JP2531124B2 - Method for producing resin aqueous dispersion - Google Patents
Method for producing resin aqueous dispersionInfo
- Publication number
- JP2531124B2 JP2531124B2 JP6057830A JP5783094A JP2531124B2 JP 2531124 B2 JP2531124 B2 JP 2531124B2 JP 6057830 A JP6057830 A JP 6057830A JP 5783094 A JP5783094 A JP 5783094A JP 2531124 B2 JP2531124 B2 JP 2531124B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- water
- alkyl group
- unsaturated alkyl
- reaction
- 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.)
- Expired - Fee Related
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は水性塗料組成物に使用可
能な樹脂水性分散体の製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing an aqueous resin dispersion that can be used in an aqueous coating composition.
【０００２】[0002]
【従来の技術】アクリル系樹脂を主成分とする塗料に
は、乳化重合反応により合成される樹脂エマルジョンを
用いたものが、常温乾燥型塗料として建築用や家庭用等
に広く普及している。またアクリル系樹脂の他のタイプ
として、コロイダルディスパージョン型、水溶性型ある
いはこれらの中間に位置すると見られる各種のいわゆる
ハイブリッド型水性塗料があり、工業用として常温乾燥
並びに焼付塗装に供されている。水溶性型の塗料は、造
膜性、塗膜光沢、貯蔵安定性に優れてはいるが、塗装作
業性に劣るといわれ、たれ易く厚膜塗装に適さず、はけ
塗りやローラー塗り適性にも劣るという本質的欠点が指
摘されるため、水分散型樹脂を主体とする塗料に関心が
移っている。2. Description of the Related Art A paint containing an acrylic resin as a main component, which uses a resin emulsion synthesized by an emulsion polymerization reaction, is widely used as a room-temperature-drying paint for construction, household use and the like. As other types of acrylic resin, there are colloidal dispersion type, water-soluble type, and various so-called hybrid type water-based paints that are considered to be positioned in between, colloidal dispersion type, which are industrially used for room temperature drying and baking coating. . Although water-soluble paints are excellent in film-forming property, coating gloss and storage stability, they are said to be inferior in coating workability. They are easy to drip and are not suitable for thick film coating, and are suitable for brush coating and roller coating. Since the essential disadvantage of being inferior is pointed out, interest is shifting to paints mainly composed of water-dispersible resins.
【０００３】水分散型塗料の１つに、水溶性アクリル樹
脂を造膜成分兼乳化剤として、疎水性アクリル樹脂を強
制乳化させて得られる樹脂水性分散体を主成分とするタ
イプの塗料が研究されている。このものは水溶性型の特
長である造膜性、光沢の良さに加えて、塗装作業性、特
に厚膜塗装適性、はけ塗り、ローラー塗り適性、スプレ
ー塗装での微粒化の良さ、さらには乾燥が速いといった
分散型塗料のもつ長所を合せもつという特徴があり、酸
化硬化型塗料およびアミノプラスト樹脂やフェノール樹
脂、ブロックイソシアネート化合物などと組合せ、焼付
型塗料として検討されている。酸化硬化型塗料として使
用する場合、用いるアクリル樹脂はアクリル樹脂骨格の
側鎖部に、酸化重合性の基、例えば不飽和脂肪酸基、ア
リル基、ジシクロペンテニル基などの不飽和アルキル基
を導入したものが使用対象となる。As one of the water-dispersion type paints, a type of paint whose main component is a resin aqueous dispersion obtained by forcibly emulsifying a hydrophobic acrylic resin using a water-soluble acrylic resin as a film forming component and an emulsifier ing. In addition to the water-soluble type's features of film-forming property and gloss, this product has coating workability, especially thick film coating suitability, brush coating, roller coating suitability, atomization by spray coating, and further It is characterized by having the advantages of the dispersion type paint that it dries quickly, and is being studied as a baking type paint in combination with an oxidative curing type paint and aminoplast resin, phenol resin, blocked isocyanate compound, and the like. When used as an oxidation-curable coating, the acrylic resin used has an oxidatively polymerizable group, for example, an unsaturated fatty acid group, an allyl group, or an unsaturated alkyl group such as dicyclopentenyl group, introduced in the side chain portion of the acrylic resin skeleton. Things will be used.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上述の
２種類の樹脂を配合し乳化する樹脂水性分散体には、長
期にわたり懸濁安定性に優れる分散体を得ることが難し
く、貯蔵中に懸濁樹脂粒子が凝集を起こして沈降した
り、巨視的な樹脂相として析離する傾向が強いという問
題点があり、この樹脂水性分散体を塗料用樹脂成分とし
て使用すると、製造後短期間には外観や膜品質上に問題
がないものの、長期間の貯蔵中には艶引け、ブツなどの
塗膜欠陥を生じ、実用面で重大な問題点を残している。However, it is difficult to obtain a dispersion having excellent suspension stability for a long period of time in an aqueous resin dispersion in which the above-mentioned two kinds of resins are mixed and emulsified, and the suspension is suspended during storage. There is a problem that the resin particles tend to aggregate and settle, or have a strong tendency to separate out as a macroscopic resin phase.If this resin aqueous dispersion is used as a resin component for paints, the appearance will be reduced in a short time after production. Although there is no problem in terms of film quality and film quality, coating defects such as glossiness and lumps occur during long-term storage, leaving serious problems in practical use.
【０００５】本発明は上記問題点の解決を計るものであ
って、本発明の目的は、不飽和脂肪酸などの不飽和基を
側鎖に有する水溶性アクリル樹脂ならびに疎水性アクリ
ル樹脂から、酸化硬化型でしかも貯蔵安定性に優れた樹
脂水性分散体を与える製造方法を提供することにある。The present invention is intended to solve the above problems, and an object of the present invention is to oxidize and cure a water-soluble acrylic resin and a hydrophobic acrylic resin having an unsaturated group such as an unsaturated fatty acid in a side chain. It is an object of the present invention to provide a method for producing a resin aqueous dispersion which is a mold and is excellent in storage stability.
