JP2010053340A - Rust preventive paint composition for steel sheet - Google Patents
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本発明は、アクリル−ポリウレタンウレア樹脂系の鋼板用防錆塗料組成物に関する。 The present invention relates to a rust preventive coating composition for steel plates of acrylic-polyurethane urea resin system.
鋼板は、建築材や自動車材、家電品、生活用品等の用途に広く供されており、これらを錆から防ぎ、その美観を保つ目的で、従来、反応型クロメート処理剤や塗布型クロメート処理剤が用いられてきた。しかし、これらクロメート処理剤を用いる場合には、水質汚染防止法に規定される特別な排水処理が必要となり、また近年ではクロメート化合物（六価クロム等）が有する毒性自体について問題提起がなされている。 Steel plates are widely used in applications such as building materials, automobile materials, household appliances, and household goods. Conventionally, reactive chromate treatment agents and coating chromate treatment agents have been used to prevent these from rusting and to maintain their aesthetics. Has been used. However, when these chromate treatment agents are used, special waste water treatment as stipulated in the Water Pollution Control Law is required, and in recent years, problems have been raised regarding the toxicity itself of chromate compounds (hexavalent chromium, etc.). .
そこで斯界では、クロメート化合物を用いない水系防錆塗料が種々提案されている。そのような水系防錆塗料には、塗膜の防錆性（耐塩水性）が優れることの他、耐アルカリ性や、塗装後の鋼板を成形加工する際の追従性（加工性）、鋼板との密着性等、種々の性能が要求される。 Therefore, various water-based anticorrosive paints that do not use a chromate compound have been proposed in this field. Such water-based anti-corrosion paints have excellent anti-rust properties (salt water resistance) of the coating film, as well as alkali resistance, followability when forming the coated steel sheet (workability), Various performances such as adhesion are required.
そうした水系防錆塗料としては、例えば、特定酸価のポリウレタンの存在下でラジカル重合性単量体を重合してなる水分散液（エマルジョン）を用いてなるもの（例えば特許文献１）が知られており、特に防錆性に優れるとされている。しかし、当該エマルジョンは貯蔵安定性が不良であり、エマルジョン型の水系防錆塗料としての基本的な性能を欠いている。 As such an aqueous rust preventive paint, for example, a paint using an aqueous dispersion (emulsion) obtained by polymerizing a radical polymerizable monomer in the presence of polyurethane having a specific acid value is known (for example, Patent Document 1). It is said to be particularly excellent in rust prevention. However, the emulsion has poor storage stability and lacks basic performance as an emulsion-type water-based anticorrosive paint.
本発明は、貯蔵安定性が良好であり、かつ、塗膜の防錆性や加工性、耐アルカリ性等に優れる鋼板用防錆塗料組成物を提供することを課題とする。 This invention makes it a subject to provide the antirust coating composition for steel plates which is excellent in storage stability, and is excellent in the antirust property of a coating film, workability, alkali resistance, etc.
本発明者は鋭意検討を重ねた結果、下記のアクリル−ポリウレタンウレア樹脂水分散液を用いれば、前記課題を解決できる鋼板用防錆塗料組成物を提供できることを見出した。 As a result of intensive studies, the present inventor has found that the use of the following acrylic-polyurethane urea resin aqueous dispersion can provide a rust-proof coating composition for steel sheets that can solve the above-mentioned problems.
即ち本発明は、ポリカーボネートポリオールを含むポリオール類（ａ１−１）、アニオン性官能基含有ポリオール類（ａ１−２）、脂肪族ジイソシアネートを含むポリイソシアネート類（ａ２）、活性水素含有基を有するアクリル化合物（ａ３）、ならびにポリアミン類および／またはポリヒドラジン類（ａ４）を反応成分とするポリウレタン樹脂（Ａ）、ならびに水の存在下で、一般式（１）：ＣＨ２＝ＣＲ１ＣＯＯＲ２（式中、Ｒ１は水素原子またはメチル基を、Ｒ２は炭素数１〜１８のアルキル基を表す。）で表される（メタ）アクリル酸アルキルエステル類（ｂ１）を含む重合性単量体（Ｂ）を重合反応させて得られるアクリル−ポリウレタンウレア樹脂水分散液、を用いてなる鋼板用防錆塗料組成物に関する。 That is, the present invention relates to a polyol (a1-1) containing a polycarbonate polyol, an anionic functional group-containing polyol (a1-2), a polyisocyanate containing an aliphatic diisocyanate (a2), and an acrylic compound having an active hydrogen-containing group. (A3) and a polyurethane resin (A) having polyamines and / or polyhydrazines (a4) as reaction components, and water in the presence of general formula (1): CH 2 = CR 1 COOR 2 (wherein , R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 18 carbon atoms.) A polymerizable monomer (B1) containing (meth) acrylic acid alkyl esters (b1) It is related with the rust preventive coating composition for steel plates using the acrylic-polyurethane urea resin aqueous dispersion obtained by superposing | polymerizing.
本発明に係る鋼板用防錆塗料組成物は、長期間保存しても外観や粘度に変化が殆ど生じないなど、貯蔵安定性が良好である。また、これにより得られる塗膜は、塩水雰囲気やアルカリ性雰囲気に置いても白化や膨潤したりせず、基材（鋼鈑）に錆を生じさせないなど、防錆性や耐アルカリ性に優れる。さらに、かかる塗膜は、成形加工に付されても割れや剥がれ等の損傷が生じないなど、加工性にも優れる。他にも、かかる塗膜は耐アルコール性にも優れる。そのため、該鋼板用防錆塗料組成物は、建築材や自動車材、家電製品、生活用品等の用途に好適である。 The rust preventive coating composition for steel sheet according to the present invention has good storage stability, such as little change in appearance and viscosity even after long-term storage. Moreover, the coating film obtained by this is excellent in rust prevention and alkali resistance, such as being not whitened or swollen even when placed in a salt water atmosphere or an alkaline atmosphere, and does not cause rust on the base material (steel iron). Furthermore, such a coating film is excellent in workability, such as being free from damage such as cracking or peeling even when subjected to molding. In addition, such a coating film is excellent in alcohol resistance. Therefore, the rust preventive paint composition for steel sheet is suitable for applications such as building materials, automobile materials, home appliances, and household goods.
本発明に係る鋼板用防錆塗料組成物（以下、単に組成物という）は、前記したように、ポリカーボネートポリオールを含むポリオール類（ａ１−１）（以下、（ａ１−１）成分という）、アニオン性官能基含有ポリオール類（ａ１−２）（以下、（ａ１−２）成分という）、脂肪族ジイソシアネートを含むポリイソシアネート類（ａ２）（以下、（ａ２）成分という）、活性水素含有基を有するアクリル化合物（ａ３）（以下、（ａ３）成分という）、ならびにポリアミン類および／またはポリヒドラジン類（ａ４）（以下、（ａ４）成分という）を反応成分とするポリウレタン樹脂（Ａ）、ならびに水の存在下で、一般式（１）：ＣＨ２＝ＣＲ１ＣＯＯＲ２（式中、Ｒ１は水素原子またはメチル基を、Ｒ２は炭素数１〜１８のアルキル基を表す。）で表される（メタ）アクリル酸アルキルエステル類（ｂ１）（以下、（ｂ１）成分という）を含む重合性単量体（Ｂ）を重合反応させて得られるアクリル−ポリウレタンウレア樹脂水分散液を用いてなるものである。なお、以下、便宜的に、（ａ１−１）成分と（ａ１−２）成分を（ａ１）成分と総称することがある。 As described above, the anticorrosive paint composition for steel sheet according to the present invention (hereinafter simply referred to as “composition”) includes a polyol (a1-1) containing polycarbonate polyol (hereinafter referred to as “component (a1-1)”), an anion. Functional group-containing polyols (a1-2) (hereinafter referred to as component (a1-2)), polyisocyanates containing aliphatic diisocyanate (a2) (hereinafter referred to as component (a2)), and active hydrogen-containing groups Acrylic compound (a3) (hereinafter referred to as component (a3)), polyurethane resin (A) having polyamines and / or polyhydrazines (a4) (hereinafter referred to as component (a4)) as reaction components, and water in the presence of the general formula (1): CH 2 = CR 1 COOR 2 ( wherein R 1 represents a hydrogen atom or a methyl group, R 2 is C1-18 alkyl Acrylic-polyurethane urea obtained by polymerizing a polymerizable monomer (B) containing (meth) acrylic acid alkyl ester (b1) (hereinafter referred to as (b1) component) represented by: A resin aqueous dispersion is used. Hereinafter, for convenience, the component (a1-1) and the component (a1-2) may be collectively referred to as the component (a1).
（ａ１−１）成分をなすポリカーボネートポリオールとしては、各種公知のものを特に制限なく用い得る。具体的には、例えば、多価アルコールとジメチルカーボネートの脱メタノール縮合反応物や、多価アルコールとジフェニルカーボネートの脱フェノール縮合反応物、多価アルコールとエチレンカーボネートの脱エチレングリコール縮合反応物等が挙げられ、これらは１種を単独で、または２種以上を組み合わせて用い得る。本発明の組成物は、ポリカーボネートポリオールを必須とすることにより、貯蔵安定性、塗膜の防錆性、耐アルカリ性、加工性および耐アルコール性が良好となっている。 As the polycarbonate polyol constituting the component (a1-1), various known ones can be used without particular limitation. Specifically, for example, a demethanol condensation reaction product of polyhydric alcohol and dimethyl carbonate, a dephenol condensation reaction product of polyhydric alcohol and diphenyl carbonate, a deethylene glycol condensation reaction product of polyhydric alcohol and ethylene carbonate, etc. These may be used alone or in combination of two or more. The composition of the present invention has good storage stability, anticorrosiveness of the coating film, alkali resistance, workability and alcohol resistance by making the polycarbonate polyol essential.
