを用いる場合、オフラインで、両工程を別個に実施する方法が好適に選択される。 In addition, as an apparatus for performing the heating and pressurizing step (ii), there are an endless press machine, a flat press machine, and the like, and any of them can be suitably used in the present invention, but can be incorporated into a printing apparatus as necessary, Moreover, the endless press machine which can perform a heating-pressing process continuously can be used conveniently. Furthermore, the printing machine used in the printing process (i), the apparatus, and a dryer used for drying the ink as necessary are connected in series, and the printing process (i) and the heating and pressing process ( ii) may be performed inline, or both steps may be performed separately offline. In addition, when using the glittering ink which takes an oxidation polymerization type drying system, the method of implementing both processes separately off-line is selected suitably.
また、加熱加圧処理を施す際の駆動速度や時間に関しては特に制限はないが、例えばエンドレスプレス機の場合は１〜４０ｍ／ｍiｎの範囲、平プレス機の場合は１〜３０秒の範囲で処理を行うことが好ましい。 Moreover, there is no restriction | limiting in particular about the drive speed and time at the time of performing a heating-pressing process, For example, in the range of 1-40 m / min in the case of an endless press, and in the range of 1-30 seconds in the case of a flat press. It is preferable to carry out the treatment.
＜５．平版印刷用非光輝性インキを印刷する工程（ｉｉｉ）＞
続いて、必要に応じて実施できる、非光輝性インキを印刷する工程（ｉｉｉ）（以下、単に「印刷工程（ｉｉｉ）」ともいう）について説明する。
本発明では、必要に応じて、加熱加圧工程（ｉｉ）の後、または、印刷工程（ｉ）と加熱加圧工程（ｉｉ）との間に、印刷工程（ｉｉｉ）を実施してもよい。印刷工程（ｉｉｉ）を実施することにより、優れた光輝性を有する有色印刷物（例えばゴールド（メタリックイエロー）色、ブロンズ色、メタリックブルー色、メタリックレッド色、メタリックブラック色）が得られる。
<5. Step of printing non-brilliant ink for lithographic printing (iii)>
Subsequently, a step (iii) of printing non-brilliant ink (hereinafter also simply referred to as “printing step (iii)”) that can be performed as necessary will be described.
In the present invention, if necessary, the printing step (iii) may be performed after the heating and pressing step (ii) or between the printing step (i) and the heating and pressing step (ii). . By performing the printing step (iii), a colored printed matter (for example, gold (metallic yellow) color, bronze color, metallic blue color, metallic red color, metallic black color) having excellent glitter can be obtained.
加熱加圧工程（ｉｉ）の後に印刷工程（ｉｉｉ）を行う場合、有色化しながらも、印刷物の鏡面性を好適なまま維持できる観点から、非光輝性インキにより形成される層中に存在する、顔料の付与量は、０．０３〜０．３ｇ／ｍ2であることが好ましく、０．０５〜０．２５ｇ／ｍ2であることがより好ましく、０．０８〜０．２５ｇ／ｍ2であることが特に好ましい。 When performing the printing step (iii) after the heating and pressurizing step (ii), it is present in a layer formed from the non-brilliant ink from the viewpoint of maintaining the specularity of the printed matter while being colored, application amount of the pigment is preferably from 0.03 to 0.3 g / m 2, more preferably from 0.05~0.25g / m 2, in 0.08~0.25g / m 2 It is particularly preferred.
一方、印刷工程（ｉ）と加熱加圧工程（ｉｉ）との間で、印刷工程（ｉｉｉ）を実施する場合、光輝性インキを印刷したのち、続けて非光輝性インキを印刷し、その後、上記に記載したような方式によりインキを乾燥した後、加熱加圧工程（ｉｉ）を実施することが好ましい。 On the other hand, when the printing step (iii) is performed between the printing step (i) and the heating and pressing step (ii), after printing the glitter ink, the non-brilliant ink is subsequently printed, It is preferable to carry out the heating and pressing step (ii) after drying the ink by the method described above.
＜６．印刷物の特性＞
本発明における光輝性インキを用いた印刷物は、後述する条件により測定される光沢値が３５０〜６００であることが好ましく、４００〜６００であることがより好ましく、４５０〜６００であることが特に好ましい。
<6. Characteristics of printed matter>
The printed matter using the glitter ink in the present invention preferably has a gloss value of 350 to 600, more preferably 400 to 600, and particularly preferably 450 to 600, measured under the conditions described later. .