【０００６】[0006]
【課題を解決するための手段】本発明は、下記樹脂Ａと
樹脂Ｂとの２０／８０〜９０／１０（重量比）の混合物
にジイソシアネート化合物を加えて、下記粘度測定条件
による粘度が１０〜３００％増粘するように分子間架橋
を行わせ、続いて樹脂の全カルボキシル基の４０〜１０
０モル％の塩基を加えて中和し、攪拌下に水を加えて乳
化分散することを特徴とする樹脂水性分散体の製造方法
である。 樹脂Ａ；樹脂骨格の側鎖部に不飽和アルキル基を全樹脂
中に５〜６０重量％有し、かつ塩基で中和することによ
り水可溶性となり得る酸価２０〜１００、水酸基価４０
〜１５０、数平均分子量１，０００〜１００，０００の
水溶性アクリル樹脂。 樹脂Ｂ；樹脂骨格の側鎖部に不飽和アルキル基を全樹脂
中に５〜６０重量％有し、かつ塩基で中和しても水不溶
性である酸価２０未満、水酸基価４０〜１５０、数平均
分子量１，０００〜１００，０００の疎水性アクリル樹
脂。 粘度測定条件；樹脂固形分６０重量％のメチルイソブチ
ルケトン溶液とし、温度２０℃で測定する。According to the present invention, a diisocyanate compound is added to a mixture of the following resin A and resin B in a ratio of 20/80 to 90/10 (weight ratio) to give a viscosity of 10 to 10 under the following viscosity measurement conditions. Intermolecular cross-linking is performed to increase the viscosity by 300%, and then 40 to 10 of all carboxyl groups of the resin
This is a method for producing an aqueous resin dispersion, which comprises adding 0 mol% of a base for neutralization, and adding water under stirring for emulsion dispersion. Resin A: An unsaturated alkyl group in the side chain portion of the resin skeleton in an amount of 5 to 60% by weight based on the total resin, and an acid value of 20 to 100 and a hydroxyl value of 40 which may be water-soluble by neutralizing with a base.
-150, a water-soluble acrylic resin having a number average molecular weight of 1,000 to 100,000. Resin B; having an unsaturated alkyl group in the side chain of the resin skeleton in an amount of 5 to 60% by weight based on the whole resin, and water-insoluble even when neutralized with a base, an acid value of less than 20, a hydroxyl value of 40 to 150, A hydrophobic acrylic resin having a number average molecular weight of 1,000 to 100,000. Viscosity measurement conditions: Measured at a temperature of 20 ° C. with a methyl isobutyl ketone solution having a resin solid content of 60% by weight.
【０００７】本発明の樹脂水性分散体の製造方法に用い
られる樹脂Ａならびに樹脂Ｂは、α，βエチレン性単量
体の重合体を樹脂骨核として有している。α，βエチレ
ン性単量体としては、一般のアクリル系樹脂の製造に使
用される全ての単量体が使用可能であり、たとえばアク
リル酸、メタクリル酸、イタコン酸、クロトン酸、マレ
イン酸などに代表されるカルボキシル基含有単量体、ア
クリル酸ヒドロキシエチル、メタクリル酸ヒドロキシエ
チル、アクリル酸ヒドロキシプロピル、メタクリル酸ヒ
ドロキシプロピル、Ｎ−メチロールアクリルアミド、Ｎ
−メチロールメタクリルアミドなどに代表されるヒドロ
キシル基含有単量体、下記式The resin A and the resin B used in the method for producing an aqueous resin dispersion of the present invention have a polymer of α, β ethylenic monomer as a resin nucleus. As the α, β ethylenic monomer, all monomers used in the production of general acrylic resins can be used. For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, etc. Representative carboxyl group-containing monomers, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-methylol acrylamide, N
A hydroxyl group-containing monomer represented by methylol methacrylamide, the following formula
【化１】 （式中、Ｒ1はＨまたはＣＨ3を示し、Ｒ2はＣnＨ2n+1、
但し、ｎは１≦ｎ≦１８の整数で示されるアルキル基を
示す。）で表わされるアクリル酸エステル、メタクリル
酸エステル類などがある。このほか、アクリロニトリ
ル、メタクリロニトリル、アクリルアミド、メタクリル
アミド、Ｎ−メトキシアクリルアミド、Ｎ−メトキシメ
タクリルアミド、アリルアクリレート、アリルメタクリ
レート、スチレン、ビニルトルエン、グリシジルメタク
リレート、ジシクロペンテニルメタクリレートなどがあ
げられる。Embedded image (In the formula, R 1 represents H or CH 3 , R 2 represents C n H 2n + 1 ,
However, n represents an alkyl group represented by an integer of 1 ≦ n ≦ 18. ) Acrylic acid ester and methacrylic acid ester represented by In addition, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-methoxyacrylamide, N-methoxymethacrylamide, allyl acrylate, allyl methacrylate, styrene, vinyltoluene, glycidyl methacrylate, dicyclopentenyl methacrylate and the like can be mentioned.
【０００８】本発明で用いられる樹脂Ａならびに樹脂Ｂ
は、上述の単量体類を重合して得られる樹脂骨格を有す
るが、その骨格の側鎖部に酸化硬化性を有する不飽和ア
ルキル基が導入されている。不飽和アルキル基と骨格と
の結合形態は特に限定されないが、経済的かつ容易に製
造可能なものとして次の（１）〜（４）のものが例示で
きる。Resin A and Resin B used in the present invention
Has a resin skeleton obtained by polymerizing the above-mentioned monomers, and an unsaturated alkyl group having oxidative curability is introduced into the side chain portion of the skeleton. The bond form between the unsaturated alkyl group and the skeleton is not particularly limited, but the following (1) to (4) can be exemplified as those which can be produced economically and easily.
【化２】 （式中、Ｒ1はＨまたはＣＨ3、Ｒ3は不飽和アルキル基
を示す。）Embedded image (In the formula, R 1 represents H or CH 3 , and R 3 represents an unsaturated alkyl group.)
【０００９】不飽和アルキル基としては、乾性油脂肪
酸、半乾性油脂肪酸、脱水ヒマシ油脂肪酸などの不飽和
脂肪酸を起源とする不飽和アルキル基、アリル基または
ジシクロペンテニル基が好ましく、これらは１種以上の
ものが含まれていてもよい。The unsaturated alkyl group is preferably an unsaturated alkyl group derived from an unsaturated fatty acid such as a dry oil fatty acid, a semi-dry oil fatty acid, or a dehydrated castor oil fatty acid, an allyl group or a dicyclopentenyl group. More than one species may be included.
【００１０】上記（１）はアクリル酸またはメタクリル
酸を含むアクリル樹脂を製造後、これに不飽和脂肪酸の
グリシジルエステルを反応させるか、またはグリシジル
アクリレートもしくはグリシジルメタクリレートに不飽
和脂肪酸を反応させた単量体を予め合成し、これと他の
共重合性単量体とを重合させて容易に製造される。
（２）は（１）の不飽和脂肪酸のグリシジルエステルに
代えて、不飽和アルコールのグリシジルエーテル類を用
い、（１）と同様の手法によって容易に製造し得る。
（３）は不飽和脂肪酸とＮ−メチルモノエタノールアミ
ンとから得られる下記成分とカルボン酸含有アクリル樹
脂とから脱水エステル化反応により容易に製造すること
ができる。 Ｒ3ＣＯＯＮ（ＣＨ3）ＣＨ2ＣＨ2ＯＨ （式中、Ｒ3は不飽和アルキル基を示す。） （４）は不飽和アルコールのアクリル酸またはメタクリ
ル酸エステル系単量体と他の単量体との共重合により容
易に製造される。上記のアクリル樹脂は単量体を溶液重
合、乳化重合、懸濁重合、塊状重合など公知の重合反応
によって重合することにより製造される。The above (1) is a unit amount obtained by producing an acrylic resin containing acrylic acid or methacrylic acid and then reacting this with a glycidyl ester of an unsaturated fatty acid, or by reacting glycidyl acrylate or glycidyl methacrylate with an unsaturated fatty acid. It is easily manufactured by preliminarily synthesizing a body and polymerizing it with another copolymerizable monomer.