該多価アルコールとしては、各種公知のものを特に制限なく用い得る。具体的には、例えば、脂肪族グリコール〔１，６−ヘキサンジオール、ジエチレングリコール、プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、ネオペンチルグリコール、ペンタンジオール、３−メチル−１，５−ペンタンジオール、オクタンジオール、１，４−ブチンジオール、ジプロピレングリコール等〕、脂環族グリコール〔１，４−シクロヘキサンジグリコール、１，４−シクロヘキサンジメタノール等〕等が挙げられ、これらは１種を単独で、または２種以上を組み合わせて用い得る。 As the polyhydric alcohol, various known ones can be used without particular limitation. Specifically, for example, aliphatic glycol [1,6-hexanediol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1, 5-pentanediol, octanediol, 1,4-butynediol, dipropylene glycol, etc.], alicyclic glycols [1,4-cyclohexanediglycol, 1,4-cyclohexanedimethanol, etc.] and the like. One kind can be used alone, or two or more kinds can be used in combination.
なお、ポリカーボネートポリオールの物性は特に限定されないが、例えば、数平均分子量（ゲルパーミエーションクロマトグラフィーによるポリスチレン換算値をいう。以下、同様。）は、塗膜の防錆性や、基材に対する密着性等を考慮して、通常、５００〜３０００程度であるのが好ましい。 The physical properties of the polycarbonate polyol are not particularly limited. For example, the number average molecular weight (referred to a polystyrene conversion value by gel permeation chromatography; the same applies hereinafter) is the rust prevention property of the coating film and the adhesion to the substrate. In view of the above, it is usually preferable to be about 500 to 3000.
また、（ａ１−１）成分が、さらにビスフェノール類のアルキレンオキシド付加物を含有する場合には、特に塗膜の耐アルカリ性、加工性および耐アルコール性等が良好となる。該付加物をなすビスフェノール類としては、２，２−ビス（４’−オキシフェニル）プロパン（ビスフェノールＡ）、４，４’イソプロピリデンビスフェノール、４，４’ヒドロキシビスフェノール、４，４’スルフォニルビスフェノール、４，４’ヒドロキシベンゾフェノン等が挙げられる。また、該ビスフェノール類に付加反応させるアルキレンオキシド化合物としては、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド等が挙げられる。該付加物としては、塗膜の防錆性の観点より、特に、ビスフェノールＡとプロピレンオキシドとの付加反応物が好ましい。なお、該ビスフェノール類に対する該アルキレンオキシド化合物の付加モル数は、通常２〜１００程度である。また、当該付加物の数平均分子量は、通常、３００〜６０００程度である。 Further, when the component (a1-1) further contains an alkylene oxide adduct of bisphenols, the alkali resistance, processability, alcohol resistance, etc. of the coating film are particularly good. Examples of the bisphenols forming the adduct include 2,2-bis (4′-oxyphenyl) propane (bisphenol A), 4,4′isopropylidene bisphenol, 4,4′hydroxy bisphenol, 4,4′sulfonyl bisphenol, 4,4′hydroxybenzophenone and the like. Examples of the alkylene oxide compound that undergoes an addition reaction with the bisphenol include ethylene oxide, propylene oxide, butylene oxide, and the like. As the adduct, an addition reaction product of bisphenol A and propylene oxide is particularly preferable from the viewpoint of rust prevention of the coating film. In addition, the addition mole number of this alkylene oxide compound with respect to this bisphenol is about 2-100 normally. Moreover, the number average molecular weight of the said adduct is about 300-6000 normally.
なお、（ａ１−１）成分中のポリカーボネートポリオールと、ビスフェノール類のアルキレンオキシド付加物との含有量は特に限定されないが、組成物の貯蔵安定性や、塗膜の防錆性、特に耐アルカリ性および加工性等の観点より、前者が１０〜９９重量％、および後者が９０〜１重量％程度であるのが好ましい。 The content of the polycarbonate polyol in the component (a1-1) and the alkylene oxide adduct of bisphenols is not particularly limited, but the storage stability of the composition and the rust prevention property of the coating film, particularly alkali resistance and From the viewpoint of workability and the like, the former is preferably about 10 to 99% by weight and the latter is about 90 to 1% by weight.
（ａ１−２）成分は、アクリル−ポリウレタンウレア樹脂に水分散性を付与するために用いる。具体例としては、カルボキシル基含有ポリオール〔２，２−ジメチロールプロピオン酸、２，２−ジメチロールブタン酸等〕やその中和塩、スルホン基含有ジカルボン酸〔５−スルホイソフタル酸、４−スルホイソフタル酸、４−スルホフタル酸、スルホテレフタル酸、４−スルホナフタレン−２，７−ジカルボン酸、５−（４−スルホフェノキシ）イソフタル酸等〕やその中和塩等が挙げられ、これらは１種を単独で、または２種以上を組み合わせて用い得る。これらの中でも該カルボキシル基含有ポリオールが好ましく、特に前記２，２−ジメチロールプロピオン酸および／または２，２−ジメチロールブタン酸は入手が容易であることから好ましい。 The component (a1-2) is used for imparting water dispersibility to the acrylic-polyurethane urea resin. Specific examples include carboxyl group-containing polyols [2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, etc.] and neutralized salts thereof, sulfone group-containing dicarboxylic acids [5-sulfoisophthalic acid, 4-sulfo Isophthalic acid, 4-sulfophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- (4-sulfophenoxy) isophthalic acid, etc.] and neutralized salts thereof, and the like. May be used alone or in combination of two or more. Among these, the carboxyl group-containing polyol is preferable, and the 2,2-dimethylolpropionic acid and / or 2,2-dimethylolbutanoic acid are particularly preferable because they are easily available.
なお、前記したカルボキシル基含有ポリオールの中和塩及びスルホン基含有ジカルボン酸の中和塩を形成させるために用いる塩基性化合物としては、例えば、アルカリ金属水酸化物〔水酸化カリウム、水酸化ナトリウム等〕、アルカノールアミン〔トリエタノールアミン、トリイソプロパノールアミン、Ｎ−アルキルジエタノールアミン、Ｎ，Ｎ’−ジアルキルモノエタノールアミン、Ｎ−アルキルジイソプロパノールアミン、Ｎ，Ｎ’−ジアルキルモノイソプロパノールアミン等〕、３級アミン〔トリメチルアミン、トリエチルアミン、トリイソプロピルアミン、トリブチルアミン等〕、アンモニア等が挙げられ、これらは１種を単独で、または２種以上を組み合わせて用い得る。 Examples of the basic compound used for forming the neutralized salt of the carboxyl group-containing polyol and the neutralized salt of the sulfone group-containing dicarboxylic acid include alkali metal hydroxides [potassium hydroxide, sodium hydroxide, etc. ], Alkanolamine [triethanolamine, triisopropanolamine, N-alkyldiethanolamine, N, N′-dialkylmonoethanolamine, N-alkyldiisopropanolamine, N, N′-dialkylmonoisopropanolamine, etc.], tertiary amine [Trimethylamine, triethylamine, triisopropylamine, tributylamine and the like], ammonia and the like can be mentioned, and these can be used alone or in combination of two or more.
（ａ２）成分は、脂肪族ジイソシアネートを必須としており、このことにより、塗膜の防錆性、耐アルカリ性、加工性および耐アルコール性等が良好となる。該脂肪族ジイソシアネートとしては、具体的には、分岐状ジイソシアネートおよび／または非分岐状ジイソシアネートが挙げられる。 The component (a2) essentially comprises an aliphatic diisocyanate, which improves the rust resistance, alkali resistance, processability, alcohol resistance, and the like of the coating film. Specific examples of the aliphatic diisocyanate include branched diisocyanates and / or unbranched diisocyanates.
該分岐状ジイソシアネートとは、具体的には、「アルキル基で置換されたアルキレン基」を分子内に有するジイソシアネート類であって、後述する他のジイソシアネート類を除いたものをいい、各種公知のもの、好ましくは、２，２，４−トリメチルヘキサメチレンジイソシアネートおよび／または２，４，４−トリメチルヘキサメチレンジイソシアネートを用い得る。また、これらはアダクト体、アロファネート体等であってもよい。 The branched diisocyanate specifically refers to diisocyanates having an “alkylene group substituted with an alkyl group” in the molecule, excluding other diisocyanates described later, and various known ones. Preferably, 2,2,4-trimethylhexamethylene diisocyanate and / or 2,4,4-trimethylhexamethylene diisocyanate can be used. These may be adduct bodies, allophanate bodies and the like.
また、該非分岐状ジイソシアネートとは、「アルキル基で置換されていないアルキレン基」を分子内に有するジイソシアネート類であって、後述する他のジイソシアネート類を除いたものをいい、各種公知のもの、好ましくは、ブタン−１，４−ジイソシアネート、１，６−ヘキサメチレンジイソシアネート、リジンジイソシアネート等が挙げられる。また、これらはアダクト体、アロファネート体等であってもよい。該非分岐状ジイソシアネートのうち、特に１，６−ヘキサメチレンジイソシアネートのアダクト体は、特に塗膜の耐アルコール性等の点より好ましい。 The unbranched diisocyanate is a diisocyanate having an “alkylene group not substituted with an alkyl group” in the molecule, excluding other diisocyanates described later, and various known ones, preferably Includes butane-1,4-diisocyanate, 1,6-hexamethylene diisocyanate, lysine diisocyanate, and the like. These may be adduct bodies, allophanate bodies and the like. Among the unbranched diisocyanates, 1,6-hexamethylene diisocyanate adducts are particularly preferable from the viewpoint of alcohol resistance of the coating film.