＜７．後処理工程＞
本発明の印刷物の製造方法によって得られた印刷物に対して、従来既知の後処理を施してもよい。前記後処理として、例えばエンボス処理、ラミネート処理などが挙げられる。
<7. Post-processing process>
You may perform conventionally known post-processing with respect to the printed matter obtained by the manufacturing method of the printed matter of this invention. Examples of the post-processing include embossing and laminating.
＜８．基材＞
本発明の印刷物の製造方法では、平版印刷方式にて印刷される用紙基材であれば、コート紙やアート紙に代表される塗工紙や、上質紙及び低級紙に代表される非塗工紙などのような一般的な印刷用紙が好適に使用できる。特に、用紙表面が平滑な塗工紙の方が、より光沢性が発現しやすく好ましい。
<8. Base material>
In the method for producing a printed matter of the present invention, as long as it is a paper base material printed by a lithographic printing method, coated paper represented by coated paper and art paper, and non-coated material represented by high-quality paper and low-quality paper General printing paper such as paper can be suitably used. In particular, coated paper having a smooth paper surface is preferred because it is more likely to exhibit gloss.
以下に、実施例により本発明を更に詳細に説明する。ただし、以下の実施例は本発明の権利範囲を何ら制限するものではない。また、特に断らない限り、「部」は、「質量部」を表し、「％」は「質量％」を表す。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples do not limit the scope of rights of the present invention. Unless otherwise specified, “part” represents “part by mass” and “%” represents “% by mass”.
＜金属顔料（Ａ）の粒子径・厚さの測定条件＞
金属顔料（Ａ）の粒子径及び厚さは、日本電子社製走査型電子顕微鏡（ＪＳＭ−６３９０ＬＡ）を用い、前述した方法にて計測した。
<Measurement conditions of particle diameter and thickness of metal pigment (A)>
The particle diameter and thickness of the metal pigment (A) were measured by the method described above using a scanning electron microscope (JSM-6390LA) manufactured by JEOL.
＜重量平均分子量の測定条件＞
重量平均分子量の測定には、東ソー社製ゲルパーメーションクロマトグラフィー（ＨＬＣ−８０２０）、及び東ソー社製カラム（ＴＳＫ−ＧＥＬ）を用いた。
<Measurement conditions of weight average molecular weight>
For the measurement of the weight average molecular weight, gel permeation chromatography (HLC-8020) manufactured by Tosoh Corporation and a column (TSK-GEL) manufactured by Tosoh Corporation were used.
＜粘度の測定条件＞
樹脂及びインキの粘度は、Ｔｈｅｒｍｏ ＥＬＥＣＴＲＯＮ ＣＯＲＰＯＲＡＴＩＯＮ社製レオメータ（ＨＡＡＫＥ Ｒｈｅｏｓｔｒｅｓｓ６００）を用い、２５℃、シェアレート１１７／ｓの条件で測定した。
<Measurement conditions for viscosity>
The viscosity of the resin and the ink was measured under the conditions of 25 ° C. and a shear rate of 117 / s using a thermometer manufactured by Thermo Electronics Corporation (HAAKE Rheotress 600).
＜鏡面光沢度の測定条件＞
印刷物の鏡面光沢度（６０°光沢度）は、村上色彩技術研究所製デジタル光沢計（ＧＭ−２６Ｄ）を用い、下記の条件にて測定した。なお、上記光沢度が高い程、鏡面性が高いことを表す。
測定面積：約３×３ｍｍ
測定窓面積：直径１０ｍｍ
光源ランプ：ハロゲンランプ（１２Ｖ、５０Ｗ）
<Measurement conditions for specular gloss>
The specular gloss (60 ° gloss) of the printed material was measured under the following conditions using a digital gloss meter (GM-26D) manufactured by Murakami Color Research Laboratory. Note that the higher the glossiness, the higher the specularity.
