JPH09316389A - Water-based coating composition - Google Patents
Water-based coating compositionInfo
- Publication number
- JPH09316389A JPH09316389A JP13826496A JP13826496A JPH09316389A JP H09316389 A JPH09316389 A JP H09316389A JP 13826496 A JP13826496 A JP 13826496A JP 13826496 A JP13826496 A JP 13826496A JP H09316389 A JPH09316389 A JP H09316389A
- Authority
- JP
- Japan
- Prior art keywords
- water
- coating composition
- unsaturated carboxylic
- dispersible resin
- monomer
- 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.)
- Pending
Links
Landscapes
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は水分散性樹脂が乾燥
時ほぼ無色透明な皮膜を形成し、用いた細粒骨剤が有す
る色彩、形状等を生かし、構造物(壁、屋根、床等)の
素地面を保護、化粧仕上げに有効な水性被覆組成物に関
する。TECHNICAL FIELD The present invention relates to a structure (wall, roof, floor, etc.) of a water-dispersible resin that forms a colorless and transparent film when dried and makes full use of the color, shape and the like of the fine granules used. ) The present invention relates to an aqueous coating composition which protects the ground and is effective for cosmetic finishing.
【0002】[0002]
【従来の技術】従来より、構造物(壁、屋根、床等)の
表面保護、化粧材として、フラット塗料やリシン塗料、
吹き付けタイル(クレーター状、凹凸状)、スタッコ、
ローラー模様塗料等が使用されてきた。2. Description of the Related Art Conventionally, as a surface protection for structures (walls, roofs, floors, etc.) and as a decorative material, flat paint or lysine paint,
Sprayed tile (crater shape, uneven shape), stucco,
Roller pattern paints have been used.
【0003】そうした被覆材には一般に着色材として有
機または無機顔料が使用されているものの、これらの被
覆材は、色調が単調になり高級感に欠けるという問題が
あった。Although organic or inorganic pigments are generally used as colorants in such coating materials, these coating materials have a problem that the color tone is monotonous and lacks a high-class feeling.
【0004】そこで、大理石に代表される天然石に近い
深みのある落ちついた色調を発現し、而も安価でしかも
簡単な施工に適用し得る被覆材として、結合材と着色材
からなる水性被覆組成物が種々提案され実用に供されて
いる。Therefore, an aqueous coating composition composed of a binder and a coloring material is used as a coating material that exhibits a deep and subdued color tone close to that of natural stone typified by marble, and is inexpensive and applicable to simple construction. Have been proposed and put to practical use.
【0005】このような被覆材は、具体的には、乾燥時
ほぼ無色透明な皮膜を形成する水分散性樹脂を結合材と
して用い、また、天然石や陶磁器等の細粒骨材を着色材
として用いたものであり、スプレーやコテにて仕上げる
ことができる。Specifically, such a coating material uses, as a binder, a water-dispersible resin that forms a substantially colorless and transparent film when dried, and uses a fine aggregate such as natural stone or ceramics as a coloring material. It is used and can be finished with a spray or iron.
【0006】[0006]
【発明が解決しようとする課題】しかし、これら被覆材
に用いられる水分散性樹脂は雨や洗浄時の水により、特
に夏期の高温時における降雨にて白化現象を起こし着色
骨材の本来の色彩、形状等が白ボケして見苦しい外観に
なり易いとう問題を有していた。However, the water-dispersible resin used in these coating materials causes a whitening phenomenon due to rain or water during washing, especially when it is raining at high temperature in summer, and the original color of the colored aggregate. However, there is a problem that the shape and the like are dim and the appearance is unsightly.
【0007】その回避に水分散性樹脂の調整時に使用す
る界面活性剤の使用量を減じる方法等が報告されてい
る。しかし、この方法においては、界面活性剤の減量に
より水分散性樹脂の機械安定性が劣り、スプレー塗装適
性や長期保存する場合の保存安定性に劣るという問題が
発生していた。To avoid this, a method of reducing the amount of the surfactant used when preparing the water-dispersible resin has been reported. However, in this method, there was a problem that the mechanical stability of the water-dispersible resin was poor due to the reduction in the amount of the surfactant, and the spray coating suitability and the storage stability in the case of long-term storage were poor.