なお、（ａ２）成分には、他のジイソシアネート類を含ませることができる。具体的には、例えば、芳香族系ジイソシアネート〔１，５−ナフチレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、４，４′−ジフェニルジメチルメタンジイソシアネート、４，４’−ジベンジルイソシアネート、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート、トリレンジイソシアネート等〕、脂環族系ジイソシアネート〔シクロヘキサン−１，４−ジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネート、１，３−ビス（イソシアネートメチル）シクロヘキサン、メチルシクロヘキサンジイソシアネート、ダイマージイソシアネート等〕、トリイソシアネート化合物〔トリフェニルメタントリイソシアネート、ポリメチレンポリフェニルイソシアネート等〕等を含むことができ、これらは１種を単独で、または２種以上を組み合わせて用い得る。また、対応するものについてはアダクト体や、アロファネート体等であってもよい。これらの使用量は、（ａ２）成分中を１００重量％とした場合において、通常０〜１００重量％程度の範囲で用い得る。 The component (a2) can contain other diisocyanates. Specifically, for example, aromatic diisocyanate [1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate Tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, etc.], alicyclic diisocyanates [cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane- 4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate Over DOO, dimer diisocyanate], triisocyanate compound [triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate] and the like can contain, it may be used alone or in combination of two or more, of them. Moreover, about a corresponding thing, an adduct body, an allophanate body, etc. may be sufficient. These amounts can be used in the range of usually about 0 to 100% by weight when the amount of the component (a2) is 100% by weight.
（ａ３）成分は、具体的には、分子内に（メタ）アクリロイル基と活性水素含有基（例えば水酸基）を少なくとも一つずつ有する重合性単量体をいい、各種公知のもの、例えば、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、および（メタ）アクリル酸ヒドロキシブチルからなる群より選ばれる少なくとも１種を好ましく用い得る。なお、該（ａ３）成分を用いないと、得られるアクリル−ポリウレタンウレア樹脂水分散液の貯蔵安定性や、塗膜の防錆性等が不良となる。 The component (a3) specifically refers to a polymerizable monomer having at least one (meth) acryloyl group and active hydrogen-containing group (for example, hydroxyl group) in the molecule, and various known ones such as ( At least one selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate may be preferably used. In addition, when this (a3) component is not used, the storage stability of the acrylic-polyurethane urea resin aqueous dispersion obtained, the antirust property of the coating film, and the like will be poor.
（ａ４）成分は、ポリウレタン樹脂（Ａ）の鎖伸長剤および／または鎖長停止剤として作用する成分であり、各種公知のものポリアミン類および／またはポリヒドラジン類を特に制限なく用い得る。該ポリアミン類としては、具体的には、例えば、芳香族ポリアミン〔トリレンジアミン、キシリレンジアミン、ジフェニルジアミン、ジアミノジフェニルメタン等〕、脂環族ポリアミン〔イソホロンジアミン、ジシクロヘキシルメタン−４，４′−ジアミン等〕、脂肪族ポリアミン〔エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、トリエチレンテトラミン、ジエチレントリアミン等〕、水酸基含有ポリアミン〔２−ヒドロキシエチルエチレンジアミン、２−ヒドロキシエチルプロピレンジアミン、ジ−２−ヒドロキシエチルエチレンジアミン、ジ−２−ヒドロキシエチルプロピレンジアミン、２−ヒドロキシプロピルエチレンジアミン、ジ−２−ヒドロキシプロピルエチレンジアミン等〕が挙げられる。また、該ポリヒドラジン類としては、脂肪族ジカルボン酸ヒドラジド〔コハク酸ジヒドラジド、アジピン酸ジヒドラジド、グルタル酸ジヒドラジド、ドデカン二酸ジヒドラジド等〕、芳香族ジカルボン酸ヒドラジド〔イソフタル酸ジヒドラジド、フタル酸ジヒドラジド、ナフタレンジカルボン酸ジヒドラジド等〕が挙げられる。これらは１種を単独で、または２種以上を組み合わせて用い得る。 The component (a4) is a component that acts as a chain extender and / or a chain length terminator of the polyurethane resin (A), and various known polyamines and / or polyhydrazines can be used without particular limitation. Specific examples of the polyamines include aromatic polyamines [tolylenediamine, xylylenediamine, diphenyldiamine, diaminodiphenylmethane, etc.], alicyclic polyamines [isophoronediamine, dicyclohexylmethane-4,4′-diamine]. Etc.], aliphatic polyamines [ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, etc.], hydroxyl group-containing polyamines [2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di 2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc.]. The polyhydrazines include aliphatic dicarboxylic acid hydrazides (succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, dodecanedioic acid dihydrazide, etc.), aromatic dicarboxylic acid hydrazides (isophthalic acid dihydrazide, phthalic acid dihydrazide, naphthalene dicarboxylic acid). Acid dihydrazide etc.]. These may be used alone or in combination of two or more.
なお、本発明では、鎖長停止剤として各種公知のモノアミン類（ａ５）（以下、（ａ５）成分という）を用い得る。具体的には、例えば、モノアルキルモノアミン〔モノメチルアミン、モノエチルアミン、モノ−ｎ−プロピルアミン、モノイソプロピルアミン、モノ−ｎ−ブチルアミン、モノイソブチルアミン等〕、ジアルキルモノアミン〔ジメチルアミン、ジエチルアミン、ジ−ｎ−プロピルアミン、ジ−ｎ−ブチルアミン等〕、これら以外の水酸基含有モノアミン〔モノエタノールモノアミン、ジエタノールモノアミン、２−アミノ−２−メチル−１−プロパノール等〕等が挙げられ、これらは１種を単独で、または２種以上を組み合わせて用い得る。 In the present invention, various known monoamines (a5) (hereinafter referred to as component (a5)) can be used as chain length terminators. Specifically, for example, monoalkyl monoamine [monomethylamine, monoethylamine, mono-n-propylamine, monoisopropylamine, mono-n-butylamine, monoisobutylamine, etc.], dialkylmonoamine [dimethylamine, diethylamine, di- n-propylamine, di-n-butylamine, etc.), and other hydroxyl group-containing monoamines [monoethanol monoamine, diethanol monoamine, 2-amino-2-methyl-1-propanol, etc.] and the like. It can be used alone or in combination of two or more.
ポリウレタン樹脂（Ａ）の製造方法は特に限定されず、例えば、前記（ａ１）成分〜（ａ４）成分（および必要に応じて（ａ５）成分）を通常５０〜１５０℃程度の温度で一括反応させる方法や、前記（ａ１）成分〜（ａ３）成分を通常５０〜１５０℃程度の温度で一旦反応させてウレタンプレポリマー（Ａ’）（以下、ウレタンプレポリマー（Ａ’）という）を製造し、次いで、該ウレタンプレポリマー（Ａ’）と前記（ａ４）成分（および必要に応じて（ａ５）成分）とを、必要に応じて前記塩基性化合物の存在下で、通常５０〜１００℃程度の温度で反応させる方法が挙げられる。 The production method of the polyurethane resin (A) is not particularly limited. For example, the components (a1) to (a4) (and the component (a5) as necessary) are generally reacted at a temperature of about 50 to 150 ° C. The method and the components (a1) to (a3) are usually reacted once at a temperature of usually about 50 to 150 ° C. to produce a urethane prepolymer (A ′) (hereinafter referred to as urethane prepolymer (A ′)), Subsequently, the urethane prepolymer (A ′) and the component (a4) (and the component (a5) if necessary) are usually added at a temperature of about 50 to 100 ° C. in the presence of the basic compound as necessary. The method of making it react at temperature is mentioned.
（ａ１）成分〜（ａ４）成分（および必要に応じて（ａ５）成分）の使用量は特に限定されないが、通常は、（ａ２）成分のイソシアネート基の当量値（ＮＣＯ）と、（ａ１）成分、（ａ３）成分および（ａ４）成分（ならびに必要に応じて（ａ５）成分）の活性水素含有基の当量値の合計値（Ｘ）との比（ＮＣＯ／Ｘ）が、１／２〜２／１程度、好ましくは１／１．５〜１．５／１程度となる範囲であればよい。
なお、「イソシアネート基の当量値（ＮＣＯ）」とは、（ａ２）成分１モルのグラム数（ｇ）を該（ａ２）成分のイソシアネート基数で割って得た値をいう。
また、「活性水素含有基の当量値（Ｘ）」とは、（ａ１）成分１モルのグラム数（ｇ）を該（ａ１）成分の水酸基数で割って得た値（Ｘａ１）と、（ａ３）成分１モルのグラム数（ｇ）を該（ａ３）成分の水酸基数で割って得た値（Ｘａ３）と、（ａ４）成分１モルのグラム数（ｇ）を該（ａ４）成分のアミノ基および／またはヒドラジド基で割って得た値（Ｘａ４）とを合計した値（Ｘａ１＋Ｘａ３＋Ｘａ４）、又は、当該合計値に、必要に応じて更に、（ａ５）成分１モルのグラム数（ｇ）を該（ａ５）成分のアミノ基数で割って得た値（Ｘａ５）を加えた値（Ｘａ１＋Ｘａ３＋Ｘａ４＋Ｘａ５）をいう。
The amount of the (a1) component to the (a4) component (and optionally the (a5) component) is not particularly limited. Usually, the equivalent value (NCO) of the isocyanate group of the (a2) component and (a1) The ratio (NCO / X) of the equivalent value of the active hydrogen-containing group of the component, (a3) component and (a4) component (and optionally (a5) component) to the total value (X) is 1/2 to It may be in the range of about 2/1, preferably about 1 / 1.5 to 1.5 / 1.
The “equivalent value of isocyanate group (NCO)” refers to a value obtained by dividing the number of grams (g) of 1 mole of component (a2) by the number of isocyanate groups of component (a2).