Measurement area: about 3 × 3mm
Measurement window area: Diameter 10mm
Light source lamp: Halogen lamp (12V, 50W)
＜アルキッド樹脂１製造例＞
大豆白絞油３００部と、無水フタル酸５０部を仕込み、２８０℃で２時間撹拌した後、ペンタエリスリトール３０部と、キシレン１００部を添加し、２００℃で３時間撹拌した。その後、２５０℃に昇温し更に３時間撹拌することで、重量平均分子量５，０００、酸価１４．０、粘度１０．７Ｐａ・ｓのアルキッド樹脂１を得た。
<Example of production of alkyd resin 1>
After adding 300 parts of soybean white squeezed oil and 50 parts of phthalic anhydride and stirring at 280 ° C. for 2 hours, 30 parts of pentaerythritol and 100 parts of xylene were added and stirred at 200 ° C. for 3 hours. Thereafter, the temperature was raised to 250 ° C. and further stirred for 3 hours to obtain an alkyd resin 1 having a weight average molecular weight of 5,000, an acid value of 14.0, and a viscosity of 10.7 Pa · s.
＜アルキッド樹脂２製造例＞
大豆白絞油２２０部と、無水フタル酸８０部を仕込み、２８０℃で２時間撹拌した後、ペンタエリスリトール３０部と、パラトルエンスルホン酸０．０２部と、キシレン１００部を添加し、２００℃で３時間撹拌した。その後、２５０℃に昇温し更に７時間撹拌することで、重量平均分子量１００，０００、酸価１９．４、粘度６６９．０Ｐａ・ｓのアルキッド樹脂２を得た。
<Example of production of alkyd resin 2>
After adding 220 parts of soybean white oil and 80 parts of phthalic anhydride and stirring at 280 ° C. for 2 hours, 30 parts of pentaerythritol, 0.02 part of paratoluenesulfonic acid, and 100 parts of xylene were added, and 200 ° C. For 3 hours. Thereafter, the temperature was raised to 250 ° C. and the mixture was further stirred for 7 hours to obtain an alkyd resin 2 having a weight average molecular weight of 100,000, an acid value of 19.4, and a viscosity of 669.0 Pa · s.
＜アルキッド樹脂３製造例＞
大豆白絞油２００部と、無水フタル酸１００部を仕込み、２８０℃で２時間撹拌した後、ペンタエリスリトール３０部と、パラトルエンスルホン酸０．０２部と、キシレン１００部を添加し、２００℃で３時間撹拌した。その後、２５０℃に昇温し更に１０時間撹拌することで、重量平均分子量１５０，０００、酸価９．６、粘度８２０．０Ｐａ・ｓのアルキッド樹脂３を得た。
<Example of production of alkyd resin 3>
After adding 200 parts of soybean white oil and 100 parts of phthalic anhydride and stirring at 280 ° C. for 2 hours, 30 parts of pentaerythritol, 0.02 part of paratoluenesulfonic acid, and 100 parts of xylene were added, and 200 ° C. For 3 hours. Thereafter, the temperature was raised to 250 ° C. and further stirred for 10 hours to obtain an alkyd resin 3 having a weight average molecular weight of 150,000, an acid value of 9.6, and a viscosity of 820.0 Pa · s.
＜アルキッド樹脂４製造例＞
大豆白絞油４００部と、無水フタル酸２０部を仕込み、２８０℃で２時間撹拌した後、ペンタエリスリトール３０部と、キシレン１００部を添加し、２００℃で３時間撹拌した。その後、２５０℃に昇温し更に３０分撹拌することで、重量平均分子量７００、酸価８．８、粘度６．０Ｐａ・ｓのアルキッド樹脂４を得た。
<Example of production of alkyd resin 4>
After adding 400 parts of soybean white oil and 20 parts of phthalic anhydride and stirring at 280 ° C. for 2 hours, 30 parts of pentaerythritol and 100 parts of xylene were added and stirred at 200 ° C. for 3 hours. Thereafter, the temperature was raised to 250 ° C. and the mixture was further stirred for 30 minutes to obtain an alkyd resin 4 having a weight average molecular weight of 700, an acid value of 8.8, and a viscosity of 6.0 Pa · s.
＜石油樹脂ワニス１製造例＞
石油樹脂（ＪＸＴＧエネルギー社製日石ネオポリマー１２０、重量平均分子量１，５００）４０部と、大豆油６０部を仕込み、１４０℃に昇温して３０分間攪拌した後、放冷することで、石油樹脂ワニス１を得た。
<Petroleum resin varnish 1 production example>
By charging 40 parts of petroleum resin (JXTG Energy Co., Ltd. Nisseki Neopolymer 120, weight average molecular weight 1,500) and 60 parts of soybean oil, raising the temperature to 140 ° C. and stirring for 30 minutes, the mixture is allowed to cool, A petroleum resin varnish 1 was obtained.