【0008】本発明が解決しようとする課題は、水や温
水に白化し難く、且つ機械安定性、保存安定性に優れる
水性被覆組成物を提供することにある。The problem to be solved by the present invention is to provide an aqueous coating composition which is unlikely to be bleached in water or warm water and which is excellent in mechanical stability and storage stability.
【0009】[0009]
【課題を解決するための手段】そこで、本発明者等は上
記課題を解決すべく鋭意検討を重ねた結果、結合材とし
て特定単量体成分を反応性乳化剤を用いて乳化重合した
水分散性樹脂を用いることにより、白化現象を解決し機
械安定性並びに長期保存安定性に優れることを見いだし
本発明に至った。Therefore, the inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, water-dispersibility obtained by emulsion polymerization of a specific monomer component as a binder using a reactive emulsifier. By using a resin, it was found that the whitening phenomenon was solved and the mechanical stability and long-term storage stability were excellent, and the present invention was achieved.
【0010】即ち、本発明は、モノエチレン性不飽和カ
ルボン酸アルキルエステル、及び、エチレン性不飽和カ
ルボン酸を必須の成分とする単量体成分を、スルホン基
又はサルフェート基並びにエチレン性不飽和基を分子構
造中に有する反応性乳化剤の存在下に乳化重合して得ら
れる水分散性樹脂と着色骨剤とを必須成分とすることを
特徴とする水性被覆組成物に関する。That is, according to the present invention, a monoethylenically unsaturated carboxylic acid alkyl ester and a monomer component containing an ethylenically unsaturated carboxylic acid as an essential component are used as a sulfone group or a sulfate group and an ethylenically unsaturated group. The present invention relates to an aqueous coating composition, which comprises, as essential components, a water-dispersible resin obtained by emulsion polymerization in the presence of a reactive emulsifier having in the molecular structure thereof and a colored bone agent.
【0011】[0011]
【発明の実施の形態】本発明で用いる水分散性樹脂は、
モノエチレン性不飽和カルボン酸アルキルエステル、及
び、エチレン性不飽和カルボン酸を必須の成分とする単
量体成分を、スルホン基又はサルフェート基並びにエチ
レン性不飽和基を分子構造中に有する反応性乳化剤の存
在下に乳化重合して得られるものである。BEST MODE FOR CARRYING OUT THE INVENTION The water-dispersible resin used in the present invention is
Monoethylenically unsaturated carboxylic acid alkyl ester and a monomer component containing ethylenically unsaturated carboxylic acid as an essential component, a reactive emulsifier having a sulfone group or a sulfate group and an ethylenically unsaturated group in its molecular structure. It is obtained by emulsion polymerization in the presence of.
【0012】ここで用いられるモノエチレン性不飽和カ
ルボン酸アルキルエステル類としては、特に限定される
ものではないが、例えばアクリル酸メチル、アクリル酸
エチル、アクリル酸n−ブチル、アクリル酸イソブチ
ル、アクリル酸2−エチルヘキシル、アクリル酸デシ
ル、アクリル酸ドデシル、アクリル酸2−ヒドロキシエ
チル、メタクリル酸メチル、メタクリル酸エチル、メタ
クリル酸n−ブチル、メタクリル酸イソブチル、メタク
リル酸2−エチルヘキシル、メタクリル酸デシル、メタ
クリル酸ドデシルまたはメタクリル酸2−ヒドロキシエ
チルなどが挙げられる。The monoethylenically unsaturated carboxylic acid alkyl ester used here is not particularly limited, but for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid. 2-ethylhexyl, decyl acrylate, dodecyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate. Alternatively, 2-hydroxyethyl methacrylate or the like can be used.
