JP2003221537A - Water-based printing ink composition and printing method - Google Patents
Water-based printing ink composition and printing methodInfo
- Publication number
- JP2003221537A JP2003221537A JP2002023633A JP2002023633A JP2003221537A JP 2003221537 A JP2003221537 A JP 2003221537A JP 2002023633 A JP2002023633 A JP 2002023633A JP 2002023633 A JP2002023633 A JP 2002023633A JP 2003221537 A JP2003221537 A JP 2003221537A
- Authority
- JP
- Japan
- Prior art keywords
- water
- mass
- printing
- ink composition
- soluble polymer
- 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Printing Methods (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は特定の水溶性高分子
を含有する水性印刷インキ組成物および印刷方法に関す
るものである。さらに詳しくは高い印刷濃度を有し、に
じみがなく、さらに印刷作業性等の面でも十分な性能を
有する水性印刷インキ組成物および印刷方法に関するも
のである。TECHNICAL FIELD The present invention relates to an aqueous printing ink composition containing a specific water-soluble polymer and a printing method. More specifically, the present invention relates to a water-based printing ink composition having a high printing density, no bleeding, and sufficient performance in terms of printing workability and a printing method.
【０００２】[0002]
【従来の技術】段ボール等の紙を包装基材とした分野で
は、古くから水性印刷インキが利用され、そして、最近
では、特に印刷の高速化対応として、インキ中の水分な
どがすぐに紙中に浸透して乾燥するように、極力、低粘
度のインキが利用されるようになっている。このような
低粘度インキは、速乾性ゆえに印刷効率の向上には寄与
しているが、反面、浸透する成分と共に着色剤成分が紙
中に拡散してしまう事から、印刷濃度の低下やにじみが
発生しやすいなどの問題がある。2. Description of the Related Art Water-based printing inks have been used for a long time in the field where paper such as corrugated paper is used as a packaging base material. Ink having a low viscosity is used as much as possible so that the ink penetrates into the ink and dries. Although such a low-viscosity ink contributes to the improvement of printing efficiency because of its quick-drying property, on the other hand, since the coloring agent component diffuses into the paper together with the permeating component, a decrease in print density and bleeding occur. There are problems such as easy occurrence.
【０００３】[0003]
【発明が解決しようとする課題】そこで、本発明の目的
は、上記の問題を解決することであり、低粘度であって
も十分な印刷濃度を有し、また、にじみ等の少ない印刷
物を得ることのできる水性印刷インキ組成物および印刷
方法を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and to obtain a printed matter having a sufficient printing density even with a low viscosity and less bleeding. It is an object of the present invention to provide an aqueous printing ink composition and a printing method which can be used.
【０００４】[0004]
【課題を解決するための手段】すなわち本発明は、単量
体合計１００質量部中、下記一般式（Ｉ）で示される単
量体ＡThat is, the present invention provides a monomer A represented by the following general formula (I) in 100 parts by weight of the total amount of monomers.
【化２】
（式中Ｒ１はＨまたはＣＨ３であり、Ｒ２は炭素数１〜
５の分岐または直鎖のアルキレン基であり、Ｘは水素、
リチウム、ナトリウム、カリウム、アンモニア、アルキ
ルアミン（モノエチルアミン、モノブチルアミン、およ
びトリエチルアミン等）およびアルカノールアミン（モ
ノエタノールアミン、ジエタノールアミンおよびトリエ
タノールアミン等）から選ばれた１種または２種以上で
ある）１００〜１０質量部、アクリルアミド０〜９０質
量部およびこれらと共重合可能な単量体Ｂ０〜３０質量
部との重合体であり、重量平均分子量が１００万〜４０
０万である水溶性高分子を含有することを特徴とする、
水性印刷インキ組成物および印刷方法である。[Chemical 2] (In the formula, R 1 is H or CH 3 , and R 2 is 1 to 1 carbon atoms.
5 is a branched or straight chain alkylene group, X is hydrogen,
One or more selected from lithium, sodium, potassium, ammonia, alkylamines (monoethylamine, monobutylamine, triethylamine, etc.) and alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.) 100 10 to 10 parts by mass, 0 to 90 parts by mass of acrylamide, and 0 to 30 parts by mass of a monomer B copolymerizable therewith, having a weight average molecular weight of 1,000,000 to 40.
Characterized by containing a water-soluble polymer of 0,000,
An aqueous printing ink composition and a printing method.
【０００５】（作用）段ボール等の紙を対象とした印刷
の分野において、印刷に適する水性インキの粘度は、通
常、インキの粘度管理で利用するザーン粘度計Ｎｏ．４
(離合社製)で流出秒数が１３秒以下であり、この様な低
粘度でインキを印刷すると、印刷濃度の低下やにじみが
起こりやすくなる。そこで、本発明者らは、これまでに
も高い印刷濃度を維持し、にじみのない印刷物を得るた
めの研究を重ねてきた。まず、高い印刷濃度を維持でき
る最も簡単な方法としては、顔料の含有量を多くする方
法、及び、インキ組成物をより高粘度で印刷する方法が
考えられる。しかしながら、インキ中の顔料の含有量を
多くする方法では、インキの流動性や保存安定性が低下
し、一方、インキを高粘度で印刷する方法では、印刷中
にインキが霧状になって飛散(ミスチング)し、印刷物を
汚損するという現象が見られ、また、インキ粘度を安定
に維持するのが困難なために、頻繁に粘度を調整するこ
とが必要となり、印刷作業性が低下する等、新たな問題
を引き起こす原因となる。(Function) In the field of printing for paper such as corrugated cardboard, the viscosity of the water-based ink suitable for printing is the Zahn viscometer No. Four
(Manufactured by Riaisha Co., Ltd.) has an outflow time of 13 seconds or less, and printing an ink with such a low viscosity tends to cause a decrease in print density and bleeding. Therefore, the inventors of the present invention have repeatedly conducted research to maintain a high print density and obtain a printed matter without bleeding. First, as the simplest method capable of maintaining a high print density, a method of increasing the pigment content and a method of printing the ink composition with a higher viscosity can be considered. However, the method of increasing the pigment content in the ink lowers the fluidity and storage stability of the ink, while the method of printing the ink with high viscosity causes the ink to become fog and scatter during printing. (Misting), the phenomenon of staining the printed matter is seen, and since it is difficult to maintain the ink viscosity stable, it is necessary to frequently adjust the viscosity, which lowers the printing workability. It causes a new problem.
【０００６】そこで、本発明者らは、この様な条件下で
どのようなメカニズムであれば、高い印刷濃度を有し、
新たな問題の発生のないインキ組成物を得ることができ
るかについて検討を行った。そして、印刷物の濃度低下
やにじみが、インキ中の水分等が紙中に浸透するのに伴
って、顔料も一緒に拡散してしまうことが一因であるこ
とに着目した結果、本発明で特定する水溶性高分子を利
用すると、水分等が紙中に浸透しても、高い印刷濃度を
維持し、にじみのない印刷物を得る事ができることを見
出し、本発明を完成させたものである。Therefore, the inventors of the present invention have a high print density by any mechanism under such conditions.
It was examined whether or not an ink composition without a new problem could be obtained. Then, as a result of focusing on the fact that the decrease in the density of the printed matter and the bleeding are due to the fact that the pigment diffuses together with the water content in the ink penetrating into the paper, the present invention specifies It was found that the use of such a water-soluble polymer makes it possible to maintain a high printing density even when water penetrates into the paper and to obtain a printed matter without bleeding, and thus completed the present invention.
【０００７】本発明で利用する水溶性高分子は、水性塗
工剤組成物の粘度調整剤として既知の材料であり、例え
ば、特開平１１−３１０７５１号公報などでは、増粘効
果によりカーテンコーティング用塗工剤のカーテン切れ
を防止する材料として知られている。しかしながら、単
純に水溶性高分子の増粘効果により、印刷時のインキの
粘度を高くしても、前記のようなミスチングによる印刷
物の汚損や、粘度調整による印刷作業性の低下という問
題が発生する。一方、インキを印刷に適する粘度まで低
下させるためには、希釈剤が多く必要となることから、
インキ中の顔料濃度が低下して、むしろ、印刷濃度の点
では不利となる。The water-soluble polymer used in the present invention is a material known as a viscosity modifier for an aqueous coating composition. For example, JP-A No. 11-310751 discloses a curtain-coating agent due to its thickening effect. It is known as a material that prevents curtain breakage of coating agents. However, even if the viscosity of the ink at the time of printing is increased simply by the thickening effect of the water-soluble polymer, problems such as stains on the printed matter due to misting as described above and deterioration of printing workability due to viscosity adjustment occur. . On the other hand, in order to reduce the viscosity of the ink to a level suitable for printing, a large amount of diluent is required,
The pigment concentration in the ink is reduced, which is rather disadvantageous in terms of print density.