＜石油樹脂ワニス２製造例＞
石油樹脂（ＪＸＴＧエネルギー社製日石ネオポリマー１６０、重量平均分子量３，５００）２０部と、石油樹脂（ＪＸＴＧエネルギー社製日石ネオポリマー１３０、重量平均分子量１，８００）２０部と、大豆油６０部とを仕込み、１６０℃に昇温して６０分間攪拌した後、放冷することで、石油樹脂ワニス２を得た。
<Petroleum resin varnish 2 production example>
Petroleum resin (JXTG Energy's Nisseki Neopolymer 160, weight average molecular weight 3,500) 20 parts, Petroleum resin (JXTG Energy's Nisseki Neopolymer 130, weight average molecular weight 1,800) 20 parts, soybean oil 60 parts was charged, heated to 160 ° C., stirred for 60 minutes, and then allowed to cool to obtain petroleum resin varnish 2.
＜ロジン変性フェノール樹脂ワニス１製造例＞
特開平０９−２４９７２６号公報の、実施例５に記載の方法と同様にして合成した、重量平均分子量１３１，０００、酸価２４．３である、ロジン変性フェノール樹脂１を３８部と、大豆油を３０部と、非芳香族系溶剤であるＡＦソルベント５号（ＪＸＴＧエネルギー社製、アニリン点８８．２度）３１部とを仕込み、１８０℃に昇温して３０分間攪拌した。その後放冷し、ゲル化剤としてエチルアセトアセテートアルミニウムジイソプロポキシド（川研ファインケミカル社製ＡＬＣＨ）１．０部を仕込んだのち、１９０℃で３０分間攪拌することで、ロジン変性フェノール樹脂ワニス１を得た。
<Example of production of rosin-modified phenolic resin varnish 1>
38 parts of rosin-modified phenolic resin 1 having a weight average molecular weight of 131,000 and an acid value of 24.3, synthesized in the same manner as that described in Example 5 of JP-A 09-249726 30 parts and 31 parts of AF Solvent No. 5 (manufactured by JXTG Energy Co., Ltd., aniline point 88.2 degrees), which is a non-aromatic solvent, were heated to 180 ° C. and stirred for 30 minutes. Thereafter, the mixture was allowed to cool, and 1.0 part of ethyl acetoacetate aluminum diisopropoxide (ALCH manufactured by Kawaken Fine Chemical Co., Ltd.) was added as a gelling agent, followed by stirring at 190 ° C. for 30 minutes, whereby rosin-modified phenolic resin varnish 1 Got.
＜ロジン変性フェノール樹脂ワニス２製造例＞
特開２０１６−１５５９０７号公報の、樹脂合成の実施例２に記載の方法と同様にして合成した、重量平均分子量１０，０００、酸価２３．６であるロジン変性フェノール樹脂２を４４部と、大豆油を２９部と、非芳香族系溶剤であるＡＦソルベント５号（ＪＸＴＧエネルギー社製、アニリン点８８．２度）２６部とを仕込み、１９０℃に昇温して３０分間攪拌した。その後放冷し、ゲル化剤としてエチルアセトアセテートアルミニウムジイソプロポキシド（川研ファインケミカル社製ＡＬＣＨ）１．０部を仕込んだのち、１９０℃で３０分間攪拌することで、ロジン変性フェノール樹脂ワニス２を得た。
<Production example of rosin-modified phenolic resin varnish 2>
44 parts of rosin-modified phenol resin 2 having a weight average molecular weight of 10,000 and an acid value of 23.6, synthesized in the same manner as in the method described in Example 2 of resin synthesis in JP-A-2016-155907, 29 parts of soybean oil and 26 parts of AF Solvent No. 5 (manufactured by JXTG Energy Co., Ltd., aniline point 88.2 degrees), which is a non-aromatic solvent, were charged, heated to 190 ° C. and stirred for 30 minutes. Thereafter, the mixture was allowed to cool, and after adding 1.0 part of ethyl acetoacetate aluminum diisopropoxide (ALCH manufactured by Kawaken Fine Chemical Co., Ltd.) as a gelling agent, the mixture was stirred at 190 ° C. for 30 minutes. Got.