The “equivalent value (X) of the active hydrogen-containing group” means a value (X a1 ) obtained by dividing the number of grams (g) of 1 mol of the component (a1) by the number of hydroxyl groups of the component (a1), (A3) The value (X a3 ) obtained by dividing the number of grams (g) of 1 mol of the component by the number of hydroxyl groups of the (a3) component, and the number of grams (g) of 1 mol of (a4) component (a4) The value obtained by dividing the amino group and / or hydrazide group of the component (X a4 ) and the total value (X a1 + X a3 + X a4 ), or the total value, if necessary, (a5) component The value (X a1 + X a3 + X a4 + X a5 ) obtained by adding the value (X a5 ) obtained by dividing 1 mol of grams (g) by the number of amino groups of the component (a5).
こうして得られるポリウレタン樹脂（Ａ）の物性は特に限定されないが、通常、得られるアクリル−ポリウレタンウレア樹脂水分散液の貯蔵安定性等の観点より、酸価（ＪＩＳ−Ｋ−００７０）が１０〜５０ｍｇＫＯＨ／ｇ程度、二重結合当量値が通常２０００〜５５０００程度である。なお、「二重結合当量値」とは、（ａ３）成分に由来する重合性炭素−炭素二重結合一つあたりのポリウレタン樹脂（Ａ）のグラム数（固形分換算）をいう。 The physical properties of the polyurethane resin (A) thus obtained are not particularly limited, but the acid value (JIS-K-0070) is usually 10 to 50 mgKOH from the viewpoint of storage stability of the resulting acrylic-polyurethane urea resin aqueous dispersion. / G, and the double bond equivalent value is usually about 2000 to 55000. In addition, a "double bond equivalent value" means the gram number (in solid content conversion) of the polyurethane resin (A) per polymerizable carbon-carbon double bond derived from the component (a3).
重合性単量体（Ｂ）における（ｂ１）成分は、一般式（１）：ＣＨ２＝ＣＲ１ＣＯＯＲ２（式中、Ｒ１は水素原子またはメチル基を、またＲ２は炭素数１〜１８のアルキル基を表す。なお、Ｒ２は分岐構造を有していてもよい。）で表される（メタ）アクリル酸アルキルエステル類である。 The component (b1) in the polymerizable monomer (B) has the general formula (1): CH 2 = CR 1 COOR 2 (wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents a carbon number of 1 to It represents an alkyl group of 18. R 2 may have a branched structure.) (Meth) acrylic acid alkyl esters represented by
該（ｂ１）成分の具体例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸イソミリスチルおよび（メタ）アクリル酸ステアリル等が挙げられ、これらは１種を単独で、または２種以上を組み合わせて用い得る。 Specific examples of the component (b1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic. Acid hexyl, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate and (meth) ) Stearyl acrylate and the like can be mentioned, and these can be used alone or in combination of two or more.
なお、重合性単量体（Ｂ）は、（ｂ１）成分以外のラジカル重合性単量体（以下、（ｂ２）成分という）を含み得る。（ｂ２）成分としては、例えば、脂環族（メタ）アクリレート〔（メタ）アクリル酸２−シクロヘキシル、（メタ）アクリル酸シクロペンチル、（メタ）アクリル酸イソボルニル等〕、芳香族（メタ）アクリレート〔（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸２−フェニルエチル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル、スチレン、α−メチルスチレン等〕、ハロゲン元素含有（メタ）アクリレート〔（メタ）アクリル酸トリフルオロエチル、（メタ）アクリル酸ヘキサフルオロイソプロピル、（メタ）アクリル酸２−クロロエチル等〕等が挙げられ、これらは１種を単独で、または２種以上を組み合わせて用い得る。（ｂ２）成分は、重合性単量体（Ｂ）中、５０モル％未満であるのが好ましい。 The polymerizable monomer (B) may contain a radical polymerizable monomer other than the component (b1) (hereinafter referred to as the component (b2)). As the component (b2), for example, alicyclic (meth) acrylate [2-methacrylic acid (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, etc.], aromatic (meth) acrylate [( Phenoxyethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, styrene, α-methylstyrene, etc.], halogen element-containing (meth) acrylate [(meta ) Trifluoroethyl acrylate, hexafluoroisopropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, etc.], and the like can be used alone or in combination of two or more. The component (b2) is preferably less than 50 mol% in the polymerizable monomer (B).
本発明に係るアクリル−ポリウレタンウレア樹脂水分散液は、ポリウレタン樹脂（Ａ）および水の存在下で、重合性単量体（Ｂ）を重合反応させることにより得ることができる。なお、重合性単量体（Ｂ）は、ポリウレタン樹脂（Ａ）と水を含む反応系に外部より添加する態様だけでなく、前記ウレタンプレポリマー（Ａ’）に予め混合させておく態様で利用することができ、特に後者の態様は、（ｂ１）成分として疎水性の強いもの（Ｒ２の炭素数が多いもの）を用いる場合に好ましい。 The acrylic-polyurethane urea resin aqueous dispersion according to the present invention can be obtained by polymerizing the polymerizable monomer (B) in the presence of the polyurethane resin (A) and water. In addition, the polymerizable monomer (B) is used not only in an aspect of being added from the outside to the reaction system containing the polyurethane resin (A) and water, but also in an aspect of being previously mixed with the urethane prepolymer (A ′). In particular, the latter embodiment is preferable when a highly hydrophobic component (a component having a large number of carbon atoms in R 2 ) is used as the component (b1).
水としては、市水、蒸留水、脱イオン水等が挙げられる。また、水とともに、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、イソブチルアルコール、ｓｅｃ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール、ｓｅｃ−アミルアルコール、ジアセトンアルコール、プロピレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル等のアルコール系溶剤を用い得る。 Examples of water include city water, distilled water, deionized water and the like. In addition to water, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, sec-amyl alcohol, diacetone alcohol, propylene glycol monomethyl ether Alcohol solvents such as ethylene glycol monobutyl ether can be used.
重合性単量体（Ｂ）を重合させる際の反応温度は、通常６０〜１００℃程度である。また、ポリウレタン樹脂（Ａ）（固形分換算）に対する重合性単量体（Ｂ）の使用量は特に限定されないが、得られる水分散液の貯蔵安定性の観点より、通常３〜５０重量％程度である。 The reaction temperature for polymerizing the polymerizable monomer (B) is usually about 60 to 100 ° C. The amount of the polymerizable monomer (B) used relative to the polyurethane resin (A) (in terms of solid content) is not particularly limited, but is usually about 3 to 50% by weight from the viewpoint of storage stability of the resulting aqueous dispersion. It is.
前記重合反応の際には、各種公知の重合開始剤を使用することができる。具体的には、例えば、有機過酸化物〔過酸化ベンゾイルやイソブチリルパーオキサイド、オクタノイルパーオキサイド、クミルパーオキシオクテート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシアセテート、ラウリルパーオキサイド、ジーｔーブチルパーオキサイド、ジ−２−エチルヘキシルパーオキシジンカーボネイト等〕、アゾ化合物〔アゾビスイソブチロニトリル、アゾビスイソブチルバレロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル等〕、無機パーオキサイド化合物〔過硫酸カリウムや過硫酸アンモニウム、過酸化水素等〕が挙げられ、これらは１種を単独で、または２種以上を組み合わせて用い得る。該重合開始剤の使用量は、重合性単量体（Ｂ）に対して通常０．１〜５重量部程度である。 In the polymerization reaction, various known polymerization initiators can be used. Specifically, for example, organic peroxides [benzoyl peroxide, isobutyryl peroxide, octanoyl peroxide, cumyl peroxyoctate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Acetate, lauryl peroxide, di-t-butyl peroxide, di-2-ethylhexyl peroxydine carbonate, etc.], azo compounds [azobisisobutyronitrile, azobisisobutylvaleronitrile, 2,2′-azobis (2, 4-dimethylvaleronitrile, etc.] and inorganic peroxide compounds [potassium persulfate, ammonium persulfate, hydrogen peroxide, etc.], which can be used alone or in combination of two or more. The amount of the agent used is usually 0.1 to 5 with respect to the polymerizable monomer (B). It is about the amount part.
こうして得られるアクリル−ポリウレタンウレア樹脂水分散液は、実用上の観点より、固形分濃度が通常２０〜５０重量％程度、粘度が１０〜１００００ｍＰａ・ｓ／２５℃程度であり、ｐＨが６〜１０程度である。また、該アクリル−ポリウレタンウレア樹脂の数平均分子量は、貯蔵安定性の観点より、通常１０００〜１００００００程度である。 The acrylic-polyurethane urea resin aqueous dispersion thus obtained has a solid concentration of usually about 20 to 50% by weight, a viscosity of about 10 to 10,000 mPa · s / 25 ° C., and a pH of 6 to 10 from a practical viewpoint. Degree. The number average molecular weight of the acrylic-polyurethane urea resin is usually about 1,000 to 1,000,000 from the viewpoint of storage stability.
該アクリル−ポリウレタンウレア樹脂水分散液は、通常はそのままでも鋼板用防錆塗料組成物として用い得るが、必要に応じて、各種公知の架橋剤（メラミン、イソシアネート、フェノール等）や、着色剤、耐ブロッキング剤、フッ素系化合物、消泡剤等を併用することもできる。また、塗膜の防錆効果を向上させるため、或いは塗膜と鋼板との密着性を向上させるために、各種シリカゾルやシランカップリング剤を併用できる。 The acrylic-polyurethane urea resin aqueous dispersion can be used as it is as a rust-proof coating composition for steel sheets, but various known crosslinking agents (melamine, isocyanate, phenol, etc.), colorants, Anti-blocking agents, fluorine compounds, antifoaming agents, and the like can be used in combination. Various silica sols and silane coupling agents can be used in combination to improve the rust prevention effect of the coating film or to improve the adhesion between the coating film and the steel sheet.