【0013】また、本発明においては、上記モノエチレ
ン性不飽和カルボン酸アルキルエステルと共に芳香族ビ
ニル単量体を用いることにより、更に耐候性を向上させ
ることができる。このような芳香族ビニル単量体として
は、特に限定されるものではないが、例えば、スチレ
ン、α−メチルスチレン、P-tertーブチルスチレン
またはビニルトルエン等が挙げられる。Further, in the present invention, weather resistance can be further improved by using an aromatic vinyl monomer together with the above-mentioned monoethylenically unsaturated carboxylic acid alkyl ester. Such an aromatic vinyl monomer is not particularly limited, but examples thereof include styrene, α-methylstyrene, P-tert-butylstyrene, vinyltoluene and the like.
【0014】さらに上記したモノエチレン性不飽和カル
ボン酸としては、特に限定されるものではないが、例え
ば、アクリル酸、メタクリル酸、クロトン酸、イタコン
酸またはマレイン酸等が挙げられる。なかでも分散安定
性の点からアクリル酸、メタクリル酸が好ましい。The above-mentioned monoethylenically unsaturated carboxylic acid is not particularly limited, but examples thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and the like. Of these, acrylic acid and methacrylic acid are preferable from the viewpoint of dispersion stability.
【0015】上記した単量体成分の使用割合は、特に制
限されるものではないが、長期保存安定性の点から全単
量体成分中、エチレン性不飽和カルボン酸の使用量が、
単量体成分の全重量に対して0.1〜5.0重量%であ
ることが好ましい。The ratio of the above-mentioned monomer components to be used is not particularly limited, but from the viewpoint of long-term storage stability, the amount of ethylenically unsaturated carboxylic acid used in all the monomer components is
It is preferably 0.1 to 5.0% by weight based on the total weight of the monomer components.
【0016】また、これらの単量体の他に、たとえば、
ジビニルベンゼンやジビニルアクリレート等のような、
いわゆる架橋性単量体(架橋剤類)を用いてもよい。In addition to these monomers, for example,
Like divinylbenzene or divinyl acrylate,
So-called crosslinkable monomers (crosslinking agents) may be used.
【0017】上記単量体成分を乳化重合して水分散性樹
脂を製造する方法としては、乳化剤としてスルホン基又
はサルフェート基並びにエチレン性不飽和基を分子構造
中に有する反応性乳化剤を用いていればよく、特に限定
されるものではない。As a method for producing a water-dispersible resin by emulsion polymerization of the above-mentioned monomer components, a reactive emulsifier having a sulfone group or a sulfate group and an ethylenically unsaturated group in its molecular structure is used as an emulsifier. However, there is no particular limitation.
【0018】このスルホン基又はサルフェート基並びに
エチレン性不飽和基を同一分子中に含む共重合可能な反
応性乳化剤としては、特に限定されないが、例えば、ポ
リオキシエチレンアルキルフェニルサルフェートのプロ
ペニル基導入タイプ、ポリオキシエチレンアルキルフェ
ニルエーテルのアリル基導入タイプ、ジアルキルスルホ
サクシネートのビニル基導入タイプなどが挙げられる。The reactive emulsifier capable of copolymerization containing the sulfone group or the sulfate group and the ethylenically unsaturated group in the same molecule is not particularly limited, but for example, a propenyl group-introduced type of polyoxyethylene alkylphenyl sulfate, Examples thereof include an allyl group-introduced type of polyoxyethylene alkylphenyl ether and a vinyl group-introduced type of dialkylsulfosuccinate.
【0019】また、その使用量は特に限定されるもので
はないが、全単量体成分に対して0.1〜5.0重量%
の範囲であることが白化防止の点から好ましい。The amount used is not particularly limited, but is 0.1 to 5.0% by weight based on the total monomer components.
From the viewpoint of whitening prevention, it is preferable that the range is
【0020】着色骨材としては、特に限定されるもので
はなく、黒寒水石、蛇紋岩、螢石などの天然有色砂やた
とえば陶磁器砕粒、焼成硅砂などの人工着色砂などが挙
げられる。The colored aggregate is not particularly limited, and examples thereof include natural colored sand such as black cold water stone, serpentine, and fluorite, and artificial colored sand such as ceramic crushed grains and calcined silica sand.
