JPH08113750A - Aqueous ink composition, and production of binder - Google Patents
Aqueous ink composition, and production of binderInfo
- Publication number
- JPH08113750A JPH08113750A JP25330394A JP25330394A JPH08113750A JP H08113750 A JPH08113750 A JP H08113750A JP 25330394 A JP25330394 A JP 25330394A JP 25330394 A JP25330394 A JP 25330394A JP H08113750 A JPH08113750 A JP H08113750A
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- Japan
- Prior art keywords
- vinyl chloride
- monomer
- weight
- ink composition
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塩ビ壁紙または床材用
水性インキとして用いられる水性インキ組成物、及びそ
のバインダーの製造方法に関するものであり、特には印
刷適性が良好で基材との接着性に優れた水性インキ組成
物、及びそのバインダーとして有効な塩化ビニル重合体
または塩化ビニル系共重合体の凝集物の少ない製造方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based ink composition used as a water-based ink for vinyl chloride wallpaper or floor materials, and a method for producing a binder thereof, and particularly, it has good printability and adheres to a substrate. The present invention relates to a water-based ink composition having excellent properties, and a method for producing a vinyl chloride polymer or vinyl chloride copolymer effective as a binder thereof with few aggregates.
【０００２】[0002]
【従来の技術】壁紙、床材、クロス等には建装材用塩ビ
加工材が一般に用いられており、実用上の厳しい諸耐性
（接着性、耐光性、耐水性、耐摩耗性、耐薬品性、耐汚
染性）が求められており、これらの要求特性から、従来
有機溶剤型インキが用いられてきた。昨今、衛生性、大
気中への有機溶剤の揮散の問題、省資源、省エネルギー
などの面から印刷インキの水性化が望まれ一部実用化さ
れつつある。しかしながら、この分野で要求される厳し
い諸耐性及び印刷適性、印刷効果に優れた水性インキは
未だ知られていないのが現状である。2. Description of the Related Art PVC processed materials for building materials are generally used for wallpaper, floor materials, cloths, etc., and have severe practical resistances (adhesiveness, light resistance, water resistance, abrasion resistance, chemical resistance). Properties and stain resistance) are required, and organic solvent type inks have been conventionally used because of these required properties. In recent years, water-based printing inks have been demanded from the viewpoints of hygiene, the problem of volatilization of organic solvent into the atmosphere, resource saving, energy saving, etc. However, the present situation is that a water-based ink excellent in severe resistance, printability, and printing effect required in this field has not yet been known.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、前記した従
来技術が有するような問題点がなく、良好な印刷適性、
基材との優れた接着性を発現する塩化ビニル重合体また
は塩化ビニル系共重合体及びその凝集物の少ない製造方
法を開発し、特性の優れた水性インキ組成物を提供する
ためになされたものである。SUMMARY OF THE INVENTION The present invention does not have the above-mentioned problems of the prior art and has good printability,
What was made in order to develop a method for producing a vinyl chloride polymer or a vinyl chloride-based copolymer that exhibits excellent adhesion to a substrate and a method for reducing the amount of aggregates thereof, and to provide an aqueous ink composition having excellent properties Is.
【０００４】[0004]
【課題を解決するための手段】本発明の水性インキ組成
物、及びそのバインダー用塩化ビニル重合体または塩化
ビニル系共重合体の製造方法は前記の課題を解決したも
のである。本発明の塩ビ壁紙または床材用水性インキ組
成物は、カルボキシル基含有モノマー30〜50重量％とそ
の他の共重合可能なモノマー50〜70重量％とからなるモ
ノマー組成でアルコール中で50〜60℃で溶液重合させて
得られるアクリル系共重合体を塩基性化合物で中和率が
60％以上になるように中和して水性溶液とし、ここへ塩
化ビニル60〜 100重量％とその他の共重合可能なモノマ
ー０〜40重量％とからなるモノマーまたはモノマー混合
物を添加し重合させて得られる塩化ビニル重合体または
塩化ビニル系共重合体をバインダーとすることを特徴と
するものである。The water-based ink composition of the present invention and the method for producing a vinyl chloride polymer or a vinyl chloride-based copolymer for a binder thereof solve the above-mentioned problems. The water-based ink composition for vinyl chloride wallpaper or flooring of the present invention has a monomer composition of 30 to 50% by weight of a carboxyl group-containing monomer and 50 to 70% by weight of another copolymerizable monomer in alcohol at 50 to 60 ° C. Acrylic copolymer obtained by solution polymerization with
Neutralize to 60% or more to make an aqueous solution, and add a monomer or monomer mixture consisting of 60 to 100% by weight of vinyl chloride and 0 to 40% by weight of other copolymerizable monomer, and polymerize. The obtained vinyl chloride polymer or vinyl chloride copolymer is used as a binder.