(2) can be easily produced in the same manner as in (1) by using glycidyl ethers of unsaturated alcohol in place of the glycidyl ester of unsaturated fatty acid of (1).
(3) can be easily produced from the following components obtained from unsaturated fatty acids and N-methylmonoethanolamine and a carboxylic acid-containing acrylic resin by a dehydration esterification reaction. R 3 COON (CH 3 ) CH 2 CH 2 OH (In the formula, R 3 represents an unsaturated alkyl group.) (4) is an acrylic acid or methacrylic acid ester monomer of an unsaturated alcohol and another monomer. Easily produced by copolymerization with the body. The above acrylic resin is produced by polymerizing a monomer by a known polymerization reaction such as solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization.
【００１１】本発明において、樹脂Ａは塩基により中和
することにより、水に安定に溶解する程度の極性を有
し、酸価が２０〜１００、水酸基価が４０〜１５０、数
平均分子量が１，０００〜１００，０００の範囲にある
ものが対象となる。酸価２０未満では水溶性に乏しく、
樹脂Ｂを安定に乳化することができず、また、１００を
越える場合、塗料組成物としたとき塗膜の耐水性を損な
い好ましくない。樹脂Ａ中の水酸基はジイソシアネート
化合物との反応点として不可欠なものであり、水酸基価
が４０未満では反応点として不足し、１５０を越えると
塗膜の耐水性に悪影響を与え好ましくない。樹脂Ａの分
子量は数平均分子量で、１，０００未満では塗膜の耐久
性に不安があり、一方、１００，０００を越えると乳化
工程での樹脂粘度が過度に高まり、製造工程に負荷がか
かり現実的ではない。In the present invention, the resin A has such a polarity that it can be stably dissolved in water by being neutralized with a base, has an acid value of 20 to 100, a hydroxyl value of 40 to 150, and a number average molecular weight of 1 Those in the range of 1,000 to 100,000 are targeted. If the acid value is less than 20, the water solubility is poor,
Resin B cannot be stably emulsified, and when it exceeds 100, it is not preferable because the coating composition is impaired in water resistance of the coating film. The hydroxyl group in the resin A is indispensable as a reaction point with the diisocyanate compound. If the hydroxyl value is less than 40, it will be insufficient as a reaction point, and if it exceeds 150, the water resistance of the coating film will be adversely affected, which is not preferable. The molecular weight of the resin A is a number average molecular weight. If it is less than 1,000, the durability of the coating film may be uncertain, while if it exceeds 100,000, the resin viscosity in the emulsification step is excessively increased, which imposes a load on the production step. Not realistic.
【００１２】本発明の樹脂Ｂは極性の低い疎水性アクリ
ル樹脂からなり、樹脂水性分散体中の分散相成分を構成
する。樹脂Ｂは酸価が２０未満、水酸基価が４０〜１５
０、数平均分子量が１，０００〜１００，０００の樹脂
が対象となる。酸価２０以上では親水性が強く、分散相
を形成し難く好ましくない。水酸基価ならびに数平均分
子量は、前述の樹脂Ａの場合と同じ理由により上記範囲
が重要となる。The resin B of the present invention comprises a hydrophobic acrylic resin having a low polarity and constitutes a disperse phase component in the resin aqueous dispersion. Resin B has an acid value of less than 20 and a hydroxyl value of 40 to 15
Resins having a number average molecular weight of 0 and 1,000 to 100,000 are targeted. When the acid value is 20 or more, the hydrophilicity is strong and it is difficult to form a dispersed phase, which is not preferable. The above range is important for the hydroxyl value and the number average molecular weight for the same reason as in the case of the resin A.
【００１３】本発明に用いる樹脂Ａおよび樹脂Ｂは、樹
脂中に占める不飽和アルキル基の重量比率が５〜６０重
量％の範囲にあることが必須の条件である。不飽和アル
キル基、アリル基またはジシクロペンテニル基の重量比
率が５重量％未満では酸化重合反応の反応点が不足し、
耐久性のある塗膜が得難く、また６０重量％を越えて導
入されると、逆に過度な重合反応が進み塗膜をもろくし
好ましくない。The resin A and the resin B used in the present invention have an essential condition that the weight ratio of the unsaturated alkyl group in the resin is in the range of 5 to 60% by weight. If the weight ratio of the unsaturated alkyl group, the allyl group or the dicyclopentenyl group is less than 5% by weight, the reaction points of the oxidative polymerization reaction are insufficient,
It is difficult to obtain a durable coating film, and when it is introduced in an amount of more than 60% by weight, on the contrary, an excessive polymerization reaction proceeds to make the coating film brittle, which is not preferable.
【００１４】樹脂水性分散体を構成する樹脂Ａと樹脂Ｂ
の比率は重量比で２０／８０〜９０／１０の範囲とする
ことが必要である。樹脂Ａが２０重量％未満では、乳化
剤としての量的不足から微細で安定な懸濁体が得られ
ず、また９０重量％を越える場合は製造上には何ら問題
はないが、樹脂Ａ単独の水溶液に極めて近い性質の樹脂
水性分散体となり、利用価値が乏しく意味をなさない。Resin A and Resin B constituting the resin aqueous dispersion
It is necessary that the weight ratio be within the range of 20/80 to 90/10. If the amount of Resin A is less than 20% by weight, a fine and stable suspension cannot be obtained due to a lack of quantity as an emulsifier, and if it exceeds 90% by weight, there is no problem in production. It becomes a resin aqueous dispersion having properties very similar to an aqueous solution, and its utility value is poor and does not make sense.
【００１５】本発明の樹脂水性分散体の製造方法では、
上記の樹脂Ａおよび樹脂Ｂの２種類の樹脂混合物に少量
のジイソシアネート化合物を反応させ、樹脂Ａと樹脂Ｂ
の一部を化学的に架橋した構造を有する架橋成分とし、
その架橋成分と樹脂Ａとの乳化力により、樹脂Ｂを安定
に乳化分散させる。In the method for producing an aqueous resin dispersion of the present invention,
A small amount of a diisocyanate compound is reacted with the above-mentioned two kinds of resin mixture of resin A and resin B to form resin A and resin B.