【0021】水分散性樹脂は、被覆組成物全重量の固形
分で約2〜50%用いるのが好ましい。2%以上におい
ては形成される被覆層の強度が優れたものとなってクラ
ック等の発生を防止でき、一方、50%以下においては
乾燥性が良好となる。The water dispersible resin is preferably used in an amount of about 2 to 50% based on the total solid content of the coating composition. If it is 2% or more, the strength of the coating layer formed is excellent and cracks and the like can be prevented, while if it is 50% or less, the drying property is good.
【0022】素地面に本発明の被覆組成物を施工する方
法としては、たとえば吹付け法コテ塗り法が適当であ
る。両施工法とも一般にあらかじめ所定の色調に調合し
た被覆組成物を付着せしめ、その上に色調の異なる被覆
組成物を斑点状に重ねる工程からなっている。ただし、
斑点色のない種類のものでは前記の色調の異なる被覆組
成物を斑点状に重ねる工程が省略されうる。さらに必要
に応じて光沢を出す場合、透明な樹脂溶液を塗布又は噴
霧する。As a method for applying the coating composition of the present invention on the ground surface, for example, a spraying method and a trowel coating method are suitable. Both of the construction methods generally include a step of depositing a coating composition prepared in advance in a predetermined color tone and superimposing a coating composition having a different color tone on the coating composition in spots. However,
In the case of the non-speckled type, the step of overlapping the coating compositions having different color tones in a speckled manner may be omitted. Further, if a gloss is to be obtained as necessary, a transparent resin solution is applied or sprayed.
【0023】乾燥時にほぼ無色透明な皮膜を形成するも
のであり、屋外で使用するものである為耐候性に優れ、
耐温水白化性に優れたものでなければならない。It forms a nearly colorless and transparent film when dried, and since it is used outdoors, it has excellent weather resistance,
It must have excellent resistance to warm water whitening.
【0024】[0024]
【実施例】つぎに実施例をあげて本発明の被覆組成物を
説明するが、本発明はかかる実施例のみに限定されるも
のではない。EXAMPLES The coating composition of the present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【0025】参考例1(反応性乳化剤使用によるカルボ
キシル基含有水分散性樹脂A−1の製造) 攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を
備えた反応容器に脱イオン水35部を入れ、窒素を吹き
込みながら80℃まで昇温した。攪拌下、過硫酸ソーダ
0.1部を添加し、続いて2−エチルヘキシルアクリレ
ート21部、メタクリル酸メチル26.9部、アクリル
酸1部、アクアロンHS−1025(第一工業製薬
(株)製;ポリオキシエチレンアルキルフェニルエーテ
ルアンモニウム塩で反応性基を持つ:固形分25%)4
部、脱イオン水10部からなる単量体混合物を反応容器
内温80±3℃に保ちながら150分かけて滴下し重合
せしめた。滴下終了後同温度にて30分間攪拌し、アン
モニア水にて内容物のpHを8.0に調整した。その
後、内容物を冷却し、固形分濃度が50.0%になるよ
うに脱イオン水で調整し、100メッシュ金網にて濾過
した。100メッシュ金網不通過の凝集物は、0.1%
(対生成分散液比)以下であった。このカルボキシル基
含有重合体の水性分散液をA−1とする。Reference Example 1 (Production of Carboxyl Group-Containing Water-Dispersible Resin A-1 Using Reactive Emulsifier) Deionized water 35 was added to a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel. Then, the temperature was raised to 80 ° C. while blowing nitrogen. Under stirring, 0.1 part of sodium persulfate was added, followed by 21 parts of 2-ethylhexyl acrylate, 26.9 parts of methyl methacrylate, 1 part of acrylic acid, Aqualon HS-1025 (Daiichi Kogyo Seiyaku Co., Ltd.); Polyoxyethylene alkylphenyl ether ammonium salt with reactive groups: solid content 25%) 4
Part and 10 parts of deionized water were added dropwise over 150 minutes while maintaining the internal temperature of the reaction vessel at 80 ± 3 ° C. for polymerization. After completion of dropping, the mixture was stirred at the same temperature for 30 minutes, and the pH of the content was adjusted to 8.0 with aqueous ammonia. Then, the content was cooled, adjusted to a solid content concentration of 50.0% with deionized water, and filtered through a 100-mesh wire net. Aggregate that does not pass through 100 mesh is 0.1%
(Ratio to generated dispersion liquid) or less. The aqueous dispersion of this carboxyl group-containing polymer is designated as A-1.