【０００５】また、本発明のバインダー用塩化ビニル重
合体または塩化ビニル系共重合体の製造方法は、カルボ
キシル基含有モノマー30〜50重量％とその他の共重合可
能なモノマー50〜70重量％とからなるモノマー組成でア
ルコール中で50〜60℃で溶液重合させて得られるアクリ
ル系共重合体を塩基性化合物で中和率が60％以上になる
ように中和して水性溶液とし、ここへ塩化ビニル60〜 1
00重量％とその他の共重合可能なモノマー０〜40重量％
とからなるモノマーまたはモノマー混合物を添加し重合
させることを特徴とするものである。The method for producing a vinyl chloride polymer or a vinyl chloride copolymer for a binder according to the present invention comprises the steps of using 30 to 50% by weight of a carboxyl group-containing monomer and 50 to 70% by weight of another copolymerizable monomer. Acrylic copolymer obtained by solution polymerization at 50-60 ° C in alcohol with the following monomer composition is neutralized with a basic compound to a neutralization rate of 60% or more to form an aqueous solution, and chlorided here. Vinyl 60-1
00% by weight and other copolymerizable monomers 0-40% by weight
It is characterized in that a monomer or a mixture of monomers consisting of and is added and polymerized.
【０００６】以下に本発明についてさらに詳しく説明す
る。本発明においてアクリル系共重合体の製造に用いる
モノマーのうち、カルボキシル基含有モノマーとして
は、例えばアクリル酸、メタクリル酸、イタコン酸、ク
ロトン酸等があげられる。これらの中ではアクリル酸、
メタクリル酸が好ましく１種類のみ用いても２種類以上
を併用してもよいが、使用範囲は下記のその他の共重合
可能なモノマーとの合計量の30〜50重量％である。30重
量％未満の場合は溶液重合後の塩基性化合物による中和
でアクリル系共重合体が水溶化しずらいし、50重量％を
超える場合はアクリル系共重合体の水性溶液中で、次工
程として、塩化ビニル等を重合または共重合させる際の
重合安定性が悪く凝集物（スケール）が発生しやすい。The present invention will be described in more detail below. Among the monomers used for producing the acrylic copolymer in the present invention, examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, itaconic acid, crotonic acid and the like. Among these, acrylic acid,
Methacrylic acid is preferably used alone or in combination of two or more, but the range of use is 30 to 50% by weight based on the total amount of the following other copolymerizable monomers. When it is less than 30% by weight, the acrylic copolymer is difficult to be water-solubilized by neutralization with a basic compound after solution polymerization, and when it exceeds 50% by weight in the aqueous solution of the acrylic copolymer in the next step. As a result, the polymerization stability at the time of polymerizing or copolymerizing vinyl chloride or the like is poor and aggregates (scale) are likely to occur.
【０００７】その他の共重合可能なモノマーとしては、
例えばアクリル酸もしくはメタクリル酸のメチル、エチ
ル、プロピル、イソプロピル、ブチル、イソブチル、オ
クチル、２−エチルヘキシル、ラウリル、ステアリルあ
るいはシクロヘキシルエステルなどの炭素数１〜18のア
ルキル基を有する（メタ）アクリル酸アルキルエステ
ル、スチレン、α−メチルスチレン、ビニルトルエン、
酢酸ビニル、プロピオン酸ビニル、アクリロニトリル、
エチレン、ブタジエン、イソプレン、Ｎ−メチロール
（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）
アクリルアミド、グリシジル（メタ）アクリレート等が
あげられる。Other copolymerizable monomers include
(Meth) acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms such as acrylic acid or methacrylic acid methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, 2-ethylhexyl, lauryl, stearyl or cyclohexyl ester. , Styrene, α-methylstyrene, vinyltoluene,
Vinyl acetate, vinyl propionate, acrylonitrile,
Ethylene, butadiene, isoprene, N-methylol (meth) acrylamide, N-butoxymethyl (meth)
Examples thereof include acrylamide and glycidyl (meth) acrylate.
【０００８】カルボキシル基含有モノマーとその他の共
重合可能なモノマーとを溶液重合させるには公知の方法
によることができる。例えばベンゾイルパーオキサイ
ド、ジブチルパーオキサイド、アゾビスイソブチロニト
リル、アゾビスイソバレロニトリル等のラジカルを発生
する重合開始剤の存在下に、イソプロピルアルコール、
エタノールなどのアルコール系有機溶剤中で50〜60℃の
温度で共重合させる。ただし、この温度範囲以外で重合
させたアクリル系共重合体の水性溶液中で、次工程とし
て、塩化ビニル等を重合または共重合させると重合安定
性が悪く凝集物が発生しやすい。Solution polymerization of the carboxyl group-containing monomer and the other copolymerizable monomer can be carried out by a known method. For example, in the presence of a radical-generating polymerization initiator such as benzoyl peroxide, dibutyl peroxide, azobisisobutyronitrile, azobisisovaleronitrile, isopropyl alcohol,
Copolymerize in an alcoholic organic solvent such as ethanol at a temperature of 50 to 60 ° C. However, in the aqueous solution of an acrylic copolymer polymerized outside this temperature range, if vinyl chloride or the like is polymerized or copolymerized in the next step, the polymerization stability is poor and aggregates are easily generated.