本発明の組成物の塗装対象である鋼板としては、普通鋼板や、アルミめっき鋼板、ステンレス鋼板、リン酸亜鉛処理鋼板、亜鉛めっき鋼板、亜鉛合金めっき鋼板等の処理鋼板が挙げられる。なお、亜鉛合金めっきとしては、Ｚｎ−Ａｌ、Ｚｎ−Ｍｇ、Ｚｎ−Ｎｉ、Ｚｎ−Ａｌ−Ｍｇ等が挙げられる。また、鋼板には、当該組成物からなる塗膜の密着性を向上させるために、下塗層（ポリエステル樹脂系塗料、エポキシ樹脂系塗料、エポキシ変性ポリエステル樹脂系塗料等の塗膜層）が予め設けられていてもよい。 Examples of the steel plate to be coated with the composition of the present invention include treated steel plates such as plain steel plates, aluminized steel plates, stainless steel plates, zinc phosphate treated steel plates, galvanized steel plates, and zinc alloy plated steel plates. In addition, as zinc alloy plating, Zn-Al, Zn-Mg, Zn-Ni, Zn-Al-Mg, etc. are mentioned. In addition, in order to improve the adhesion of the coating film made of the composition, the steel sheet has an undercoat layer (polyester resin-based paint, epoxy resin-based paint, epoxy-modified polyester resin-based paint film layer, etc.) in advance. It may be provided.
前記塗装手段としては特に限定されず、例えば、ナチュラルロールコート法、リバースロールコート、カーテンフローコート法等を例示できる。なお、該鋼板用防錆塗料組成物の塗装は、前記表面処理鋼板が未成形の段階で行ってもよく（プレコート法）、また、前記表面処理鋼板を成形加工した後に行ってもよい（ポストコート法）。 The coating means is not particularly limited, and examples thereof include a natural roll coat method, a reverse roll coat method, and a curtain flow coat method. The coating of the rust-proof coating composition for steel sheet may be performed when the surface-treated steel sheet is not yet formed (pre-coating method) or after the surface-treated steel sheet is formed (post). Coat method).
以下、実施例および比較例を通じて本発明をより具体的に説明するが、これらにより本発明が限定されないことはもとよりである。 Hereinafter, the present invention will be described more specifically through examples and comparative examples, but the present invention is not limited thereto.
実施例１
攪拌機、還流冷却管、温度計および窒素導入管を備えた４つ口フラスコに、市販ポリカーボネートポリオール（製品名「クラレポリオールＣ２０９０」、数平均分子量２０００；クラレ（株）製）２８７．７重量部、２，２−ジメチロールブタン酸３９．６重量部、２，２，４−トリメチルヘキサメチレンジイソシアネートと２，４，４−トリメチルヘキサメチレンジイソシアネートの混合物（製品名「ＶＥＳＴＡＮＡＴ ＴＭＤＩ」、エボニックデグサジャパン（株）製）１７２．７重量部、およびアクリル酸２−ヒドロキシエチル１２．２重量部を仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約５．０重量％のウレタンプレポリマーを得た。次いで、メタクリル酸メチル１２５．０重量部を添加し、混合した。次いで、得られた混合物の６２０．０部を、別途用意した同様の４つ口フラスコ内の、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン３５．８重量部、アジピン酸ジヒドラジド４０．８重量部、トリエチルアミン２６．８重量部、ジエタノールアミン５．５重量部、水１２３７．１重量部、イソプロピルアルコール３７．３重量部）へと徐々に滴下して、反応系全体を混合し、６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．７重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３５．０重量％、粘度４０ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Example 1
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 287.7 parts by weight of a commercially available polycarbonate polyol (product name “Kuraray Polyol C2090”, number average molecular weight 2000; manufactured by Kuraray Co., Ltd.) 2,9.6 parts of 2,2-dimethylolbutanoic acid, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (product name “VESTANATM TMDI”, Evonik Degussa Japan ) Made) 172.7 parts by weight and 12.2 parts by weight of 2-hydroxyethyl acrylate were subjected to urethanization reaction at 70 ° C. for 6 hours, and urethane having a free isocyanate group content of about 5.0% by weight A prepolymer was obtained. Next, 125.0 parts by weight of methyl methacrylate was added and mixed. Subsequently, 620.0 parts of the obtained mixture was stirred in a similar four-necked flask, and the aqueous solution of a chain extender under stirring (35.8 parts by weight of isophoronediamine, 40.8 parts by weight of adipic acid dihydrazide). 26.8 parts by weight of triethylamine, 5.5 parts by weight of diethanolamine, 1237.1 parts by weight of water, and 37.3 parts by weight of isopropyl alcohol), and the whole reaction system is mixed and stirred at 60 ° C. for 2 hours. The chain extension reaction was carried out with stirring. Subsequently, 2.7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to carry out a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 35.0% by weight and a viscosity of 40 mPa · s / 25 ° C. was obtained.
実施例２
実施例１と同様の４つ口フラスコに、「クラレポリオールＣ２０９０」２８７．７重量部、２，２−ジメチロールブタン酸３９．６重量部、「ＶＥＳＴＡＮＡＴ ＴＭＤＩ」１７２．７重量部、およびアクリル酸２−ヒドロキシエチル１２．２重量部を仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約５．０重量％のプレポリマーを得た。次いで、メタクリル酸ラウリル１２５．０重量部を添加し、混合した。次いで、得られた混合物の６２０．０部を、別途用意した同様の４つ口フラスコ内の、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン３５．８重量部、アジピン酸ジヒドラジド４０．８重量部、トリエチルアミン２６．８重量部、ジエタノールアミン５．５重量部、水１２３７．１重量部、イソプロピルアルコール３７．３重量部）へと徐々に滴下して、反応系全体を混合した。その後、反応系を６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．７重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３５．０重量％、粘度６０ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Example 2
In a four-neck flask similar to Example 1, 287.7 parts by weight of “Kuraray polyol C2090”, 39.6 parts by weight of 2,2-dimethylolbutanoic acid, 172.7 parts by weight of “VESTANATM TMDI”, and acrylic acid 12.2 parts by weight of 2-hydroxyethyl was charged, and a urethanization reaction was performed at 70 ° C. for 6 hours to obtain a prepolymer having a free isocyanate group content of about 5.0% by weight. Next, 125.0 parts by weight of lauryl methacrylate was added and mixed. Subsequently, 620.0 parts of the obtained mixture was stirred in a similar four-necked flask, and the aqueous solution of a chain extender under stirring (35.8 parts by weight of isophoronediamine, 40.8 parts by weight of adipic acid dihydrazide). And 36.8 parts by weight of triethylamine, 5.5 parts by weight of diethanolamine, 1237.1 parts by weight of water, and 37.3 parts by weight of isopropyl alcohol), and the whole reaction system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to carry out a chain extension reaction. Subsequently, 2.7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to carry out a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 35.0% by weight and a viscosity of 60 mPa · s / 25 ° C. was obtained.
実施例３
実施例１と同様の４つ口フラスコに、「クラレポリオールＣ２０９０」２１８．６重量部、市販ビスフェノールＡ・プロピレンオキシド付加物（製品名「アデカポリエーテルＢＰＸ−５５」；数平均分子量７９０；（株）ＡＤＥＫＡ製）５４．６重量部、２，２−ジメチロールブタン酸３９．６重量部、「ＶＥＳＴＡＮＡＴ ＴＭＤＩ」１８７．２重量部、およびアクリル酸２−ヒドロキシエチル１２．３重量部を仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約５．０重量％のプレポリマーを得た。次いで、メタクリル酸メチル１２５．０重量部を添加し、混合した。次いで、得られた混合物の６２０．０部を、別途用意した同様の４つ口フラスコ内の、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン３６．２重量部、アジピン酸ジヒドラジド４６．７重量部、トリエチルアミン２６．８重量部、ジエタノールアミン５．６重量部、水１２４８．９重量部、イソプロピルアルコール３７．３重量部）へと徐々に滴下して、反応系全体を混合した。その後、反応系を６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．８重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３５．０重量％、粘度６０ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Example 3
In a four-necked flask similar to that in Example 1, 218.6 parts by weight of “Kuraray polyol C2090”, a commercially available bisphenol A / propylene oxide adduct (product name “Adeka polyether BPX-55”; number average molecular weight 790; ADEKA) 54.6 parts by weight, 2,2-dimethylolbutanoic acid 39.6 parts by weight, "VESTANATM TMDI" 187.2 parts by weight, and 2-hydroxyethyl acrylate 12.3 parts by weight, The urethanization reaction was carried out at 6 ° C. for 6 hours to obtain a prepolymer having a free isocyanate group content of about 5.0% by weight. Next, 125.0 parts by weight of methyl methacrylate was added and mixed. Next, 620.0 parts of the obtained mixture was stirred in a similar four-necked flask, and the aqueous solution of a chain extender in an agitated state (36.2 parts by weight of isophoronediamine, 46.7 parts by weight of adipic acid dihydrazide). And 36.8 parts by weight of triethylamine, 5.6 parts by weight of diethanolamine, 1248.9 parts by weight of water, and 37.3 parts by weight of isopropyl alcohol), and the whole reaction system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to carry out a chain extension reaction. Next, 2.8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to conduct a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 35.0% by weight and a viscosity of 60 mPa · s / 25 ° C. was obtained.
