JP2007106896A - Water-based ink composition and printed matter using the same - Google Patents

Water-based ink composition and printed matter using the same Download PDF

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JP2007106896A
JP2007106896A JP2005299477A JP2005299477A JP2007106896A JP 2007106896 A JP2007106896 A JP 2007106896A JP 2005299477 A JP2005299477 A JP 2005299477A JP 2005299477 A JP2005299477 A JP 2005299477A JP 2007106896 A JP2007106896 A JP 2007106896A
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acrylic acid
ink composition
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Kenji Iihama
健治 飯▲浜▼
Mitsuho Maeda
満穂 前田
Tokuyuki Morikawa
徳幸 森川
Tomoo Fukuura
朝生 福浦
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National Printing Bureau
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based ink composition capable of obtaining coating film properties excellent in water resistance, alkali resistance and the like and excellent in redissolvability, and to provide printed matters using the composition. <P>SOLUTION: The water-based ink composition comprises a water-soluble resin comprising an (α-methyl)styrene-(meth)acrylic acid-(meth)acrylic ester copolymer and a base, wherein the copolymer comprises 50-65 wt.% (α-methyl)styrene, 0.1-15 wt.% (meth)acrylic ester having a 12-18C long chain alkyl and 5-25 wt.% (meth)acrylic ester having nonionic alkylene oxide and has 50-150 mgKOH/g acid value and 5,000-30,000 weight-average molecular weight. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、耐水性、耐アルカリ性等に優れた塗膜物性が得られ、再溶解性に優れた水性インキ組成物及びその印刷物に関するものである。   The present invention relates to a water-based ink composition having excellent water resistance, alkali resistance, and the like, and having excellent re-solubility and a printed product thereof.

印刷インキは、使われる溶剤によって油性インキと水性インキに大別される。油性インキは溶剤にトルエン、キシレン等の有機溶剤が用いられ、水性インキは水、アルコールが用いられる。油性インキに用いられる有機溶剤は、インキの流動性、転移性、乾燥性を向上させる。しかしながら、工場から排出された溶剤は、有機化学物質を排出するため、工場周辺での悪臭、作業環境の問題等を発生させ、地球環境、人体に悪影響を及ぼす。一方、水性インキは、有機化学物質の排出がなく、作業環境の改善等が図れ、地球環境の保護、人体への悪影響を防ぐだけでなく、生産性にも優れる。このようなことから、近年、印刷業界は、水性インキの使用が求められている。   Printing inks are roughly classified into oil-based inks and water-based inks depending on the solvent used. Oil-based inks use organic solvents such as toluene and xylene as solvents, and water-based inks use water and alcohol. The organic solvent used for the oil-based ink improves the fluidity, transferability, and drying properties of the ink. However, since the solvent discharged from the factory discharges organic chemical substances, it generates a bad odor around the factory, a problem of the working environment, etc., and has an adverse effect on the global environment and the human body. On the other hand, water-based inks do not emit organic chemical substances, improve the working environment, and protect the global environment and prevent adverse effects on the human body, and are excellent in productivity. For these reasons, in recent years, the printing industry has been required to use water-based ink.

しかし、従来の水性インキに使用される水溶性樹脂は、良好な顔料分散性と印刷適性を得るためには酸価が200mgKOH/g以上必要であり、塗膜(印刷物)の耐水性、耐アルカリ性等が劣っていた。従来、水溶性スチレン−(メタ)アクリル系樹脂を使用した水性インキは、塗膜の耐水性を向上させるためにスチレンの配合比を60wt%以上と高くしているが、スチレンの配合比が高くなると樹脂の疎水性が強くなり、水溶化するためには200mgKOH/g以上の高酸価で製造しなければならなくなり、塗膜の耐アルカリ性等が劣っていた。また、塗膜(印刷物)の耐水性、耐アルカリ性を向上させた低酸価(100〜200mgKOH/g)の水溶性樹脂は、水溶化するために重量平均分子量が4,500〜10,000と小さくなり、結果として顔料分散性が劣っていた。   However, water-soluble resins used in conventional water-based inks require an acid value of 200 mgKOH / g or more in order to obtain good pigment dispersibility and printability, and the water resistance and alkali resistance of the coating film (printed matter). Etc. were inferior. Conventionally, water-based inks using water-soluble styrene- (meth) acrylic resins have a high styrene compounding ratio of 60 wt% or more in order to improve the water resistance of the coating film, but the styrene compounding ratio is high. As a result, the hydrophobicity of the resin became strong, and in order to make it water-soluble, it had to be produced with a high acid value of 200 mgKOH / g or more, and the alkali resistance of the coating film was inferior. In addition, the water-soluble resin having a low acid value (100 to 200 mgKOH / g) with improved water resistance and alkali resistance of the coating film (printed material) has a weight average molecular weight of 4,500 to 10,000 for water solubility. As a result, the pigment dispersibility was poor.

また、塗膜(印刷物)の耐水性、耐アルカリ性等を改善するために、水溶性樹脂又は水分散性樹脂を使用して顔料を分散した高濃度顔料分散体に、その後水分散性樹脂を添加して水性インキを製造しているが、異なる樹脂を使用するためにインキの粘度上昇が起こり、貯蔵安定性に問題があった。   In addition, in order to improve the water resistance, alkali resistance, etc. of the coating film (printed material), the water-dispersible resin is added to the high-concentration pigment dispersion in which the pigment is dispersed using a water-soluble resin or a water-dispersible resin. However, since water-based inks are manufactured, the use of different resins raises the viscosity of the inks, which causes a problem in storage stability.