【０００９】得られたアクリル系共重合体を水性溶液と
するには、塩基性化合物、例えばモノメチルアミン、モ
ノエチルアミン、ジメチルアミン、ジエチルアミン、ト
リメチルアミン、トリエチルアミン、モノメタノールア
ミン、ジメタノールアミン、トリメタノールアミン、ジ
メチルアミノエタノール等のアミン類、苛性カリウム、
苛性ソーダ、アンモニア水等の無機塩基性化合物などか
ら選択された塩基性化合物を添加し、部分的に、あるい
は全部中和し、混合攪拌した後に所定量の水を添加す
る。本発明においてはアンモニア水を用いることが好ま
しく、また、アクリル系共重合体中の全カルボキシル基
の60％以上を中和することが必要である。中和率が60％
未満の場合はアクリル系共重合体の水性溶液中で、次工
程として、塩化ビニル等を重合または共重合させると重
合安定性が悪く凝集物が発生しやすい。The obtained acrylic copolymer can be made into an aqueous solution by using a basic compound such as monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, monomethanolamine, dimethanolamine, trimethanolamine. , Amines such as dimethylaminoethanol, potassium caustic,
A basic compound selected from inorganic basic compounds such as caustic soda and ammonia water is added, partially or completely neutralized, and after mixing and stirring, a predetermined amount of water is added. In the present invention, it is preferable to use aqueous ammonia, and it is necessary to neutralize 60% or more of all the carboxyl groups in the acrylic copolymer. 60% neutralization rate
If it is less than the above, polymerization stability is poor and aggregates are likely to occur when vinyl chloride or the like is polymerized or copolymerized in the next step in an aqueous solution of an acrylic copolymer.
【００１０】次に、上記のアクリル系共重合体の水性溶
液中で、塩化ビニルもしくは塩化ビニルとこれと共重合
可能なモノマーとの混合物を重合させる。この時、アク
リル系共重合体は分散剤として機能する。アクリル系共
重合体の水性溶液の使用範囲は、固形分換算で塩化ビニ
ル重合体または塩化ビニル系共重合体の固形分に対し２
〜50重量％とすればよく、より好ましくは４〜30重量％
の範囲である。使用量が少ない場合、分散力（乳化力）
が低下し、印刷適性が不十分となる。多過ぎる場合は耐
水性、耐薬品性が不十分となる。Next, vinyl chloride or a mixture of vinyl chloride and a monomer copolymerizable therewith is polymerized in an aqueous solution of the above acrylic copolymer. At this time, the acrylic copolymer functions as a dispersant. The use range of the aqueous solution of the acrylic copolymer is 2 based on the solid content of the vinyl chloride polymer or the vinyl chloride copolymer in terms of solid content.
-50% by weight, more preferably 4-30% by weight
Range. Dispersing power (emulsifying power) when the amount used is small
And the printability becomes insufficient. If it is too large, the water resistance and chemical resistance will be insufficient.
【００１１】塩化ビニルと共重合可能なモノマーとして
は、例えばアクリル酸もしくはメタクリル酸のメチル、
エチル、プロピル、イソプロピル、ブチル、イソブチ
ル、オクチル、２−エチルヘキシル、ラウリル、ステア
リルあるいはシクロヘキシルエステルなどの炭素数１〜
18のアルキル基を有する（メタ）アクリル酸アルキルエ
ステル、スチレン、α−メチルスチレン、ビニルトルエ
ン、酢酸ビニル、プロピオン酸ビニル、アクリロニトリ
ル、エチレン、ブタジエン、イソプレン、Ｎ−メチロー
ル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メ
タ）アクリルアミド、グリシジル（メタ）アクリレート
等があげられる。これらのモノマーは塩化ビニルだけで
は発現できない塗膜特性（柔軟性、抗張力など）及びバ
インダーとしての顔料保持性を改良・付与するために使
用されるが、本発明の効果を損わない限り40重量％以下
の範囲で使用することができ、１種類のみを用いても２
種以上を併用してもよい。Monomers copolymerizable with vinyl chloride include, for example, methyl acrylic acid or methacrylic acid,
1 to 1 carbon atoms such as ethyl, propyl, isopropyl, butyl, isobutyl, octyl, 2-ethylhexyl, lauryl, stearyl or cyclohexyl ester
(Meth) acrylic acid alkyl ester having 18 alkyl groups, styrene, α-methylstyrene, vinyltoluene, vinyl acetate, vinyl propionate, acrylonitrile, ethylene, butadiene, isoprene, N-methylol (meth) acrylamide, N-butoxy Examples thereof include methyl (meth) acrylamide and glycidyl (meth) acrylate. These monomers are used to improve and impart coating properties (flexibility, tensile strength, etc.) that cannot be exhibited by vinyl chloride alone and pigment retention as a binder, but 40 wt% unless impairing the effect of the present invention % Can be used in the range of 2% or less, and even if only one type is used, it is 2
You may use together 1 or more types.