＜光輝性インキ製造例＞
表１記載の金属顔料、アルキッド樹脂、石油樹脂ワニス、ロジン変性フェノール樹脂ワニスを、それぞれ表２の配合比で、ミキサーを備えた混合容器中に、前記ミキサーで混合・撹拌しながら投入した。投入後、撹拌したまま混合物を８０℃まで昇温し、同温下で１２０分撹拌を続けた。前記混合物を３０℃まで冷却したのち、金属ドライヤー（東洋インキ社製ＭＫドライヤー）と、乳化抑制剤（イソトリデカノール）とを、それぞれ表２の配合比になるように混合容器内に投入し、ミキサーで均一になるまで撹拌した。そして更に、増粘剤（ＪＸＴＧエネルギー社製ポリブテンＨＶ−１９００）と、キリ油と、重合植物油とを、それぞれ表２の配合比になるように混合容器内に投入し、インキの粘度が１０．０〜４０．０Ｐａ・ｓになるように調整することで、光輝性インキ１〜２７を得た。
<Examples of glitter ink production>
The metal pigment, alkyd resin, petroleum resin varnish, and rosin modified phenolic resin varnish shown in Table 1 were charged into the mixing vessel equipped with the mixer in the mixing ratio shown in Table 2 while mixing and stirring with the mixer. After the addition, the mixture was heated to 80 ° C. with stirring, and stirring was continued for 120 minutes at the same temperature. After the mixture is cooled to 30 ° C., a metal dryer (Toyo Ink MK dryer) and an emulsification inhibitor (isotridecanol) are introduced into the mixing container so that the mixing ratios shown in Table 2 are obtained. The mixture was stirred with a mixer until uniform. Further, a thickener (polybutene HV-1900 manufactured by JXTG Energy Co., Ltd.), drill oil, and polymerized vegetable oil were introduced into the mixing container so as to have a mixing ratio shown in Table 2, and the viscosity of the ink was 10. By adjusting so that it may be set to 0-40.0 Pa.s, the glitter ink 1-27 was obtained.
＜インキ１〜２７の評価＞
上記で製造した光輝性インキ１〜２７を使用し、下記印刷条件の下で、単色ベタと網点（１〜１００％の１０％刻み）とが入った絵柄の印刷を行うことで、汚れ耐性、紙面の着肉性について評価を行った。評価結果は、表２に示す通りであった。
<Evaluation of inks 1 to 27>
By using the glitter inks 1 to 27 produced above and printing the pattern containing solid monochrome and halftone dots (10% increments of 1 to 100%) under the following printing conditions, stain resistance is achieved. Then, evaluation was made on the inking property of the paper. The evaluation results were as shown in Table 2.
＜印刷条件＞
印刷機 ：ＬＩＴＨＲＯＮＥ２６（小森コーポレーション社製）
用紙 ：ミラーコート・プラチナ（１２７．９ｇ／ｍ2）（王子製紙社製）
湿し水 ：アクワユニティＣ ２．０％水道水希釈液（東洋インキ社製）
水量値 ：２０ポイント（ただし汚れ耐性の評価では、下記記載の通りとした）
印刷速度：６０００枚／時
版 ：ＳＵＰＥＲＩＡ ＸＰ−Ｆ（富士フィルム社製）
印刷部数：２０００枚（ただし汚れ耐性の評価では、下記記載の通りとした）
<Printing conditions>
Printing machine: Lithrone 26 (manufactured by Komori Corporation)
Paper: Mirror coat platinum (127.9 g / m 2 ) (Oji Paper Co., Ltd.)
Dampening solution: AQUAUNITY C 2.0% tap water dilution (Toyo Ink Co., Ltd.)