【０００８】本発明の水溶性高分子を利用すると、イン
キが低粘度であっても高い印刷濃度を維持し、にじみの
ない印刷物が得られるのは、インキの水分等が紙中に浸
透しても、顔料粒子を紙の表面で歩留まらせる事ができ
るという、増粘とは全く異なる作用によるものと考えら
れる。なお、水性塗工剤の分野においては、粘度調整剤
としてポリアクリル酸等の他の水溶性高分子材料もよく
知られている。しかしながら、これら他の水溶性高分子
材料を添加すると、インキの保存中での顔料分散安定性
が低下し、また、低粘度でもミスチングの発生が多く見
られるようになる。それに対して、本発明の水溶性高分
子では、顔料分散安定性を低下させる事がなく、また、
ミスチングの発生の少ないインキ組成物を得ることがで
きるものである。以下、本発明を具体的に説明する。When the water-soluble polymer of the present invention is used, a high print density can be maintained even if the ink has a low viscosity, and a printed matter without bleeding can be obtained because the water content of the ink penetrates into the paper. However, it is considered that the pigment particles can be retained on the surface of the paper, which is a completely different action from the thickening. In the field of water-based coating agents, other water-soluble polymer materials such as polyacrylic acid are well known as viscosity modifiers. However, when these other water-soluble polymer materials are added, the pigment dispersion stability during storage of the ink is lowered, and misting often occurs even at low viscosity. On the other hand, the water-soluble polymer of the present invention does not decrease the pigment dispersion stability, and
It is possible to obtain an ink composition with less misting. Hereinafter, the present invention will be specifically described.
【０００９】[0009]
【発明の実施の形態】本発明の水性印刷インキ組成物お
よび印刷方法に含有される水溶性高分子を構成する単量
体Ａとしては、（メタ）アクリルアミドメタンスルホン
酸（塩）、（メタ）アクリルアミドエタンスルホン酸
（塩）、（メタ）アクリルアミドプロパンスルホン酸
（塩）、（メタ）アクリルアミドメチルエタンスルホン
酸（塩）、（メタ）アクリルアミドブタンスルホン酸
（塩）、（メタ）アクリルアミドメチルプロパンスルホ
ン酸（塩）、（メタ）アクリルアミドジメチルエタンス
ルホン酸（塩）、（メタ）アクリルアミドペンタンスル
ホン酸（塩）、（メタ）アクリルアミドメチルブタンス
ルホン酸（塩）、アクリルアミドジメチルプロパンスル
ホン酸（塩）、アクリルアミドエチルプロパンスルホン
酸（塩）、アクリルアミドエチルメチルエタンスルホン
酸（塩）およびアクリルアミドプロピルエタンスルホン
酸（塩）などの炭素数１〜５の分岐または直鎖のアルキ
レン基を有する化合物があげられ、これらを単独あるい
は２種以上使用することができる。これらのうちで好ま
しいものは（メタ）アクリルアミドメタンスルホン酸
（塩）、（メタ）アクリルアミドエタンスルホン酸
（塩）、（メタ）アクリルアミドプロパンスルホン酸
（塩）、（メタ）アクリルアミドメチルエタンスルホン
酸（塩）、（メタ）アクリルアミドブタンスルホン酸
（塩）、（メタ）アクリルアミドメチルプロパンスルホ
ン酸（塩）および（メタ）アクリルアミドペンタンスル
ホン酸（塩）であり、更に好ましいものは１−（メタ）
アクリルアミドメタンスルホン酸（塩）、２−アクリル
アミドプロパンスルホン酸（塩）、２−アクリルアミド
−ｎ−ブタンスルホン酸（塩）、２−アクリルアミド−
２−メチルプロパンスルホン酸（塩）および２−アクリ
ルアミド−１−メチルプロパンスルホン酸（塩）の単独
または２種以上の併用である。これら（メタ）アクリル
アミド−Ｎ−アルカンスルホン酸（塩）は酸、部分中和
塩または中和塩のいずれでも使用できる。中和塩を形成
するのに使用できるイオン種の具体例としては、水素、
リチウム、ナトリウム、カリウム、アンモニア、アルキ
ルアミン（モノエチルアミン、モノブチルアミン、およ
びトリエチルアミン等）およびアルカノールアミン（モ
ノエタノールアミン、ジエタノールアミンおよびトリエ
タノールアミン等）があげられ、これらを単独あるいは
２種以上使用することができる。BEST MODE FOR CARRYING OUT THE INVENTION As the monomer A constituting the water-soluble polymer contained in the aqueous printing ink composition and printing method of the present invention, (meth) acrylamide methanesulfonic acid (salt), (meth) Acrylamideethanesulfonic acid (salt), (meth) acrylamidopropanesulfonic acid (salt), (meth) acrylamidomethylethanesulfonic acid (salt), (meth) acrylamidobutanesulfonic acid (salt), (meth) acrylamidomethylpropanesulfonic acid (Salt), (meth) acrylamide dimethylethane sulfonic acid (salt), (meth) acrylamide pentane sulfonic acid (salt), (meth) acrylamide methyl butane sulfonic acid (salt), acrylamido dimethyl propane sulfonic acid (salt), acrylamidoethyl Propanesulfonic acid (salt), acrylic acid Examples thereof include compounds having a branched or straight chain alkylene group having 1 to 5 carbon atoms such as ethylmethylethanesulfonic acid (salt) and acrylamidopropylethanesulfonic acid (salt). These may be used alone or in combination of two or more. it can. Among these, preferred are (meth) acrylamidomethanesulfonic acid (salt), (meth) acrylamidoethanesulfonic acid (salt), (meth) acrylamidopropanesulfonic acid (salt), (meth) acrylamidomethylethanesulfonic acid (salt). ), (Meth) acrylamidobutanesulfonic acid (salt), (meth) acrylamidomethylpropanesulfonic acid (salt) and (meth) acrylamidopentanesulfonic acid (salt), and more preferred is 1- (meth)
Acrylamide methanesulfonic acid (salt), 2-acrylamidopropanesulfonic acid (salt), 2-acrylamido-n-butanesulfonic acid (salt), 2-acrylamido-
2-Methylpropanesulfonic acid (salt) and 2-acrylamido-1-methylpropanesulfonic acid (salt) are used alone or in combination of two or more kinds. These (meth) acrylamide-N-alkanesulfonic acids (salts) can be used as an acid, a partially neutralized salt or a neutralized salt. Specific examples of ionic species that can be used to form the neutralized salt include hydrogen,
Examples include lithium, sodium, potassium, ammonia, alkylamines (monoethylamine, monobutylamine, triethylamine, etc.) and alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.), and use these alone or in combination of two or more. You can
【００１０】水性印刷インキ組成物および印刷方法に含
有される水溶性高分子を形成する単量体である単量体Ａ
の割合は、全単量体１００質量部中、１００〜１０質量
部であり、好ましくは１００〜５０質量部、更に好まし
くは１００〜８０質量部である。単量体Ａの質量が１０
質量部以下の場合は、印刷適性が低下するので好ましく
ない。Monomer A, which is a monomer forming a water-soluble polymer contained in an aqueous printing ink composition and printing method
The ratio is 100 to 10 parts by mass, preferably 100 to 50 parts by mass, and more preferably 100 to 80 parts by mass in 100 parts by mass of all the monomers. The mass of monomer A is 10
When the amount is less than the amount by mass, the printability is deteriorated, which is not preferable.
【００１１】本発明の水性印刷インキ組成物および印刷
方法に含有される水溶性高分子を構成する共重合可能な
単量体Ｂとしては、例えば次のものが挙げられるが、こ
れらに限定されない。
（ａ）カルボキシル基含有エチレン性不飽和単量体：
（メタ）アクリル酸（塩）、（イソ）クロトン酸
（塩）、２−ペンテン酸（塩）、２−エチルアクリル酸
（塩）、マレイン酸（塩）、イタコン酸（塩）、グルタ
コン酸（塩）など、
（ｂ）カルボキシレート基含有エチレン性不飽和単量
体：（メタ）メチルアクリレート、２−ヒドロキシエチ
ル（メタ）アクリレート、２−エトキシエチル（メタ）
アクリレート、２−シアノエチル（メタ）アクリレート
など、
（ｃ）カルボキシアミド基含有エチレン性不飽和単量
体：Ｎ−メチル（メタ）アクリルアミド、Ｎ−２−ヒド
ロキシメチル（メタ）アクリルアミド、Ｎ−２−ヒドロ
キシエチル（メタ）アクリルアミド、Ｎ、Ｎ−ビス２−
ヒドロキシエチル（メタ）アクリルアミドなど、
（ｄ）スルホン酸基含有エチレン性不飽和単量体：ビニ
ルスルホン酸、アリルスルホン酸、メタリルスルホン酸
など、
（ｅ）ニトリル基含有エチレン性不飽和単量体：（メ
タ）アクリロニトリルなど、
（ｆ）アミノ基含有エチレン性不飽和単量体：Ｎ−ビニ
ル−２−ピロリドンなど、
（ｇ）アルデヒド基含有エチレン性不飽和単量体：アク
ロレインなど、
（ｈ）ポリアルキレングリコール鎖（分子量４４〜２０
００）含有エチレン性不飽和単量体：ポリエチレングリ
コールモノ（メタ）アクリレート、メトキシポリエチレ
ングリコール（メタ）アクリレートなど。Examples of the copolymerizable monomer B constituting the water-soluble polymer contained in the aqueous printing ink composition and the printing method of the present invention include, but are not limited to, the followings. (A) Carboxyl group-containing ethylenically unsaturated monomer:
(Meth) acrylic acid (salt), (iso) crotonic acid (salt), 2-pentenoic acid (salt), 2-ethylacrylic acid (salt), maleic acid (salt), itaconic acid (salt), glutaconic acid ( (B) Carboxylate group-containing ethylenically unsaturated monomer: (meth) methyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-ethoxyethyl (meth)
(C) Carboxamide group-containing ethylenically unsaturated monomer such as acrylate and 2-cyanoethyl (meth) acrylate: N-methyl (meth) acrylamide, N-2-hydroxymethyl (meth) acrylamide, N-2-hydroxy Ethyl (meth) acrylamide, N, N-bis2-
(D) Sulfonic acid group-containing ethylenically unsaturated monomer such as hydroxyethyl (meth) acrylamide: vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, etc. (e) Nitrile group-containing ethylenically unsaturated monomer : (Meth) acrylonitrile, etc., (f) amino group-containing ethylenically unsaturated monomer: N-vinyl-2-pyrrolidone, etc. (g) aldehyde group-containing ethylenically unsaturated monomer: acrolein, etc., (h) Polyalkylene glycol chain (molecular weight 44-20
00) -containing ethylenically unsaturated monomer: polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol (meth) acrylate and the like.
