JP2018158986A - Aqueous flexographic ink composition for pack - Google Patents
Aqueous flexographic ink composition for pack Download PDFInfo
- Publication number
- JP2018158986A JP2018158986A JP2017056417A JP2017056417A JP2018158986A JP 2018158986 A JP2018158986 A JP 2018158986A JP 2017056417 A JP2017056417 A JP 2017056417A JP 2017056417 A JP2017056417 A JP 2017056417A JP 2018158986 A JP2018158986 A JP 2018158986A
- Authority
- JP
- Japan
- Prior art keywords
- water
- ink composition
- meth
- paper
- acrylic
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 35
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 35
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 17
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 13
- 239000000049 pigment Substances 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- -1 ester compound Chemical class 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 239000000123 paper Substances 0.000 claims description 78
- 239000000839 emulsion Substances 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 25
- 230000009477 glass transition Effects 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 9
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- 239000011248 coating agent Substances 0.000 abstract description 25
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 12
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 3
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- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
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- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は紙器用水性フレキソインキ組成物に関する。より詳しくは、各種印刷用紙にフレキソ印刷を行った際に、良好な印刷効果を有し、優れた品質の印刷物を得るのに適した紙器用水性フレキソインキ組成物に関する。 The present invention relates to a water-based flexographic ink composition for paper containers. More specifically, the present invention relates to a water-based flexographic ink composition for paper containers that has a good printing effect when flexographic printing is performed on various types of printing paper, and is suitable for obtaining an excellent quality printed matter.
段ボールの生産方式は、シート状の段ボール紙に直接フレキソ印刷を行うポストプリント方式とライナー紙にフレキソ印刷した表ライナー紙と中芯紙及び裏ライナー紙をコルゲーター機で貼合するプレプリント方式に大別する事ができる。近年、プレプリント方式で印刷した表ライナー紙と中芯紙及び裏ライナー紙を貼合するコルゲーター機は、貼合速度が最大４５０（ｍ／ｍｉｎ）となる最新鋭のコルゲーター機で貼合するケースが増えている。貼合速度の高速化に伴い、コルゲーター機貼合時の加工温度は、１５０℃〜１７０℃と従来のコルゲーター機の９０℃〜１３０℃に比較して４０℃〜６０℃高くなっている。しかし、実用化されている印刷インキに使用する水溶性アクリル系樹脂のガラス転移温度は、１００℃未満にありコルゲーター貼合工程において表ライナー紙に印刷した印刷インキが取られる問題が発生している。また水溶性アクリル系樹脂に使用する中和剤は沸点が１７１℃のモノエタノールアミンが多く使用されているため、貼合時の加工温度で揮発しきれずに、インキ皮膜中に残存し、インキ取られトラブルが発生し易い欠点がある。そのためアクリル系樹脂が高いガラス転移温度を有し、その中和剤が貼合時の加工温度より低い沸点を有する有機アミンを使用した水溶性アクリル系樹脂の開発が要求されるようになってきている。 Corrugated board production methods are largely divided into a post-printing system that directly performs flexographic printing on sheet-like corrugated paper, and a pre-printing system that uses a corrugator machine to bond flexographically printed front liner paper, core paper, and back liner paper. Can be separated. In recent years, corrugator machines for bonding front liner paper, core paper, and back liner paper printed by the preprint method are used for bonding with the latest corrugator machines with a maximum bonding speed of 450 (m / min). Is increasing. With the increase in the bonding speed, the processing temperature at the time of pasting the corrugator machine is 40 ° C to 60 ° C higher than 150 ° C to 170 ° C and 90 ° C to 130 ° C of the conventional corrugator machine. However, the glass transition temperature of the water-soluble acrylic resin used for the printing ink that has been put into practical use is less than 100 ° C., and there is a problem that the printing ink printed on the front liner paper is taken in the corrugator bonding process. . In addition, the neutralizing agent used for water-soluble acrylic resins is often monoethanolamine having a boiling point of 171 ° C. Therefore, it does not completely evaporate at the processing temperature at the time of bonding, and remains in the ink film to remove the ink. There is a drawback that trouble is likely to occur. Therefore, the development of water-soluble acrylic resins using organic amines that have a high glass transition temperature and whose neutralizing agent has a boiling point lower than the processing temperature at the time of bonding has come to be required. Yes.
本発明の課題は、再溶解性、版からみ性などの印刷適性、耐摩擦性、耐水性などの塗膜物性に優れ、また、コルゲーター加工時においてインキ取られがない紙器用水性フレキソインキ組成物を得ることである。 An object of the present invention is an aqueous flexo ink composition for paper containers that is excellent in printing properties such as re-solubility and plate squeezing property, coating film properties such as friction resistance and water resistance, and in which ink is not removed during corrugator processing. Is to get.
発明者は、（メタ）アクリル酸と、炭素数２〜１２のアルコールと(メタ)アクリル酸とのエステル化合物である（メタ）アクリル酸エステルと、α−メチルスチレンとを含むモノマーの重合物であるアクリル共重合体であって、α−メチルスチレンが、アクリル共重合体の固形分１００重量％に対して４５〜６５重量％であり、更には、中和剤として沸点が１３０〜１７３℃の有機アミンを用いた紙器用水性フレキソインキ組成物を使用することで上記課題を解決できることを見出した。 The inventor is a polymer of a monomer containing (meth) acrylic acid, (meth) acrylic acid ester which is an ester compound of 2 to 12 carbon atoms and (meth) acrylic acid, and α-methylstyrene. A certain acrylic copolymer, wherein α-methylstyrene is 45 to 65% by weight based on 100% by weight of the solid content of the acrylic copolymer, and further has a boiling point of 130 to 173 ° C. as a neutralizing agent. It has been found that the above-mentioned problems can be solved by using a water-based flexographic ink composition for paper containers using an organic amine.
すなわち本発明は、水溶性アクリル系樹脂と、顔料と、水とを含有する紙器用水性フレキソインキ組成物であって、
水溶性アクリル系樹脂が（メタ）アクリル酸と、（メタ）アクリル酸エステルと、α−メチルスチレンとを含むモノマーの重合物であるアクリル共重合体の有機アミン中和物であり、
有機アミンの沸点が１３０〜１７３℃であり、
α−メチルスチレンに由来する部分が、アクリル共重合体の固形分１００重量％に対して４５〜６５重量％であり、
（メタ）アクリル酸エステルが（メタ）アクリル酸と炭素数２〜１２のアルコールとのエステル化合物を含むことを特徴とする紙器用水性フレキソインキ組成物に関する。
That is, the present invention is an aqueous flexo ink composition for paper containers containing a water-soluble acrylic resin, a pigment, and water,
The water-soluble acrylic resin is an organic amine neutralized product of an acrylic copolymer that is a polymer of monomers including (meth) acrylic acid, (meth) acrylic acid ester, and α-methylstyrene,
The boiling point of the organic amine is 130-173 ° C.,
The part derived from α-methylstyrene is 45 to 65% by weight based on 100% by weight of the solid content of the acrylic copolymer,
The present invention relates to an aqueous flexo ink composition for paper containers, wherein the (meth) acrylic acid ester contains an ester compound of (meth) acrylic acid and an alcohol having 2 to 12 carbon atoms.