上記貯蔵安定性の問題を解決するために、アルカリ可溶型水溶性樹脂を固形分として3〜20重量%、水分散性樹脂を固形分として5〜30重量%、数平均分子量2,000以上のポリオキシエチレンアルキルフェニルエーテルを固形分として0.5〜5重量%含有されてなる水性インキ組成物が開示されている(特許文献1参照)。   In order to solve the above storage stability problem, the alkali-soluble water-soluble resin is 3 to 20% by weight as the solid content, the water-dispersible resin is 5 to 30% by weight as the solid content, and the number average molecular weight is 2,000 or more. A water-based ink composition containing 0.5 to 5% by weight of polyoxyethylene alkylphenyl ether as a solid content is disclosed (see Patent Document 1).

また、水分散性スチレン−(メタ)アクリル酸アルキルエステル−(メタ)アクリル酸系樹脂で顔料を練肉した後、水分散性エチレン−(メタ)アクリル酸系樹脂を添加して水性印刷インキを製造し、耐水性、耐溶剤性、耐アルカリ性等に優れた塗膜を形成し、かつ、貯蔵安定性に優れた水性印刷インキを容易に製造することができる技術が開示されている(特許文献2参照)。   Also, after kneading the pigment with a water-dispersible styrene- (meth) acrylic acid alkyl ester- (meth) acrylic acid resin, a water-dispersible ethylene- (meth) acrylic acid resin is added to form an aqueous printing ink. Techniques have been disclosed that can easily produce water-based printing inks that are manufactured and form a coating film excellent in water resistance, solvent resistance, alkali resistance, etc., and excellent in storage stability (Patent Documents). 2).

α−メチルスチレンとメタクリル酸メチル及びカルボキシル基を有するエチレン性不飽和化合物を必須成分とする水性アクリル樹脂であって、全構成モノマーにおけるα−メチルスチレンとメタクリル酸メチルの量が60〜80重量%であり、かつα−メチルスチレン/メタクリル酸メチル=5/95〜30/70の割合である水性アクリル樹脂と、カルボジイミド系硬化剤を含むことを特徴とする水性印刷インキ組成物が開示されている(特許文献3参照)。
特許第3301267号公報(第1−5頁) 特開平07−041719号公報(第1−4頁) 特開2003−26980号公報(第1−8頁)
An aqueous acrylic resin comprising α-methylstyrene, methyl methacrylate, and an ethylenically unsaturated compound having a carboxyl group as essential components, wherein the amount of α-methylstyrene and methyl methacrylate in all constituent monomers is 60 to 80% by weight. And a water-based printing ink composition comprising an aqueous acrylic resin having a ratio of α-methylstyrene / methyl methacrylate = 5/95 to 30/70 and a carbodiimide-based curing agent. (See Patent Document 3).
Japanese Patent No. 3301267 (page 1-5) JP 07-041719 A (page 1-4) JP 2003-26980 A (pages 1-8)

しかしながら、特許第3301267号公報は、アルカリ可溶型水溶性樹脂、水分散性樹脂及びポリオキシエチレンアルキルフェニルエーテルを配合する必要があり、エチレンオキシド付加数、ポリオキシエチレンアルキルフェニルエーテルの配合によって乾燥性、耐水性が劣る傾向があった。また、特開平07−041719号公報は、水分散性樹脂を用いるため、フレキソ印刷又はグラビア印刷の際、インキ転移後のアニロックスロールや版表面に残留して半乾き状態になったインキが、次回の回転時に供給されるインキによって再び溶解する場合におけるインキの再溶解性が劣るという問題があった。特開2003−26980号公報は、水溶性樹脂又は水分散性樹脂を使用して顔料を分散し、その後カルボジイミド基を有する架橋剤等を添加して、塗膜の耐久性を向上させる方法も提案されているが、添加剤の効果の持続性とインキの貯蔵安定性等に問題があった。   However, in Japanese Patent No. 3301267, it is necessary to blend an alkali-soluble water-soluble resin, a water-dispersible resin, and polyoxyethylene alkylphenyl ether. The water resistance tended to be inferior. In addition, since JP 07-041719 A uses a water-dispersible resin, an anilox roll after ink transfer or an ink that has remained in a semi-dried state on the surface of a plate during flexographic printing or gravure printing will be used next time. There is a problem that the re-dissolvability of the ink is inferior when the ink is dissolved again by the ink supplied at the time of rotation. JP-A-2003-26980 also proposes a method of improving the durability of a coating film by dispersing a pigment using a water-soluble resin or a water-dispersible resin and then adding a crosslinking agent having a carbodiimide group. However, there are problems in the durability of the effect of the additive and the storage stability of the ink.

本発明は、前述した問題点を解決することを目的としたもので、所定の割合で配合された重量平均分子量が5,000〜30,000の(αメチル)スチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル共重合体をアンモニア又はアミン等で中和した水溶性樹脂を用いることによって、環境負荷軽減及び作業環境改善はもちろん、生産性にも優れ、インキ粘度が過度に高くなることなく、再溶解性に優れる水性インキ組成物が得られ、本発明の水性インキ組成物によって得られる印刷物の塗膜は、印刷適性に優れ、耐水性、耐アルカリ性等に優れる印刷物を提案するものである。   The present invention aims to solve the above-mentioned problems, and (α-methyl) styrene- (meth) acrylic acid having a weight average molecular weight of 5,000 to 30,000 blended at a predetermined ratio. By using a water-soluble resin obtained by neutralizing a (meth) acrylic acid ester copolymer with ammonia or amine, it not only reduces environmental burden and improves the working environment, but also has excellent productivity and excessively high ink viscosity. The water-based ink composition excellent in re-dissolvability is obtained, and the coating film of the printed material obtained by the water-based ink composition of the present invention proposes a printed material excellent in printability, water resistance, alkali resistance, etc. is there.