As a crosslinking component having a structure in which a part of is chemically crosslinked,
The emulsifying power of the cross-linking component and the resin A allows the resin B to be stably emulsified and dispersed.
【００１６】ジイソシアネート化合物は、その使用量が
少量であり、かつ２つの樹脂を架橋する働きだけである
ため、特に構造を限定する必要はない。ジイソシアネー
ト化合物として市販され、容易に使用し得る代表的なも
のとしては、トリレンジイソシアネート、ジフェニルメ
タンジイソシアネート、ナフチレンジイソシアネート、
ヘキサメチレンジイソシアネート、イソホロンジイソシ
アネート、２，２，４−トリメチルヘキサメチレンジイ
ソシアネート、キシリレンジイソシアネート、ジシクロ
ヘキシルメタジイソシアネート、リジンジイソシアネー
トなどが例示される。勿論上記例示以外のものであって
も１分子中に２個のイソシアネート基を有するものは全
て使用可能であり、また２個以上のイソシアネート基を
有するものもこれらに組み合せて用いることが可能であ
る。Since the diisocyanate compound is used in a small amount and only functions to crosslink two resins, it is not necessary to particularly limit the structure. Commercially available as a diisocyanate compound, as typical ones that can be easily used, tolylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, dicyclohexyl metadiisocyanate, lysine diisocyanate and the like are exemplified. Of course, other than those exemplified above, those having two isocyanate groups in one molecule can all be used, and those having two or more isocyanate groups can also be used in combination. .
【００１７】ジイソシアネート化合物の使用量は、ジイ
ソシアネート化合物反応後の下記粘度測定条件下で測定
された樹脂粘度が、反応前の樹脂混合物の同測定条件下
での樹脂粘度に比べて１０〜３００％高くなるような量
とする。 粘度測定条件 樹脂をメチルイソブチルケトンに溶解して固形分６０％
の溶液とし、２０℃にてＢ型粘度計で測定する。The amount of the diisocyanate compound used is such that the resin viscosity measured under the following viscosity measurement conditions after the reaction of the diisocyanate compound is 10 to 300% higher than the resin viscosity of the resin mixture before the reaction under the same measurement conditions. The amount should be Viscosity measurement conditions Resin is dissolved in methyl isobutyl ketone and solid content is 60%
And a B-type viscometer at 20 ° C.
【００１８】増粘率が１０％未満では、ジイソシアネー
ト処理のない従来の樹脂水性分散体と大差なくて貯蔵安
定性改善効果に乏しく、３００％を越えて増粘させると
反応中にゲル化を起こすなど、製造上の問題を生じ易く
適当ではない。If the viscosity increase rate is less than 10%, there is little difference from the conventional resin aqueous dispersion without diisocyanate treatment, and the effect of improving storage stability is poor, and if the viscosity exceeds 300%, gelation occurs during the reaction. However, it is not suitable because it easily causes manufacturing problems.
【００１９】ジイソシアネート化合物の反応は、まず樹
脂Ａおよび樹脂Ｂを均一に混合し、温度を室温〜１５０
℃、望ましくは５０〜１２０℃に加熱し、攪拌しながら
ジイソシアネート化合物を滴下し、滴下後１〜６時間程
度、同一温度で攪拌を続けることにより行われる。樹脂
Ａおよび樹脂Ｂはいずれも一般にその分子量から相当粘
度の高いものであり、無溶剤で上記の混合ならびに反応
を進めることは難しく、通常イソシアネート化合物と反
応性のない有機溶剤に溶解し、樹脂溶液として取扱う
が、ジイソシアネート化合物についても必要により、ジ
イソシアネートと反応性のない有機溶剤に溶解して反応
に用いてもよい。この目的に用いる溶剤としては、一般
に活性水素を持たない溶剤、例えばエーテル類、ケトン
類、エステル類、炭化水素類などが適している。水溶性
のない溶剤を使用する場合は、反応後減圧ないし凍結乾
燥等により、樹脂の乳化を阻害しない程度まで脱溶剤す
る必要がある。脱溶剤後、粘度を下げて取扱いを容易に
するために、改めて親水性の有機溶剤を加えてもよい。
しかし水性塗料組成物としての本来の意味から、可能な
限り溶剤量を制限することが望ましく、通常最終樹脂１
００部に対して６０〜７０部がその上限である。In the reaction of the diisocyanate compound, first, the resin A and the resin B are uniformly mixed, and the temperature is from room temperature to 150.
It is carried out by heating to 50 ° C., preferably 50 to 120 ° C., dropping the diisocyanate compound while stirring, and continuing stirring at the same temperature for about 1 to 6 hours after dropping. Both the resin A and the resin B are generally highly viscous due to their molecular weights, and it is difficult to proceed the above mixing and reaction without a solvent, and the resin is usually dissolved in an organic solvent that is not reactive with an isocyanate compound to give a resin solution. However, if necessary, the diisocyanate compound may be dissolved in an organic solvent which is not reactive with diisocyanate and used for the reaction. As a solvent used for this purpose, a solvent having no active hydrogen is generally suitable, for example, ethers, ketones, esters, hydrocarbons and the like. When a water-insoluble solvent is used, it is necessary to remove the solvent by post-reaction pressure reduction or freeze-drying to the extent that it does not hinder the emulsification of the resin. After removing the solvent, a hydrophilic organic solvent may be added again in order to reduce the viscosity and facilitate handling.
However, from the original meaning as an aqueous coating composition, it is desirable to limit the amount of solvent as much as possible, and usually the final resin 1
The upper limit is 60 to 70 parts with respect to 00 parts.
【００２０】上記のようにして製造された樹脂混合物に
対し、そのカルボキシル基の４０〜１００モル％に相当
する塩基を加えて中和し、しかるのち充分に攪拌しなが
ら水を徐々に加えて樹脂水性分散体とする。塩基として
は、塗料業界で一般に使用されるアルキルアミン類、ア
ルカノールアミン類、アンモニアなどが適している。中
和率が４０モル％未満では樹脂の親水性が不足し、充分
な乳化力が期待できない。また１００モル％を越えて用
いてもそれによる利点はない。樹脂混合物の粘度が高い
場合には、乳化に当り加温して系の温度を２５℃から約
９０℃に上げ乳化することも可能である。さらにオート
クレーブ等の耐圧密閉容器を使用すれば、乳化温度をさ
らに高くすることができる。The resin mixture prepared as described above is neutralized by adding a base corresponding to 40 to 100 mol% of the carboxyl groups, and then water is gradually added to the resin mixture with sufficient stirring. Use as an aqueous dispersion. Suitable bases are alkylamines, alkanolamines, ammonia and the like which are commonly used in the paint industry. If the neutralization rate is less than 40 mol%, the hydrophilicity of the resin will be insufficient and sufficient emulsifying power cannot be expected. Further, even if it is used in excess of 100 mol%, there is no advantage. When the viscosity of the resin mixture is high, it is possible to raise the temperature of the system from 25 ° C. to about 90 ° C. during emulsification to emulsify. Furthermore, if a pressure-resistant closed container such as an autoclave is used, the emulsification temperature can be further increased.