また本発明は、前記アクリル共重合体が、重量平均分子量５０００〜２５０００であり、かつ、酸価１５０〜３００ｍｇＫＯＨ／ｇであることを特徴とする上記紙器用水性フレキソインキ組成物に関する。 The present invention also relates to the above-mentioned aqueous flexo ink composition for paper containers, wherein the acrylic copolymer has a weight average molecular weight of 5000 to 25000 and an acid value of 150 to 300 mgKOH / g.
また本発明は、前記有機アミンがＮ，Ｎ−ジメチルエタノールアミンであることを特徴とする上記紙器用水性フレキソインキ組成物に関する。 The present invention also relates to the above-mentioned aqueous flexo ink composition for paper containers, wherein the organic amine is N, N-dimethylethanolamine.
また本発明は、さらに、コア／シェル型アクリルエマルジョンを含有することを特徴とする上記紙器用水性フレキソインキ組成物に関する。 The present invention further relates to the above-mentioned water-based flexographic ink composition for paper containers, further comprising a core / shell type acrylic emulsion.
また本発明は、前記コア／シェル型アクリルエマルジョンのガラス転移温度が１０℃〜５０℃であることを特徴とする上記紙器用水性フレキソインキ組成物に関する。 The present invention also relates to the above-mentioned water-based flexographic ink composition for paper containers, wherein the core / shell type acrylic emulsion has a glass transition temperature of 10 ° C. to 50 ° C.
また本発明は、前記水溶性アクリル系樹脂と前記コア／シェル型アクリルエマルジョンとの固形分重量比が、水溶性アクリル系樹脂：コア／シェル型アクリルエマルジョン＝９０：１０〜５０：５０であることを特徴とする上記紙器用水性フレキソインキ組成物に関する。 In the present invention, the solid content weight ratio between the water-soluble acrylic resin and the core / shell type acrylic emulsion is water-soluble acrylic resin: core / shell type acrylic emulsion = 90: 10 to 50:50. And a water-based flexographic ink composition for paper containers.
また本発明は、印刷紙基材と、上記紙器用水性フレキソインキ組成物の印刷層とからなる印刷物に関する。 Moreover, this invention relates to the printed matter which consists of a printing paper base material and the printing layer of the said water-based flexographic ink composition for paper containers.
また本発明は、印刷紙基材がコルゲート加工用ライナー紙である、上記印刷物に関する。 Moreover, this invention relates to the said printed matter whose printing paper base material is a liner paper for corrugating.
また本発明は、上記印刷物を用いたコルゲート加工段ボールに関する。 The present invention also relates to a corrugated cardboard using the printed matter.
本発明の紙器用水性フレキソインキ組成物は、再溶解性、版からみ性などの印刷適性に優れ、また塗膜にした場合、耐摩擦性、耐水性などにも優れ、さらには、コルゲーター加工時においてインキ取られながなく、耐熱性に優れる紙器用水性フレキソインキ組成物を提供できることがわかった。 The water-based flexographic ink composition for paper containers of the present invention is excellent in printability such as re-dissolution property and plate squeezing property, and when made into a coating film, it is also excellent in friction resistance, water resistance, etc. It was found that an aqueous flexo ink composition for paper containers having no heat removal and excellent heat resistance can be provided.
以下、本発明の構成について詳しく説明する。本発明の水性フレキソインキ組成物における水溶性アクリル系樹脂は、（メタ）アクリル酸と、（メタ）アクリル酸エステルと、α−メチルスチレンとを含むモノマーの重合物であるアクリル共重合体の有機アミン中和物である。
本発明における（メタ）アクリル酸エステルは、（メタ）アクリル酸と炭素数２〜１２のアルコールとのエステル化合物である。
炭素数２〜１２のアルコールとしては、エタノール、プロパン−１−オール、ブタン−１−オール、ペンタン−1−オール、ヘキサン−１−オール、ヘプタン−１−オール、オクタン−１−オール、ノナン−１−オール、デカン−１−オール、ウンデカン−１−オール、ドデカン−１−オールが挙げられる。
ここで、炭素数２〜１２のアルコールは水酸基を２個以上有する多価アルコールであっても良い。具体的にはジプロピレングリコール、エチレングリコール、プロピレングリコール、ペンタンジオールおよびヘキサンジオール等のアルキレングリコール；ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール。ポリエチレングリコール、トリプロピレングリコールおよびポリプロピレングリコール等の炭素数が１２以下のポリアルキレングリコールが挙げられる。
Hereinafter, the configuration of the present invention will be described in detail. The water-soluble acrylic resin in the water-based flexographic ink composition of the present invention is an organic acrylic copolymer that is a polymer of monomers containing (meth) acrylic acid, (meth) acrylic acid ester, and α-methylstyrene. A neutralized amine.
The (meth) acrylic acid ester in the present invention is an ester compound of (meth) acrylic acid and an alcohol having 2 to 12 carbon atoms.
Examples of the alcohol having 2 to 12 carbon atoms include ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, hexane-1-ol, heptan-1-ol, octan-1-ol, and nonane- Examples include 1-ol, decan-1-ol, undecan-1-ol, and dodecan-1-ol.
Here, the alcohol having 2 to 12 carbon atoms may be a polyhydric alcohol having two or more hydroxyl groups. Specifically, alkylene glycols such as dipropylene glycol, ethylene glycol, propylene glycol, pentanediol and hexanediol; diethylene glycol, triethylene glycol and tetraethylene glycol. Examples thereof include polyalkylene glycols having 12 or less carbon atoms such as polyethylene glycol, tripropylene glycol, and polypropylene glycol.
具体的な（メタ）アクリル酸エステルとしては、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルへキシル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート等のアルキル鎖を有する（メタ）アクリレートが挙げられる。
また、炭素数２〜１２のアルコールであり、水酸基を２個以上有する多価アルコールのエステル化物としては、エチレングリコールアクリレート、ジエチレングリコールアクリレート、トリエチレングリコールアクリレート、ポリエチレングリコールアクリレート等を使用することができる。
これらのうち、好ましくは炭素数が２〜８の水酸基を１個有するアルコールより得られた（メタ）アクリル酸エステルである。
Specific (meth) acrylic acid esters include ethyl (meth) acrylate, n-propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethyl. Examples include (meth) acrylates having an alkyl chain such as xyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl (meth) acrylate.
Moreover, ethylene glycol acrylate, diethylene glycol acrylate, triethylene glycol acrylate, polyethylene glycol acrylate, etc. can be used as the esterification product of a polyhydric alcohol which is an alcohol having 2 to 12 carbon atoms and having two or more hydroxyl groups.
Among these, (meth) acrylic acid ester obtained from an alcohol having one hydroxyl group having 2 to 8 carbon atoms is preferred.