【００１２】塩化ビニル重合体または塩化ビニル系共重
合体は、塩化ビニルまたは塩化ビニルとこれと共重合可
能なモノマーとの混合物を、前述のアクリル系共重合体
の水性溶液（要すればさらに水を添加する）中に分散し
た分散系で、攪拌下に、例えば、過硫酸アンモニウム、
過硫酸カリウム、過硫酸ナトリウム、過酸化水素などか
ら選択した水性重合開始剤、あるいはこれらと酸性亜硫
酸ソーダ、ロンガリット、Ｌ−アスコルビン酸などの還
元剤とを組み合わせたレドックス系触媒からなる水性重
合開始剤を用いて通常の条件で重合反応させれば得るこ
とができる。得られた塩化ビニル重合体または塩化ビニ
ル系共重合体はバインダーとなるものであるが、これは
アクリル系共重合体を分散剤とする水性分散液（エマル
ジョン）となっている。しかし、そのまま本発明の水性
インキ組成物の製造に用いることができる。The vinyl chloride polymer or vinyl chloride-based copolymer is obtained by adding vinyl chloride or a mixture of vinyl chloride and a monomer copolymerizable therewith to an aqueous solution of the above-mentioned acrylic copolymer (additionally water if necessary). Is added) under stirring with stirring, for example ammonium persulfate,
Aqueous polymerization initiator selected from potassium persulfate, sodium persulfate, hydrogen peroxide, etc., or an aqueous polymerization initiator comprising a redox catalyst combining these with a reducing agent such as acidic sodium sulfite, Rongalit, L-ascorbic acid, etc. It can be obtained by carrying out a polymerization reaction under normal conditions. The obtained vinyl chloride polymer or vinyl chloride-based copolymer serves as a binder, which is an aqueous dispersion (emulsion) containing an acrylic copolymer as a dispersant. However, it can be used as it is for the production of the aqueous ink composition of the present invention.
【００１３】本発明の水性インキ組成物を製造する際に
使用する顔料としては、酸化チタン、フタロシアニン、
モノアゾ、ジアゾ、キナクリドン等があげられるが、必
ずしもこれらに限定されるものではない。また、本発明
の水性インキ組成物には、必要に応じて、アミノ樹脂、
エポキシ樹脂等の熱硬化性樹脂、ポリエステル樹脂、ア
クリル樹脂等の熱可塑性樹脂を配合することができる
し、さらに必要に応じて、充填剤、可塑剤、増粘剤、防
腐剤、消泡剤、レベリング剤等の添加剤も併用すること
ができる。Pigments used in producing the water-based ink composition of the present invention include titanium oxide, phthalocyanine,
Examples thereof include monoazo, diazo, quinacridone, etc., but are not limited thereto. Further, the water-based ink composition of the present invention, if necessary, an amino resin,
A thermosetting resin such as an epoxy resin, a polyester resin, a thermoplastic resin such as an acrylic resin can be blended, and further, if necessary, a filler, a plasticizer, a thickener, a preservative, an antifoaming agent, Additives such as a leveling agent can also be used in combination.
【００１４】[0014]
【実施例】つぎに、具体的実施例ならびに比較例をあげ
るが、本発明は実施例に限定されるものではない。なお
例中の部および％は重量部と重量％を示す。 合成例１（アクリル系共重合体溶液−１の合成） 攪拌機、コンデンサー、温度計及び窒素ガス導入口を備
えた重合容器に、窒素置換後、イソプロピルアルコール
2,300部、触媒パーロイルＩＰＰ［日本油脂（株）商品
名］40部を仕込み、窒素ガス雰囲気下に攪拌しながら60
℃に昇温した。次にあらかじめ計量したメチルメタクリ
レート 300部、エチルアクリレート 300部、アクリル酸
400部の混合液を、内温60℃で上記重合容器中へ攪拌下
に４時間を要して均一に追加し、さらに60℃で２時間反
応させて重合を終了した。その後、重合容器を減圧（-6
50mmHg）にしてイソプロピルアルコールを 1,000部抜き
出し、25％アンモニア水 730部と脱イオン水 200部を添
加して１時間攪拌した後、30℃に冷却した。得られたア
クリル系共重合体溶液の固形分濃度は30.2％、粘度430c
ps（25℃）、pH 6.7であった。EXAMPLES Next, specific examples and comparative examples will be given, but the present invention is not limited to the examples. The parts and% in the examples mean parts by weight and% by weight. Synthesis Example 1 (Synthesis of Acrylic Copolymer Solution-1) A polymerization vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet was purged with nitrogen and then isopropyl alcohol was added.