実施例４
実施例１と同様の４つ口フラスコに、「クラレポリオールＣ２０９０」２１８．６重量部、「アデカポリエーテルＢＰＸ−５５」５４．６重量部、「ＶＥＳＴＡＮＡＴ ＴＭＤＩ」１８７．２重量部、２，２−ジメチロールブタン酸３９．６重量部、およびアクリル酸２−ヒドロキシエチル１２．３重量部を仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約５．０重量％のプレポリマーを得た。次いで、メタクリル酸ラウリル１２５．０重量部を添加し、混合した。次いで、得られた混合物の６２０．０部を、別途用意した同様の４つ口フラスコ内の、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン３６．２重量部、アジピン酸ジヒドラジド４６．７重量部、トリエチルアミン２６．８重量部、ジエタノールアミン５．６重量部、水１２４８．９重量部、イソプロピルアルコール３７．３重量部、）へと徐々に滴下して、反応系全体を混合した。その後、反応系を６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．８重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３５．０重量％、粘度７０ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Example 4
In a four-necked flask similar to that in Example 1, 218.6 parts by weight of “Kuraray polyol C2090”, 54.6 parts by weight of “ADEKA polyether BPX-55”, 187.2 parts by weight of “VESTANATM TMDI”, 2,2 -39.6 parts by weight of dimethylolbutanoic acid and 12.3 parts by weight of 2-hydroxyethyl acrylate were added, and urethanization reaction was performed at 70 ° C for 6 hours, and the content of free isocyanate groups was about 5.0% by weight. Of a prepolymer was obtained. Next, 125.0 parts by weight of lauryl methacrylate was added and mixed. Next, 620.0 parts of the obtained mixture was stirred in a similar four-necked flask, and the aqueous solution of a chain extender in an agitated state (36.2 parts by weight of isophoronediamine, 46.7 parts by weight of adipic acid dihydrazide). And 26.8 parts by weight of triethylamine, 5.6 parts by weight of diethanolamine, 1248.9 parts by weight of water, and 37.3 parts by weight of isopropyl alcohol), and the whole reaction system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to carry out a chain extension reaction. Next, 2.8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to conduct a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 35.0% by weight and a viscosity of 70 mPa · s / 25 ° C. was obtained.
実施例５
実施例１と同様の４つ口フラスコに、「クラレポリオールＣ２０９０」２１３重量部、２，２−ジメチロールブタン酸３６．３重量部、ヘキサメチレンジイソシアネートのアダクト体（製品名「デュラネートＤ−２０１」、旭化成ケミカルズ（株）製）３０１重量部、およびアクリル酸２−ヒドロキシエチル１２重量部を仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約３重量％のプレポリマーを得た。次いで、メタクリル酸メチル１３８重量部を添加し、混合した。次いで、得られた混合物の６８０部を、別途用意した同様の４つ口フラスコ内の、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン９重量部、アジピン酸ジヒドラジド１９．３重量部、トリエチルアミン２４．６重量部、ジエタノールアミン２．２重量部、水１６２６重量部、イソプロピルアルコール４１重量部）へと徐々に滴下して、反応系全体を混合した。その後、反応系を６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）３重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３０重量％、粘度２００ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Example 5
In a four-necked flask similar to Example 1, 213 parts by weight of “Kuraray polyol C2090”, 36.3 parts by weight of 2,2-dimethylolbutanoic acid, and an adduct of hexamethylene diisocyanate (product name “Duranate D-201”). , Manufactured by Asahi Kasei Chemicals Corporation) and 12 parts by weight of 2-hydroxyethyl acrylate, urethanated at 70 ° C. for 6 hours, and a prepolymer having a free isocyanate group content of about 3% by weight Got. Next, 138 parts by weight of methyl methacrylate was added and mixed. Subsequently, 680 parts of the obtained mixture was stirred in a similar four-necked flask, and the aqueous solution of a chain extender (9 parts by weight of isophorone diamine, 19.3 parts by weight of adipic acid dihydrazide, 24. 6 parts by weight, diethanolamine 2.2 parts by weight, water 1626 parts by weight, isopropyl alcohol 41 parts by weight), and the whole reaction system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to carry out a chain extension reaction. Next, 3 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to carry out a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 30% by weight and a viscosity of 200 mPa · s / 25 ° C. was obtained.
実施例６
実施例１と同様の４つ口フラスコに、「クラレポリオールＣ２０９０」２２９重量部、２，２−ジメチロールブタン酸３６．３重量部、ヘキサメチレンジイソシアネートのアロファネート体（製品名「デュラネートＸ−３１３６」、旭化成ケミカルズ（株）製）２８４．４重量部、およびアクリル酸２−ヒドロキシエチル１２重量部を仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約３重量％のプレポリマーを得た。次いで、メタクリル酸メチル１３８重量部を添加し、混合した。次いで、得られた混合物の６８０部を、別途用意した同様の４つ口フラスコ内の、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン９重量部、アジピン酸ジヒドラジド２５．２重量部、トリエチルアミン２４．６重量部、ジエタノールアミン２．２重量部、水１６４１重量部、イソプロピルアルコール４１重量部）へと徐々に滴下して、反応系全体を混合した。その後、反応系を６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）３重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３０重量％、粘度１５０ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Example 6
In a four-necked flask similar to Example 1, 229 parts by weight of “Kuraray polyol C2090”, 36.3 parts by weight of 2,2-dimethylolbutanoic acid, and an allophanate of hexamethylene diisocyanate (product name “Duranate X-3136”) , Manufactured by Asahi Kasei Chemicals Co., Ltd.) 284.4 parts by weight and 12 parts by weight of 2-hydroxyethyl acrylate, subjected to urethanization at 70 ° C. for 6 hours, and a free isocyanate group content of about 3% by weight A prepolymer was obtained. Next, 138 parts by weight of methyl methacrylate was added and mixed. Subsequently, 680 parts of the obtained mixture was stirred in a similar four-necked flask, and the chain extender aqueous solution under stirring (9 parts by weight of isophorone diamine, 25.2 parts by weight of adipic acid dihydrazide, 24. 6 parts by weight, diethanolamine 2.2 parts by weight, water 1641 parts by weight, isopropyl alcohol 41 parts by weight), and the whole reaction system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to carry out a chain extension reaction. Next, 3 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to carry out a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 30% by weight and a viscosity of 150 mPa · s / 25 ° C. was obtained.
比較例１
実施例１と同様の４つ口フラスコに、「クラレポリオールＣ２０９０」２７９．７重量部、２，２−ジメチロールブタン酸３９．６重量部、イソホロンジイソシアネート１８０．８重量部、およびアクリル酸２−ヒドロキシエチルを１２．３部仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約５．０重量％のプレポリマーを得た。次いで、メタクリル酸メチル１２５．０重量部を添加し、混合した。次いで、得られた混合物の６２０．０部を、別途用意した同様の４つ口フラスコ内の、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン３６．０重量部、アジピン酸ジヒドラジド４４．２重量部、トリエチルアミン２６．８重量部、ジエタノールアミン５．６重量部、水１２４３．９重量部、イソプロピルアルコール３７．３重量部）へと徐々に滴下して、反応系全体を混合した。その後、反応系を６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．８重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３５．０重量％、粘度１００ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Comparative Example 1
In a four-necked flask similar to that in Example 1, 279.7 parts by weight of “Kuraray polyol C2090”, 39.6 parts by weight of 2,2-dimethylolbutanoic acid, 180.8 parts by weight of isophorone diisocyanate, and 2-acrylic acid 2- 12.3 parts of hydroxyethyl was charged, and urethanization reaction was performed at 70 ° C. for 6 hours to obtain a prepolymer having a free isocyanate group content of about 5.0% by weight. Next, 125.0 parts by weight of methyl methacrylate was added and mixed. Next, 620.0 parts of the obtained mixture was stirred in a similar four-necked flask, and the aqueous solution of chain extender (36.0 parts by weight of isophorone diamine, 44.2 parts by weight of adipic acid dihydrazide) was stirred. And 26.8 parts by weight of triethylamine, 5.6 parts by weight of diethanolamine, 1243.9 parts by weight of water, and 37.3 parts by weight of isopropyl alcohol), and the whole reaction system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to carry out a chain extension reaction. Next, 2.8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to conduct a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 35.0% by weight and a viscosity of 100 mPa · s / 25 ° C. was obtained.
比較例２
実施例１と同様の４つ口フラスコに、「クラレポリオールＣ２０９０」２７９．７重量部、２，２−ジメチロールブタン酸３９．６重量部、イソホロンジイソシアネート１８０．８重量部、アクリル酸２−ヒドロキシエチルを１２．３部仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約５．０重量％のプレポリマーを得た。次いで、メタクリル酸ラウリル１２５．０重量部を添加し、混合した。次いで、得られた混合物の６２０．０部を、別途用意した同様の４つ口フラスコ内の、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン３６．０重量部、アジピン酸ジヒドラジド４４．２重量部、トリエチルアミン２６．８重量部、ジエタノールアミン５．６重量部、水１２４３．９重量部イソプロピルアルコール３７．３重量部）へと徐々に滴下して、反応系全体を混合した。その後、反応系を６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．８重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３５．０重量％、粘度１２０ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Comparative Example 2
In a four-necked flask similar to that in Example 1, 279.7 parts by weight of “Kuraray polyol C2090”, 39.6 parts by weight of 2,2-dimethylolbutanoic acid, 180.8 parts by weight of isophorone diisocyanate, 2-hydroxy acrylate 12.3 parts of ethyl was charged and subjected to urethanization reaction at 70 ° C. for 6 hours to obtain a prepolymer having a free isocyanate group content of about 5.0% by weight. Next, 125.0 parts by weight of lauryl methacrylate was added and mixed. Next, 620.0 parts of the obtained mixture was stirred in a similar four-necked flask, and the aqueous solution of chain extender (36.0 parts by weight of isophorone diamine, 44.2 parts by weight of adipic acid dihydrazide) was stirred. And 26.8 parts by weight of triethylamine, 5.6 parts by weight of diethanolamine, 1243.9 parts by weight of water and 37.3 parts by weight of isopropyl alcohol), and the whole reaction system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to carry out a chain extension reaction. Next, 2.8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to conduct a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 35.0% by weight and a viscosity of 120 mPa · s / 25 ° C. was obtained.