（メタ）アクリル酸と炭素数２〜１２のアルコールとのエステル化合物である（メタ）アクリル酸エステルを水溶性アクリル系樹脂の原料として用いることでインキ組成物の版からみ性の抑制に優れる。 By using (meth) acrylic acid ester, which is an ester compound of (meth) acrylic acid and an alcohol having 2 to 12 carbon atoms, as a raw material for the water-soluble acrylic resin, it is excellent in suppressing the tangling property of the ink composition.
本発明では、ライナー紙の接着性とコルゲート加工時の耐熱性のバランスなどの塗膜性能をコントロールするため、水溶性アクリル系樹脂の構成モノマーとしてα−メチルスチレンを含む。α−メチルスチレンに由来する部分の割合は、水溶性アクリル系樹脂の固形分１００重量％に対して４５〜６５重量％であり、この範囲では接着性に優れ、耐熱性に優れる塗膜が得られる。４５重量％未満ではコルゲート加工時に十分な耐熱性が得られず、６５重量％を越えると樹脂合成時にアクリル樹脂溶液が白濁し、インキ組成物に使用した場合、塗膜が硬くなり接着性が大きく低下しやすく、摩擦等に対して塗膜が剥がれやすい。
さらにスチレンをα−メチルスチレンと併用することでライナー紙との接着性と、コルゲート加工時の耐熱をバランスできることで好ましい。
In the present invention, α-methylstyrene is included as a constituent monomer of the water-soluble acrylic resin in order to control the coating film performance such as the balance between the adhesiveness of the liner paper and the heat resistance during corrugating. The proportion of the part derived from α-methylstyrene is 45 to 65% by weight with respect to 100% by weight of the solid content of the water-soluble acrylic resin. In this range, a coating film having excellent adhesion and heat resistance is obtained. It is done. If it is less than 45% by weight, sufficient heat resistance cannot be obtained during corrugating. If it exceeds 65% by weight, the acrylic resin solution becomes cloudy at the time of resin synthesis. It tends to decrease, and the coating film tends to peel off due to friction and the like.
Furthermore, it is preferable that styrene is used in combination with α-methylstyrene because the adhesiveness to the liner paper and the heat resistance during corrugating can be balanced.
本発明における水溶性アクリル系樹脂は、公知の重合方法に従い製造できる。
例えば溶液重合の場合、その構成モノマーの所定量を適当な有機溶媒の存在下で重合し、その後有機アミンを添加して中和し、更に水を添加し、脱溶剤することにより水溶性アクリル樹脂が得られる。
重合時には重合開始剤として過酸化ベンゾイル、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、アゾビスイソブチロニトリル等の触媒を用いることができる。
The water-soluble acrylic resin in the present invention can be produced according to a known polymerization method.
For example, in the case of solution polymerization, a predetermined amount of the constituent monomer is polymerized in the presence of an appropriate organic solvent, and then neutralized by adding an organic amine, and then water is added to remove the solvent, thereby removing the water-soluble acrylic resin. Is obtained.
In the polymerization, a catalyst such as benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, azobisisobutyronitrile or the like can be used as a polymerization initiator.
本発明に使用できる有機アミンは沸点が１３０〜１７３℃であり、モルホリン系、ピペラジン系、アミノアルコール系などがあるが、水への溶解性、樹脂の水性化能、樹脂の経時安定性の点から、特にアミノアルコール系が好ましい。アミノアルコール系としては、Ｎ，Ｎ−ジメチルエタノールアミン(沸点１３３℃)、Ｎ−メチルエタノールアミン(沸点１５５℃)、Ｎ，Ｎ−ジエチルエタノールアミン(沸点１６０℃)、モノエタノールアミン(沸点１７１℃)などが挙げられる。 Organic amines that can be used in the present invention have a boiling point of 130 to 173 ° C., and include morpholine-based, piperazine-based, and aminoalcohol-based ones. Therefore, amino alcohol type is particularly preferable. As amino alcohols, N, N-dimethylethanolamine (boiling point 133 ° C.), N-methylethanolamine (boiling point 155 ° C.), N, N-diethylethanolamine (boiling point 160 ° C.), monoethanolamine (boiling point 171 ° C.) ) And the like.
沸点が１３０〜１７３℃の有機アミンを使用することによりコルゲーター加工の高速化に伴い、貼合温度上げても、貼合時の乾燥不良を改善し、また耐熱性に優れ、インキ取られを解決できる塗膜が得られる。 By using an organic amine with a boiling point of 130 to 173 ° C, the corrugator process speeds up, so even if the bonding temperature is raised, drying defects during bonding are improved, heat resistance is improved, and ink removal is solved. A coating film that can be obtained is obtained.
有機アミンの添加量は樹脂中のカルボキシル基の中和率が７０〜１２０％となる範囲が好ましい。中和率が低すぎると、得られる水性アクリル系樹脂がエマルジョンとなり顔料等の分散に適さない。中和率が高過ぎると得られる水溶性アクリル系樹脂の粘度が高くなる傾向があるため取扱いづらくなる場合がある。 The addition amount of the organic amine is preferably in a range where the neutralization rate of the carboxyl group in the resin is 70 to 120%. If the neutralization rate is too low, the resulting aqueous acrylic resin becomes an emulsion and is not suitable for dispersing pigments and the like. If the neutralization rate is too high, the resulting water-soluble acrylic resin tends to increase in viscosity, which may make it difficult to handle.
良好なフレキソ印刷適性とコルゲーター加工性の観点から有機アミンがＮ，Ｎ−ジメチルエタノールアミンであることが好ましい。 From the viewpoint of good flexographic printing suitability and corrugator processability, the organic amine is preferably N, N-dimethylethanolamine.
水溶性アクリル系樹脂の重量平均分子量は、５０００〜２５０００であることが好ましい。重量平均分子量が５０００未満では耐水性が劣る傾向であり、２５０００を超えると再溶解性が劣る傾向である。更に好ましくは１００００〜２００００である。
なお、重量平均分子量はＧＰＣ（ゲルパーミエーションクロマトグラフィー）装置を用いてポリスチレン換算分子量として求めた。
It is preferable that the weight average molecular weight of water-soluble acrylic resin is 5000-25000. When the weight average molecular weight is less than 5,000, the water resistance tends to be inferior, and when it exceeds 25,000, the resolubility tends to be inferior. More preferably, it is 10000-20000.
In addition, the weight average molecular weight was calculated | required as polystyrene conversion molecular weight using the GPC (gel permeation chromatography) apparatus.
水溶性アクリル系樹脂のガラス転移温度（Ｔｇ）は１００〜１３０℃が好ましい。１００〜１３０℃の間で、耐熱性と樹脂の顔料分散性のバランスに優れる傾向である。ここでいうガラス転移温度下記のＷｏｏｄの式により求めた計算上のガラス転移温度である。
Ｗｏｏｄの式：
１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋Ｗ３／Ｔｇ３＋・・・・・・＋Ｗｘ／Ｔｇｘ
（式中、Ｔｇ１〜Ｔｇｘは単独重合体のガラス転移温度（絶対温度）、Ｗ１〜Ｗｘは重合分率、Ｔｇは計算上のガラス転移温度を表す）
The glass transition temperature (Tg) of the water-soluble acrylic resin is preferably 100 to 130 ° C. It tends to be excellent in the balance between heat resistance and resin pigment dispersibility between 100 and 130 ° C. The glass transition temperature here is a calculated glass transition temperature obtained by the following Wood formula.