【0026】参考例2(反応性乳化剤使用によるカルボ
キシル基含有水分散性樹脂A−2の製造) 攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を
備えた反応容器に脱イオン水35部を入れ、窒素を吹き
込みながら80℃まで昇温した。攪拌下、過硫酸ソーダ
0.1部を添加し、続いて2−エチルヘキシルアクリレ
ート21部、メタクリル酸メチル16.9部、スチレン
10部、アクリル酸1部、アクアロンHS−1025
(第一工業製薬(株)製;ポリオキシエチレンアルキル
フェニルエーテルアンモニウム塩で反応性基を持つ:固
形分25%)4部、脱イオン水10部からなる単量体混
合物を反応容器内温80±3℃に保ちながら150分か
けて滴下し重合せしめた。滴下終了後同温度にて30分
間攪拌し、アンモニア水にて内容物のpHを8.0に調
整した。Reference Example 2 (Production of Carboxyl Group-Containing Water-Dispersible Resin A-2 by Using Reactive Emulsifier) Deionized water 35 was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel. Then, the temperature was raised to 80 ° C. while blowing nitrogen. With stirring, 0.1 part of sodium persulfate was added, followed by 21 parts of 2-ethylhexyl acrylate, 16.9 parts of methyl methacrylate, 10 parts of styrene, 1 part of acrylic acid, Aqualon HS-1025.
(Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; polyoxyethylene alkylphenyl ether ammonium salt having a reactive group: solid content 25%) 4 parts, and a monomer mixture consisting of 10 parts of deionized water was heated at a reaction container internal temperature of 80. While keeping the temperature at ± 3 ° C, the mixture was added dropwise over 150 minutes for polymerization. After completion of dropping, the mixture was stirred at the same temperature for 30 minutes, and the pH of the content was adjusted to 8.0 with aqueous ammonia.
【0027】その後、内容物を冷却し、固形分濃度が5
0.0%になるように脱イオン水で調整し、100メッ
シュ金網にて濾過した。100メッシュ金網不通過の凝
集物は、0.1%(対生成分散液比)以下であった。After that, the content is cooled to a solid content of 5
It was adjusted to 0.0% with deionized water and filtered through a 100-mesh wire net. Aggregates that did not pass through the 100-mesh wire net were 0.1% or less (ratio to generated dispersion liquid).
【0028】このカルボキシル基含有重合体の水性分散
液をA−2とする。The aqueous dispersion of the carboxyl group-containing polymer is designated as A-2.
【0029】参考例3(反応性乳化剤使用によるカルボ
キシル基非含有水分散性樹脂A−3の製造) 攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を
備えた反応容器に脱イオン水35部を入れ、窒素を吹き
込みながら80℃まで昇温した。攪拌下、過硫酸ソーダ
0.1部を添加し、続いて2−エチルヘキシルアクリレ
ート21部、メタクリル酸メチル27.9部、アクアロ
ンHS−1025(第一工業製薬(株)製;ポリオキシ
エチレンアルキルフェニルエーテルアンモニウム塩で反
応性基を持つ)4部、脱イオン水10部からなる単量体
混合物を反応容器内温80±3℃に保ちながら150分
かけて滴下し重合せしめた。滴下終了後同温度にて30
分間攪拌し、アンモニア水にて内容物のpHを8.0に
調整した。その後、内容物を冷却し、固形分濃度が5
0.0%になるように脱イオン水で調整し、100メッ
シュ金網にて濾過した。100メッシュ金網不通過の凝
集物は、0.1%(体生成分散液比)以下であった。Reference Example 3 (Production of carboxyl group-free water-dispersible resin A-3 using a reactive emulsifier) Deionized water was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel. 35 parts was added and the temperature was raised to 80 ° C. while blowing nitrogen. While stirring, 0.1 part of sodium persulfate was added, followed by 21 parts of 2-ethylhexyl acrylate, 27.9 parts of methyl methacrylate, and Aqualon HS-1025 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; polyoxyethylene alkylphenyl). A monomer mixture consisting of 4 parts of an ether ammonium salt (having a reactive group) and 10 parts of deionized water was added dropwise over 150 minutes to carry out polymerization while maintaining the temperature in the reaction vessel at 80 ± 3 ° C. 30 at the same temperature after dropping
After stirring for a minute, the pH of the contents was adjusted to 8.0 with aqueous ammonia. After that, the contents are cooled to a solid content of 5
It was adjusted to 0.0% with deionized water and filtered through a 100-mesh wire net. Aggregates that did not pass through the 100-mesh wire net were 0.1% or less (ratio of body-forming dispersion liquid).