比較例３
実施例１と同様の４つ口フラスコに、「クラレポリオールＣ２０９０」２１１．９重量部、「アデカポリエーテルＢＰＸ−５５」５３．０重量部、２，２−ジメチロールブタン酸３９．６重量部、イソホロンジイソシアネート１９５．５重量部、アクリル酸２−ヒドロキシエチル１２．４重量部を仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約５．０重量％のプレポリマーを得た。次いで、メタクリル酸メチル１２５．０重量部を添加し、混合した。次いで、得られた混合物の６２０．０部を、別途用意した同様の４つ口フラスコ内の、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン３６．４重量部、アジピン酸ジヒドラジド５０．２重量部、トリエチルアミン２６．８重量部、ジエタノールアミン５．６重量部、水１２５５．８重量部、イソプロピルアルコール３７．３重量部）へと徐々に滴下して、反応系全体を混合した。その後、反応系を６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．８重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３５．０重量％、粘度１３０ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Comparative Example 3
In a four-necked flask similar to that in Example 1, 211.9 parts by weight of “Kuraray polyol C2090”, 53.0 parts by weight of “adecapolyether BPX-55”, 39.6 parts by weight of 2,2-dimethylolbutanoic acid A prepolymer having 195.5 parts by weight of isophorone diisocyanate and 12.4 parts by weight of 2-hydroxyethyl acrylate, subjected to urethanization reaction at 70 ° C. for 6 hours, and having a free isocyanate group content of about 5.0% by weight Got. Next, 125.0 parts by weight of methyl methacrylate was added and mixed. Next, 620.0 parts of the obtained mixture was stirred in a similar four-necked flask, and the aqueous solution of chain extender (36.4 parts by weight of isophoronediamine, 50.2 parts by weight of adipic acid dihydrazide) in a stirred state. 26.8 parts by weight of triethylamine, 5.6 parts by weight of diethanolamine, 1255.8 parts by weight of water, and 37.3 parts by weight of isopropyl alcohol), and the whole reaction system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to carry out a chain extension reaction. Next, 2.8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to conduct a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 35.0% by weight and a viscosity of 130 mPa · s / 25 ° C. was obtained.
比較例４
実施例１と同様の４つ口フラスコに、「クラレポリオールＣ２０９０」２１１．９重量部、「アデカポリエーテルＢＰＸ−５５」５３．０重量部、２，２−ジメチロールブタン酸３９．６重量部、実施例１と同様の４つ口フラスコに、イソホロンジイソシアネート１９５．５重量部、アクリル酸２−ヒドロキシエチル１２．４重量部を仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約５．０重量％のプレポリマーを得た。次いで、メタクリル酸ラウリル１２５．０重量部を添加し、混合した。次いで、得られた混合物の６２０．０部を、別途用意した同様の４つ口フラスコ内の、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン３６．４重量部、アジピン酸ジヒドラジド５０．２重量部、トリエチルアミン２６．８重量部、ジエタノールアミン５．６重量部、水１２５５．８重量部、イソプロピルアルコール３７．３重量部）へと徐々に滴下して、反応系全体を混合した。その後、反応系を６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．８重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３５．０重量％、粘度１４０ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Comparative Example 4
In a four-necked flask similar to that in Example 1, 211.9 parts by weight of “Kuraray polyol C2090”, 53.0 parts by weight of “adecapolyether BPX-55”, 39.6 parts by weight of 2,2-dimethylolbutanoic acid In the same four-necked flask as in Example 1, 195.5 parts by weight of isophorone diisocyanate and 12.4 parts by weight of 2-hydroxyethyl acrylate were subjected to urethanization reaction at 70 ° C. for 6 hours. A prepolymer with a content of about 5.0% by weight was obtained. Next, 125.0 parts by weight of lauryl methacrylate was added and mixed. Next, 620.0 parts of the obtained mixture was stirred in a similar four-necked flask, and the aqueous solution of chain extender (36.4 parts by weight of isophoronediamine, 50.2 parts by weight of adipic acid dihydrazide) in a stirred state. 26.8 parts by weight of triethylamine, 5.6 parts by weight of diethanolamine, 1255.8 parts by weight of water, and 37.3 parts by weight of isopropyl alcohol), and the whole reaction system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to carry out a chain extension reaction. Next, 2.8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to conduct a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 35.0% by weight and a viscosity of 140 mPa · s / 25 ° C. was obtained.
比較例５
実施例１と同様の４つ口フラスコに、市販ポリエステルジオール（製品名「クラレポリオールＰ２０１０」、数平均分子量２０００；クラレ（株）製）２１８．６重量部、「アデカポリエーテルＢＰＸ−５５」５４．６重量部、２，２−ジメチロールブタン酸３９．６重量部、「ＶＥＳＴＡＮＡＴ ＴＭＤＩ」１８７．２重量部、およびアクリル酸２−ヒドロキシエチル１２．３重量部を仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約５．０重量％のプレポリマーを得た。次いで、メタクリル酸メチル１２５．０重量部を添加し、混合した。次いで、得られた混合物の６２０．０部を、別途用意した同様の４つ口フラスコ内の、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン３６．２重量部、アジピン酸ジヒドラジド４６．７重量部、トリエチルアミン２６．８重量部、ジエタノールアミン５．６重量部、水１２４８．９重量部、イソプロピルアルコール３７．３重量部）へと徐々に滴下して、反応系全体を混合した。その後、反応系を６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．８重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３５．０重量％、粘度６０ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Comparative Example 5
In a four-necked flask similar to that in Example 1, 218.6 parts by weight of a commercially available polyester diol (product name “Kuraray polyol P2010”, number average molecular weight 2000; manufactured by Kuraray Co., Ltd.), “ADEKA Polyether BPX-55” 54 .6 parts by weight, 2,2-dimethylolbutanoic acid 39.6 parts by weight, “VESTANATM TMDI” 187.2 parts by weight, and 2-hydroxyethyl acrylate 12.3 parts by weight, urethane at 70 ° C. for 6 hours A prepolymer having a free isocyanate group content of about 5.0% by weight was obtained. Next, 125.0 parts by weight of methyl methacrylate was added and mixed. Next, 620.0 parts of the obtained mixture was stirred in a similar four-necked flask, and the aqueous solution of a chain extender in an agitated state (36.2 parts by weight of isophoronediamine, 46.7 parts by weight of adipic acid dihydrazide). And 36.8 parts by weight of triethylamine, 5.6 parts by weight of diethanolamine, 1248.9 parts by weight of water, and 37.3 parts by weight of isopropyl alcohol), and the whole reaction system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to carry out a chain extension reaction. Next, 2.8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to conduct a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 35.0% by weight and a viscosity of 60 mPa · s / 25 ° C. was obtained.
比較例６
実施例１と同様の４つ口フラスコに、「クラレポリオールＰ２０１０」２１８．６重量部、「アデカポリエーテルＢＰＸ−５５」５４．６重量部、２，２−ジメチロールブタン酸３９．６重量部、「ＶＥＳＴＡＮＡＴ ＴＭＤＩ」１８７．２重量部、アクリル酸２−ヒドロキシエチル１２．３重量部を仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約５．０重量％のプレポリマーを得た。次いで、メタクリル酸ラウリル１２５．０重量部を添加し、混合した。次いで、得られた混合物の６２０．０部を、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン３６．２重量部、アジピン酸ジヒドラジド４６．７重量部、トリエチルアミン２６．８重量部、ジエタノールアミン５．６重量部、水１２４８．９重量部、イソプロピルアルコール３７．３重量部）へと徐々に滴下して、反応系全体を混合した。その後、反応系を６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．８重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３５．０重量％、粘度８０ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Comparative Example 6
In the same four-necked flask as in Example 1, 218.6 parts by weight of “Kuraray polyol P2010”, 54.6 parts by weight of “Adeka polyether BPX-55”, 39.6 parts by weight of 2,2-dimethylolbutanoic acid. , "VESTANATM TMDI" 187.2 parts by weight and 2-hydroxyethyl acrylate 12.3 parts by weight, urethanation reaction is carried out at 70 ° C for 6 hours, and the content of free isocyanate groups is about 5.0% by weight A prepolymer was obtained. Next, 125.0 parts by weight of lauryl methacrylate was added and mixed. Next, 620.0 parts of the resulting mixture was added to an agitated chain extender aqueous solution (36.2 parts by weight of isophorone diamine, 46.7 parts by weight of adipic acid dihydrazide, 26.8 parts by weight of triethylamine, 5.6 parts of diethanolamine). Parts by weight, 1248.9 parts by weight of water, 37.3 parts by weight of isopropyl alcohol), and the whole reaction system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to carry out a chain extension reaction. Next, 2.8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to conduct a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 35.0% by weight and a viscosity of 80 mPa · s / 25 ° C. was obtained.