【００２１】本発明で得られる樹脂水性分散体は不飽和
基を有するため、酸化硬化型塗料組成物として使用でき
る。この場合一般の硬化剤は不要で、上記成分に加え
て、さらに酸化重合を促進するための、いわゆるドライ
ヤーと呼ばれる各種の金属塩、金属錯体等を組合せて使
用されるクリヤー塗料として、または顔料を配合したエ
ナメル塗料として使用できる。Since the resin aqueous dispersion obtained in the present invention has an unsaturated group, it can be used as an oxidation-curable coating composition. In this case, a general curing agent is not necessary, and in addition to the above-mentioned components, various metal salts called so-called dryers, which are used in combination with various metal salts so-called dryers, metal complexes, etc., or as a clear coating, or a pigment is used. Can be used as a blended enamel paint.
【００２２】[0022]
【発明の効果】本発明によれば、水溶性アクリル樹脂と
疎水性アクリル樹脂とから樹脂水性分散体を製造するに
当り、両樹脂分子の一部をジイソシアネート化合物によ
り架橋するという新規な処理を加えるとともに、上記水
溶性アクリル樹脂および疎水性アクリル樹脂として不飽
和基を有する樹脂を使用することにより、酸化硬化性を
有し、かつ貯蔵安定性に優れ、長期貯蔵や加温下での貯
蔵において安定で、光沢、外観性、塗装作業性などに優
れる水性塗料組成物として使用可能な樹脂水性分散体が
得られる。According to the present invention, when a resin aqueous dispersion is produced from a water-soluble acrylic resin and a hydrophobic acrylic resin, a novel treatment of crosslinking a part of both resin molecules with a diisocyanate compound is added. In addition, by using a resin having an unsaturated group as the above-mentioned water-soluble acrylic resin and hydrophobic acrylic resin, it has an oxidative curing property and is excellent in storage stability, and is stable in long-term storage and storage under heating. Thus, an aqueous resin dispersion that can be used as an aqueous coating composition having excellent gloss, appearance, and coating workability can be obtained.
【００２３】[0023]
【実施例】以下実施例をもって本発明の内容をさらに詳
述する。なお、各例中％および部は、重量％および重量
部を示す。EXAMPLES The contents of the present invention will be described in more detail with reference to the following examples. In addition,% and part in each example show weight% and weight part.
【００２４】（１）樹脂Ａの製造 温度計、還流冷却器、窒素ガス導入管、攪拌機を装備し
たガラス製フラスコに、表１のＡ（１）に示す配合比に
従い、反応溶剤としてメチルイソブチルケトン３６．０
部を入れ、窒素ガスを通気しながら、１１５〜１２０℃
に加熱した。攪拌下に、アクリル酸７．３部、２−ヒド
ロキシエチルメタクリレート６．０部、ｎ−ブチルメタ
アクリレート１９．７部、スチレン９．０部、ｔ−ブチ
ルペルオキシ−２−エチルヘキサノエート１．７部の混
合溶液を、約２時間を要して添加した。約１時間攪拌
後、ｔ−ブチルペルオキシ−２−エチルヘキサノエート
０．２部、メチルイソブチルケトン２．０部からなる溶
液を約５分を要して滴下した。滴下後さらに約３時間攪
拌を続け、高酸価アクリル樹脂を合成し、続いて２段目
の反応として、このアクリル樹脂溶液に表１の原料
（２）に示す脱水ヒマシ油脂肪酸グリシジルエステル１
８．０部および反応触媒としてトリエチルアミン０．１
部を加え、１２０〜１３０℃の反応温度にて攪拌しなが
ら３時間反応させ、側鎖に不飽和アルキル基を有する樹
脂Ａ（１）を得た。樹脂特性値を表１に示す。(1) Production of Resin A A glass flask equipped with a thermometer, a reflux condenser, a nitrogen gas inlet tube, and a stirrer was charged with methyl isobutyl ketone as a reaction solvent according to the compounding ratio shown in A (1) of Table 1. 36.0
Part, and ventilating nitrogen gas, 115-120 ℃
Heated to. With stirring, 7.3 parts of acrylic acid, 6.0 parts of 2-hydroxyethyl methacrylate, 19.7 parts of n-butyl methacrylate, 9.0 parts of styrene, t-butylperoxy-2-ethylhexanoate. 7 parts of the mixed solution was added over about 2 hours. After stirring for about 1 hour, a solution containing 0.2 part of t-butylperoxy-2-ethylhexanoate and 2.0 parts of methyl isobutyl ketone was added dropwise over about 5 minutes. After the dropwise addition, stirring was continued for about 3 hours to synthesize a high acid value acrylic resin, and then, as a second step reaction, dehydrated castor oil fatty acid glycidyl ester 1 shown in the raw material (2) of Table 1 was added to this acrylic resin solution.
8.0 parts and triethylamine 0.1 as reaction catalyst
Parts were added, and the mixture was reacted at a reaction temperature of 120 to 130 ° C. for 3 hours with stirring to obtain a resin A (1) having an unsaturated alkyl group in its side chain. The resin characteristic values are shown in Table 1.
【００２５】同様にして表１に示すＡ（２）、Ａ（３）
の配合に基づき、それぞれの高酸価アクリル樹脂を合成
し、さらにそれぞれの不飽和脂肪酸グリシジルエステル
を反応させて側鎖に不飽和アルキル基を有する水溶性ア
クリル樹脂Ａ（２）、Ａ（３）を得た。また、表１の原
料（１）のＡ（４）の配合に基づき、反応溶剤としてエ
チレングリコールジメチルエーテルを用いた他は上記と
同様の合成方法により高酸価アクリル樹脂を合成し、次
に表１の原料（２）のＡ（４）に記載のメチルモノエタ
ノールアミンとサフラワー油脂肪酸とのアミド化物を混
合し、１３５〜１５０℃で約５時間、脱水エステル化反
応を行い、不飽和アルキル基を側鎖に有する水溶性アク
リル樹脂Ａ（４）を得た。なお、表１中Ａ（４）の固形
分値が８０％となっているのは、脱水エステル化に際
し、反応水と同時にエチレングリコールジメチルエーテ
ルの一部が溜出するため、反応終了後に固形分を８０％
に再調整したためである。Similarly, A (2) and A (3) shown in Table 1 are shown.