Charge 2,300 parts, catalyst Perloyl IPP [trade name of NOF CORPORATION] 40 parts, and stir under nitrogen gas atmosphere with stirring 60
The temperature was raised to ° C. Next weighed 300 parts of methyl methacrylate, 300 parts of ethyl acrylate, acrylic acid
400 parts of the mixed solution was uniformly added to the above polymerization vessel at an internal temperature of 60 ° C. under stirring for 4 hours, and further reacted at 60 ° C. for 2 hours to complete the polymerization. After that, depressurize the polymerization vessel (-6
The content was adjusted to 50 mmHg), 1,000 parts of isopropyl alcohol was extracted, 730 parts of 25% aqueous ammonia and 200 parts of deionized water were added, and the mixture was stirred for 1 hour and then cooled to 30 ° C. The resulting acrylic copolymer solution had a solid content of 30.2% and a viscosity of 430c.
It had a ps (25 ° C) and a pH of 6.7.
【００１５】合成例２〜12（アクリル系共重合体溶液−
２〜12の合成） 合成例１と同様にして表１に示されるモノマーの種類、
重合温度で重合し、表１に示される中和率までカルボキ
シル基を25％アンモニア水で中和してアクリル系共重合
体溶液−２〜12を得た。Synthesis Examples 2 to 12 (acrylic copolymer solution-
2 to 12) In the same manner as in Synthesis Example 1, the types of monomers shown in Table 1,
Polymerization was carried out at the polymerization temperature, and the carboxyl groups were neutralized with 25% ammonia water up to the neutralization rate shown in Table 1 to obtain acrylic copolymer solutions-2 to 12.
【００１６】[0016]
【表１】 [Table 1]
【００１７】実施例１ 攪拌機、コンデンサー、温度計及び窒素ガス導入口を備
えたステンレス製重合容器に、合成例１で得たアクリル
系共重合体溶液−１を 250部（共重合体固形分75部）、
脱イオン水 1,480部及び25％アンモニア水 2.5部を入れ
窒素置換後、過硫酸アンモニウム７部を仕込み窒素ガス
雰囲気下に攪拌しながら60℃に昇温した。次に内温60℃
で塩化ビニルモノマー 500部を上記重合容器へ攪拌下に
６時間を要して均一に追加し、さらに60℃で２時間反応
させて重合を終了した。その後30℃迄冷却し、 100メッ
シュのろ布でろ過し塩化ビニル重合体エマルジョンを得
た。ろ布上の凝集物の量は全エマルジョンに対し wetで
0.1％であり、得られたエマルジョンの固形分濃度は2
5.4％、粘度は 10cps（25℃）、pH 9.1であった。Example 1 In a stainless steel polymerization container equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet, 250 parts of the acrylic copolymer solution-1 obtained in Synthesis Example 1 (copolymer solid content: 75 Part),
After adding 1,480 parts of deionized water and 2.5 parts of 25% ammonia water and replacing the atmosphere with nitrogen, 7 parts of ammonium persulfate was charged and the temperature was raised to 60 ° C. with stirring under a nitrogen gas atmosphere. Next, the internal temperature is 60 ℃
Then, 500 parts of vinyl chloride monomer was uniformly added to the above polymerization vessel with stirring for 6 hours, and further reacted at 60 ° C. for 2 hours to complete the polymerization. Then, the mixture was cooled to 30 ° C. and filtered through a 100-mesh filter cloth to obtain a vinyl chloride polymer emulsion. The amount of aggregates on the filter cloth is wet for all emulsions.
0.1%, and the resulting emulsion has a solid content of 2
The viscosity was 5.4%, the viscosity was 10 cps (25 ° C), and the pH was 9.1.