本発明は、(αメチル)スチレン50〜65重量%、炭素数が12〜18の長鎖アルキル基を有した(メタ)アクリル酸エステル0.1〜15重量%、非イオン性のアルキレンオキサイド基を有した(メタ)アクリル酸エステル5〜25重量%を含有してなる、酸価が50〜150mgKOH/gで、かつ、重量平均分子量が5,000〜30,000の(αメチル)スチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル共重合体と、塩基からなる水溶性樹脂を含む水性インキ組成物である。   The present invention relates to (α-methyl) styrene 50 to 65% by weight, (meth) acrylic acid ester 0.1 to 15% by weight having a long-chain alkyl group having 12 to 18 carbon atoms, nonionic alkylene oxide group (Α-methyl) styrene having an acid value of 50 to 150 mgKOH / g and a weight average molecular weight of 5,000 to 30,000, comprising 5 to 25% by weight of (meth) acrylic acid ester having A water-based ink composition comprising a (meth) acrylic acid- (meth) acrylic acid ester copolymer and a water-soluble resin comprising a base.

また、水性インキ組成物によって、基材に印刷されてなる印刷物である。   Moreover, it is a printed matter printed on a base material with a water-based ink composition.

本発明の水溶性スチレン−(メタ)アクリル系樹脂を使用した水性インキでは、スチレンの配合比を50〜65重量%とし、塗膜の耐水性を向上させ、水溶化させるためにカルボキシル基を有する(メタ)アクリル酸のほかに非イオン性のアルキレンオキサイドを有した(メタ)アクリル酸エステルを共重合させることで、50〜150mgKOH/gの低酸価の水溶性樹脂が製造できる。よって、環境負荷軽減及び作業環境改善はもちろん、生産性にも優れ、インキ粘度が低粘度であり、再溶解性に優れる水性インキ組成物が得られる。   In the water-based ink using the water-soluble styrene- (meth) acrylic resin of the present invention, the blending ratio of styrene is set to 50 to 65% by weight, the water resistance of the coating film is improved, and a carboxyl group is included for water-solubilization. By copolymerizing (meth) acrylic acid ester having nonionic alkylene oxide in addition to (meth) acrylic acid, a water-soluble resin having a low acid value of 50 to 150 mgKOH / g can be produced. Accordingly, an aqueous ink composition that is excellent in productivity, low ink viscosity, and excellent re-dissolvability as well as environmental load reduction and work environment improvement can be obtained.

本発明の水性インキ組成物によって得られる印刷物の塗膜は、印刷適性に優れ、耐水性、耐アルカリ性等に優れる印刷物が得られる。   The coating film of the printed matter obtained by the water-based ink composition of the present invention is excellent in printability, and a printed matter excellent in water resistance, alkali resistance and the like is obtained.

本発明の実施するための最良の形態を図面を参照して説明する。しかしながら、本発明は以下に述べる実施するための最良の形態に限定されるものではなく、特許請求の範囲記載における技術的思想の範囲内であれば、その他のいろいろな実施の形態が含まれる。   The best mode for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the best mode for carrying out the invention described below, and includes various other embodiments within the scope of the technical idea described in the scope of claims.

本発明は、顔料、水溶性樹脂、アルコール及び/又は水及び添加剤を含有した水性インキ組成物である。水溶性樹脂である水溶性スチレン−(メタ)アクリル系樹脂は、酸価50〜150mgKOH/g、重量平均分子量5,000〜30,000の(αメチル)スチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル共重合体を塩基で中和したpH8.0〜10.0の水溶液である。(αメチル)スチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル共重合は、(αメチル)スチレン50〜65重量%、炭素数が12〜18の長鎖アルキル基を有した(メタ)アクリル酸エステル0.1〜15重量%、非イオン性のアルキレンオキサイド基を有した(メタ)アクリル酸エステル5〜25重量%の配合を含むことによって得られる。   The present invention is a water-based ink composition containing a pigment, a water-soluble resin, alcohol and / or water and an additive. The water-soluble styrene- (meth) acrylic resin, which is a water-soluble resin, is an (α-methyl) styrene- (meth) acrylic acid- (meth) having an acid value of 50 to 150 mgKOH / g and a weight average molecular weight of 5,000 to 30,000. ) A pH 8.0-10.0 aqueous solution obtained by neutralizing an acrylate copolymer with a base. (Α-methyl) styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer had (α-methyl) styrene 50 to 65% by weight and a long chain alkyl group having 12 to 18 carbon atoms (meth) It is obtained by including 0.1 to 15% by weight of an acrylate ester and 5 to 25% by weight of a (meth) acrylate ester having a nonionic alkylene oxide group.

スチレン−(メタ)アクリル系樹脂は、スチレンの共重合比が50〜65重量%と高く、長鎖アルキル基として炭素数が12〜18有した(メタ)アクリル酸エステルAと親水性官能基として非イオン性のアルキレンオキサイド基を有した(メタ)アクリル酸エステルBを含有する低酸価の水溶性樹脂を用いることを特徴とする。   The styrene- (meth) acrylic resin has a high copolymerization ratio of styrene of 50 to 65% by weight, a (meth) acrylic ester A having 12 to 18 carbon atoms as a long-chain alkyl group, and a hydrophilic functional group. A low acid value water-soluble resin containing (meth) acrylic acid ester B having a nonionic alkylene oxide group is used.

スチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル共重合体は、スチレン50〜65重量%、(メタ)アクリル酸6〜13重量%、(メタ)アクリル酸エステル22〜44重量%から作製した。(メタ)アクリル酸エステルは、長鎖アルキル基として炭素数が12〜18有した(メタ)アクリル酸エステルA、親水性官能基として非イオン性のアルキレンオキサイド基を有した(メタ)アクリル酸エステルB及び(メタ)アクリル酸エステルCからなる。   Styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer is prepared from 50 to 65% by weight of styrene, 6 to 13% by weight of (meth) acrylic acid, and 22 to 44% by weight of (meth) acrylic acid ester. did. The (meth) acrylic acid ester is a (meth) acrylic acid ester A having 12 to 18 carbon atoms as a long-chain alkyl group, and a (meth) acrylic acid ester having a nonionic alkylene oxide group as a hydrophilic functional group B and (meth) acrylic acid ester C.

本発明の水性インキ組成物における水溶性(αメチル)スチレン−(メタ)アクリル系樹脂は酸価が50〜150mgKOH/gの範囲にあることに特徴があり、酸価が50mgKOH/gより低いと樹脂に十分な溶解性がなくなり、また、酸価が150mgKOH/gを超えると樹脂の溶解性が高くなり、印刷物の耐水性、耐アルカリ性が低下する。   The water-soluble (α-methyl) styrene- (meth) acrylic resin in the water-based ink composition of the present invention is characterized in that the acid value is in the range of 50 to 150 mgKOH / g, and the acid value is lower than 50 mgKOH / g. If the resin has insufficient solubility, and the acid value exceeds 150 mgKOH / g, the resin has high solubility, and the water resistance and alkali resistance of the printed matter are lowered.

本発明の水性インキ組成物における水溶性(αメチル)スチレン−(メタ)アクリル系樹脂の重量平均分子量は5,000〜30,000の範囲にあることに特徴があり、分子量が5,000より小さいと、印刷物の耐水性、耐摩擦性が悪くなり、また、分子量が30,000を超えると、樹脂に十分な溶解性がなくなり、印刷適性が悪くなる。本発明の水性インキ組成物における水溶性(αメチル)スチレン−(メタ)アクリル系樹脂の(αメチル)スチレンの共重合割合が50〜65重量%にあることに特徴があり、50重量%より少ないと、樹脂の疎水性が低下し、印刷物の十分な耐水性が得られなくなり、(αメチル)スチレンの共重合割合は65重量%を超えると、樹脂の疎水性が強くなり、低酸価での溶解性が悪くなり、印刷物の刷色濃度が低下する。   The water-soluble (α-methyl) styrene- (meth) acrylic resin in the water-based ink composition of the present invention is characterized in that the weight average molecular weight is in the range of 5,000 to 30,000, and the molecular weight is from 5,000. If it is small, the water resistance and friction resistance of the printed matter will deteriorate, and if the molecular weight exceeds 30,000, the resin will not have sufficient solubility and the printability will deteriorate. The water-soluble (α-methyl) styrene- (meth) acrylic resin in the water-based ink composition of the present invention is characterized in that the copolymerization ratio of (α-methyl) styrene is 50 to 65% by weight, from 50% by weight If the amount is too small, the hydrophobicity of the resin will be lowered, and sufficient water resistance of the printed matter will not be obtained. If the copolymerization ratio of (α-methyl) styrene exceeds 65% by weight, the hydrophobicity of the resin will become strong, and the low acid value will be low. The solubility in the ink becomes poor, and the printing color density of the printed matter decreases.

本発明の水性インキ組成物における水溶性(αメチル)スチレン−(メタ)アクリル系樹脂の長鎖アルキル基として炭素数が12〜18有した(メタ)アクリル酸エステルAは、0.1〜15重量%の範囲で共重合に用いる。(メタ)アクリル酸エステルAの共重合割合が0.1重量%より少ないと、インキ作製において顔料分散性が悪くなり、印刷物の刷色濃度が低下してしまう。他方、(メタ)アクリル酸エステルAの共重合割合が15重量%を超えると、水性樹脂の疎水性が高すぎて、溶解性が悪くなり、印刷物の刷色濃度が低下する。本発明において、(メタ)アクリル酸エステルAの共重合割合は、好ましくは5〜10重量%の範囲である。   The (meth) acrylic acid ester A having 12 to 18 carbon atoms as the long-chain alkyl group of the water-soluble (α-methyl) styrene- (meth) acrylic resin in the water-based ink composition of the present invention is 0.1 to 15 Used for copolymerization in the range of% by weight. When the copolymerization ratio of the (meth) acrylic ester A is less than 0.1% by weight, the pigment dispersibility is deteriorated in ink preparation, and the printing color density of the printed matter is lowered. On the other hand, when the copolymerization ratio of (meth) acrylic acid ester A exceeds 15% by weight, the hydrophobicity of the aqueous resin is too high, the solubility becomes poor, and the printing color density of the printed matter is lowered. In the present invention, the copolymerization ratio of (meth) acrylic acid ester A is preferably in the range of 5 to 10% by weight.

(メタ)アクリル酸エステルAは、(メタ)アクリル酸ラウリル、(メタ)アクリル酸セチル、(メタ)アクリル酸ステアリル等が挙げられる。   Examples of the (meth) acrylic acid ester A include lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and the like.