Wood's formula:
1 / Tg = W1 / Tg1 + W2 / Tg2 + W3 / Tg3 + ... + Wx / Tgx
(In the formula, Tg1 to Tgx are glass transition temperatures (absolute temperatures) of homopolymers, W1 to Wx are polymerization fractions, and Tg is a calculated glass transition temperature)
本発明における水溶性アクリル系樹脂の酸価は、水への溶解性、水溶性フレキソインキ組成物の再溶解性、版からみの発生を抑制する点で、１５０ｍｇＫＯＨ／ｇ以上、良好な耐水性の観点から３００ｍｇＫＯＨ／ｇ以下が好ましい
樹脂の酸価の測定は、樹脂１ｇ中に含有するカルボキシル基を中和するのに必要とする水酸化カリウムのｍｇ数で、ＪＩＳ Ｋ００７０に準拠した。
The acid value of the water-soluble acrylic resin in the present invention is 150 mgKOH / g or more in terms of water solubility, re-solubility of the water-soluble flexographic ink composition, and suppression of tangling. From the viewpoint, 300 mgKOH / g or less is preferable. The acid value of the resin was measured in terms of mg of potassium hydroxide required for neutralizing the carboxyl group contained in 1 g of the resin, and was based on JIS K0070.
本発明の水性フレキソインキ組成物は、溶解性が向上しフレキソ印刷時の版からみ性トラブルを大きく改善できることから、コア／シェル型アクリルエマルジョンを併用することが好ましい。 The aqueous flexographic ink composition of the present invention is preferably used in combination with a core / shell type acrylic emulsion because the solubility is improved and the problem of tangling of the plate during flexographic printing can be greatly improved.
コア／シェル型アクリルエマルジョンとしては、（メタ）アクリル系共重合樹脂を用いることができ、具体的には、（メタ）アクリル酸アルキルエステルと、（メタ）アクリル酸アルキルエステル以外の（メタ）アクリロイル基含有モノマーと、スチレンと、α−メチルスチレンと、マレイン酸、フマル酸等の不飽和カルボン酸またはそのエステル等から合成される（メタ）アクリル系共重合樹脂を用いることができる。 As the core / shell type acrylic emulsion, a (meth) acrylic copolymer resin can be used. Specifically, (meth) acrylic acid alkyl ester and (meth) acryloyl other than (meth) acrylic acid alkyl ester are used. A (meth) acrylic copolymer resin synthesized from a group-containing monomer, styrene, α-methylstyrene, an unsaturated carboxylic acid such as maleic acid or fumaric acid, or an ester thereof can be used.
コア／シェル型アクリルエマルジョンは、公知の乳化重合方法に従い製造できる。
例えば高分子乳化剤の存在下でアクリルモノマー類を重合することにより製造できる。また、重合時には重合開始剤として過酸化ベンゾイル、アゾビスイソブチロニトリル等の触媒を用いることができる。
The core / shell type acrylic emulsion can be produced according to a known emulsion polymerization method.
For example, it can be produced by polymerizing acrylic monomers in the presence of a polymer emulsifier. In the polymerization, a catalyst such as benzoyl peroxide or azobisisobutyronitrile can be used as a polymerization initiator.
コア／シェル型アクリルエマルジョンのガラス転移温度は１０〜５０℃の範囲が、印刷インキの成膜性、再溶解性の点で好ましい。ガラス転移温度は、ＤＳＣによる公知方法で測定できる。また酸価は２０〜８０ｍｇＫＯＨ／ｇの範囲が耐水性の点で好ましい The glass transition temperature of the core / shell type acrylic emulsion is preferably in the range of 10 to 50 ° C. from the viewpoint of the film formability and re-dissolvability of the printing ink. The glass transition temperature can be measured by a known method using DSC. The acid value is preferably in the range of 20 to 80 mgKOH / g from the viewpoint of water resistance.
水溶性アクリル系樹脂とコア／シェル型アクリルエマルジョンの固形分重量比は水溶性アクリル系樹脂：コア／シェル型アクリルエマルジョン＝９０：１０〜５０：５０であることが好ましい。この範囲内にすることでインキの再溶解性を維持し、更にフレキソ印刷時のフレキソ印刷時の版からみ性トラブル抑制において効果的である。 The solid content weight ratio of the water-soluble acrylic resin and the core / shell type acrylic emulsion is preferably water-soluble acrylic resin: core / shell type acrylic emulsion = 90: 10 to 50:50. By making it within this range, the re-dissolvability of the ink is maintained, and further, it is effective in suppressing the tangling trouble at the time of flexographic printing.
水性フレキソインキ組成物には顔料を使用する。顔料としては、一般の水性印刷インキ組成物に使用される無機顔料、有機顔料、体質顔料等を使用することができる。 A pigment is used in the aqueous flexographic ink composition. As the pigment, inorganic pigments, organic pigments, extender pigments and the like used in general aqueous printing ink compositions can be used.
本発明の紙器用水性フレキソインキ組成物に配合される顔料としては、有機顔料として、アゾ系、フタロシアニン系、アントラキノン系、ペリレン系、ペリノン系、キナクリドン系、チオインジゴ系、ジオキサジン系、イソインドリノン系、キノフタロン系、アゾメチンアゾ系、ジクトピロロピロール系、イソインドリン系などの顔料が挙げられる。
また、無機顔料として、カーボンブラック、酸化チタン、酸化亜鉛、硫化亜鉛、硫酸バリウム、炭酸カルシウム、酸化クロム、シリカ、ベンガラ、アルミニウム、マイカ（雲母）などが挙げられる。
また、白インキには酸化チタン、墨インキにはカーボンブラック、金、銀インキにはアルミニウム、パールインキにはマイカ（雲母）を使用することがコストや着色力の点から好ましい。
Examples of the pigment blended in the aqueous flexo ink composition for paper containers of the present invention include organic pigments such as azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, and isoindolinone. , Quinophthalone-based, azomethineazo-based, dictopyrrolopyrrole-based, and isoindoline-based pigments.
Examples of inorganic pigments include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, bengara, aluminum, and mica (mica).
In view of cost and coloring power, it is preferable to use titanium oxide for white ink, carbon black for black ink, aluminum for silver ink, and mica for pearl ink.
本発明に使用する水はイオン交換水を用いることが好ましい。 The water used in the present invention is preferably ion exchange water.
水性フレキソインキ組成物には、水と混和する有機溶剤を使用することができる。有機溶剤としては、例えばメチルアルコール、エチルアルコール、イソプロピルアルコール、ｎ−プロピルアルコール等のアルコール類や、プロピレングリコール、グリセリン等の多価アルコール類、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、エチルカルビトール等のエーテル類等がある。 An organic solvent miscible with water can be used in the aqueous flexographic ink composition. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and n-propyl alcohol, polyhydric alcohols such as propylene glycol and glycerin, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono There are ethers such as propyl ether and ethyl carbitol.