Water amount value: 20 points (however, in the evaluation of stain resistance, it is as described below)
Printing speed: 6000 sheets / hour Plate: SUPERIA XP-F (Fuji Film)
Number of printed copies: 2000 sheets (however, in the evaluation of stain resistance, it was as described below)
＜汚れ耐性の評価方法＞
まず、上記印刷機において水量値を２０ポイントに設定し、上記インキをそれぞれ２００部印刷した。印刷後、印刷物を目視で観察して汚れが見られなかった場合は、前記水量値を１ポイント下げ、再度２００部印刷を行った。上記を繰り返して、印刷物に汚れが見られたときの水量値を確認することで、汚れ耐性を評価した。評価基準は以下の通りとし、◎、○、△を実用範囲とした。
◎：水量値を１０としても汚れが発生しなかった。
〇：水量値が１０〜１２のときに汚れが発生した。
△：水量値が１３〜１５のときに汚れが発生した。
×：水量値が１６以上のときに汚れが発生した。
<Evaluation method of stain resistance>
First, the water amount value was set to 20 points in the printer, and 200 copies of the ink were printed. After printing, when the printed material was visually observed and no stain was seen, the water amount was lowered by 1 point, and 200 copies were printed again. By repeating the above, the stain resistance was evaluated by confirming the water amount value when the printed material was stained. The evaluation criteria are as follows, and ◎, ○, and Δ are practical ranges.
(Double-circle): Dirt did not generate | occur | produce even if the water quantity value was set to 10.
◯: Dirt was generated when the water amount value was 10-12.
(Triangle | delta): Dirt generate | occur | produced when the water quantity value was 13-15.
X: Dirt was generated when the amount of water was 16 or more.
＜着肉性の評価方法＞
上記印刷条件で印刷を行い、パイリングや白抜けの有無を目視で確認することで、着肉性の評価を行った。評価基準は以下の通りとし、◎、○、△を実用範囲とした。
◎：パイリング、白抜けなどはなく着肉性は良好であった。
〇：パイリングや白抜けは見られたが、インキ２１よりも良好であった。
△：インキ２１におけるパイリングや白抜けの度合いと同程度であった。
×：パイリングや白抜けが見られ、インキ２１よりも酷かった。
<Evaluation method of inking properties>
Printing was performed under the above printing conditions, and the inking property was evaluated by visually confirming the presence or absence of piling and white spots. The evaluation criteria are as follows, and ◎, ○, and Δ are practical ranges.
(Double-circle): There was no piling and white-out and the fleshing property was favorable.
◯: Piling and white spots were observed, but better than ink 21.
(Triangle | delta): It was the same grade as the degree of the piling in the ink 21, or a white spot.
X: Piling and white spots were observed, which was more severe than ink 21.
＜実施例１〜３５、比較例１〜９＞
上記で製造した光輝性インキ１〜２７を使用し、上記印刷条件の下で行った印刷により得られた印刷物と、エンドレスプレス機（松本機械製作社製）を使用し、表３〜４に示した条件の下で、加熱加圧処理を行った。そして得られた印刷物について、鏡面光沢度、プレス板曇りの評価を行った。評価結果は、表３〜４に示す通りであった。
<Examples 1-35 and Comparative Examples 1-9>
Tables 3 to 4 show the printed matter obtained by printing performed under the above printing conditions using the glitter inks 1 to 27 produced above and an endless press machine (manufactured by Matsumoto Machine Manufacturing Co., Ltd.). The heating and pressurizing treatment was performed under the conditions described above. And about the obtained printed matter, mirror surface glossiness and press board fogging were evaluated. The evaluation results were as shown in Tables 3-4.
＜鏡面光沢度の評価方法＞
エンドレスプレス機にて加熱加圧処理した後、上記印刷物のベタ部について、上記方法で鏡面光沢度を測定した。評価基準は以下の通りとし、◎、○、△を実用範囲とした。
◎：測定光沢度が４５０以上
〇：測定光沢度が４００以上４５０未満
△：測定光沢度が３５０以上４００未満
×：測定光沢度が３５０未満
<Evaluation method of specular gloss>
After heat-pressing with an endless press, the glossiness of the specular surface of the solid part of the printed matter was measured by the above method. The evaluation criteria are as follows, and ◎, ○, and Δ are practical ranges.