Water-soluble acrylic resin A (2), A (3) which has unsaturated acid group in side chain by synthesizing each high acid value acrylic resin and further reacting each unsaturated fatty acid glycidyl ester Got In addition, a high acid value acrylic resin was synthesized by the same synthetic method as above except that ethylene glycol dimethyl ether was used as a reaction solvent based on the blending of A (4) of the raw material (1) in Table 1. Of the raw material (2), A (4), mixed with an amidated product of methylmonoethanolamine and safflower oil fatty acid, and subjected to dehydration esterification reaction at 135 to 150 ° C. for about 5 hours to obtain an unsaturated alkyl group. A water-soluble acrylic resin A (4) having a in the side chain was obtained. In addition, the solid content value of A (4) in Table 1 is 80% because a part of ethylene glycol dimethyl ether is distilled out at the same time as the reaction water during dehydration esterification. 80%
Because it was readjusted to.
【００２６】[0026]
【表１】 [Table 1]
【００２７】（２）樹脂Ｂの製造 前項（１）のＡ（１）〜Ａ（３）と同様にして、表２の
原料（１）に示す配合に基づきアクリル樹脂を合成し、
続いて原料（２）を加えて２段目の反応を行い、不飽和
アルキル基を有する樹脂Ｂ（１）、Ｂ（３）を得た。ま
た、原料（１）のアクリルモノマーとしてグリシジルメ
タクリレートを用い、２段目の反応に不飽和脂肪酸を用
いた他は合成条件はＢ（１）、Ｂ（３）と全く同一の方
法で不飽和アルキル基を有する樹脂Ｂ（２）を得た。さ
らに、反応溶剤をメチルイソブチルケトンに代えてエチ
レングリコールジメチルエーテルを用いた他は前項
（１）と同様にして樹脂Ｂ（４）を得た。(2) Production of Resin B In the same manner as A (1) to A (3) in the above item (1), an acrylic resin was synthesized based on the composition shown in the raw material (1) of Table 2,
Subsequently, the raw material (2) was added and the second stage reaction was carried out to obtain resins B (1) and B (3) having an unsaturated alkyl group. In addition, except that glycidyl methacrylate was used as the acrylic monomer of the raw material (1) and unsaturated fatty acid was used in the reaction in the second step, the synthesis conditions were exactly the same as those for B (1) and B (3), and the unsaturated alkyl was used. A resin B (2) having a group was obtained. Further, a resin B (4) was obtained in the same manner as in the above item (1) except that ethylene glycol dimethyl ether was used instead of methyl isobutyl ketone as the reaction solvent.
【００２８】[0028]
【表２】 [Table 2]
【００２９】実施例１ 前記（１）の樹脂Ａの製造と同一の樹脂合成装置を用
い、樹脂Ａ（１）５５部、樹脂Ｂ（１）４５部をフラス
コに取り、９０〜１１０℃に加温攪拌しながら、これに
ヘキサメチレンジイソシアネート０．３６部とメチルイ
ソブチルケトン３．６部からなるジイソシアネート溶液
を約５分間を要して滴下し、滴下後１時間同温度に保っ
た。反応終了後、固形分を６０％に調整し、反応開始前
の樹脂混合物の粘度と比較したところ、温度２０℃での
粘度が１２４０センチポイズから１９００センチポイズ
に上昇した。Example 1 55 parts of Resin A (1) and 45 parts of Resin B (1) were placed in a flask and heated to 90 to 110 ° C. using the same resin synthesizing apparatus as used for the production of Resin A in (1) above. A diisocyanate solution consisting of 0.36 part of hexamethylene diisocyanate and 3.6 parts of methyl isobutyl ketone was added dropwise to the mixture while warm stirring for about 5 minutes, and the temperature was kept at the same temperature for 1 hour after the addition. After completion of the reaction, the solid content was adjusted to 60% and compared with the viscosity of the resin mixture before the start of the reaction, the viscosity at a temperature of 20 ° C. increased from 1240 centipoises to 1900 centipoises.
【００３０】反応物を８０〜９０℃に保ち、減圧操作に
よりメチルイソブチルケトンのほぼ全量を系外に抜き取
り、新たに希釈溶剤として３−メチル−３−メトキシブ
タノール１０．５部を加え、固形分約８５％の樹脂を得
た。次にこの樹脂に４０℃でトリエチルアミン２．６部
を加え、均一に混合した後、強力な卓上攪拌機を用いて
攪拌しながら脱イオン水８４．９部を徐々に加え、固形
分３８％で透明感のある乳白色樹脂水性分散体を得た。The reaction product was kept at 80 to 90 ° C., and almost all the amount of methyl isobutyl ketone was taken out of the system by depressurizing operation, and 10.5 parts of 3-methyl-3-methoxybutanol was newly added as a diluting solvent to obtain a solid content. About 85% resin was obtained. Next, 2.6 parts of triethylamine was added to this resin at 40 ° C., and after uniformly mixing, 84.9 parts of deionized water was gradually added to the resin while stirring with a powerful bench stirrer, and the solid content was 38% and transparent. A milky white resin aqueous dispersion having a feeling was obtained.
【００３１】上記樹脂水性分散体を室温で６ケ月貯蔵し
たが、樹脂の凝集や沈降物の発生等が認められず、貯蔵
安定性に優れていた。また、加温下での貯蔵安定性を評
価するため４０℃で１ケ月間貯蔵したが、凝集や沈降物
の発生を認めず、安定性に富むことが確認された。ジイ
ソシアネート添加反応前後の粘度、増粘の度合、樹脂水
性分散体の固形分、外観、貯蔵安定性の結果を表３に示
す。When the above resin aqueous dispersion was stored at room temperature for 6 months, no agglomeration of resin or generation of sediment was observed, and the storage stability was excellent. Further, in order to evaluate the storage stability under heating, the product was stored at 40 ° C. for 1 month, but no aggregation or sedimentation was observed and it was confirmed that the product was highly stable. Table 3 shows the results of the viscosity before and after the diisocyanate addition reaction, the degree of thickening, the solid content of the resin aqueous dispersion, the appearance, and the storage stability.
【００３２】実施例２〜３ 表３に示される実施例２〜３のそれぞれの配合に基づ
き、実施例１と全く同じ方法で、実施例２〜３の樹脂水
性分散体を得た。ジイソシアネート添加反応前後の粘
度、増粘の度合、樹脂水性分散体の固形分、外観、貯蔵
安定性評価の結果を表３に示す。いずれの樹脂水性分散
体も貯蔵安定性に優れるものであった。Examples 2 to 3 Based on the respective formulations of Examples 2 to 3 shown in Table 3, the resin aqueous dispersions of Examples 2 to 3 were obtained in exactly the same manner as in Example 1. Table 3 shows the results of evaluation of the viscosity before and after the diisocyanate addition reaction, the degree of thickening, the solid content of the resin aqueous dispersion, the appearance, and the storage stability. All the resin aqueous dispersions were excellent in storage stability.