【００１８】実施例２〜６、比較例１〜６ 実施例１と同様にして表２に示されるアクリル系共重合
体溶液の種類、量及び重合モノマーの種類、量で塩化ビ
ニル重合体または塩化ビニル系共重合体のエマルジョン
をつくり、得られたエマルジョンを 100メッシュのろ布
でろ過しろ布上の凝集物の量を測定した。前記の全ての
実施例と比較例について、全エマルジョンの重量に対す
る wet凝集物の重量の百分率を求め、重合安定性の尺度
として、下記の判断基準に基づいて３段階評価し表２に
示した。 〇：２％未満、△：２〜10％、×：10％超Examples 2 to 6 and Comparative Examples 1 to 6 In the same manner as in Example 1, the type and amount of the acrylic copolymer solution shown in Table 2 and the type and amount of the polymerized monomers were determined according to the type and amount of vinyl chloride polymer or chloride. A vinyl-based copolymer emulsion was prepared, and the obtained emulsion was filtered through a 100-mesh filter cloth to measure the amount of aggregates on the filter cloth. For all of the above Examples and Comparative Examples, the percentage of the weight of the wet agglomerate with respect to the weight of the total emulsion was determined, and three levels were evaluated based on the following criteria as a measure of polymerization stability, and shown in Table 2. ◯: Less than 2%, △: 2-10%, ×: Over 10%
【００１９】[0019]
【表２】 [Table 2]
【００２０】実施例７ 攪拌機、コンデンサー、温度計及び窒素ガス導入口を備
えたステンレス製重合容器に合成例１で得たアクリル系
共重合体溶液−１を 670部（共重合体固形分 200部）、
脱イオン水 1,560部及び25％アンモニア水 6.7部を入れ
窒素置換後、過硫酸アンモニウム７部を仕込み窒素ガス
雰囲気下に攪拌しながら60℃に昇温した。次に内温60℃
で塩化ビニルモノマー 500部を上記重合容器へ攪拌下に
６時間を要して均一に追加し、さらに60℃で２時間反応
させて重合を終了し、その後30℃迄冷却し塩化ビニル重
合体エマルジョンを得た。得られたエマルジョンの固形
分濃度は25.4％、粘度は 13cps（25℃）、pH 8.5であっ
た。別のステンレス製容器に上記で得られた塩化ビニル
重合体エマルジョン65部を入れ、プロペラ付攪拌機で攪
拌しながら、顔料ＴＢ-700［大日精化（株）商品名］10
部、分散剤・消泡剤サーフィノール104 ［日信化学
（株）商品名］ 0.5部及び脱イオン水24.5部を添加し、
その後１時間攪拌を続け水性インキ組成物を得た。Example 7 In a stainless steel polymerization vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet, 670 parts of the acrylic copolymer solution-1 obtained in Synthesis Example 1 (200 parts of copolymer solids) ),
After adding 1,560 parts of deionized water and 6.7 parts of 25% ammonia water and substituting with nitrogen, 7 parts of ammonium persulfate was charged and the temperature was raised to 60 ° C. with stirring under a nitrogen gas atmosphere. Next, the internal temperature is 60 ℃
Then, 500 parts of vinyl chloride monomer was added uniformly to the above polymerization vessel with stirring for 6 hours, and further reacted at 60 ° C. for 2 hours to complete the polymerization, and then cooled to 30 ° C. and vinyl chloride polymer emulsion. Got The obtained emulsion had a solid content concentration of 25.4%, a viscosity of 13 cps (25 ° C) and a pH of 8.5. Into another stainless steel container, place 65 parts of the vinyl chloride polymer emulsion obtained above into a pigment TB-700 [trade name of Dainichiseika Chemicals Co., Ltd.] while stirring with a stirrer equipped with a propeller.
Parts, dispersant / antifoaming agent Surfynol 104 [Nisshin Chemical Co., Ltd. trade name] 0.5 parts and deionized water 24.5 parts,
Then, stirring was continued for 1 hour to obtain a water-based ink composition.
【００２１】別に、ガラス板上に下記配合のペーストレ
ジンゾルを膜厚が 200μｍになるようにドクターナイフ
で塗布し、 160℃で５分間加熱乾燥を行って塩化ビニル
フィルムを得た。 ペーストレジン： Ｇｅｏｎ 121 ［塩化ビニル樹脂、日本ゼオン（株）商品名］ 100部 ＤＯＰ 60部 Ｍａｒｋ ＦＣ−１［安定剤、アデカ・アーガス化学（株）商品名］ 3部 炭酸カルシウム 20部 酸化チタン 10部 メチルエチルケトン 5部 ユニフォームＡＺ ［発泡剤、大塚化学（株）商品名］ 4部Separately, a paste resin sol having the following composition was coated on a glass plate with a doctor knife so as to have a film thickness of 200 μm, and dried by heating at 160 ° C. for 5 minutes to obtain a vinyl chloride film. Paste resin: Geon 121 [Vinyl chloride resin, Nippon Zeon Co., Ltd. trade name] 100 parts DOP 60 parts Mark FC-1 [Stabilizer, Adeka Argus Chemical Co., Ltd. trade name] 3 parts Calcium carbonate 20 parts Titanium oxide 10 Part Methyl ethyl ketone 5 parts Uniform AZ [blowing agent, Otsuka Chemical Co., Ltd. trade name] 4 parts
【００２２】この塩化ビニルフィルムに先に得た水性イ
ンキ組成物をグラビア印刷し、 105℃で２分間乾燥し
た。印刷時の印刷適性及び印刷後の製品のインキの接着
性を下記の判定方法に基づいて評価した。その結果、共
に良好であった。 印刷適性：グラビア印刷時の流動性の良否で判断した。 接着性：得られた印刷物上に市販粘着テープ（ニチバン
製、セロハンテープ）を貼り、爪で５〜６回強く擦った
後に粘着テープを剥がす。粘着テープを剥がした面の印
刷インキと塩化ビニルフィルムの接着性を観察した。The aqueous ink composition obtained above was gravure-printed on this vinyl chloride film and dried at 105 ° C. for 2 minutes. The printability during printing and the ink adhesiveness of the product after printing were evaluated based on the following judgment methods. As a result, both were good. Printability: Judgment was made based on whether the fluidity during gravure printing was good or bad. Adhesiveness: A commercially available adhesive tape (Nichiban, cellophane tape) is attached on the obtained printed matter, and the adhesive tape is peeled off after being strongly rubbed with a nail 5 to 6 times. The adhesiveness between the printing ink and the vinyl chloride film on the surface from which the adhesive tape was peeled off was observed.