A: Measurement glossiness is 450 or more ◯: Measurement glossiness is 400 or more and less than 450 Δ: Measurement glossiness is 350 or more and less than 400 ×: Measurement glossiness is less than 350
＜プレス板汚れの評価方法＞
エンドレスプレス機にて加熱加圧処理した後、前記エンドレスプレス機のプレス板を目視で観察し、汚れ度合いを確認した。評価基準は以下の通りとし、◎、○、△を実用範囲とした。
◎：インキ取られやプレス板の曇りは見られなかった。
〇：インキ取られやプレス板の曇りは見られたが、実施例３よりも良好であった。
△：実施例３におけるインキ取られやプレス板の曇り度合いと同程度であった。
×：インキ取られやプレス板の曇りが見られ、実施例３よりも酷かった。
<Press board dirt evaluation method>
After heat-pressing with an endless press, the press plate of the endless press was visually observed to check the degree of contamination. The evaluation criteria are as follows, and ◎, ○, and Δ are practical ranges.
(Double-circle): The ink was removed and the fogging of the press plate was not seen.
◯: Although ink was removed and fogging of the press plate was observed, it was better than Example 3.
(Triangle | delta): It was comparable as the ink removal in Example 3, and the fogging degree of a press board.
X: Ink was removed and the fogging of the press plate was observed, which was worse than Example 3.
表２〜４の結果より、平版印刷用光輝性インキが平均厚さ１５〜１００ｎｍ且つ平均粒子径が１〜３０μｍである金属顔料及びバインダー樹脂とを含み、基材上に前記平版印刷用光輝性インキを印刷する工程（ｉ）と、印刷物を４０〜１３０℃かつ１０〜５００ｋｇｆ／ｃｍ2の条件で加熱加圧処理する工程（ｉｉ）をこの順に行うことにより、汚れ耐性、着肉性、鏡面光沢度、プレス板曇り耐性のいずれにおいても良好な結果であることが明らかとなった。 From the results of Tables 2 to 4, the lithographic printing glitter ink contains a metallic pigment having an average thickness of 15 to 100 nm and an average particle diameter of 1 to 30 μm and a binder resin, and the lithographic printing glitter on the substrate. By performing in this order the step (i) for printing ink and the step (ii) for heating and pressurizing the printed material under the conditions of 40 to 130 ° C. and 10 to 500 kgf / cm 2 , stain resistance, wear resistance, mirror surface It was revealed that both the glossiness and press plate haze resistance were good results.
＜非光輝性黄インキの製造例＞
特開２０１６−５３１４３号公報の、実施例２に記載の方法と同様にして、非光輝性黄インキを製造した。
<Production example of non-brilliant yellow ink>
A non-brilliant yellow ink was produced in the same manner as in the method described in Example 2 of JP-A-2006-53143.
＜非光輝性黄インキを使用した印刷物の製造例と評価＞
上記実施例１５にて製造した印刷物（以下、「処理済印刷物」と呼ぶ）と、前記実施例１５にて加熱加圧処理を施す前の印刷物（以下、「処理前印刷物」と呼ぶ）とをそれぞれ準備し、各印刷物のベタ部の上に、上記非光輝性黄インキをベタ印刷した。なお、非光輝性黄インキの印刷にあたっては、上記光輝性インキの印刷で使用したものと同じ印刷機、湿し水を使用し、水量値を１５ポイント、印刷速度を６０００枚／時とした。また、その他の印刷条件を調整し、黄顔料の付与量が０．０５ｇ／ｍ2となるようにした。
<Production examples and evaluation of printed matter using non-brilliant yellow ink>
The printed matter manufactured in Example 15 (hereinafter referred to as “processed printed matter”) and the printed matter before being subjected to the heat and pressure treatment in Example 15 (hereinafter referred to as “pre-processed printed matter”). Each was prepared, and the above non-brilliant yellow ink was solid-printed on the solid part of each printed matter. In the printing of the non-brilliant yellow ink, the same printer and dampening water as those used in the printing of the glittering ink were used, the water amount value was 15 points, and the printing speed was 6000 sheets / hour. In addition, other printing conditions were adjusted so that the applied amount of yellow pigment was 0.05 g / m 2 .
上記で得られた、処理済印刷物上に非光輝性黄インキを印刷したもの（以下、「処理済金色印刷物」と呼ぶ）の光沢性と、処理前印刷物上に非光輝性黄インキを印刷したもの（以下、「処理前金色印刷物」と呼ぶ）の光沢性とを、目視にて比較した。その結果、処理前金色印刷物に比べて、処理済金色印刷物の光沢性が優れていることが確認された。 The gloss obtained by printing the non-brilliant yellow ink on the processed printed matter obtained above (hereinafter referred to as “treated golden printed matter”) and the non-brilliant yellow ink printed on the pre-printed printed matter. The glossiness of the product (hereinafter referred to as “golden print before treatment”) was visually compared. As a result, it was confirmed that the gloss of the processed golden print was superior to that of the pre-treatment gold print.