また、その他の添加剤成分としては、耐摩擦性、滑り性等を付与するためのパラフィン系ワックス、ポリエチレン系ワックス、カルナバワックス等のワックス類やオレイン酸アミド、ステアリン酸アミド、エルカ酸アミド等の脂肪酸アミド類及び印刷時の発泡を抑制するためのシリコン系、非シリコン系消泡剤及び顔料の濡れを向上させる各種分散剤等を適宜使用することもできる。 Other additive components include waxes such as paraffin wax, polyethylene wax, carnauba wax, oleic acid amide, stearic acid amide, erucic acid amide, etc. for imparting friction resistance, slipperiness, etc. Fatty acid amides, silicon-based and non-silicon-based antifoaming agents for suppressing foaming at the time of printing, various dispersants for improving pigment wetting, and the like can also be used as appropriate.
本発明に係わる水性フレキソインキ組成物は、グラビア、フレキソ印刷インキの製造に一般的に使用されているアイガーミル、サンドミル、ガンマミル、アトライター等を用いて分散を行い、所定の粘度になるよう調整を行なうことで製造される。このようにして得られた水性フレキソインキ組成物は、印刷時に適正粘度になるまで水または水混和性有機溶剤、例えばエチルアルコール、イソプロピルアルコール、ノルマルプロピルアルコールなどのアルコール系有機溶剤を混合した溶剤を用いて希釈し、ツーロール方式やドクターチャンバー方式を使用するフレキソ印刷やロールコーター、アプリケーター等でライナー紙などに印刷紙基材の一部または全面に印刷または塗工される。 The aqueous flexographic ink composition according to the present invention is dispersed using an Eiger mill, a sand mill, a gamma mill, an attritor or the like generally used in the production of gravure and flexographic printing inks, and adjusted so as to have a predetermined viscosity. Manufactured by performing. The aqueous flexographic ink composition thus obtained is prepared by mixing a solvent mixed with water or a water-miscible organic solvent such as ethyl alcohol, isopropyl alcohol, and normal propyl alcohol until the viscosity becomes an appropriate value at the time of printing. It is diluted by use, and is printed or coated on a part or the entire surface of the printing paper substrate on liner paper or the like by flexographic printing using a two-roll method or a doctor chamber method, a roll coater, an applicator or the like.
フレキソ印刷に使用する場合には、その粘度（ザーンカップＮo.４）が無希釈から１０秒〜３０秒で印刷される事があるが、好ましくは水でザーンカップＮo.４で１０〜１２秒に希釈したインキである。
この水溶性アクリル樹脂を使用した水性フレキソインキ組成物をライナー紙にフレキソ印刷を行うと、良好な印刷効果を有していることが分かった。また、優れたコルゲーター加工適性を有するコルゲート加工用ライナー紙が得られ、コルゲート加工段ボールを得ることが可能となった。
When used for flexographic printing, its viscosity (Zahn cup No. 4) may be printed from 10 seconds to 30 seconds after undiluted, but preferably 10 to 12 seconds with water in Zaan cup No. 4 Ink diluted to
It was found that when a water-based flexographic ink composition using this water-soluble acrylic resin was flexographically printed on a liner paper, it had a good printing effect. In addition, a corrugated liner paper having excellent corrugator processing suitability was obtained, and corrugated cardboard could be obtained.
本発明で用いられる印刷紙基材としてはライナー紙、白ライナーや上質紙などのパルプ系繊維材料である。また、その他の基材としては、プラスチックフィルム、これらの複合材料の使用も可能である。
前記パルプ系繊維材料としては、広葉樹晒クラフトパルプ、針葉樹晒クラフトパルプ等の化学とこれらを原料として用いた原紙等が挙げられる。これらの原紙は、公知の長網多筒型抄紙機、長網ヤンキー型抄紙機、円網抄紙機等で抄造される上質紙、中質紙、片艶紙及びクラフト紙等の酸性紙、中性紙、アルカリ性紙、およびパルプモールド成型機にて成型された成型体を包含するものである。
The printing paper base material used in the present invention is a pulp-based fiber material such as liner paper, white liner or fine paper. In addition, as other substrates, plastic films and composite materials thereof can be used.
Examples of the pulp fiber material include chemistry of hardwood bleached kraft pulp, softwood bleached kraft pulp, and raw paper using these as raw materials. These base papers include high-quality paper, medium-quality paper, glossy paper, kraft paper, and other acidic paper produced by known long-net multi-cylinder paper machines, long-net Yankee-type paper machines, circular net paper machines, etc. It includes a molded paper molded by a paper, an alkaline paper, and a pulp molding machine.
印刷物の塗工量は，使用する印刷紙基材の種類や水性フレキソインキ組成物の粘度、浸透性等により適宜決定される。 The coating amount of the printed material is appropriately determined depending on the type of printing paper substrate used, the viscosity of the water-based flexographic ink composition, the permeability, and the like.
本発明の印刷物において、本発明の水性フレキソインキ組成物を印刷または塗工された部分は耐熱性、耐水性、耐摩擦性、コルゲート加工等の耐久性を更に向上させるため、水性フレキソインキ組成物を印刷、乾燥させた基材の一部または全面にＯＰワニスやノンスリップワニスを基材の表面に重ね刷りすることができる。 In the printed matter of the present invention, the portion printed or coated with the aqueous flexographic ink composition of the present invention is further improved in durability such as heat resistance, water resistance, friction resistance, corrugating, etc. An OP varnish or a non-slip varnish can be overprinted on the surface of the substrate on a part or the entire surface of the substrate that has been printed and dried.
ＯＰワニス、ノンスリップワニスとしては（メタ）アクリル酸と、（メタ）アクリル酸エステルを含む水溶性アクリル共重合体、必要に応じてコア／シェル型アクリルエマルジョンを併用することができる。また、必要に応じて二酸化ケイ素やワックスや水を添加することができる。特にノンスリップワニスとしては、基材の表面のスベリ性を付与する目的で二酸化ケイ素を２０重量％〜４０重量％添加することが好ましい。 As OP varnish and non-slip varnish, (meth) acrylic acid, a water-soluble acrylic copolymer containing (meth) acrylic acid ester, and a core / shell type acrylic emulsion as required can be used in combination. Further, silicon dioxide, wax or water can be added as necessary. In particular, as a non-slip varnish, it is preferable to add 20% to 40% by weight of silicon dioxide for the purpose of imparting the smoothness of the surface of the substrate.
本発明の水性フレキソインキ用組成物は、紙基材の他、プラスチックフィルムなどと貼合し複合基材にも使用し、成形加工し、容器にすることも可能である。例えば段ボール状箱、テトラパック、ゲーベルトップ、円筒形（カートカン）等いずれでもよく、形状に限定されない。 The aqueous flexographic ink composition of the present invention can be bonded to a plastic film or the like in addition to a paper substrate, used for a composite substrate, molded, and formed into a container. For example, any of a cardboard box, a tetra pack, a gobel top, a cylindrical shape (cart can), etc. may be used, and the shape is not limited.