本発明の水性インキ組成物における水溶性(αメチル)スチレン−(メタ)アクリル系樹脂の親水性官能基として非イオン性のアルキレンオキサイド基(エチレンオキサイド(EO)又はプロピレンオキサイド(PO))を有した(メタ)アクリル酸エステルBは、5〜25重量%の範囲で共重合に用いる。(メタ)アクリル酸エステルBの共重合割合が5重量%より少ないと、樹脂を水溶化するため親水性が劣ることにより、顔料分散性が悪くなり、印刷物の刷色濃度が低下してしまう。他方、(メタ)アクリル酸エステルBの共重合割合が25重量%を超えると、水性樹脂の親水性が高すぎて、印刷物の耐水性が低下する。本発明において、(メタ)アクリル酸エステルBの共重合割合は、好ましくは10〜20重量%の範囲である。   The water-based ink composition of the present invention has a nonionic alkylene oxide group (ethylene oxide (EO) or propylene oxide (PO)) as a hydrophilic functional group of the water-soluble (α-methyl) styrene- (meth) acrylic resin. The (meth) acrylic acid ester B is used for copolymerization in the range of 5 to 25% by weight. If the copolymerization ratio of (meth) acrylic ester B is less than 5% by weight, the resin is water-solubilized and the hydrophilicity is inferior, so that the pigment dispersibility is deteriorated and the printing color density of the printed matter is lowered. On the other hand, when the copolymerization ratio of the (meth) acrylic acid ester B exceeds 25% by weight, the hydrophilicity of the aqueous resin is too high, and the water resistance of the printed matter is lowered. In the present invention, the copolymerization ratio of (meth) acrylic acid ester B is preferably in the range of 10 to 20% by weight.

(メタ)アクリル酸エステルBは、(メタ)アクリル酸−2−メトキシエチル、(メタ)アクリル酸−2−エトキシエチル、(メタ)アクリル酸エチルカルビトール、(メタ)アクリル酸メトキシトリエチレングリコール、(メタ)アクリル酸メトキシテトラエチレングリコール、(メタ)アクリル酸フェノキシジエチレングリコール、(メタ)アクリル酸メトキシジプロピレングリコール、(メタ)アクリル酸メトキシトリプロピレングリコール等が挙げられるが、これらに限定されるものではない。   (Meth) acrylic acid ester B is (meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid-2-ethoxyethyl, (meth) acrylic acid ethyl carbitol, (meth) acrylic acid methoxytriethylene glycol, Examples include (meth) acrylic acid methoxytetraethylene glycol, (meth) acrylic acid phenoxydiethylene glycol, (meth) acrylic acid methoxydipropylene glycol, and (meth) acrylic acid methoxytripropylene glycol. Absent.

(メタ)アクリル酸エステルCは、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、アクリル酸ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸ノルマルオクチル、(メタ)アクリル酸−2−エチルヘキシル等が挙げることができる。   (Meth) acrylic acid ester C is (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid propyl, butyl acrylate, (meth) acrylic acid isobutyl, (meth) acrylic acid normal octyl, ( (Meth) acrylic acid-2-ethylhexyl etc. can be mentioned.

本発明の水性インキ組成物における水溶性(αメチル)スチレン−(メタ)アクリル系樹脂のカルボキシル基の中和に用いる塩基としては、例えば、アンモニア又はジメチルアミン、トリメチルアミン、ジエチルアミン、トリエチルアミン、N、N−ジメチルエタノールアミン、N、N−ジエチルエタノールアミン、モノエタノールアミン、トリエタノールアミン、モルホリン、トリエチレンジアミン等が挙げられるが、これらに限定されるものではない。   Examples of the base used for neutralizing the carboxyl group of the water-soluble (α-methyl) styrene- (meth) acrylic resin in the water-based ink composition of the present invention include ammonia or dimethylamine, trimethylamine, diethylamine, triethylamine, N, N -Examples include, but are not limited to, dimethylethanolamine, N, N-diethylethanolamine, monoethanolamine, triethanolamine, morpholine, and triethylenediamine.

本発明における水溶性(αメチル)スチレン−(メタ)アクリル系樹脂は、従来公知の塊状重合、溶液重合、乳化重合及び懸濁重合等の重合方法で製造し、塩基で中和することにより得られる。   The water-soluble (α-methyl) styrene- (meth) acrylic resin in the present invention is produced by a conventionally known polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization, and neutralized with a base. It is done.

本発明の水性インキ組成物には、その機能を阻害しない範囲で必要に応じて、水溶性または水分散性樹脂を併用することができる。   In the water-based ink composition of the present invention, a water-soluble or water-dispersible resin can be used in combination as necessary as long as the function is not inhibited.

本発明の水性インキ組成物における水溶性(αメチル)スチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル系樹脂は、樹脂固形分が20〜30重量%になるように塩基を添加して中和することで、pH8.0〜10.0の樹脂水溶液を作製する。pHが8.0より低すぎると、エマルション状の樹脂溶液となり顔料分散性が低下し、pHが10.0より高すぎると樹脂水溶液の粘度が高くなり取り扱いづらくなる場合がある。   The water-soluble (α-methyl) styrene- (meth) acrylic acid- (meth) acrylic acid ester resin in the water-based ink composition of the present invention has a base added so that the resin solid content is 20 to 30% by weight. By neutralizing, an aqueous resin solution having a pH of 8.0 to 10.0 is prepared. When the pH is lower than 8.0, an emulsion-like resin solution is obtained, and the pigment dispersibility is lowered.