【００３３】実施例４ 前記（１）の水溶性アクリル樹脂の製造で用いたのと同
一の樹脂合成装置を用い、樹脂Ａ（４）６５部、樹脂Ｂ
（４）３５部を用い、イソホロンジイソシアネート０．
６７部とエチレングリコールジメチルエーテル５．０部
のジイソシアネート溶液を用いた他は実施例１と同様に
反応させてジイソシアネート反応物を作り、脱溶剤工程
をすることなく、トリエチルアミン２．８部と脱イオン
水１４３．８部を用いて実施例１と同様に中和し、水分
散化を行い、実施例４の樹脂水性分散体を得た。ジイソ
シアネート添加前後の粘度、増粘の度合、樹脂水性分散
体の固形分、外観、貯蔵安定性評価の結果を表３に示
す。このものも実施例１〜３と同様に貯蔵安定性に優れ
たものであった。Example 4 Using the same resin synthesizing apparatus as used in the production of the water-soluble acrylic resin of (1) above, 65 parts of resin A (4) and resin B were used.
(4) 35 parts of isophorone diisocyanate was used.
A diisocyanate reaction product was prepared in the same manner as in Example 1 except that 67 parts of ethylene glycol dimethyl ether and 5.0 parts of diisocyanate solution were used, and 2.8 parts of triethylamine and deionized water were used without a solvent removal step. Using 143.8 parts, neutralization was carried out in the same manner as in Example 1 to disperse it in water to obtain an aqueous resin dispersion of Example 4. Table 3 shows the results of evaluation of viscosity before and after addition of diisocyanate, degree of thickening, solid content of resin aqueous dispersion, appearance, and storage stability. This was also excellent in storage stability as in Examples 1 to 3.
【００３４】なお、実施例４は反応溶剤としてエチレン
グリコールジメチルエーテルを用いているので、粘度の
測定は初期混合物、ならびに最終反応物のそれぞれを１
００〜１２０℃で減圧脱溶剤し、メチルイソブチルケト
ンにて固形分６０％に希釈して測定した。In Example 4, since ethylene glycol dimethyl ether was used as the reaction solvent, the viscosity was measured by measuring the initial mixture and the final reaction product at 1% respectively.
The solvent was removed under reduced pressure at 00 to 120 ° C., and the solid content was diluted to 60% with methyl isobutyl ketone for measurement.
【００３５】実施例５ 実施例１の樹脂水性分散体の固形分１００部に対し、ル
チル型酸化チタン８０部、ナフテン酸コバルトをコバル
ト金属量として０．０５部、ナフテン酸マンガンを金属
量として０．１部、さらにレベリング剤として信越シリ
コーンＸ−２４−３００５（商品名、信越化学工業
（株）製）０．５部を加え、サンドミルにより顔料分散
した。顔料分散後、トリエチルアミン０．３部を加え、
脱イオン水により約１８００センチポイズに粘度を調整
して酸化硬化型白エナメルを得た。製造直後および２５
℃の恒温室に６ケ月間貯蔵後の白エナメルをリン酸亜鉛
処理鉄板上にはけ塗りし、塗膜性能試験を行った。試験
結果を表４に示す。塗膜性能は貯蔵による影響は全く無
く、貯蔵安定性に優れていた。Example 5 80 parts of rutile-type titanium oxide, 0.05 part of cobalt naphthenate as a cobalt metal amount and 0.05 part of manganese naphthenate as a metal amount relative to 100 parts of the solid content of the resin aqueous dispersion of Example 1. 1 part and 0.5 part of Shin-Etsu Silicone X-24-3005 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a leveling agent were added, and the pigment was dispersed by a sand mill. After dispersing the pigment, add 0.3 parts of triethylamine,
The viscosity was adjusted to about 1800 centipoise with deionized water to obtain an oxidation-curable white enamel. Immediately after production and 25
White enamel after storage for 6 months in a constant temperature chamber at ℃ was brushed on a zinc phosphate-treated iron plate, and a coating film performance test was conducted. Table 4 shows the test results. The coating performance was not affected by storage at all and was excellent in storage stability.
【００３６】実施例６〜８ 実施例５と同様の固形分組成となる白エナメルを実施例
２、３、４の樹脂水性分散体を用いて実施例５と同様に
して製造し、それぞれ実施例６、７、８とした。ただ
し、実施例７に限り、白エナメルの中和用には、トリエ
チルアミンに代えてジメチルアミノエタノール０．２部
を使用した。次に実施例５と同様にそれぞれリン酸亜鉛
処理鉄板上にはけ塗りし、塗膜性能試験を行った。試験
結果を表４に示す。上記実施例６〜８のいずれの場合も
貯蔵による塗膜性能の変化は無く、貯蔵安定性に優れる
ものであった。Examples 6 to 8 White enamel having the same solid content composition as in Example 5 was produced in the same manner as in Example 5 using the resin aqueous dispersions of Examples 2, 3 and 4, and each example was used. It was set to 6, 7, and 8. However, only in Example 7, 0.2 part of dimethylaminoethanol was used instead of triethylamine for neutralizing the white enamel. Next, in the same manner as in Example 5, each of the zinc phosphate-treated iron plates was brush coated and a coating film performance test was conducted. Table 4 shows the test results. In any of the above Examples 6 to 8, there was no change in coating film performance due to storage, and the storage stability was excellent.
【００３７】[0037]
【表３】 [Table 3]
【００３８】[0038]
【表４】 [Table 4]
【００３９】比較例１ 実施例１において、水溶性樹脂と疎水性樹脂の混合物と
ジイソシアネートとの架橋反応のみを省略し、それ以外
の工程ならびに成分量を同じくして実施例１に対応する
樹脂水性分散体を製造し、比較例１の樹脂特性値を表５
に示す。Comparative Example 1 In Example 1, the resin aqueous solution corresponding to Example 1 was used except that the crosslinking reaction between the mixture of the water-soluble resin and the hydrophobic resin and the diisocyanate was omitted, and the other steps and the amounts of components were the same. A dispersion was prepared, and the resin characteristic values of Comparative Example 1 are shown in Table 5.
Shown in
【００４０】比較例２ 比較例１で得られた固形分３８％の樹脂水性分散体を用
い、実施例５と全く同じ方法で、同じ固形分比率の白エ
ナメルを製造し、比較例２とした。比較例２についての
塗膜性能試験結果を表５に示す。Comparative Example 2 Using the resin aqueous dispersion having a solid content of 38% obtained in Comparative Example 1, white enamel having the same solid content ratio was produced in exactly the same manner as in Example 5 to obtain Comparative Example 2. . The coating film performance test results for Comparative Example 2 are shown in Table 5.