【００２３】実施例８〜11、比較例７ 実施例７と同様にして表３に示される重合モノマーの種
類、量で塩化ビニル系共重合体のエマルジョンをつく
り、得られたエマルジョンを用い、実施例７と同様にし
て水性インキ組成物を得、同様の方法で印刷適性と接着
性の評価を行い、結果を表３に示した。ただし、評価結
果は〇：良好、△：やや不良、×：不良で示した。Examples 8 to 11 and Comparative Example 7 In the same manner as in Example 7, vinyl chloride type copolymer emulsions were prepared according to the types and amounts of the polymerizing monomers shown in Table 3, and the emulsions obtained were used. An aqueous ink composition was obtained in the same manner as in Example 7, and printability and adhesiveness were evaluated by the same method, and the results are shown in Table 3. However, the evaluation results are indicated by ◯: good, Δ: somewhat bad, and x: bad.
【００２４】[0024]
【表３】 [Table 3]
【００２５】比較例８ 攪拌機、コンデンサー、温度計及び窒素ガス導入口を備
えた重合容器に、窒素置換後、合成例１で得たアクリル
系共重合体溶液−１を 830部（共重合体固形分250部）
及び脱イオン水 1,420部を仕込み窒素ガス雰囲気下に攪
拌しながら80℃に昇温した。一方、あらかじめ過硫酸ア
ンモニウム 2.5部を脱イオン水 247.5部に溶解した水溶
液およびメチルメタクリレート 250部、ブチルアクリレ
ート 250部の混合液をそれぞれ内温80℃の上記重合容器
中へ攪拌下に４時間を要して均一に追加し、さらに80℃
で２時間反応させて重合を終了し、その後30℃迄冷却し
アクリル系共重合体エマルジョンを得た。得られたエマ
ルジョンの固形分濃度は25.1％、粘度は 15cps（25
℃）、pH 6.5であった。得られたエマルジョンを用い実
施例７と同様にして水性インキ組成表を得、同様の方法
で印刷適性と接着性の評価を行った。印刷適性は良好で
あったが、印刷インキと塩化ビニルフィルムの接着性は
不良であった。Comparative Example 8 In a polymerization vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet, 830 parts (copolymer solid) of the acrylic copolymer solution-1 obtained in Synthesis Example 1 was replaced with nitrogen. Min 250)
And 1,420 parts of deionized water were charged and the temperature was raised to 80 ° C. under stirring in a nitrogen gas atmosphere. On the other hand, an aqueous solution prepared by previously dissolving 2.5 parts of ammonium persulfate in 247.5 parts of deionized water and a mixed solution of 250 parts of methyl methacrylate and 250 parts of butyl acrylate were placed in the above polymerization vessel having an internal temperature of 80 ° C. under stirring for 4 hours. And evenly add it to 80 ℃
The reaction was carried out for 2 hours to complete the polymerization, and then the mixture was cooled to 30 ° C. to obtain an acrylic copolymer emulsion. The resulting emulsion has a solids concentration of 25.1% and a viscosity of 15 cps (25
℃), pH 6.5. A water-based ink composition table was obtained using the obtained emulsion in the same manner as in Example 7, and printability and adhesiveness were evaluated by the same method. The printability was good, but the adhesion between the printing ink and the vinyl chloride film was poor.