段ボールの生産方式は、シート状の段ボール紙に直接フレキソ印刷を行うポストプリント方式とライナー紙にフレキソ印刷した表ライナー紙と中芯紙及び裏ライナー紙をコルゲーター機で貼合するプレプリント方式に大別する事ができる。本発明においては、プレプリント方式が好適に使用でき、コルゲート加工することによりコルゲート加工段ボールが得られる。プレプリント方式では印刷した表ライナー紙と中芯紙及び裏ライナー紙を貼合するコルゲーター機は、貼合速度が最大４５０（ｍ／ｍｉｎ）にも及び、また、コルゲート時の加工温度が１５０℃〜１７０℃以上となる最新鋭のコルゲーター機で貼合するケースが増えており、本発明の紙器用水性フレキソインキ組成物を適用することができる。 Corrugated board production methods are largely divided into a post-printing system that directly performs flexographic printing on sheet-like corrugated paper, and a pre-printing system that uses a corrugator machine to bond flexographically printed front liner paper, core paper, and back liner paper. Can be separated. In the present invention, a preprint system can be suitably used, and corrugated cardboard can be obtained by corrugating. In the preprint method, the corrugator machine that bonds the printed front liner paper, core paper, and back liner paper has a maximum bonding speed of 450 (m / min), and the processing temperature during corrugation is 150 ° C. The case where it bonds by the state-of-the-art corrugator machine which will be -170 degreeC or more is increasing, and the water-based flexographic ink composition for paper containers of this invention can be applied.
以下、実施例により本発明を説明するが、本発明はこれに限定されるものでない。尚、実施例中「部」とは「重量部」を、「％」とは「重量％」をそれぞれ表わす。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.
＜水溶性アクリル系樹脂の合成＞
（合成例１）
攪拌機、還流冷却器、温度制御装置、および窒素導入管を備えた反応容器中に、イソプロパノールを９０部とエタノールを９０部仕込んで、窒素ガスの雰囲気下に温度８０℃にまで昇温した。これにアクリル酸３０部、アクリル酸ブチル１０部、メタクリル酸エチル１５部およびα−メチルスチレン４５部、アゾビスイソブチロニトリル（ＡＩＢＮ）４部と、イソプロパノール２０部とからなる混合物を２時間かけて滴下した。
滴下終了後も、同温度で、撹拌し続け５時間反応を行なった後、６０℃にまで降温した。樹脂中のカルボキシル基と当量のＮ，Ｎ−ジエチルエタノールアミン（ＤＥＥＡ）４９部とイオン交換水２０部とからなる混合物を加えて、均一になるまで攪拌した。次いで、イオン交換水の２００部を加えて、均一に攪拌を行なったのち、減圧蒸留により、イソプロパノールとエタノールを留去させ、その後固形分を３０％に調整した。得られた水溶性アクリル系樹脂（樹脂（１））は酸価２３４ｍｇＫＯＨ／ｇ、重量平均分子量１７０００、計算によるガラス転移温度９８℃であった。
<Synthesis of water-soluble acrylic resin>
(Synthesis Example 1)
In a reaction vessel equipped with a stirrer, a reflux condenser, a temperature controller, and a nitrogen introduction tube, 90 parts of isopropanol and 90 parts of ethanol were charged, and the temperature was raised to 80 ° C. in an atmosphere of nitrogen gas. A mixture of 30 parts of acrylic acid, 10 parts of butyl acrylate, 15 parts of ethyl methacrylate and 45 parts of α-methylstyrene, 4 parts of azobisisobutyronitrile (AIBN) and 20 parts of isopropanol was taken over 2 hours. And dripped.
After completion of the dropwise addition, stirring was continued at the same temperature for 5 hours, and then the temperature was lowered to 60 ° C. A mixture of 49 parts of N, N-diethylethanolamine (DEEA) equivalent to the carboxyl group in the resin and 20 parts of ion-exchanged water was added and stirred until uniform. Next, 200 parts of ion-exchanged water was added and stirred uniformly, and then isopropanol and ethanol were removed by distillation under reduced pressure, and then the solid content was adjusted to 30%. The obtained water-soluble acrylic resin (resin (1)) had an acid value of 234 mgKOH / g, a weight average molecular weight of 17000, and a calculated glass transition temperature of 98 ° C.
（合成例２〜２４）
表１に記載した配合に従い、合成例１と同様な方法により水溶性アクリル系樹脂（樹脂（２）〜（２４））を得た。表１にガラス転移温度、酸価および重量平均分子量を示す。尚、いずれの樹脂においても有機アミンは樹脂中のカルボキシル基と当量になるよう添加し、樹脂溶液の最終的な固形分は３０％に調整した。合成例１９〜２４は、比較例用である。
(Synthesis Examples 2 to 24)
According to the formulation described in Table 1, water-soluble acrylic resins (resins (2) to (24)) were obtained in the same manner as in Synthesis Example 1. Table 1 shows the glass transition temperature, acid value, and weight average molecular weight. In any resin, the organic amine was added so as to be equivalent to the carboxyl group in the resin, and the final solid content of the resin solution was adjusted to 30%. Synthesis Examples 19 to 24 are for comparative examples.
尚、実施例、比較例に用いた有機アミンは下記の通りである。
（１）ＭＯＰ：モルホリン（沸点１２８℃）
（２）ＤＭＥＡ：Ｎ，Ｎ−ジメチルエタノールアミン(沸点１３３℃)、
（３）ＤＥＥＡ：Ｎ，Ｎ−ジエチルエタノールアミン(沸点１６０℃)、
（４）ＭＥＡ：モノエタノールアミン(沸点１７１℃)
（５）ｔＢＭＥＡ：ｔ−ブチルエタノールアミン（沸点１７５℃）
In addition, the organic amine used for the Example and the comparative example is as follows.
(1) MOP: morpholine (boiling point 128 ° C.)
(2) DMEA: N, N-dimethylethanolamine (boiling point 133 ° C.),
(3) DEEA: N, N-diethylethanolamine (boiling point 160 ° C.),
(4) MEA: monoethanolamine (boiling point 171 ° C.)
(5) tBMEA: t-butylethanolamine (boiling point 175 ° C.)