本発明の水性インキ組成物は、上記水溶性(αメチル)スチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル系樹脂、塩基の他、顔料などの着色剤、必要に応じて消泡剤等の添加剤を加え、公知の方法で製造される。   The water-based ink composition of the present invention includes the water-soluble (α-methyl) styrene- (meth) acrylic acid- (meth) acrylic ester resin, a base, a colorant such as a pigment, and an antifoaming agent as necessary. Etc. are added by a known method.

顔料としては、無機顔料、有機顔料又は体質顔料等を用いることができる。また、本発明の水性インキ組成物に必要に応じて添加剤を混合することができる。添加剤としては、顔料分散剤、消泡剤、レベリング剤、ポリエチレンワックス等の耐摩擦性向上剤等が挙げられる。   As the pigment, an inorganic pigment, an organic pigment, an extender pigment, or the like can be used. Moreover, an additive can be mixed with the water-based ink composition of the present invention as necessary. Examples of additives include pigment dispersants, antifoaming agents, leveling agents, and friction resistance improvers such as polyethylene wax.

本発明の水性インキ組成物に水及び/又はアルコールを混合して粘度調整を行うことができる。粘度調整に用いるアルコールとしては、メタノール、エタノール、1−プロパノール、2−プロパノール等が挙げられるが、これらに限定されるものではない。   Viscosity can be adjusted by mixing water and / or alcohol with the water-based ink composition of the present invention. Examples of alcohol used for viscosity adjustment include, but are not limited to, methanol, ethanol, 1-propanol, 2-propanol and the like.

水性インキ組成物は、水性グラビア印刷、水性フレキソ印刷、水性インクジェット印刷等を用いた商業印刷、諸証券印刷等で印刷可能である。印刷物は、耐水性、耐アルカリ性等に優れた塗膜が得られる。特に本発明の水性インキ組成物は、インキ特性から水性グラビア印刷インキ組成物として用いることが好ましい。   The water-based ink composition can be printed by water-based gravure printing, water-based flexographic printing, water-based ink jet printing, commercial printing, securities printing, or the like. A printed film having excellent water resistance, alkali resistance and the like can be obtained. In particular, the water-based ink composition of the present invention is preferably used as a water-based gravure printing ink composition from the viewpoint of ink characteristics.

本発明の水性インキ組成物で印刷される基材は特に限定されることなく、紙葉類、プラスチック、ビニール等が挙げられる。   The base material printed with the water-based ink composition of the present invention is not particularly limited, and examples thereof include paper sheets, plastics, and vinyl.

以下、実施例を用いて本発明を更に詳細に説明するが、本発明の内容は、これらの実施例の範囲に限定されるものではない。   EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, the content of this invention is not limited to the range of these Examples.

(実施例1〜7)
表1に示すモノマー組成比で(αメチル)スチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル共重合体を作製して、塩基にアンモニア水を用いて中和し、樹脂水溶液(固形分25重量%)を得た。次に、その樹脂水溶液64重量%、1−プロパノールを16重量%及びフタロシアニンブルー顔料(ファーストゲンブルーFGF、大日本インキ化学工業(株)製)を20重量%の配合で遊星型ボールミル(フリッチュ社製P−5型)を使用して1時間混練して、高濃度顔料分散体のミルベースを作製した。そして、そのミルベース80重量%に、先の水溶性(αメチル)スチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル系樹脂水溶液(樹脂固形分25重量%)を16重量%、アルコール4重量%、消泡剤2重量%及びワックス3重量%を混合し、良く撹拌して水性インキ組成物を製造した。
(Examples 1-7)
A (α-methyl) styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer was prepared with the monomer composition ratio shown in Table 1, neutralized with ammonia water as a base, and an aqueous resin solution (solid content) 25% by weight). Next, a planetary ball mill (Fritsch) containing 64% by weight of the resin aqueous solution, 16% by weight of 1-propanol and 20% by weight of phthalocyanine blue pigment (Fastgen Blue FGF, manufactured by Dainippon Ink & Chemicals, Inc.). P-5 type) was kneaded for 1 hour to prepare a mill base of a high concentration pigment dispersion. Then, 80% by weight of the mill base, 16% by weight of the water-soluble (α-methyl) styrene- (meth) acrylic acid- (meth) acrylic acid ester resin aqueous solution (resin solid content 25% by weight), and 4% by weight of alcohol. %, 2% by weight of antifoaming agent and 3% by weight of wax were mixed and stirred well to prepare a water-based ink composition.

Figure 2007106896
Figure 2007106896

(比較例1〜7)
表2に示すモノマー組成比でスチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル共重合体を作製して、塩基にアンモニア水を用いて中和し、樹脂水溶液(固形分25重量%)を得た。次に、その樹脂水溶液64重量%、1−プロパノールを16重量%及びフタロシアニンブルー顔料(ファーストゲンブルーFGF、大日本インキ化学工業(株)製)を20重量%の配合で遊星型ボールミル(フリッチュ社製P−5型)を使用して1時間混練して、高濃度顔料分散体のミルベースを作製した。そして、そのミルベース80重量%に、先の水溶性スチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル系樹脂水溶液(樹脂固形分25重量%)を16重量%、アルコール4重量%、消泡剤2重量%及びワックス3重量%を混合し、良く撹拌して水性インキ組成物を製造した。
(Comparative Examples 1-7)
A styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer was prepared with the monomer composition ratio shown in Table 2, neutralized with ammonia water as a base, and an aqueous resin solution (solid content 25 wt%). Got. Next, a planetary ball mill (Fritsch) containing 64% by weight of the resin aqueous solution, 16% by weight of 1-propanol and 20% by weight of phthalocyanine blue pigment (Fastgen Blue FGF, manufactured by Dainippon Ink & Chemicals, Inc.). P-5 type) was kneaded for 1 hour to prepare a mill base of a high concentration pigment dispersion. Then, 80% by weight of the mill base, 16% by weight of the aqueous water-soluble styrene- (meth) acrylic acid- (meth) acrylic acid ester resin aqueous solution (resin solid content 25% by weight), 4% by weight of alcohol, and defoaming A water-based ink composition was prepared by mixing 2% by weight of the agent and 3% by weight of the wax and stirring well.