【００１２】水性印刷インキ組成物および印刷方法に含
有される水溶性高分子を形成する単量体である単量体Ｂ
の割合は、全単量体１００質量部中、０〜３０質量部で
あり、好ましくは０〜１０質量部、更に好ましくは０〜
５質量部である。単量体Ｂの質量が３０質量部を超える
場合は、印刷適性が低下するので好ましくない。Monomer B which is a monomer forming a water-soluble polymer contained in the aqueous printing ink composition and printing method
Is 0 to 30 parts by mass, preferably 0 to 10 parts by mass, and more preferably 0 to 100 parts by mass of all the monomers.
5 parts by mass. When the mass of the monomer B exceeds 30 parts by mass, printability is deteriorated, which is not preferable.
【００１３】水性印刷インキ組成物および印刷方法に含
有される水溶性高分子を形成するアクリルアミドの割合
は、全単量体１００質量部中、０〜９０質量部であり、
好ましくは０〜５０質量部、更に好ましくは０〜２０質
量部である。アクリルアミドの質量が９０質量部を超え
る場合は、印刷適性が低下するので好ましくない。水性
印刷インキ組成物および印刷方法に含有される水溶性高
分子の重量平均分子量は、１００万〜４００万であり、
好ましくは１２０万〜３００万、更に好ましくは１５０
万〜２５０万である。水溶性高分子の重量平均分子量が
１００万未満の場合は、にじみなどが多くなり、一方、
重量平均分子量が４００万を超える場合は、印刷適性、
顔料分散安定性が低下するので好ましくない。水溶性高
分子の重量平均分子量は、ゲルパーミエーションクロマ
トグラフィー（以下ＧＰＣと略す）によって測定され
る。本発明で実施した重量平均分子量を測定したＧＰＣ
は、装置本体は東ソー（株）製ＨＬＣ−８０２０、カラ
ムは東ソー（株）製ＴＳＫｇｅｌ Ｇ６０００ ＰＷ
ＸＬ、検出器は装置本体内蔵の示差屈折計検出器であ
る。測定は、溶離液として０．２Ｍリン酸緩衝液を流量
０．６ｍｌ／分で用い、カラム温度は４０℃とし、供試
体の水溶性高分子は０．１質量％の溶離液溶液としたも
のを５０μｌ注入する条件で行った。分子量算出の標準
物質には住友精化（株）製ＰＥＯ−１５、ＰＥＯ−８、
東ソー（株）製ＴＳＫ ｓｔａｎｄａｒｄ ＰＯＬＹ
（ＥＴＨＹＬＥＮＥ ＯＸＩＤＥ）ＳＥ−１５０、ＳＥ
−３０、ＳＥ−８を使用した。The proportion of acrylamide forming the water-soluble polymer contained in the water-based printing ink composition and the printing method is 0 to 90 parts by mass based on 100 parts by mass of all the monomers.
It is preferably 0 to 50 parts by mass, more preferably 0 to 20 parts by mass. When the mass of acrylamide exceeds 90 parts by mass, printability is deteriorated, which is not preferable. The weight average molecular weight of the water-soluble polymer contained in the aqueous printing ink composition and the printing method is 1 to 4,000,000,
Preferably 1.2 to 3 million, more preferably 150
It is between 10,000 and 2.5 million. When the weight average molecular weight of the water-soluble polymer is less than 1,000,000, bleeding and the like increase, while
If the weight average molecular weight exceeds 4 million, printability,
Pigment dispersion stability is reduced, which is not preferable. The weight average molecular weight of the water-soluble polymer is measured by gel permeation chromatography (hereinafter abbreviated as GPC). GPC for measuring the weight average molecular weight carried out in the present invention
The device body is Tosoh Corp. HLC-8020, and the column is Tosoh Corp. TSKgel G6000 PW.
The XL and the detector are differential refractometer detectors built in the apparatus body. The measurement was carried out using 0.2 M phosphate buffer as an eluent at a flow rate of 0.6 ml / min, the column temperature was 40 ° C., and the water-soluble polymer of the sample was a 0.1 mass% eluent solution. Was performed under the condition of injecting 50 μl. The standard substances for calculating the molecular weight are PEO-15 and PEO-8 manufactured by Sumitomo Seika Chemicals Ltd.
Tosoh Corporation TSK standard POLY
(ETHYLENE OXIDE) SE-150, SE
-30 and SE-8 were used.
【００１４】水性印刷インキ組成物および印刷方法に含
有される水溶性高分子の合成は、公知の方法で行われ
る。合成方法の具体例としては、単量体Ａ、必要により
アクリルアミドおよび単量体Ｂとの混合水溶液に過硫酸
アンモニウム、過硫酸カリウムなどの過硫酸塩あるいは
２，２’−アゾビス（２−アミジノプロパン）塩酸塩な
どの水溶性ラジカル重合触媒を加え、通常４０〜１２０
℃で重合する方法などがあげられるが、合成方法は特に
限定されない。The water-soluble polymer contained in the aqueous printing ink composition and the printing method is synthesized by a known method. As a specific example of the synthetic method, a persulfate such as ammonium persulfate or potassium persulfate or 2,2′-azobis (2-amidinopropane) is added to a mixed aqueous solution of Monomer A, acrylamide and Monomer B if necessary. A water-soluble radical polymerization catalyst such as hydrochloride is added, and usually 40 to 120
Examples of the method include polymerization at ° C, but the synthetic method is not particularly limited.
【００１５】水性印刷インキ組成物および印刷方法に含
有される水溶性高分子の量は、０．０１〜５質量％であ
り、好ましくは０．０５〜３質量％、更に好ましくは
０．１〜２質量％である。水溶性高分子の含有量が少な
くなれば、得られる本発明の効果は少なくなり、また、
水溶性高分子の含有量が５質量％を超える量を使用して
も、得られる本発明の効果はあまり向上せず、乾燥性や
耐水性などへの影響を考慮すると、より多量に含有させ
ることは好ましくない。The amount of the water-soluble polymer contained in the aqueous printing ink composition and the printing method is 0.01 to 5% by mass, preferably 0.05 to 3% by mass, more preferably 0.1 to 3% by mass. It is 2% by mass. When the content of the water-soluble polymer is small, the effect of the present invention obtained is small, and
Even if the content of the water-soluble polymer exceeds 5% by mass, the effect of the present invention obtained is not improved so much, and considering the influence on the drying property and water resistance, the content of the water-soluble polymer is increased. Is not preferable.
【００１６】本発明の水性印刷インキ組成物および印刷
方法は、さらに顔料、水性バインダー樹脂、水性媒体、
および、必要に応じてその他の各種水性印刷インキ用添
加剤を含むものである。The aqueous printing ink composition and printing method of the present invention further include a pigment, an aqueous binder resin, an aqueous medium,
And, it contains various other additives for water-based printing inks, if necessary.
【００１７】そして、本発明で使用する顔料としては、
一般に水性印刷インキ組成物で使用できる各種の無機顔
料や有機顔料が利用できる。具体的に無機顔料として
は、酸化チタン、ベンガラ、アンチモンレッド、カドミ
ウムイエロー、コバルトブルー、紺青、群青、カーボン
ブラック、黒鉛など有色顔料、および、炭酸カルシウ
ム、カオリン、クレー、硫酸バリウム、水酸化アルミニ
ウム、タルク等の体質顔料を挙げることができる。さら
に有機顔料としては、溶性アゾ顔料、不溶性アゾ顔料、
アゾレーキ顔料、縮合アゾ顔料、銅フタロシアニン顔
料、縮合多環顔料などを挙げることができ、これらを、
単独あるいは２種以上使用できる。なお、これら顔料の
含有量は、通常、水性印刷インキ組成物中の３〜６０質
量％程度である。The pigment used in the present invention includes
Generally, various inorganic pigments and organic pigments that can be used in aqueous printing ink compositions can be used. Specific inorganic pigments include titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, dark blue, ultramarine blue, carbon black, colored pigments such as graphite, and calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, An extender pigment such as talc can be used. Further, as the organic pigment, a soluble azo pigment, an insoluble azo pigment,
Examples thereof include azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, and the like.
They can be used alone or in combination of two or more. The content of these pigments is usually about 3 to 60 mass% in the aqueous printing ink composition.