表１
＜コア／シェル型アクリルエマルジョンの合成＞
（合成例２５）
攪拌機、還流冷却器、温度制御装置、および窒素導入管を備えた反応容器中にイソプロピルアルコール７０部を仕込み、攪拌を開始するとともに、窒素ガスを吹き込みながら８０℃まで昇温させた。ここにアクリル酸８部、スチレン２５部、メタクリル酸ｔ−ブチル１０部、アクリル酸ブチル１４部、アゾビスイソブチロニトリル４部、およびイソプロピルアルコール３０部よりなる溶液を３時間かけて滴下した。２時間後にアゾビスイソブチロニトリル０．５部を添加し、さらに２時間攪拌を継続した後反応を終了した。次に得られた樹脂のカルボキシル基と同じ当量の２５％アンモニア水および、イオン交換水１００部を徐々に加え樹脂溶液を得た。その後減圧蒸留によりイソプロピルアルコールを留去し、シェル部となる水溶性樹脂溶液を得た。得られた水溶性樹脂溶液に窒素ガスを吹き込みながら８０℃まで加熱した。ここにスチレン１８部、アクリル酸２−エチルへキシル２５部の混合物を滴下しながら、同時に過硫酸アンモニウム１部、イオン交換水６部よりなる溶液を２時間かけて滴下した。さらに２時間反応させた後、固形分を４０％に調整し、酸価６２ｍｇＫＯＨ／ｇ、樹脂全体のガラス転移温度（Ｔｇ）が７℃、コア／シェル比（固形分）４３／５７のアクリルエマルジョン（エマルジョン（１））を得た。表２に結果を示す。
<Synthesis of core / shell type acrylic emulsion>
(Synthesis Example 25)
In a reaction vessel equipped with a stirrer, a reflux condenser, a temperature controller, and a nitrogen introduction tube, 70 parts of isopropyl alcohol was charged, and stirring was started, and the temperature was raised to 80 ° C. while blowing nitrogen gas. A solution consisting of 8 parts of acrylic acid, 25 parts of styrene, 10 parts of t-butyl methacrylate, 14 parts of butyl acrylate, 4 parts of azobisisobutyronitrile and 30 parts of isopropyl alcohol was added dropwise over 3 hours. After 2 hours, 0.5 part of azobisisobutyronitrile was added, and stirring was continued for another 2 hours, and then the reaction was terminated. Next, 25% ammonia water equivalent to the carboxyl group of the obtained resin and 100 parts of ion-exchanged water were gradually added to obtain a resin solution. Thereafter, isopropyl alcohol was distilled off under reduced pressure to obtain a water-soluble resin solution serving as a shell portion. The resulting water-soluble resin solution was heated to 80 ° C. while blowing nitrogen gas. While dropwise adding a mixture of 18 parts of styrene and 25 parts of 2-ethylhexyl acrylate, a solution consisting of 1 part of ammonium persulfate and 6 parts of ion-exchanged water was added dropwise over 2 hours. After further reaction for 2 hours, the solid content was adjusted to 40%, an acrylic emulsion having an acid value of 62 mgKOH / g, a glass transition temperature (Tg) of the entire resin of 7 ° C., and a core / shell ratio (solid content) of 43/57. (Emulsion (1)) was obtained. Table 2 shows the results.
（合成例２６〜２８）
表２に記載した配合に従い、合成例２５と同様な方法によりコア／シェル型アクリルエマルジョン（エマルジョン（２）〜（４））を得た。尚、いずれのエマルジョンにおいてもアンモニア水はシェル部となる水溶性樹脂溶液のカルボキシル基と当量になるよう添加し、エマルジョンの最終的な固形分は４０％に調整した。表２にコア／シェル比（固形分）、ガラス転移温度（Ｔｇ）および酸価を示す。
(Synthesis Examples 26 to 28)
A core / shell acrylic emulsion (emulsions (2) to (4)) was obtained in the same manner as in Synthesis Example 25 according to the formulation described in Table 2. In any of the emulsions, ammonia water was added so as to be equivalent to the carboxyl group of the water-soluble resin solution serving as the shell portion, and the final solid content of the emulsion was adjusted to 40%. Table 2 shows the core / shell ratio (solid content), glass transition temperature (Tg), and acid value.
表２
実施例１
カーボンブラック（ＲＥＧＡＬ２５０Ｒ、Ｃａｂｏｔ社製）２４部、合成例１で得られた水溶性アクリル系樹脂（樹脂（１））２８部、サーフィノール１０４（消泡剤、エアープロダクト社製）１部、ケミパールＷ−４００（ポリエチレンワックス、三井化学社製）５部、イオン交換水２６部の混合物をペイントコンディショナーにて２時間分散し、墨顔料分散液を得た。
前記墨顔料分散液全量に対して合成例２７で得たコア／シェル型アクリルエマルジョン（エマルジョン（３））１６部を混合、撹拌し、紙器用水性フレキソインキ組成物（インキ（１））を得た。水溶性アクリル系樹脂とコア／シェル型アクリルエマルジョンの固形分重量比は５７：４３である。表３にインキの配合および水溶性アクリル系樹脂とコア／シェル型アクリルエマルジョンの固形分重量比を示す。
Example 1
24 parts of carbon black (REGAL250R, manufactured by Cabot), 28 parts of water-soluble acrylic resin (resin (1)) obtained in Synthesis Example 1, 1 part of Surfynol 104 (antifoaming agent, manufactured by Air Products), Chemipearl A mixture of 5 parts of W-400 (polyethylene wax, Mitsui Chemicals) and 26 parts of ion-exchanged water was dispersed for 2 hours with a paint conditioner to obtain a black pigment dispersion.
16 parts of the core / shell type acrylic emulsion (emulsion (3)) obtained in Synthesis Example 27 is mixed and stirred with respect to the total amount of the black pigment dispersion, thereby obtaining an aqueous flexo ink composition (ink (1)) for paper containers. It was. The solid content weight ratio of the water-soluble acrylic resin and the core / shell type acrylic emulsion is 57:43. Table 3 shows the composition of the ink and the solid content weight ratio between the water-soluble acrylic resin and the core / shell acrylic emulsion.
実施例２〜２９、比較例１〜７
表３、４に記載した配合に従い、実施例１と同様な方法により水性フレキソインキ組成物（インキ（２）〜（３６））を得た。尚、インキ（３０）〜（３６）は比較例用である。
水溶性アクリル系樹脂とコアとシェル型アクリルエマルジョンの固形分重量比を表３，４に示す。
Examples 2-29, Comparative Examples 1-7
A water-based flexographic ink composition (inks (2) to (36)) was obtained in the same manner as in Example 1 according to the formulation described in Tables 3 and 4. Inks (30) to (36) are for comparative examples.
Tables 3 and 4 show solid weight ratios of the water-soluble acrylic resin, the core, and the shell type acrylic emulsion.
得られた水性フレキソインキ組成物を茶ライナー原紙（商品名：ＡＢＯ１７０／王子マテリア社製）にワイヤーバー＃４で塗布し、塗膜物性としてコルゲート加工時の耐熱性、耐摩擦性、耐水性、再溶解性、また、印刷適性として印刷機を用いた印刷物により版からみ性を評価した。下記に評価方法および評価基準を示す。評価結果を表３、４に示す。 The obtained water-based flexographic ink composition was applied to a tea liner base paper (trade name: ABO170 / manufactured by Oji Materia Co., Ltd.) with a wire bar # 4, and the coating film properties were heat resistance, friction resistance, water resistance during corrugation processing, The re-dissolvability and the print entanglement were evaluated by printed matter using a printing machine as printability. The evaluation method and evaluation criteria are shown below. The evaluation results are shown in Tables 3 and 4.