【００２６】比較例９〜10 比較例８と同様にして表４に示される重合モノマーの種
類、量でアクリル系共重合体エマルジョンをつくり、得
られたエマルジョンを用い実施例７と同様にして水性イ
ンキ組成物を得、同様の方法で印刷適性と接着性の評価
を行い、結果を表４に示した。Comparative Examples 9 to 10 Acrylic copolymer emulsions were prepared in the same manner as in Comparative Example 8 with the types and amounts of the polymerizing monomers shown in Table 4, and the obtained emulsions were used to prepare an aqueous solution in the same manner as in Example 7. An ink composition was obtained, printability and adhesiveness were evaluated by the same method, and the results are shown in Table 4.
【００２７】[0027]
【表４】 [Table 4]
【００２８】[0028]
【発明の効果】本発明の水性インキ組成物は、その印刷
適性が良好で、得られたインキ膜の接着性にも極めて優
れているため、壁紙、床材等の塩ビ加工材用インキとし
て有用であり、また本発明の製造方法で塩化ビニル重合
体または塩化ビニル系共重合体を製造した場合の凝集物
（スケール）の発生が極めて少ない。INDUSTRIAL APPLICABILITY The aqueous ink composition of the present invention has good printability and is extremely excellent in the adhesiveness of the obtained ink film, and thus is useful as an ink for vinyl chloride processing materials such as wallpaper and floor materials. Further, when the vinyl chloride polymer or the vinyl chloride-based copolymer is produced by the production method of the present invention, the generation of aggregates (scale) is extremely small.
Claims (2)
％とその他の共重合可能なモノマー50〜70重量％とから
なるモノマー組成でアルコール中で50〜60℃で溶液重合
させて得られるアクリル系共重合体を塩基性化合物で中
和率が60％以上になるように中和して水性溶液とし、こ
こへ塩化ビニル60〜 100重量％とその他の共重合可能な
モノマー０〜40重量％とからなるモノマーまたはモノマ
ー混合物を添加し重合させて得られる塩化ビニル重合体
または塩化ビニル系共重合体をバインダーとすることを
特徴とする塩ビ壁紙または床材用水性インキ組成物。1. An acrylic copolymer obtained by solution polymerization in alcohol at 50 to 60 ° C. with a monomer composition comprising 30 to 50% by weight of a carboxyl group-containing monomer and 50 to 70% by weight of another copolymerizable monomer. The polymer is neutralized with a basic compound to a neutralization ratio of 60% or more to form an aqueous solution, and from this, vinyl chloride 60 to 100% by weight and other copolymerizable monomers 0 to 40% by weight are added. A vinyl chloride wallpaper or a floor ink aqueous ink composition, characterized in that a vinyl chloride polymer or a vinyl chloride copolymer obtained by adding and polymerizing the following monomer or monomer mixture is used as a binder.
％とその他の共重合可能なモノマー50〜70重量％とから
なるモノマー組成でアルコール中で50〜60℃で溶液重合
させて得られるアクリル系共重合体を塩基性化合物で中
和率が60％以上になるように中和して水性溶液とし、こ
こへ塩化ビニル60〜 100重量％とその他の共重合可能な
モノマー０〜40重量％とからなるモノマーまたはモノマ
ー混合物を添加し重合させることを特徴とする塩ビ壁紙
または床材用水性インキ組成物のバインダーとして用い
る塩化ビニル重合体または塩化ビニル系共重合体の製造
方法。2. An acrylic copolymer obtained by solution polymerization in alcohol at 50 to 60 ° C. with a monomer composition comprising 30 to 50% by weight of a carboxyl group-containing monomer and 50 to 70% by weight of another copolymerizable monomer. The polymer is neutralized with a basic compound to a neutralization ratio of 60% or more to form an aqueous solution, and from this, vinyl chloride 60 to 100% by weight and other copolymerizable monomers 0 to 40% by weight are added. A method for producing a vinyl chloride polymer or a vinyl chloride copolymer used as a binder for a water-based ink composition for a vinyl chloride wallpaper or floor material, which comprises adding the following monomer or a mixture of monomers and polymerizing the mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25330394A JPH08113750A (en) | 1994-10-19 | 1994-10-19 | Aqueous ink composition, and production of binder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25330394A JPH08113750A (en) | 1994-10-19 | 1994-10-19 | Aqueous ink composition, and production of binder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08113750A true JPH08113750A (en) | 1996-05-07 |
Family
ID=17249420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25330394A Pending JPH08113750A (en) | 1994-10-19 | 1994-10-19 | Aqueous ink composition, and production of binder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08113750A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012505278A (en) * | 2008-10-14 | 2012-03-01 | ソルヴェイ（ソシエテ アノニム） | Halogenated vinyl polymer composition |
-
1994
- 1994-10-19 JP JP25330394A patent/JPH08113750A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012505278A (en) * | 2008-10-14 | 2012-03-01 | ソルヴェイ（ソシエテ アノニム） | Halogenated vinyl polymer composition |
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