【００１８】次に、本発明で利用可能な水性バインダー
樹脂としては、通常の水性印刷インキ組成物で使用され
ている塩基性化合物の存在下で、水中に溶解可能な水溶
性樹脂が利用でき、まず、アクリル系樹脂、スチレン−
アクリル系樹脂、スチレン−マレイン酸系樹脂、スチレ
ン−アクリル−マレイン酸系樹脂等が挙げられるが、こ
れらは単独で又は二種以上を併用して使用することがで
きる。なお、アクリル系樹脂とは、下記のアクリル系単
量体を共重合して得られる樹脂、スチレン−アクリル系
樹脂とは、下記のスチレン系単量体とアクリル系単量体
を共重合して得られる樹脂、スチレン−マレイン酸系樹
脂とは、下記のスチレン系単量体とマレイン酸系単量体
を共重合して得られる樹脂、スチレン−アクリル−マレ
イン酸系樹脂とは、下記のスチレン系単量体、アクリル
系単量体およびマレイン酸系単量体を共重合して得られ
る樹脂であって、さらに、カルボキシル基含有単量体の
少なくとも１種を共重合成分として利用した、分子内に
カルボキシル基を有する樹脂である。Next, as the aqueous binder resin which can be used in the present invention, a water-soluble resin which can be dissolved in water in the presence of a basic compound used in a usual aqueous printing ink composition can be used. First, acrylic resin, styrene-
Examples of the acrylic resin, styrene-maleic acid resin, styrene-acrylic-maleic acid resin and the like can be used alone or in combination of two or more kinds. The acrylic resin is a resin obtained by copolymerizing the following acrylic monomers, and the styrene-acrylic resin is a copolymer obtained by copolymerizing the following styrene monomers and acrylic monomers. Resin obtained, styrene-maleic acid-based resin is a resin obtained by copolymerizing the following styrene-based monomer and maleic acid-based monomer, styrene-acrylic-maleic acid-based resin is the following styrene A molecule obtained by copolymerizing a base monomer, an acrylic monomer and a maleic acid monomer, and further utilizing at least one kind of a carboxyl group-containing monomer as a copolymerization component. It is a resin having a carboxyl group inside.
【００１９】ここで、アクリル系単量体としては、（メ
タ）アクリル酸、およびその炭素数が１〜ｌ８のアルキ
ルエステル、炭素数が２〜４のヒドロキシアルキルエス
テル等を挙げることができる。また、スチレン系単量体
としては、スチレンや、ビニルトルエン、アルキルスチ
レン等のスチレン誘導体を挙げることができる。また、
マレイン酸系単量体としては、無水マレイン酸やマレイ
ン酸、その炭素数が１〜１８のモノアルキルエステル、
炭素数が１〜１８のモノアルキルアミド、炭素数が２〜
４のモノヒドロキシアルキルエステル、炭素数が１〜１
８のジアルキルエステル、炭素数が１〜１８のジアルキ
ルアミド、炭素数が２〜４のジヒドロキシアルキルエス
テルを挙げることできる。Examples of the acrylic monomer include (meth) acrylic acid, an alkyl ester having 1 to 18 carbon atoms, and a hydroxyalkyl ester having 2 to 4 carbon atoms. Examples of styrene-based monomers include styrene and styrene derivatives such as vinyltoluene and alkylstyrene. Also,
As the maleic acid-based monomer, maleic anhydride or maleic acid, a monoalkyl ester having 1 to 18 carbon atoms,
Monoalkylamide having 1 to 18 carbon atoms, 2 carbon atoms
4 monohydroxyalkyl ester with 1 to 1 carbon atoms
Examples thereof include dialkyl ester having 8 carbon atoms, dialkylamide having 1 to 18 carbon atoms, and dihydroxyalkyl ester having 2 to 4 carbon atoms.
【００２０】これら反応成分を用いて、アクリル系樹
脂、スチレン−アクリル系樹脂、スチレン−マレイン酸
系樹脂、及びスチレン−アクリル−マレイン酸系樹脂の
合成は、公知の方法で行われる。合成方法の具体例とし
ては、各種単量体を酢酸ブチル等のエステル系溶剤、エ
チレングリコールモノプロピルエーテル、エチレングリ
コールモノブチルエーテル等のグリコール系溶剤等の不
活性な有機溶剤に溶解させた混合液に、ｔ−ブチルハイ
ドロパーオキサイド、過酸化ジｔ−ブチル等、２，２
‘−アゾビス（イソブチロニトリル）等の有機ラジカル
重合触媒を加え、通常４０〜１２０℃で重合する方法な
どがあげられるが、合成方法は特に限定されない。The acrylic resin, styrene-acrylic resin, styrene-maleic acid resin, and styrene-acrylic-maleic acid resin are synthesized by using these reaction components by a known method. As a specific example of the synthesis method, in a mixed solution prepared by dissolving various monomers in an inert solvent such as an ester solvent such as butyl acetate, a glycol solvent such as ethylene glycol monopropyl ether or ethylene glycol monobutyl ether. , T-butyl hydroperoxide, di-t-butyl peroxide, etc., 2,2
A method of adding an organic radical polymerization catalyst such as'-azobis (isobutyronitrile) and polymerizing at 40 to 120 ° C. may be mentioned, but the synthesis method is not particularly limited.
【００２１】そして、これらの水溶性樹脂の酸価として
は、水性印刷インキの印刷適性や耐水性などの面から１
００〜３５０ｍｇＫＯＨ／ｇの範囲が好適である。さら
に、本発明で利用可能な水溶性樹脂として、有機ジイソ
シアネート化合物と高分子ジオール化合物、鎖伸長剤、
反応停止剤を反応させて得られ、分子内にカルボキシル
基を有する水溶性ポリウレタン樹脂、ポリカルボン酸、
ポリアルコールおよび必要に応じてモノカルボン酸やモ
ノアルコールを反応させて得られ、分子内にカルボキシ
ル基を有する水溶性ポリエステル樹脂、ポリカルボン
酸、ポリアミンおよび必要に応じてモノカルボン酸やモ
ノアミンを反応させて得られ、分子内にカルボキシル基
を有する水溶性ポリアミド樹脂を挙げることができる。
そして、これらの水溶性樹脂の酸価としては、得られる
水性印刷インキの印刷適性や耐水性などの面から１０〜
１００ｍｇＫＯＨ／ｇ程度が好ましい。The acid value of these water-soluble resins is 1 in view of printability and water resistance of water-based printing inks.
A range of 00 to 350 mg KOH / g is suitable. Furthermore, as a water-soluble resin that can be used in the present invention, an organic diisocyanate compound, a polymer diol compound, a chain extender,
Obtained by reacting a reaction terminator, a water-soluble polyurethane resin having a carboxyl group in the molecule, polycarboxylic acid,
Obtained by reacting a polyalcohol and, if necessary, a monocarboxylic acid or a monoalcohol, and reacting a water-soluble polyester resin having a carboxyl group in the molecule, a polycarboxylic acid, a polyamine and, if necessary, a monocarboxylic acid or a monoamine. And a water-soluble polyamide resin having a carboxyl group in the molecule.
The acid value of these water-soluble resins is 10 to 10 in terms of printability and water resistance of the resulting water-based printing ink.
About 100 mgKOH / g is preferable.
【００２２】以上で挙げた水溶性樹脂は、塩基性化合物
の存在下で水中に溶解させて、水溶性樹脂ワニスとして
使用するものであるが、利用可能な塩基性化合物として
は、水酸化ナトリウム、水酸化カリウム、水酸化アンモ
ニウム等の無機塩基性化合物、トリエチルアミン、モノ
エタノールアミン、トリエタノールアミン等の有機塩基
性化合物を挙げることができ、これら塩基性化合物の使
用量は、前記水溶性樹脂を溶解させる範囲であればよい
が、通常、中和量の８０〜１２０モル％程度が適量であ
る。The above-mentioned water-soluble resin is used as a water-soluble resin varnish by dissolving it in water in the presence of a basic compound, and the usable basic compound is sodium hydroxide, Inorganic basic compounds such as potassium hydroxide and ammonium hydroxide, and organic basic compounds such as triethylamine, monoethanolamine, and triethanolamine can be mentioned. The amount of these basic compounds used is such that the water-soluble resin can be dissolved. The amount may be within the range, but the amount is usually about 80 to 120 mol% of the neutralization amount.
【００２３】さらに、水性印刷インキ組成物の乾燥性や
印刷物の光沢を付与するために、前記の水溶性樹脂と併
用する形で、通常の水性印刷インキ組成物で利用可能な
水分散性樹脂を水性バインダー成分として使用すること
ができる。水性印刷インキ組成物の分野で、最も一般的
な水分散性樹脂としては、通常の乳化剤あるいは高分子
乳化剤の存在下、ラジカル重合性単量体を重合して得ら
れる水性樹脂エマルジョンが利用され、その中でも、前
記のアクリル酸系単量体とスチレン系単量体を共重合さ
せて得られるスチレン−アクリル系水性樹脂エマルジョ
ンが好適に使用できる。Further, in order to impart the drying property of the aqueous printing ink composition and the gloss of the printed matter, a water-dispersible resin usable in a usual aqueous printing ink composition is used in combination with the above water-soluble resin. It can be used as an aqueous binder component. In the field of water-based printing ink compositions, the most common water-dispersible resin is an aqueous resin emulsion obtained by polymerizing a radical-polymerizable monomer in the presence of an ordinary emulsifier or a polymeric emulsifier, Among them, a styrene-acrylic aqueous resin emulsion obtained by copolymerizing the acrylic acid-based monomer and the styrene-based monomer can be preferably used.