また、上記処理前金色印刷物について、エンドレスプレス機（松本機械製作社製）を使用し、温度８０℃、圧力１００ｋｇｆ／ｃｍ2の条件で、加熱加圧処理を行った。その結果、加熱加圧処理前に比べ、前記加熱加圧処理後の印刷物の光沢性が向上していることが確認された。また前記加熱加圧処理後、前記エンドレスプレス機のプレス板を目視で観察したところ、インキ取られやプレス板の曇りは見られなかった。 Further, the pre-treatment gold-colored printed material was subjected to heat and pressure treatment using an endless press machine (manufactured by Matsumoto Machine Manufacturing Co., Ltd.) under the conditions of a temperature of 80 ° C. and a pressure of 100 kgf / cm 2 . As a result, it was confirmed that the gloss of the printed material after the heat and pressure treatment was improved as compared with that before the heat and pressure treatment. Further, when the press plate of the endless press machine was visually observed after the heat and pressure treatment, no ink was removed or the press plate was not fogged.
Claims (5)
前記平版印刷用光輝性インキが、平均厚さが１５〜１００ｎｍ、かつ、平均粒子径が１〜３０μｍである金属顔料（Ａ）と、バインダー樹脂とを含み、
前記バインダー樹脂が、アルキッド樹脂及び／または石油樹脂を、インキ全量に対して５〜９０質量％含み、
前記アルキッド樹脂の重量平均分子量が、１，０００〜１５０，０００であり、
前記石油樹脂の重量平均分子量が、５００〜５，０００であり、
基材上に前記平版印刷用光輝性インキを印刷する工程（ｉ）と、
印刷物を４０〜１３０℃かつ１０〜５００ｋｇｆ／ｃｍ2の条件で加熱加圧処理する工程（ｉｉ）とを、この順に行う、印刷物の製造方法。 A method for producing a printed material using glitter ink for lithographic printing,
The lithographic printing glitter ink comprises a metal pigment (A) having an average thickness of 15 to 100 nm and an average particle diameter of 1 to 30 μm, and a binder resin.
The binder resin contains alkyd resin and / or petroleum resin in an amount of 5 to 90% by mass based on the total amount of ink,
The alkyd resin has a weight average molecular weight of 1,000 to 150,000,
The petroleum resin has a weight average molecular weight of 500 to 5,000,
A step (i) of printing the lithographic printing glitter ink on a substrate;
The manufacturing method of printed matter which performs the process (ii) which heat-presses a printed matter on the conditions of 40-130 degreeC and 10-500 kgf / cm < 2 > in this order.
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| JP2003082258A (en) * | 2001-09-06 | 2003-03-19 | Toyo Aluminium Kk | Aluminum flake pigment, coating composition containing the same, ink composition and coating film thereof |
| JP2007021736A (en) * | 2005-07-12 | 2007-02-01 | Toppan Printing Co Ltd | High gloss printed matter and its manufacturing method |
| EP3165578A1 (en) * | 2015-11-09 | 2017-05-10 | Eckart GmbH | Metallic offset printing ink with mirror finish and printing method |
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| JP2901743B2 (en) * | 1990-11-07 | 1999-06-07 | 戸田工業株式会社 | Bright printing ink composition |
| JPH09268269A (en) * | 1996-03-30 | 1997-10-14 | Teikoku Ink Seizo Kk | Mirror ink and production of sheet having mirror luster image |
| EP2746349A1 (en) * | 2012-12-21 | 2014-06-25 | Eckart GmbH | Pigment preparation with metal effect pigments, method for their manufacture and use of the same |
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| JP2003082258A (en) * | 2001-09-06 | 2003-03-19 | Toyo Aluminium Kk | Aluminum flake pigment, coating composition containing the same, ink composition and coating film thereof |
| JP2007021736A (en) * | 2005-07-12 | 2007-02-01 | Toppan Printing Co Ltd | High gloss printed matter and its manufacturing method |
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