【0030】このカルボキシル基含有重合体の水性分散
液をA−3とする。An aqueous dispersion of this carboxyl group-containing polymer is designated as A-3.
【0031】参考例4(非反応性乳化剤使用によるカル
ボキシル基含有水分散性樹脂A−4の製造) 攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を
備えた反応容器に脱イオン水35部を入れ、窒素を吹き
込みながら80℃まで昇温した。攪拌下、過硫酸ソーダ
0.1部を添加し、続いて2−エチルヘキシルアクリレ
ート21部、メタクリル酸メチル26.9部、アクリル
酸1.0部、レベノールWZ(花王(株)製;ポリオキ
シエチレンアルキルフェニルエーテルスルホン酸ソー
ダ、固形分25%)8部、脱イオン水10部からなる単
量体混合物を反応容器内温80±3℃に保ちながら15
0分かけて滴下し重合せしめた。滴下終了後同温度にて
30分間攪拌し、アンモニア水にて内容物のpHを8.
0に調整した。その後、内容物を冷却し、固形分濃度が
50.0%になるように脱イオン水で調整し、100メ
ッシュ金網にて濾過した。100メッシュ金網不通過の
凝集物は、0.1%(体生成分散液比)以下であった。Reference Example 4 (Production of carboxyl group-containing water-dispersible resin A-4 by using non-reactive emulsifier) Deionized water was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel. 35 parts was added and the temperature was raised to 80 ° C. while blowing nitrogen. With stirring, 0.1 part of sodium persulfate was added, followed by 21 parts of 2-ethylhexyl acrylate, 26.9 parts of methyl methacrylate, 1.0 part of acrylic acid, Rebenol WZ (manufactured by Kao Corporation; polyoxyethylene). A monomer mixture consisting of 8 parts of sodium alkylphenyl ether sulfonate, solid content 25%) and 10 parts of deionized water was added while keeping the temperature in the reaction vessel at 80 ± 3 ° C.
The mixture was added dropwise over 0 minutes for polymerization. After completion of dropping, the mixture was stirred at the same temperature for 30 minutes, and the pH of the contents was adjusted to 8. with ammonia water.
Adjusted to zero. Then, the content was cooled, adjusted to a solid content concentration of 50.0% with deionized water, and filtered through a 100-mesh wire net. Aggregates that did not pass through the 100-mesh wire net were 0.1% or less (ratio of body-forming dispersion liquid).
【0032】このカルボキシル基含有重合体の水性分散
液をA−4とする。An aqueous dispersion of this carboxyl group-containing polymer is designated as A-4.
【0033】以上の参考例1〜4の重合体水性分散液及
びクリアフィルムの物性を測定した結果下表のようにな
った。The physical properties of the polymer aqueous dispersions and clear films of Reference Examples 1 to 4 above were measured and the results are shown in the table below.