Figure 2007106896
Figure 2007106896

(比較例8)
酸価87、重量平均分子量100,000〜200,000の水分散性樹脂溶液(ジョンソンポリマー社製 ジョンクリル7001 樹脂固形分42重量% pH8.4)を38.4重量%、イオン交換水を25.6重量%、1−プロパノールを16重量%及びフタロシアニンブルー顔料(ファーストゲンブルーFGF、大日本インキ化学工業(株)製)を20重量%の配合で遊星型ボールミル(フリッチュ社製P−5型)を使用して1時間混練して、高濃度顔料分散体のミルベースを作製した。そして、そのミルベース80重量%に、先の水分散性樹脂溶液(ジョンソンポリマー社製 ジョンクリル7001 樹脂固形分42重量%)を9.6重量%、イオン交換水を6.4重量%、アルコールを4重量%、消泡剤を2重量%及びワックスを3重量%混合し、良く撹拌して水性インキ組成物が得られた。
(Comparative Example 8)
38.4% by weight of an aqueous dispersible resin solution having an acid value of 87 and a weight average molecular weight of 100,000 to 200,000 (Johncrill 7001 resin solid content 42% by weight, pH 8.4, manufactured by Johnson Polymer Co., Ltd.) and 25 ion-exchanged water. 1.6% by weight, 16% by weight of 1-propanol, and 20% by weight of phthalocyanine blue pigment (Fastgen Blue FGF, manufactured by Dainippon Ink & Chemicals, Inc.) ) For 1 hour to prepare a mill base of a high concentration pigment dispersion. Further, 9.6% by weight of the above water-dispersible resin solution (Johncrill 7001 resin solid content 42% by weight, manufactured by Johnson Polymer Co., Ltd.), 6.4% by weight of ion-exchange water, and alcohol are added to 80% by weight of the mill base. A water-based ink composition was obtained by mixing 4% by weight, 2% by weight of an antifoaming agent and 3% by weight of a wax and stirring well.

(比較例9)
酸価213、重量平均分子量12,500の水溶性樹脂溶液(ジョンソンポリマー社製 ジョンクリル63 樹脂固形分30重量% pH8.5)を53.3重量%、イオン交換水を10.7重量%、1−プロパノールを16重量%及びフタロシアニンブルー顔料(ファーストゲンブルーFGF、大日本インキ化学工業(株)製)を20重量%の配合で遊星型ボールミル(フリッチュ社製P−5型)を使用して1時間混練して、高濃度顔料分散体のミルベースを作製した。そして、そのミルベース80重量%に、先の水溶性スチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル系樹脂水溶液(樹脂固形分25重量%)を16重量%、アルコール4重量%、消泡剤2重量%及びワックス3重量%を混合し、良く撹拌して水性インキ組成物が得られた。
(Comparative Example 9)
53.3% by weight of a water-soluble resin solution having an acid value of 213 and a weight average molecular weight of 1,2,500 (John Cryl 63 resin solid content 30% by weight, pH 8.5, manufactured by Johnson Polymer Co., Ltd.), 10.7% by weight of ion-exchanged water, Using a planetary ball mill (P-5 type manufactured by Fritsch) with a composition of 16% by weight of 1-propanol and 20% by weight of phthalocyanine blue pigment (Fastgen Blue FGF, manufactured by Dainippon Ink & Chemicals, Inc.) The mill base of the high concentration pigment dispersion was prepared by kneading for 1 hour. Then, 80% by weight of the mill base, 16% by weight of the aqueous water-soluble styrene- (meth) acrylic acid- (meth) acrylic acid ester resin aqueous solution (resin solid content 25% by weight), 4% by weight of alcohol, and defoaming 2% by weight of the agent and 3% by weight of the wax were mixed and stirred well to obtain a water-based ink composition.

実施例1〜7及び比較例1〜9の各水性インキ組成物を水及び/又はアルコールを加えて粘度調整を行い、コート紙上に自動彫刻版(250線/インチ)を用いてグラビア印刷適性試験機(熊谷理機工業(株))を使用して45m/minの速度で印刷し、それぞれの印刷物を得た。各印刷物は、刷色濃度、耐水性及び耐アルカリ性を評価した。   Each water-based ink composition of Examples 1 to 7 and Comparative Examples 1 to 9 was adjusted for viscosity by adding water and / or alcohol, and tested for gravure printing using an automatic engraving plate (250 lines / inch) on coated paper. Using a machine (Kumaya Riki Kogyo Co., Ltd.), printing was performed at a speed of 45 m / min to obtain each printed matter. Each printed product was evaluated for printing color density, water resistance and alkali resistance.