【００２４】また、前記のアクリル酸系単量体を単独ま
たは共重合して得られるアクリル系水性樹脂エマルジョ
ン、酢酸ビニル単量体と前記のアクリル酸系単量体を共
重合して得られる酢酸ビニル−アクリル系水性樹脂エマ
ルジョン、前記スチレン系単量体とブタジエン単量体を
共重合して得られるスチレン−ブタジエン系水性樹脂エ
マルジョン、その他、酢酸ビニル系水性樹脂エマルジョ
ン、エチレン−酢酸ビニル系水性樹脂エマルジョン、酢
酸ビニル−塩化ビニル系水性樹脂エマルジョン、エチレ
ン─酢酸ビニル−塩化ビニル系水性樹脂エマルジョン、
ブタジエン系水性樹脂エマルジョン、ウレタン系水性樹
脂エマルジョン、ゴムラテックス等の水性樹脂エマルジ
ョン等も挙げることができ、これら水性樹脂エマルジョ
ンは、１種だけの利用であっても、また２種以上の併用
であってもよい。Acrylic aqueous resin emulsions obtained by homopolymerizing or copolymerizing the above acrylic acid monomers, acetic acid obtained by copolymerizing vinyl acetate monomers and the above acrylic acid monomers. Vinyl-acrylic aqueous resin emulsion, styrene-butadiene aqueous resin emulsion obtained by copolymerizing the styrene monomer and butadiene monomer, vinyl acetate aqueous resin emulsion, ethylene-vinyl acetate aqueous resin Emulsion, vinyl acetate-vinyl chloride aqueous resin emulsion, ethylene-vinyl acetate-vinyl chloride aqueous resin emulsion,
Examples thereof include butadiene-based water-based resin emulsion, urethane-based water-based resin emulsion, and water-based resin emulsion such as rubber latex. These water-based resin emulsions may be used alone or in combination of two or more. May be.
【００２５】これら水性樹脂エマルジョンの合成は、や
はり公知の方法で行われる。合成方法の具体例として
は、ラジカル重合性開始剤と各種単量体の混合物を、通
常の乳化剤あるいは高分子乳化剤を加えた水中に滴下し
て、通常４０〜１２０℃で重合する方法などがあげられ
るが、合成方法は特に限定されない。The synthesis of these aqueous resin emulsions is also carried out by a known method. Specific examples of the synthesis method include a method in which a mixture of a radically polymerizable initiator and various monomers is dropped into water containing an ordinary emulsifier or a polymeric emulsifier, and polymerization is usually performed at 40 to 120 ° C. However, the synthesis method is not particularly limited.
【００２６】また、塩基性化合物の存在下で自己乳化性
を有する水分散性樹脂として、エチレン−アクリル酸共
重合体も利用でき、この樹脂は、前記の塩基性化合物お
よび必要に応じて乳化剤の存在下で、エチレン６０〜９
０質量％、アクリル酸またはメタクリル酸１０〜３０質
量％、その他の共重合可能なビニル基含有化合物０〜３
０質量％の組成で共重合して得られる共重合体樹脂を水
中に分散させたものである。An ethylene-acrylic acid copolymer can also be used as a water-dispersible resin having self-emulsifying property in the presence of a basic compound, and this resin contains the above-mentioned basic compound and, if necessary, an emulsifier. In the presence of ethylene 60-9
0% by mass, acrylic acid or methacrylic acid 10 to 30% by mass, and other copolymerizable vinyl group-containing compounds 0 to 3
A copolymer resin obtained by copolymerization with a composition of 0% by mass is dispersed in water.
【００２７】水性印刷インキ組成物として使用するエチ
レン−アクリル酸系共重合体のメルトインデックスは、
樹脂の水中での分散安定性およびブロッキング性などか
ら、好適には１００〜２０００ｇ／１０分、より好適に
は３００〜１０００ｇ／ｌ０分の範囲のものが利用でき
る。The melt index of the ethylene-acrylic acid copolymer used as the aqueous printing ink composition is
From the viewpoint of dispersion stability and blocking property of the resin in water, a resin having a range of preferably 100 to 2000 g / 10 minutes, more preferably 300 to 1000 g / 10 minutes can be used.
【００２８】本発明において、水溶性樹脂と水分散性樹
脂を併用する場合には、固形分の質量比率が、１００：
１０〜４００の範囲で利用するのが好ましい。そして、
特に水分散性樹脂を併用した場合に、前記水溶性高分子
の添加効果が高くなり、印刷濃度の向上やにじみの防止
効果が顕著となるが、これは顔料の紙表面での歩留まり
効果の他に、水中に微細粒子で存在する水分散性樹脂の
歩留まり効果も同時に得られるためと考えられる。In the present invention, when the water-soluble resin and the water-dispersible resin are used in combination, the mass ratio of the solid content is 100:
It is preferably used in the range of 10 to 400. And
In particular, when a water-dispersible resin is used in combination, the effect of adding the water-soluble polymer increases, and the effect of improving printing density and preventing bleeding become remarkable, but this is due to the retention effect of the pigment on the paper surface. In addition, it is considered that the yield effect of the water-dispersible resin, which is present as fine particles in water, can be obtained at the same time.
【００２９】さらに本発明の水性印刷インキ組成物は、
以上の必須成分に加えて、メタノール、エタノール、プ
ロパノール、メトキシプロパノール、Ｎ−メチルピロリ
ドン等の水混和性溶剤、顔料分散剤、ブロッキング防止
剤、消泡剤、架橋剤等の各種添加剤を添加することも任
意である。Further, the aqueous printing ink composition of the present invention comprises
In addition to the above essential components, water-miscible solvents such as methanol, ethanol, propanol, methoxypropanol, N-methylpyrrolidone, etc., various additives such as pigment dispersants, antiblocking agents, defoamers, crosslinking agents, etc. are added. It is also optional.
【００３０】以上の材料を用いて水性印刷インキ組成物
を製造する方法としては、ビーズミル、ボールミル、ア
トライター、高速攪拌機などの既知の顔料分散機によ
り、顔料を前記水溶性樹脂や顔料分散剤を用いて水中に
分散させた後、前記の水溶性高分子や残余の材料の所定
量を添加混合してインキ組成物とする方法が利用でき
る。As a method for producing an aqueous printing ink composition using the above materials, a pigment is mixed with the above water-soluble resin or pigment dispersant by a known pigment disperser such as a bead mill, a ball mill, an attritor or a high speed stirrer. It is possible to use a method in which the ink composition is prepared by dispersing it in water and then adding and mixing a predetermined amount of the above-mentioned water-soluble polymer and the remaining material to form an ink composition.
【００３１】そして、得られた水性印刷インキ組成物
は、通常、段ボールやカートン等の紙を被印刷体とし
て、フレキソ印刷機、グラビア印刷機等の印刷機を用
い、印刷時の雰囲気温度において、好ましくはザーン粘
度計Ｎｏ．４(離合社製)による流出秒数が８〜１３秒と
なる粘度で印刷することができる。なお、前記の粘度に
調整するために、水、水混和性溶剤あるいはそれらの混
合物からなる希釈剤を利用することができ、印刷中にイ
ンキ組成物が大きな粘度変化を起こさないように、継続
的に粘度管理をすることが望ましい。The aqueous printing ink composition thus obtained is usually manufactured by using a printing machine such as a flexographic printing machine or a gravure printing machine with a paper such as a corrugated board or a carton as an object to be printed, at ambient temperature at the time of printing. Preferably, Zahn viscometer No. It is possible to print at a viscosity such that the outflow seconds of No. 4 (manufactured by Rikyusha) is 8 to 13 seconds. In addition, in order to adjust the above-mentioned viscosity, water, a water-miscible solvent or a diluent composed of a mixture thereof can be used, and the ink composition is continuously treated so as not to cause a large viscosity change during printing. It is desirable to control viscosity.
【００３２】本発明の水性印刷インキ組成物および印刷
方法は、低粘度であっても得られた印刷物は高い濃度を
有し、にじみがなく、さらに印刷作業性などが良好であ
る等の優れた効果を有する水性印刷インキ組成物であ
る。The aqueous printing ink composition and printing method of the present invention are excellent in that the obtained printed matter has a high density even if it has a low viscosity, has no bleeding, and has good printing workability. It is an aqueous printing ink composition having an effect.