（１）耐熱性
コルゲート加工時の耐熱性を評価した。塗膜とアルミ箔を重ね、２５０℃で圧力２ｋｇ/ｃｍ2 、２秒間加圧した後アルミ箔をはがし、塗膜の剥離程度を目視で評価した。
◎ ； 全く剥離が認められない。
○ ； 極僅かに剥離が認められる。塗膜の３％未満
〇△；僅かに剥離が認められる。塗膜の３％以上、５％未満
△ ； 塗膜の一部が剥離している。塗膜の５％以上、３０％未満
× ； 塗膜の大部分が剥離している。塗膜の３０％以上
実用レベルは〇△以上である。
(1) Heat resistance The heat resistance during corrugating was evaluated. The coating film and the aluminum foil were overlapped, pressed at 250 ° C. under a pressure of 2 kg / cm 2 for 2 seconds, then peeled off the aluminum foil, and the degree of peeling of the coating film was visually evaluated.
A: No separation was observed.
○: Slight peeling was observed. Less than 3% of coating film ○ △; slight peeling is observed. 3% or more of the coating film and less than 5% Δ: Part of the coating film is peeled off. 5% or more and less than 30% of the coating film x: Most of the coating film is peeled off. The practical level of 30% or more of the coating film is ◯ Δ or more.
（２）耐摩擦性
学振型耐摩擦試験機で荷重５００ｇ、対上質紙で１００回擦り、インキの取られ具合を目視で評価した。
◎ ； 擦った上質紙に色がつかない。
○ ； 擦った上質紙にうっすらと色がつく。
△ ； 擦った上質紙に濃い色がつく。
× ； 擦った跡の下地が見える。
実用レベルは〇以上である。
(2) Friction resistance The load was 500 g with a Gakushin type friction resistance tester and rubbed 100 times with fine paper, and the degree of ink removal was evaluated visually.
◎; Color does not stick to the rubbed fine paper.
○: Slightly colored rubbing fine paper.
Δ: A dark color is formed on the rubbed fine paper.
×: The ground of the rubbing trace can be seen.
The practical level is ◯ or more.
（３）耐水性
塗膜を水に浸した綿棒で５回擦り、インキの取られ具合を目視で評価した。
◎ ； 擦った跡が塗膜上に残らない。
○ ； 擦った跡が塗膜上にうっすら残る。
△ ； 擦った跡が色落ちする。
× ； 擦った跡の下地が見える。
実用レベルは〇以上である。
(3) Water resistance The coating film was rubbed 5 times with a cotton swab dipped in water, and the degree of ink removal was visually evaluated.
A: Rub marks do not remain on the coating film.
○: A slight rubbing mark remains on the coating film.
Δ: The rubbing trace is discolored.
×: The ground of the rubbing trace can be seen.
The practical level is ◯ or more.
（４）再溶解性
塗膜に水を滴下させて脱脂綿で１回擦り、インキの取られ具合を目視で評価した。
◎ ； 擦った跡が塗膜上に残らない。
○ ； 擦った跡が塗膜上に極僅かに残る。
〇△：擦った跡が塗膜上にうっすら残る。
△ ； 擦った跡が色落ちする。
× ； 擦った跡の下地が見える。
実用レベルは〇△以上である
(4) Re-dissolution property Water was dropped on the coating film and rubbed once with absorbent cotton, and the degree of ink removal was visually evaluated.
A: Rub marks do not remain on the coating film.
○: Traces of rubbing remain slightly on the coating film.
○ △: A trace of rubbing remains on the coating film.
Δ: The rubbing trace is discolored.
×: The ground of the rubbing trace can be seen.
Practical level is over △△
（５）版からみ性
水性フレキソインキ組成物を印刷粘度（ザーンカップ＃４で１０秒）に調整し、小型印刷機で印刷した後３０分間空転し、空回転終了後、再度印刷して印刷物の印刷ムラを目視で評価した。
◎ ； 印刷ムラが全くない。
○ ； 印刷ムラが極僅かに認められる。
〇△；印刷ムラが僅かに認められる。
△ ； 印刷ムラが認められる。
× ； 印刷ムラが非常に目立つ。
実用レベルは〇△以上である。
(5) Plate seizure The water-based flexographic ink composition is adjusted to the printing viscosity (10 seconds with Zahn cup # 4), printed on a small printing machine, and then idled for 30 minutes. Printing unevenness was visually evaluated.
A: There is no uneven printing.
○: Slight printing unevenness is observed.
○ △: Print unevenness is slightly observed.
Δ: Printing unevenness is observed.
×: Print unevenness is very conspicuous.
The practical level is ◯ △ or more.
表３
表４
本発明の紙器用水性フレキソインキ組成物を紙基材の一部または全面に印刷、塗布して得られた印刷物、塗布物は、コルゲート加工時の耐熱性、耐摩擦性、耐水性、再溶解性に優れた塗膜を与える。また、水性フレキソインキ組成物は、版からみ性に優れる。該インキ組成物の印刷層を有する印刷物、該印刷物を用いたコルゲート加工段ボールは、紙製包装材のダンボール箱として、優れた耐久性を有し広範囲な用途に適用できる。 The printed product obtained by printing and applying the water based flexographic ink composition for paper containers of the present invention to a part or the entire surface of a paper substrate, the applied product is heat resistance, friction resistance, water resistance, redissolving during corrugating. Gives excellent coating properties. Moreover, the water-based flexographic ink composition is excellent in plate entanglement. A printed matter having a printed layer of the ink composition and a corrugated cardboard using the printed matter have excellent durability as a corrugated cardboard box for paper packaging materials and can be applied to a wide range of uses.
Claims (9)
水溶性アクリル系樹脂が（メタ）アクリル酸と、（メタ）アクリル酸エステルと、α−メチルスチレンとを含むモノマーの重合物であるアクリル共重合体の有機アミン中和物であり、
有機アミンの沸点が１３０〜１７３℃であり、
α−メチルスチレンに由来する部分が、アクリル共重合体の固形分１００重量％に対して４５〜６５重量％であり、
（メタ）アクリル酸エステルが（メタ）アクリル酸と炭素数２〜１２のアルコールとのエステル化合物を含むことを特徴とする紙器用水性フレキソインキ組成物。 An aqueous flexo ink composition for paper containers containing a water-soluble acrylic resin, a pigment, and water,
The water-soluble acrylic resin is an organic amine neutralized product of an acrylic copolymer that is a polymer of monomers including (meth) acrylic acid, (meth) acrylic acid ester, and α-methylstyrene,
The boiling point of the organic amine is 130-173 ° C.,
The part derived from α-methylstyrene is 45 to 65% by weight based on 100% by weight of the solid content of the acrylic copolymer,
An aqueous flexographic ink composition for paper containers, wherein the (meth) acrylic acid ester contains an ester compound of (meth) acrylic acid and an alcohol having 2 to 12 carbon atoms.
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