インキの再溶解性:印刷機で印刷した後、5分間停止してから再び印刷し、得られた印刷物を停止前の印刷物と比較し、画線の再現性を目視判定した。
◎:停止前と全く変わらず良好である。
○:停止直後はやや擦れていたが、すぐに回復した。
△:画線がやや擦れている。
×:画線が擦れている。
Re-solubility of ink: After printing with a printing machine, printing was stopped for 5 minutes and then printing again. The obtained printed material was compared with the printed material before stopping, and the reproducibility of the image line was visually determined.
(Double-circle): It is completely the same as before stopping.
○: Slightly rubbed immediately after stopping, but recovered immediately.
(Triangle | delta): The image line has rubbed a little.
X: The image line is rubbed.

印刷物の刷色濃度:刷色濃度はグレースケールの濃度と階調再現性を目視で評価した。
◎:刷色濃度が高く、階調再現性が良好である。
○:刷色濃度がわずかに低いが、階調再現性が良好である。
△:刷色濃度がわずかに低く、擦れている。
×:刷色濃度が低く、階調再現性が不良である。
Printing color density of printed matter: The printing color density was evaluated by visual observation of gray scale density and gradation reproducibility.
A: The printing color density is high and the gradation reproducibility is good.
○: The printing color density is slightly low, but the gradation reproducibility is good.
Δ: The printing color density is slightly low and rubbing.
X: The printing color density is low and the gradation reproducibility is poor.

印刷物の耐水性:印刷物を耐摩擦性試験機((株)東洋精機製作所製)を使用して、水で濡らした木綿布を取り付けた摩擦子(R−45mm、200g)で60回擦り、印刷物のインキの剥落具合を目視で評価した。
◎:インキの剥落が全くない。
○:インキの剥落がほとんどない。
△:インキの剥落がある。
×:インキの剥落が著しい。
Water resistance of printed matter: Using a friction tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the printed matter is rubbed 60 times with a friction piece (R-45 mm, 200 g) with a cotton cloth wetted with water. The degree of ink peeling was visually evaluated.
A: There is no ink peeling.
○: There is almost no ink peeling.
Δ: Ink is peeled off.
X: Ink peeling off remarkably.

印刷物の耐アルカリ性:印刷物を1%濃度の苛性水溶液に24時間浸漬させて、水で洗浄後に乾燥させた印刷物の刷色濃度を目視で評価した。
◎:刷色濃度の低下が全くない。
○:刷色濃度がわずかに低下する。
△:刷色濃度が低下した。
×:刷色濃度が著しく低下した。
Alkali resistance of printed matter: The printed product was immersed in a 1% strength caustic aqueous solution for 24 hours, washed with water and dried, and then the printed color density was visually evaluated.
A: No decrease in printing color density.
○: The printing color density slightly decreases.
Δ: The printing color density decreased.
X: The printing color density was remarkably lowered.

Figure 2007106896
Figure 2007106896

本発明により、再溶解性に優れた水溶性(αメチル)スチレン−(メタ)アクリル系樹脂を用いる水性インキ組成物及び耐水性、耐アルカリ性等に優れた印刷物が得られるようになった。   According to the present invention, a water-based ink composition using a water-soluble (α-methyl) styrene- (meth) acrylic resin excellent in re-solubility and a printed matter excellent in water resistance and alkali resistance can be obtained.

Claims (2)

(αメチル)スチレン50〜65重量%、炭素数が12〜18の長鎖アルキル基を有した(メタ)アクリル酸エステル0.1〜15重量%、非イオン性のアルキレンオキサイド基を有した(メタ)アクリル酸エステル5〜25重量%を含有してなる、酸価が50〜150mgKOH/gで、かつ、重量平均分子量が5,000〜30,000の(αメチル)スチレン−(メタ)アクリル酸−(メタ)アクリル酸エステル共重合体と、塩基からなる水溶性樹脂を含む水性インキ組成物。 (Α-methyl) styrene 50 to 65 wt%, (meth) acrylic acid ester 0.1 to 15 wt% having a long-chain alkyl group having 12 to 18 carbon atoms, and a nonionic alkylene oxide group ( (Α-methyl) styrene- (meth) acrylic acid containing 5 to 25% by weight of (meth) acrylic acid and having an acid value of 50 to 150 mgKOH / g and a weight average molecular weight of 5,000 to 30,000 A water-based ink composition comprising an acid- (meth) acrylic acid ester copolymer and a water-soluble resin comprising a base. 請求項1記載の水性インキ組成物によって、基材に印刷されてなる印刷物。 A printed matter printed on a substrate with the water-based ink composition according to claim 1.
JP2005299477A 2005-10-14 2005-10-14 Water-based ink composition and printed matter using the same Pending JP2007106896A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102943412A (en) * 2012-11-14 2013-02-27 海南必凯水性涂料有限公司 Wear-resistant high-gloss waterborne glazing oil and preparation method thereof
JP2013142150A (en) * 2012-01-12 2013-07-22 Sakata Corp Water-based gravure printing ink composition for carton
CN106497222A (en) * 2016-10-25 2017-03-15 中国印刷科学技术研究院 A kind of full water-based plastic flexographic ink and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013142150A (en) * 2012-01-12 2013-07-22 Sakata Corp Water-based gravure printing ink composition for carton
CN102943412A (en) * 2012-11-14 2013-02-27 海南必凯水性涂料有限公司 Wear-resistant high-gloss waterborne glazing oil and preparation method thereof
CN106497222A (en) * 2016-10-25 2017-03-15 中国印刷科学技术研究院 A kind of full water-based plastic flexographic ink and preparation method thereof

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