【００４１】[0041]
【表５】 [Table 5]
【００４２】表５に示すごとく、ジイソシアネートによ
る処理を施さない比較例１の樹脂水性分散体は、貯蔵中
に樹脂の沈降分離を起こし貯蔵安定性に問題があった。
また、この樹脂水性分散体を用いて製造された比較例２
のエナメルは、貯蔵中に塗膜光沢の著しい低下や、塗面
に凝集物に起因する突起状欠陥、いわゆるブツを多発し
安定性に問題があった。As shown in Table 5, the resin aqueous dispersion of Comparative Example 1 which was not treated with diisocyanate had a problem in storage stability due to sedimentation and separation of the resin during storage.
In addition, Comparative Example 2 produced using this resin aqueous dispersion
The enamel of (1) had a problem in stability because it had a marked decrease in the gloss of the coating film during storage and a large number of projection defects due to agglomerates on the coated surface, so-called spots.
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 Ｃ０８Ｌ 75/14 ＮＧＧ Ｃ０９Ｄ 175/14 ＰＨＵ Ｃ０９Ｄ 175/04 ＰＨＲ Ｃ０８Ｊ 3/03 ＣＦＦ 175/14 ＰＨＵ Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08L 75/14 NGG C09D 175/14 PHU C09D 175/04 PHR C08J 3/03 CFF 175/14 PHU
Claims (3)
０／１０（重量比）の混合物にジイソシアネート化合物
を加えて、下記粘度測定条件による粘度が１０〜３００
％増粘するように分子間架橋を行わせ、続いて樹脂の全
カルボキシル基の４０〜１００モル％の塩基を加えて中
和し、攪拌下に水を加えて乳化分散することを特徴とす
る樹脂水性分散体の製造方法。 樹脂Ａ；樹脂骨格の側鎖部に不飽和アルキル基を全樹脂
中に５〜６０重量％有し、かつ塩基で中和することによ
り水可溶性となり得る酸価２０〜１００、水酸基価４０
〜１５０、数平均分子量１，０００〜１００，０００の
水溶性アクリル樹脂。 樹脂Ｂ；樹脂骨格の側鎖部に不飽和アルキル基を全樹脂
中に５〜６０重量％有し、かつ塩基で中和しても水不溶
性である酸価２０未満、水酸基価４０〜１５０、数平均
分子量１，０００〜１００，０００の疎水性アクリル樹
脂。 粘度測定条件；樹脂固形分６０重量％のメチルイソブチ
ルケトン溶液とし、温度２０℃で測定する。1. 20/80 to 9 of the following resin A and resin B
A diisocyanate compound was added to a mixture of 0/10 (weight ratio) to give a viscosity of 10 to 300 under the following viscosity measurement conditions.
% Of the total carboxyl groups of the resin is added to neutralize, and water is added with stirring to emulsify and disperse. A method for producing an aqueous resin dispersion. Resin A: An unsaturated alkyl group in the side chain portion of the resin skeleton in an amount of 5 to 60% by weight based on the total resin, and an acid value of 20 to 100 and a hydroxyl value of 40 which may be water-soluble by neutralizing with a base.
-150, a water-soluble acrylic resin having a number average molecular weight of 1,000 to 100,000. Resin B; having an unsaturated alkyl group in the side chain of the resin skeleton in an amount of 5 to 60% by weight based on the whole resin, and water-insoluble even when neutralized with a base, an acid value of less than 20, a hydroxyl value of 40 to 150, A hydrophobic acrylic resin having a number average molecular weight of 1,000 to 100,000. Viscosity measurement conditions: Measured at a temperature of 20 ° C. with a methyl isobutyl ketone solution having a resin solid content of 60% by weight.
ネート化合物を加えた配合物の分子間架橋は、温度５０
〜１２０℃で行うものである請求項１記載の樹脂水性分
散体の製造方法。2. Intermolecular cross-linking of a compound obtained by adding a diisocyanate compound to a mixture of resin A and resin B at a temperature of 50.
The method for producing an aqueous resin dispersion according to claim 1, wherein the method is performed at 120 ° C.
が乾性油もしくは半乾性油の脂肪酸または脱水ヒマシ油
脂肪酸を起源とする不飽和アルキル基、アリル基および
ジシクロペンテニル基から選ばれる１種以上のものであ
る請求項１または２記載の樹脂水性分散体の製造方法。3. An unsaturated alkyl group of Resin A and Resin B selected from a fatty acid of a drying oil or a semi-drying oil or an unsaturated alkyl group derived from dehydrated castor oil fatty acid, an allyl group and a dicyclopentenyl group. The method for producing an aqueous resin dispersion according to claim 1 or 2, which is as described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6057830A JP2531124B2 (en) | 1994-03-28 | 1994-03-28 | Method for producing resin aqueous dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6057830A JP2531124B2 (en) | 1994-03-28 | 1994-03-28 | Method for producing resin aqueous dispersion |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61056630A Division JPH0674310B2 (en) | 1986-03-14 | 1986-03-14 | Method for producing resin aqueous dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07118356A JPH07118356A (en) | 1995-05-09 |
| JP2531124B2 true JP2531124B2 (en) | 1996-09-04 |
Family
ID=13066862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6057830A Expired - Fee Related JP2531124B2 (en) | 1994-03-28 | 1994-03-28 | Method for producing resin aqueous dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2531124B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9644704B2 (en) * | 2013-01-29 | 2017-05-09 | Johnson Electric S.A. | Vibration safe motor fixation in an actuator |
| CN107429030A (en) * | 2015-10-27 | 2017-12-01 | 积水化学工业株式会社 | Hardening resin composition and display element |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4003531B2 (en) * | 2002-05-10 | 2007-11-07 | 東亞合成株式会社 | Aqueous polymer composition |
| US7872067B2 (en) * | 2004-06-08 | 2011-01-18 | Basf Aktiengesellschaft | Amphiphilic polymer compositions and their use |
| JP5043391B2 (en) * | 2006-09-21 | 2012-10-10 | 関西ペイント株式会社 | Curable water-based resin composition |
| JP4880413B2 (en) * | 2006-09-28 | 2012-02-22 | 大日本塗料株式会社 | Water-based paint composition for plastics |
| JP7131615B2 (en) | 2018-08-27 | 2022-09-06 | コニカミノルタ株式会社 | Method for forming conductive thin wire, method for manufacturing transparent conductor, method for manufacturing device, and set of conductive ink and substrate |
-
1994
- 1994-03-28 JP JP6057830A patent/JP2531124B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9644704B2 (en) * | 2013-01-29 | 2017-05-09 | Johnson Electric S.A. | Vibration safe motor fixation in an actuator |
| CN107429030A (en) * | 2015-10-27 | 2017-12-01 | 积水化学工业株式会社 | Hardening resin composition and display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07118356A (en) | 1995-05-09 |
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