【００３３】[0033]
【実施例】以下、実施例により本発明を更に説明する
が、本発明はこれに限定されるものではない。
［水溶性高分子の製造］
製造例１
水溶性高分子Ｘ−１の合成
還流冷却器、窒素供給管、撹拌装置および温度計付きガ
ラス製反応容器に、水８９５質量部、２−アクリルアミ
ド−２−メチルプロパンスルホン酸ナトリウム１００質
量部を投入し、撹拌下、２，２’−アゾビス（２−アミ
ジノプロパン）塩酸塩の２質量％水溶液５質量部を投入
して反応させた。反応温度は５０℃を保った。滴下終了
後３時間同温度に保った後３０℃に冷却後取り出し、濃
度１０質量％、粘度１５Pa・sの水溶性高分子Ｘ−１の水
溶液を得た。この水溶性高分子Ｘ−１の重量平均分子量
をＧＰＣで測定したところ２１０万であった。EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. [Production of Water-Soluble Polymer] Production Example 1 Synthesis of Water-Soluble Polymer X-1 In a glass reaction container equipped with a reflux condenser, a nitrogen supply pipe, a stirrer and a thermometer, 895 parts by mass of water and 2-acrylamide-2. 100 parts by mass of sodium methylpropanesulfonate was added, and 5 parts by mass of a 2% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride was added and reacted with stirring. The reaction temperature was kept at 50 ° C. After the dropping was completed, the temperature was kept at the same temperature for 3 hours, cooled to 30 ° C., and taken out to obtain an aqueous solution of water-soluble polymer X-1 having a concentration of 10% by mass and a viscosity of 15 Pa · s. The weight average molecular weight of this water-soluble polymer X-1 was 2.1 million when measured by GPC.
【００３４】製造例２
水溶性高分子Ｘ−２の合成
製造例１の単量体成分を、２−アクリルアミド−２−メ
チルプロパンスルホン酸ナトリウム９５．５質量部とア
クリルアミド４．５質量部に変えた以外は、水溶性高分
子Ｘ−１の合成の場合と同様にして、濃度１０質量％、
粘度１５Pa・sの水溶性高分子Ｘ−２の水溶液を得た。こ
の水溶性高分子Ｘ−２の重量平均分子量をＧＰＣで測定
したところ２１０万であった。Production Example 2 Synthesis of Water-Soluble Polymer X-2 The monomer component of Production Example 1 was changed to 95.5 parts by mass of sodium 2-acrylamido-2-methylpropanesulfonate and 4.5 parts by mass of acrylamide. Other than the above, in the same manner as in the synthesis of the water-soluble polymer X-1, a concentration of 10 mass%,
An aqueous solution of water-soluble polymer X-2 having a viscosity of 15 Pa · s was obtained. The weight average molecular weight of this water-soluble polymer X-2 was 2.1 million when measured by GPC.
【００３５】製造例３
水溶性高分子Ｘ−３の合成
製造例１の単量体成分を、２−アクリルアミド−２−メ
チルプロパンスルホン酸ナトリウム２０質量部、アクリ
ルアミド８０質量部に変えた以外は、水溶性高分子Ｘ−
１の合成の場合と同様にして、濃度１０質量％、粘度
６．２Pa・sの水溶性高分子Ｘ−３の水溶液を得た。この
水溶性高分子Ｘ−３の重量平均分子量をＧＰＣで測定し
たところ３８０万であった。Production Example 3 Synthesis of Water-Soluble Polymer X-3 Except that the monomer component of Production Example 1 was changed to 20 parts by mass of sodium 2-acrylamido-2-methylpropanesulfonate and 80 parts by mass of acrylamide. Water-soluble polymer X-
In the same manner as in the case of the synthesis of 1, the aqueous solution of the water-soluble polymer X-3 having a concentration of 10 mass% and a viscosity of 6.2 Pa · s was obtained. The weight average molecular weight of this water-soluble polymer X-3 was 3.8 million as measured by GPC.
【００３６】製造例４
水溶性高分子Ｘ−４の合成
製造例１の単量体成分を、２−アクリルアミドプロパン
スルホン酸ナトリウム９５．５質量部とアクリルアミド
４．５質量部に変えた以外は、水溶性高分子Ｘ−１の合
成の場合と同様にして、濃度１０質量％、粘度１５Pa・s
の水溶性高分子Ｘ−４の水溶液を得た。この水溶性高分
子Ｘ−４の重量平均分子量をＧＰＣで測定したところ２
２０万であった。Production Example 4 Synthesis of Water-Soluble Polymer X-4 Except that the monomer component of Production Example 1 was changed to 95.5 parts by mass of sodium 2-acrylamidopropanesulfonate and 4.5 parts by mass of acrylamide. As in the case of the synthesis of the water-soluble polymer X-1, the concentration is 10% by mass and the viscosity is 15 Pa · s.
An aqueous solution of the water-soluble polymer X-4 was obtained. When the weight average molecular weight of this water-soluble polymer X-4 was measured by GPC, 2
It was 200,000.
【００３７】製造例５
水溶性高分子Ｘ−５の合成
製造例１の単量体成分を、２−アクリルアミド−２−メ
チルプロパンスルホン酸ナトリウム９５．１質量部、ア
クリルアミド４．５質量部、アクリル酸ナトリウム０．
４質量部に変えた以外は、水溶性高分子Ｘ−１の合成の
場合と同様にして、濃度１０質量％、粘度１５Pa・sの水
溶性高分子Ｘ−５の水溶液を得た。この水溶性高分子Ｘ
−５の重量平均分子量をＧＰＣで測定したところ２２０
万であった。Production Example 5 Synthesis of Water-Soluble Polymer X-5 The monomer component of Production Example 1 was prepared by mixing 95.1 parts by mass of sodium 2-acrylamido-2-methylpropanesulfonate, 4.5 parts by mass of acrylamide, and acryl. Sodium acid salt 0.
An aqueous solution of water-soluble polymer X-5 having a concentration of 10 mass% and a viscosity of 15 Pa · s was obtained in the same manner as in the synthesis of water-soluble polymer X-1 except that the amount was changed to 4 parts by mass. This water-soluble polymer X
When the weight average molecular weight of -5 was measured by GPC, 220
It was good.
【００３８】製造例６
水溶性高分子Ｘ−６の合成
製造例１の単量体成分を、２−アクリルアミド−２−メ
チルプロパンスルホン酸ナトリウム７５質量部、アクリ
ル酸ナトリウム２５質量部に変えた以外は水溶性高分子
Ｘ−１の合成の場合と同様にして、濃度１０質量％、粘
度１１Pa・sの水溶性高分子Ｘ−６の水溶液を得た。この
水溶性高分子Ｘ−６の重量平均分子量をＧＰＣで測定し
たところ１５０万であった。Production Example 6 Synthesis of Water-Soluble Polymer X-6 Except that the monomer component of Production Example 1 was changed to 75 parts by mass of sodium 2-acrylamido-2-methylpropanesulfonate and 25 parts by mass of sodium acrylate. In the same manner as in the synthesis of water-soluble polymer X-1, an aqueous solution of water-soluble polymer X-6 having a concentration of 10% by mass and a viscosity of 11 Pa · s was obtained. The weight average molecular weight of this water-soluble polymer X-6 was measured by GPC and found to be 1,500,000.
【００３９】製造例７
水溶性高分子Ｘ−７の合成
製造例１の単量体成分を、２−アクリルアミド−２−メ
チルプロパンスルホン酸ナトリウム８５．５質量部、ア
クリルアミド４．５質量部、Ｎ−メチル−２−ピロリド
ン１０質量部に変えた以外は、水溶性高分子Ｘ−１の合
成の場合と同様にして、濃度１０質量％、粘度１５Pa・s
の水溶性高分子Ｘ−７の水溶液を得た。この水溶性高分
子Ｘ−７の重量平均分子量をＧＰＣで測定したところ２
２０万であった。Production Example 7 Synthesis of Water-Soluble Polymer X-7 The monomer component of Production Example 1 was prepared by mixing 85.5 parts by mass of sodium 2-acrylamido-2-methylpropanesulfonate, 4.5 parts by mass of acrylamide, and N. -Methyl-2-pyrrolidone except that the amount was changed to 10 parts by mass, the concentration was 10% by mass and the viscosity was 15 Pa · s in the same manner as in the synthesis of the water-soluble polymer X-1.
An aqueous solution of the water-soluble polymer X-7 was obtained. When the weight average molecular weight of this water-soluble polymer X-7 was measured by GPC, 2
It was 200,000.
【００４０】比較製造例１
水溶性高分子Ｙ−１の合成
製造例１の単量体成分をアクリルアミド１００質量部に
変えた以外は、水溶性高分子Ｘ−１の合成の場合と同様
にして、濃度１０質量％、粘度４Pa・sの水溶性高分子Ｙ
−１の水溶液を得た。この水溶性高分子Ｙ−１の重量平
均分子量をＧＰＣで測定したところ３８０万であった。Comparative Production Example 1 Synthesis of Water-Soluble Polymer Y-1 In the same manner as in the synthesis of water-soluble polymer X-1, except that the monomer component of Production Example 1 was changed to 100 parts by mass of acrylamide. , A water-soluble polymer Y with a concentration of 10% by mass and a viscosity of 4 Pa · s
An aqueous solution of -1 was obtained. The weight average molecular weight of this water-soluble polymer Y-1 was 3.8 million as measured by GPC.
【００４１】比較製造例２
水溶性高分子Ｙ−２の合成
製造例２の反応温度を６０℃に変えた以外は、水溶性高
分子Ｘ−２の合成の場合と同様にして、濃度１０質量
％、粘度０．４Pa・sの水溶性高分子Ｙ−２の水溶液を得
た。この水溶性高分子Ｙ−２の重量平均分子量をＧＰＣ
で測定したところ８０万であった。Comparative Production Example 2 Synthesis of Water-Soluble Polymer Y-2 In the same manner as in the synthesis of water-soluble polymer X-2 except that the reaction temperature in Production Example 2 was changed to 60 ° C., the concentration was 10 mass. %, And an aqueous solution of a water-soluble polymer Y-2 having a viscosity of 0.4 Pa · s was obtained. The weight average molecular weight of this water-soluble polymer Y-2 was measured by GPC.