【0034】[0034]
【表1】 [Table 1]
【0035】評価方法: (耐水白化性)参考例1〜4により得られた重合体水性
分散液A−1〜A−4を、ガラス板上に3milアプリ
ケーターで塗工し、常温で3日間乾燥して皮膜を形成し
た。その後120℃で5分間加熱処理を行って、残存す
る水分を蒸発させて試験片とした。試験片を常温水中に
7日間浸漬し水浸漬前と水浸漬後の試験片の劣化(白
化)状態を3段階評価した。Evaluation method: (Water whitening resistance) The aqueous polymer dispersions A-1 to A-4 obtained in Reference Examples 1 to 4 were coated on a glass plate with a 3 mil applicator and dried at room temperature for 3 days. To form a film. After that, a heat treatment was performed at 120 ° C. for 5 minutes to evaporate the remaining water to obtain a test piece. The test piece was immersed in normal temperature water for 7 days, and the deterioration (whitening) state of the test piece before and after the water immersion was evaluated in three stages.
【0036】 [0036]
【0037】(機械的安定性)参考例1〜4により得ら
れた重合体水性分散液A−1〜A−4をマーロン試験機
にて回転数1000rpm,時間10分の条件で試験機にかけた。
その時に発生した凝集物発生率(対固形分%)を評価し
た。(Mechanical Stability) The polymer aqueous dispersions A-1 to A-4 obtained in Reference Examples 1 to 4 were placed in a Marlon tester under the conditions of a rotation speed of 1000 rpm and a time of 10 minutes. .
The generation rate of aggregates (relative to solid content%) generated at that time was evaluated.
【0038】(貯蔵安定性)参考例1〜4により得られ
た重合体水性分散液A−1〜A−4を50℃、30日間
放置した後の分散液の貯蔵前との粘度変化をβ型粘度計
で測定し4段階にて評価した。(Storage stability) The polymer aqueous dispersions A-1 to A-4 obtained in Reference Examples 1 to 4 were left at 50 ° C. for 30 days, and the change in viscosity of the dispersions before storage was β. It was measured with a viscometer and evaluated in four levels.
【0039】 判定基準:○ 初期粘度と30日後の粘度変化無し △ 初期粘度と30日後の粘度変化率50%以内 × 初期粘度と30日後の粘度変化率50%以上、若しくはゲル化Criteria: ○ Initial viscosity and viscosity change after 30 days no change △ Initial viscosity and viscosity change rate after 30 days within 50% × Initial viscosity and viscosity change rate after 30 days 50% or more, or gelation
【0040】実施例1、2及び比較例1、2 前記の水分散性樹脂A−1〜A−4を用い、以下の第2
表に従って、塗料配合物を調整した。Examples 1 and 2 and Comparative Examples 1 and 2 Using the above water-dispersible resins A-1 to A-4, the following second
The paint formulations were prepared according to the table.
【0041】[0041]
【表2】 [Table 2]
【0042】次いで、得られた塗料及び被覆組成物の物
性評価を以下の方法にて行った。結果を第3表に示す。Next, the physical properties of the obtained paint and coating composition were evaluated by the following methods. The results are shown in Table 3.
【0043】塗料配合物の評価方法 (皮膜耐水白化性)上記配合処方により得られた配合物
1〜5をスプレーガンにてスレート板上に均一に吹き付
け、常温で14日間乾燥して皮膜を形成した。その後1
20℃で5分間加熱処理を行って、残存する水分を蒸発
させて試験片とした。試験片を常温水中に7日間浸漬し
水浸漬前と水浸漬後の試験片の劣化(白化)状態を3段
階評価した。Evaluation Method of Paint Blends (Water Whitening Resistance of Coating) Blends 1 to 5 obtained by the above blending recipe are sprayed uniformly on a slate plate with a spray gun and dried at room temperature for 14 days to form a coating. did. Then one
A heat treatment was carried out at 20 ° C. for 5 minutes to evaporate the remaining water to obtain a test piece. The test piece was immersed in normal temperature water for 7 days, and the deterioration (whitening) state of the test piece before and after the water immersion was evaluated in three stages.
【0044】 [0044]
【0045】(貯蔵安定性)上記配合処方により得られ
た配合物1〜5を50℃、30日間放置した後の配合物
の粘度変化をストマー粘度計で測定し3段階にて評価し
た。(Storage stability) The viscosity change of each of the formulations 1 to 5 obtained by the above formulation after standing at 50 ° C. for 30 days was measured with a Stomer viscometer and evaluated in three stages.