The result was 800,000.
【００４２】比較製造例３
水溶性高分子Ｙ−３の合成
製造例２の反応温度を４０℃とし、滴下終了後８時間同
温度に保った以外は、水溶性高分子Ｘ−２の合成の場合
と同様にして、濃度１０質量％のゲル状水溶性高分子Ｙ
−３の水溶液を得た。この水溶性高分子Ｙ−３の重量平
均分子量をＧＰＣで測定したところ５００万以上であっ
た。Comparative Production Example 3 Synthesis of Water-Soluble Polymer Y-3 Synthesis of water-soluble polymer X-2 was carried out except that the reaction temperature in Production Example 2 was 40 ° C. and the temperature was kept at the same temperature for 8 hours after completion of dropping. Similarly to the case, the gel-like water-soluble polymer Y having a concentration of 10% by mass
An aqueous solution of -3 was obtained. The weight average molecular weight of this water-soluble polymer Y-3 was measured by GPC and found to be 5,000,000 or more.
【００４３】[実施例１〜１０、比較例１〜４の製造]フ
タロシアニン顔料４０質量部と水溶性樹脂ワニスＡ（ジ
ョンクリル６１Ｊ、ジョンソンポリマー社製）４０質量
部とを攪拌混合してプレミックス処理後、ビーズミルで
練肉し、さらに水２０質量部を添加混合して、実施例お
よび比較例に共通する顔料含有量が４０質量％のベース
インキ(共通ベースインキ)を調製した。さらに、表１の
配合に従って、各材料を攪拌混合し(数値は質量部を表
す)、実施例１〜１０、比較例１〜４の水溶性高分子含
有系インキ組成物を得た。なお、表１中の水溶性樹脂ワ
ニスとしては、前記の水溶性樹脂ワニスＡ、水溶性高分
子Ｙ−４としては、市販の重量平均分子量が約１８０万
のポリアクリル酸のナトリウム塩、水性樹脂エマルジョ
ンとしては、ジョンクリル７４１（ジョンソンポリマー
社製）を用いた。また、粘度調整材料として水溶性樹脂
ワニスＡと水を用いて、インキ組成物の仕上がり粘度
が、いずれも概ねザーン粘度計Ｎｏ．４で流出秒数が２
０秒になるように粘度調整を行った。[Production of Examples 1 to 10 and Comparative Examples 1 to 4] 40 parts by mass of a phthalocyanine pigment and 40 parts by mass of a water-soluble resin varnish A (John Krill 61J, manufactured by Johnson Polymer Co., Ltd.) are mixed by stirring to premix. After the treatment, the mixture was kneaded with a bead mill and 20 parts by mass of water was added and mixed to prepare a base ink having a pigment content of 40% by mass (common base ink) common to Examples and Comparative Examples. Furthermore, each material was stirred and mixed according to the formulation of Table 1 (numerical values represent parts by mass) to obtain water-soluble polymer-containing ink compositions of Examples 1-10 and Comparative Examples 1-4. The water-soluble resin varnish in Table 1 is the water-soluble resin varnish A, and the water-soluble polymer Y-4 is a commercially available sodium salt of polyacrylic acid having a weight average molecular weight of about 1.8 million, and an aqueous resin. John Krill 741 (manufactured by Johnson Polymer Co., Ltd.) was used as the emulsion. Further, when the water-soluble resin varnish A and water were used as the viscosity adjusting materials, the finish viscosities of the ink compositions were all about Zahn viscometer No. 4 outflow seconds is 2
The viscosity was adjusted so that it would be 0 seconds.
【００４４】[印刷濃度評価用インキ１〜４の製造]フタ
ロシアニン顔料４２質量部と水溶性樹脂ワニスＡ４０質
量部とを攪拌混合してプレミックス処理後、ビーズミル
で練肉し、さらに水１８質量部を添加混合して、評価用
ベースインキ１を調製した。また、フタロシアニン顔料
４４質量部と水溶性樹脂ワニスＡ４０質量部とを攪拌混
合してプレミックス処理後、ビーズミルで練肉し、さら
に水１６質量部を添加混合して、評価用ベースインキ２
を調製した。また、フタロシアニン顔料４６質量部、水
溶性樹脂ワニスＡ４０質量部、水４質量部を攪拌混合し
てプレミックス処理後、ビーズミルで練肉し、さらに水
１０質量部を添加混合して、評価用ベースインキ３を調
製した。表１の配合に従って、各材料を攪拌混合し(数
値は質量部を表す)、印刷濃度評価用インキ１〜４の水
溶性高分子非含有系インキ組成物を得た。なお、印刷濃
度評価用インキにおいても、水溶性樹脂ワニス、水性樹
脂エマルジョンは、実施例、比較例と同じ材料を用い、
また、インキ組成物の仕上がり粘度も、実施例、比較例
と同じとなるように粘度調整を行った。[Production of Printing Density Evaluation Inks 1 to 4] 42 parts by mass of a phthalocyanine pigment and 40 parts by mass of a water-soluble resin varnish A are mixed by stirring, premixed, kneaded with a bead mill, and further 18 parts by mass of water. Was added and mixed to prepare base ink 1 for evaluation. Further, 44 parts by mass of the phthalocyanine pigment and 40 parts by mass of the water-soluble resin varnish A were stirred and mixed, pre-mixed, kneaded with a bead mill, and further mixed with 16 parts by mass of water to be mixed with the evaluation base ink 2
Was prepared. Further, 46 parts by mass of the phthalocyanine pigment, 40 parts by mass of the water-soluble resin varnish A, and 4 parts by mass of water were stirred and mixed, premixed, kneaded with a bead mill, and further mixed with 10 parts by mass of water to prepare an evaluation base. Ink 3 was prepared. Each material was stirred and mixed according to the formulation of Table 1 (numerical values represent parts by mass) to obtain water-soluble polymer-free ink compositions of inks 1 to 4 for printing density evaluation. Even in the ink for printing density evaluation, the water-soluble resin varnish and the water-based resin emulsion were the same materials as those used in Examples and Comparative Examples.
In addition, the viscosity was adjusted so that the finished viscosity of the ink composition was the same as in the examples and comparative examples.
【００４５】[インキ組成物中における顔料含有量の比
較]実施例１〜１０、比較例１〜４及び印刷濃度評価用
インキ１は、インキ１００質量部中に共通ベースインキ
を３０質量部含むことから、インキ中の顔料含有量は同
じある。一方、印刷濃度評価用インキ２はインキ１００
質量部中に評価用ベースインキ１を３０質量部、印刷濃
度評価用インキ３はインキ１００質量部中に評価用ベー
スインキ２を３０質量部、印刷濃度評価用インキ４はイ
ンキ１００質量部中に評価用ベースインキ３を３０質量
部含むことから、それぞれ、実施例１〜１０及び比較例
１〜４に対する顔料含有量は、印刷濃度評価用インキ２
では１．０５倍、印刷濃度評価用インキ３では１．１０
倍、印刷濃度評価用インキ４では１．１５倍である。[Comparison of Pigment Content in Ink Compositions] Examples 1 to 10, Comparative Examples 1 to 4 and printing density evaluation ink 1 contain 30 parts by mass of the common base ink in 100 parts by mass of the ink. Therefore, the pigment content in the ink is the same. On the other hand, the ink 2 for printing density evaluation is ink 100
30 parts by mass of the evaluation base ink 1 in 30 parts by mass, 30 parts by mass of the evaluation base ink 2 in 100 parts by mass of the ink for printing density evaluation ink 3, and 30 parts by mass of the ink 4 for printing density evaluation in 100 parts by mass of ink. Since 30 parts by mass of the evaluation base ink 3 is contained, the pigment contents for Examples 1 to 10 and Comparative Examples 1 to 4 are the same as those of the printing density evaluation ink 2 respectively.
Is 1.05 times, and the printing density evaluation ink 3 is 1.10
In the case of the printing density evaluation ink 4, it is 1.15 times.
【００４６】[0046]
【表１】 [Table 1]
【００４７】[実施例１〜１０、および比較例１〜４の
評価]
顔料分散安定性
実施例１〜１０、比較例１〜４の水性印刷インキ組成物
をビンに入れて密栓し、４０℃で１０日間保存した時の
顔料の凝集による沈降物の有無から顔料分散安定性を評
価し、結果を表２に示した。
Ａ：沈降物が発生しない。
Ｂ：沈降物が発生する。[Evaluation of Examples 1 to 10 and Comparative Examples 1 to 4] Pigment Dispersion Stability The aqueous printing ink compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were placed in bottles and sealed at 40 ° C. The pigment dispersion stability was evaluated based on the presence or absence of sediment due to the aggregation of the pigment when stored for 10 days in Table 2. The results are shown in Table 2. A: No sediment is generated. B: Sediment is generated.
【００４８】印刷濃度
実施例１〜１０、比較例１〜４および印刷濃度評価用イ
ンキ１〜４をザーン粘度計Ｎｏ．４で流出秒数が１０秒
になるように水で希釈した後、二色刷フレキソ印刷機
（東谷鉄工所（株）製）を用いて、Ｋライナー(王子製
紙（株）製)に印刷した。実施例１〜１０、比較例１〜
４から得られた印刷物の色濃度を、印刷濃度評価用イン
キ１〜４から得られた印刷物の色濃度と目視で比較し、
水溶性高分子含有系インキの印刷濃度が、どれだけの顔
料含有量の水溶性高分子非含有系インキの印刷濃度に相
当するかによって、印刷濃度を評価し、結果を表２に示
した。
Ａ：顔料含有量が１．１５倍の水溶性高分子非含有系イ
ンキ（印刷濃度評価用インキ４）と印刷濃度が同程度の
もの。
Ｂ：顔料含有量が１．１０倍の水溶性高分子非含有系イ
ンキ（印刷濃度評価用インキ３）と印刷濃度が同程度の
もの。
Ｃ：顔料含有量が１．０５倍の水溶性高分子非含有系イ
ンキ（印刷濃度評価用インキ２）と印刷濃度が同程度の
もの。
Ｄ：顔料含有量が同量の水溶性高分子非含有系インキ印
刷（濃度評価用インキ１）と印刷濃度が同程あるいはそ
れ以下であり、印刷濃度向上効果の認められないのも
の。Printing Density Examples 1 to 10, Comparative Examples 1 to 4 and Printing Density Evaluation Inks 1 to 4 were applied to Zahn viscometer No. After diluting with water so that the number of outflow seconds was 10 seconds in No. 4, it was printed on a K liner (manufactured by Oji Paper Co., Ltd.) using a two-color printing flexographic printing machine (manufactured by Toya Iron Works Co., Ltd.). Examples 1-10, Comparative Examples 1-
The color density of the printed matter obtained from No. 4 is visually compared with the color density of the printed matter obtained from the printing density evaluation inks 1 to 4,
The print density was evaluated according to how much the print density of the water-soluble polymer-containing ink corresponds to the print density of the water-soluble polymer-free ink having a pigment content, and the results are shown in Table 2. A: A print density similar to that of the water-soluble polymer-free ink (print density evaluation ink 4) having a pigment content of 1.15 times. B: A print density similar to that of the water-soluble polymer-free ink (print density evaluation ink 3) having a pigment content of 1.10 times. C: The same printing density as the water-soluble polymer-free ink (printing density evaluation ink 2) having a pigment content of 1.05 times. D: The printing density is similar to or lower than that of the water-soluble polymer-free ink printing (ink for density evaluation 1) having the same pigment content, and the printing density improving effect is not recognized.
【００４９】にじみ
印刷濃度評価で利用した実施例１〜１０、比較例１〜
４、および印刷濃度評価用インキ組成物１の印刷物を目
視にて観察し、水溶性高分子を添加していない印刷濃度
評価用インキ１の印刷物におけるにじみのレベルと比較
することにより、にじみ低減効果を評価し、結果を表２
に示した。
Ａ：ほとんどにじみが見られず、にじみ低減効果の極め
て高いもの。
Ｂ：印刷濃度評価用インキ１から得られた印刷物より良
好なにじみのレベルであり、にじみ低減効果が明らかに
認められるもの。
Ｃ：印刷濃度評価用インキ１から得られた印刷物とにじ
みが同等であり、にじみ低減効果がほとんど認められな
いもの。Examples 1 to 10 and Comparative Examples 1 to 10 used for evaluation of bleeding print density
4 and the bleeding reduction effect by visually observing the printed matter of the ink composition 1 for printing density evaluation and comparing it with the level of bleeding in the printed matter of the ink 1 for printing density evaluation without addition of the water-soluble polymer. Was evaluated and the results are shown in Table 2.
It was shown to. A: Almost no bleeding was observed and the bleeding reduction effect was extremely high. B: The bleeding level is better than that of the printed matter obtained from the ink 1 for printing density evaluation, and the bleeding reduction effect is clearly recognized. C: The bleeding is equivalent to that of the printed matter obtained from the ink 1 for printing density evaluation, and the bleeding reduction effect is hardly recognized.
【００５０】ミスチング
印刷濃度評価で利用した実施例１〜１０、比較例１〜４
の印刷物を目視にて観察し、インキのミスチングによる
印刷物の汚れの度合いを評価し、結果を表２に示した。
Ａ：ミスチングによる汚れがほとんどないもの。
Ｂ：ミスチングによる汚れが僅かに観察されるもの。
Ｃ：ミスチングによる汚れが激しいもの。Examples 1 to 10 and Comparative Examples 1 to 4 used for evaluation of misting print density
The printed matter was visually observed and the degree of stain on the printed matter due to ink misting was evaluated. The results are shown in Table 2. A: There is almost no stain due to misting. B: Slightly observed stain due to misting. C: Thick stain caused by misting.
【００５１】[0051]
【表２】 [Table 2]
【００５２】[0052]
【発明の効果】本発明の水溶性高分子を含有する水性印
刷インキ組成物および印刷方法は、低粘度であっても高
い印刷濃度を有し、にじみなどがなく、印刷作業性の良
好な水性印刷インキ組成物および印刷方法である。EFFECTS OF THE INVENTION The aqueous printing ink composition and the printing method containing the water-soluble polymer of the present invention have a high printing density even with a low viscosity, have no bleeding, and have good printing workability. A printing ink composition and a printing method.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 平野 勇 大阪市西区江戸堀一丁目23番37号 サカタ インクス株式会社内 (72)発明者 福永 昌広 大阪市西区江戸堀一丁目23番37号 サカタ インクス株式会社内 Ｆターム(参考） 2H113 AA02 BA01 BB05 BC01 4J039 AD12 CA03 CA06 4J100 AF06R AJ01Q AJ02R AJ09R AL08R AL09R AM02R AM15Q AM17R AM21P AM21R AP01R AQ08R BA03R BA08R BA40R BA56P BA56R CA05 DA01 JA07 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Isamu Hirano Sakata, 1-23-37, Edobori, Nishi-ku, Osaka Inkus Co., Ltd. (72) Inventor Masahiro Fukunaga Sakata, 1-23-37, Edobori, Nishi-ku, Osaka Inkus Co., Ltd. F-term (reference) 2H113 AA02 BA01 BB05 BC01 4J039 AD12 CA03 CA06 4J100 AF06R AJ01Q AJ02R AJ09R AL08R AL09R AM02R AM15Q AM17R AM21P AM21R AP01R AQ08R BA03R BA08R BA40R BA56P BA56R CA05 DA01 JA07
Claims (4)
（Ｉ）で示される単量体Ａ 【化１】 （式中Ｒ１はＨまたはＣＨ３であり、Ｒ２は炭素数１〜
５の分岐または直鎖のアルキレン基であり、Ｘは水素、
リチウム、ナトリウム、カリウム、アンモニア、アルキ
ルアミン（モノエチルアミン、モノブチルアミン、およ
びトリエチルアミン等）およびアルカノールアミン（モ
ノエタノールアミン、ジエタノールアミンおよびトリエ
タノールアミン等）から選ばれた１種または２種以上で
ある）１００〜１０質量部、アクリルアミド０〜９０質
量部およびこれらと共重合可能な単量体Ｂ０〜３０質量
部との重合体であり、重量平均分子量が１００万〜４０
０万である水溶性高分子を含有することを特徴とする水
性印刷インキ組成物。1. A monomer A represented by the following general formula (I) in 100 parts by weight of the total amount of monomers: (In the formula, R 1 is H or CH 3 , and R 2 is 1 to 1 carbon atoms.
5 is a branched or straight chain alkylene group, X is hydrogen,
One or more selected from lithium, sodium, potassium, ammonia, alkylamines (monoethylamine, monobutylamine, triethylamine, etc.) and alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.) 100 10 to 10 parts by mass, 0 to 90 parts by mass of acrylamide, and 0 to 30 parts by mass of a monomer B copolymerizable therewith, having a weight average molecular weight of 1,000,000 to 40.
A water-based printing ink composition comprising a water-soluble polymer of 0,000.
質量％である請求項１記載の水性印刷インキ組成物。2. The content of the water-soluble polymer is 0.01 to 5
The water-based printing ink composition according to claim 1, which is a mass%.
と水分散性樹脂とを併用してなる請求項１および２記載
の水性印刷インキ組成物。3. The water-based printing ink composition according to claim 1, which further comprises a water-soluble resin and a water-dispersible resin as binder resins.
キ組成物を、印刷時の雰囲気温度において、ザーン粘度
計Ｎｏ．４による流出秒数が８〜１３秒となる粘度で印
刷することを特徴とする水性印刷インキ組成物の印刷方
法。4. The Zhan viscometer No. 3 at the atmospheric temperature at the time of printing, wherein the water-based ink composition according to claim 1 is used. 4. A method for printing an aqueous printing ink composition, which comprises printing at a viscosity such that the outflow seconds according to No. 4 is 8 to 13 seconds.
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|---|---|---|---|---|
| JP2017179356A (en) * | 2016-03-24 | 2017-10-05 | 東洋インキＳｃホールディングス株式会社 | Aqueous ink composition for decorative sheet, printed matter and laminate for decorative sheet |
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