【0046】 判定基準:○ 初期粘度と30日後の粘度変化無し △ 初期粘度と30日後の粘度変化率50%以内 × 初期粘度と30日後の粘度変化率50%以上、若しくはゲル化Criteria: ○ Initial viscosity and no viscosity change after 30 days △ Initial viscosity and viscosity change rate within 30 days within 50% × Initial viscosity and viscosity change rate after 30 days 50% or more, or gelation
【0047】[0047]
【表3】 第3表をみると本発明の方法により得られた乳化分散液
の塗料配合物は、通常の乳化剤を用いた乳化分散液の塗
料配合物より安定性に優れ、この被覆組成物は耐水白化
性に優れることが分かる。[Table 3] As shown in Table 3, the coating composition of the emulsion dispersion obtained by the method of the present invention is more stable than the coating composition of the emulsion dispersion using an ordinary emulsifier, and the coating composition has a water-whitening resistance. It turns out to be excellent.
【0048】[0048]
【発明の効果】本発明によれば、水や温水に白化し難
く、且つ機械安定性、保存安定性に優れる水性被覆組成
物を提供できる。According to the present invention, it is possible to provide an aqueous coating composition which is unlikely to be whitened by water or warm water, and which is excellent in mechanical stability and storage stability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 C09D 133/02 PFW C09D 133/02 PFW // C08F 2/24 MCB C08F 2/24 MCB ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display area C09D 133/02 PFW C09D 133/02 PFW // C08F 2/24 MCB C08F 2/24 MCB
Claims (4)
ルエステル、及び、エチレン性不飽和カルボン酸を必須
の成分とする単量体成分を、スルホン基又はサルフェー
ト基並びにエチレン性不飽和基を分子構造中に有する反
応性乳化剤の存在下に乳化重合して得られる水分散性樹
脂と着色骨剤とを必須成分とすることを特徴とする水性
被覆組成物。1. A monoethylenically unsaturated carboxylic acid alkyl ester and a monomer component containing an ethylenically unsaturated carboxylic acid as an essential component, a sulfone group or a sulfate group, and an ethylenically unsaturated group in the molecular structure. An aqueous coating composition, which comprises a water-dispersible resin obtained by emulsion polymerization in the presence of the reactive emulsifying agent and a colored bone agent as essential components.
単量体を含有する請求項1記載の組成物。2. The composition according to claim 1, which further contains an aromatic vinyl monomer as a monomer component.
が、単量体成分の全重量に対して0.1〜5.0重量%
である請求項1又は2記載の組成物。3. The amount of ethylenically unsaturated carboxylic acid used is 0.1 to 5.0% by weight based on the total weight of the monomer components.
The composition according to claim 1 or 2, which is
全重量に対して0.1〜5.0重量%である請求項1、
2又は3記載の組成物。4. The amount of the reactive emulsifier used is 0.1 to 5.0% by weight based on the total weight of the monomer components.
The composition according to 2 or 3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13826496A JPH09316389A (en) | 1996-05-31 | 1996-05-31 | Water-based coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13826496A JPH09316389A (en) | 1996-05-31 | 1996-05-31 | Water-based coating composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH09316389A true JPH09316389A (en) | 1997-12-09 |
Family
ID=15217877
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13826496A Pending JPH09316389A (en) | 1996-05-31 | 1996-05-31 | Water-based coating composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH09316389A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011068765A (en) * | 2009-09-25 | 2011-04-07 | Kikusui Chemical Industries Co Ltd | Aggregate-containing emulsion coating material |
JP2013203986A (en) * | 2012-03-29 | 2013-10-07 | Sekisui Plastics Co Ltd | Method for producing resin particle and product of the same |
-
1996
- 1996-05-31 JP JP13826496A patent/JPH09316389A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011068765A (en) * | 2009-09-25 | 2011-04-07 | Kikusui Chemical Industries Co Ltd | Aggregate-containing emulsion coating material |
JP2013203986A (en) * | 2012-03-29 | 2013-10-07 | Sekisui Plastics Co Ltd | Method for producing resin particle and product of the same |
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