比較例７
実施例１と同様の４つ口フラスコに、「クラレポリオールＰ２０１０」２１１．９重量部、「アデカポリエーテルＢＰＸ−５５」５３．０重量部、２，２−ジメチロールブタン酸３９．６重量部、イソホロンジイソシアネート１９５．５重量部、アクリル酸２−ヒドロキシエチル１２．４重量部を仕込み、７０℃で６時間ウレタン化反応を行い、遊離イソシアネート基の含有量が約５．０重量％のプレポリマーを得た。次いで、メタクリル酸メチル１２５．０重量部を添加し、混合した。次いで、得られた混合物の６２０．０部を、攪拌状態にある鎖伸長剤水溶液（イソホロンジアミン３６．４重量部、アジピン酸ジヒドラジド５０．２重量部、トリエチルアミン２６．８重量部、ジエタノールアミン５．６重量部、水１２５５．８重量部、イソプロピルアルコール３７．３重量部）へと徐々に滴下して、反応系全体を混合した。その後、反応系を６０℃で２時間攪拌保持して、鎖伸長反応を行なった。次いで、２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．８重量部を添加し、反応系を７０℃で３時間攪拌保持して重合反応を行なった。こうして固形分３５．０重量％、粘度１５０ｍＰａ・ｓ／２５℃のアクリル−ポリウレタンウレア樹脂水分散液を得た。
Comparative Example 7
In a four-necked flask similar to that in Example 1, 211.9 parts by weight of “Kuraray polyol P2010”, 53.0 parts by weight of “ADEKA polyether BPX-55”, 39.6 parts by weight of 2,2-dimethylolbutanoic acid A prepolymer having 195.5 parts by weight of isophorone diisocyanate and 12.4 parts by weight of 2-hydroxyethyl acrylate, subjected to urethanization reaction at 70 ° C. for 6 hours, and having a free isocyanate group content of about 5.0% by weight Got. Next, 125.0 parts by weight of methyl methacrylate was added and mixed. Next, 620.0 parts of the resulting mixture was added to an agitated chain extender aqueous solution (isophoronediamine 36.4 parts by weight, adipic acid dihydrazide 50.2 parts by weight, triethylamine 26.8 parts by weight, diethanolamine 5.6 parts). Parts by weight, 1255.8 parts by weight of water, 37.3 parts by weight of isopropyl alcohol), and the whole reaction system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to carry out a chain extension reaction. Next, 2.8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to conduct a polymerization reaction. Thus, an acrylic-polyurethane urea resin aqueous dispersion having a solid content of 35.0% by weight and a viscosity of 150 mPa · s / 25 ° C. was obtained.
表中、各記号は下記の化合物を表す。；
Ｃ２０９０：ポリカーボネートポリオール
ＢＰＸ−５５：ビスフェノールＡのプロピレンオキシド付加物
ＤＭＢＡ：２，２−ジメチロールブタン酸
ＴＭＤＩ：２，２，４−トリメチルヘキサメチレンジイソシアネートと２，４，４−トリメチルヘキサメチレンジイソシアネートの混合物
ＨＤＩアダクト：ヘキサメチレンジイソシアネートのアダクト体
ＨＤＩアロファネート：ヘキサメチレンジイソシアネートのアロファネート体
ＩＰＤＩ：イソホロンジイソシアネート
２−ＨＥＡ：アクリル酸２−ヒドロキシエチル
ＩＰＤＡ：イソホロンジアミン
ＡＤＨ：アジピン酸ジヒドラジド
ＭＭＡ：メタクリル酸メチル
ＬＭＡ：メタクリル酸ラウリル
In the table, each symbol represents the following compound. ;
C2090: Polycarbonate polyol BPX-55: Propylene oxide adduct of bisphenol A DMBA: 2,2-dimethylolbutanoic acid TMDI: Mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate HDI adduct: hexamethylene diisocyanate adduct HDI allophanate: hexamethylene diisocyanate allophanate IPDI: isophorone diisocyanate 2-HEA: 2-hydroxyethyl acrylate IPDA: isophoronediamine ADH: adipic acid dihydrazide MMA: methyl methacrylate LMA: methacrylic acid Lauril
〔貯蔵安定性の評価〕
上記実施例および比較例で得られた各アクリル−ポリウレタンウレア樹脂水分散液を、４０℃にて３０日間放置し、外観及び粘度の変化を以下の基準で評価した。
結果を表１に示す。
○：外観や粘度の変化がほとんどない。
×：外観において不溶物の沈殿がみられる。
[Evaluation of storage stability]
Each acrylic-polyurethane urea resin aqueous dispersion obtained in the above Examples and Comparative Examples was allowed to stand at 40 ° C. for 30 days, and changes in appearance and viscosity were evaluated according to the following criteria.
The results are shown in Table 1.
○: Almost no change in appearance or viscosity.
X: Precipitation of insoluble matter is observed in appearance.
〔塗工液の調製〕
実施例１のアクリル−ポリウレタンウレア樹脂水分散液と、市販シリカゾル（商品名「スノーテックスＮ」、日産化学（株）製）と、市販シランカップリング剤（商品名「ＫＢＭ‐４０３」、信越化学（株）製）とを、７４：２４．５：１．５の固形分重量比で配合し、塗工液を調製した。実施例２〜６、および比較例１〜７のアクリル−ポリウレタンウレア樹脂水分散液についても同様にして、塗工液を調製した。
[Preparation of coating solution]
Acrylic-polyurethane urea resin aqueous dispersion of Example 1, commercial silica sol (trade name “Snowtex N”, manufactured by Nissan Chemical Co., Ltd.), commercial silane coupling agent (trade name “KBM-403”, Shin-Etsu Chemical) Co., Ltd.) was blended at a solid content weight ratio of 74: 24.5: 1.5 to prepare a coating solution. The coating liquids were similarly prepared for the acrylic-polyurethane urea resin aqueous dispersions of Examples 2 to 6 and Comparative Examples 1 to 7.
〔塗装試験片の作製〕
実施例１に係る塗工液を、亜鉛めっき鋼板（厚さ０．８ｍｍ、幅７０ｍｍ、長さ１５０ｍｍ）に、乾燥膜厚が１μｍになるようにバーコーターにて塗布し、２５０℃で２０秒乾燥して試験片を作製した。実施例２〜６、および比較例１〜７に係る塗工液についても同様にして、試験片を作製した。
[Preparation of paint specimens]
The coating liquid according to Example 1 was applied to a galvanized steel sheet (thickness 0.8 mm, width 70 mm, length 150 mm) with a bar coater so as to have a dry film thickness of 1 μm, and at 250 ° C. for 20 seconds. A test piece was prepared by drying. Test pieces were prepared in the same manner for the coating liquids according to Examples 2 to 6 and Comparative Examples 1 to 7.
〔防錆性の評価〕
各試験片を、塩水噴霧試験機（３５℃、塩水濃度５％、噴霧時間４８時間）にかけた後、水洗いし、塗膜面の錆の発生具合を目視観察し、以下の基準により評価した。
◎：錆の発生が全く認められない。
○：部分的に若干の錆の発生が認められる。
△：全体的に錆の発生が認められる。
[Rust prevention evaluation]
Each test piece was subjected to a salt spray tester (35 ° C., salt water concentration 5%, spray time 48 hours), then washed with water, and the appearance of rust on the coating surface was visually observed and evaluated according to the following criteria.
(Double-circle): Generation | occurrence | production of rust is not recognized at all.
○: Some rust generation is observed partially.
(Triangle | delta): Generation | occurrence | production of rust is recognized as a whole.
〔耐アルカリ性の評価〕
各試験片を、アルカリ水溶液（日本ペイント製ＳＤ−２７０、濃度２０ｇ/Ｌ）に２３℃で３分間浸漬した後、塩水噴霧試験機（３５℃、塩水濃度５％、噴霧時間４８時間）にかけた。その後、各試験片を水洗いし、塗膜面の錆の発生具合を目視観察し、以下の基準により評価した。
◎：アルカリ浸漬部に錆の発生が全く認められない。
○：アルカリ浸漬部に若干の錆の発生が認められる。
△：アルカリ浸漬部の全体に錆の発生が認められる。
×：アルカリ浸漬部の全体に酷い錆の発生が認められる。
[Evaluation of alkali resistance]
Each test piece was immersed in an alkaline aqueous solution (SD-270 manufactured by Nippon Paint, concentration 20 g / L) at 23 ° C. for 3 minutes and then subjected to a salt spray tester (35 ° C., salt concentration 5%, spray time 48 hours). . Then, each test piece was washed with water, the generation | occurrence | production condition of the rust of the coating-film surface was observed visually, and the following references | standards evaluated.
(Double-circle): Generation | occurrence | production of rust is not recognized at all in an alkali immersion part.
○: Some rust is observed in the alkali-immersed part.
(Triangle | delta): Generation | occurrence | production of rust is recognized by the whole alkali immersion part.
X: Generation | occurrence | production of severe rust is recognized by the whole alkali immersion part.
〔加工性の評価〕
各試験片について、エリクセン押し出し試験機（押し出し量７ｍｍ）により押し出し加工を行なった後、塩水噴霧試験機（３５℃、塩水濃度５％、噴霧時間４８時間）にかけた。その後、各試験片を水洗いし、塗膜面の錆の発生具合を目視観察し、以下の基準により評価した。
◎：加工部に錆の発生が全く認められない。
○：加工部に若干の錆の発生が認められる。
△：加工部の全体に錆の発生が認められる。
[Evaluation of workability]
Each test piece was subjected to extrusion processing using an Erichsen extrusion tester (extrusion amount 7 mm) and then subjected to a salt spray tester (35 ° C., salt water concentration 5%, spraying time 48 hours). Then, each test piece was washed with water, the generation | occurrence | production condition of the rust of the coating-film surface was observed visually, and the following references | standards evaluated.
(Double-circle): Generation | occurrence | production of rust is not recognized at all in a processed part.
○: Some rust is observed in the processed part.
(Triangle | delta): Generation | occurrence | production of rust is recognized by the whole process part.
〔耐アルコール性の評価〕
各試験片を、エタノールに２３℃で３分間浸漬した後、塩水噴霧試験機（３５℃、塩水濃度５％、噴霧時間４８時間）にかけた。その後、各試験片を水洗いし、塗膜面の錆の発生具合を目視観察し、以下の基準により評価した。
◎：エタノール浸漬部に錆の発生が全く認められない。
○：エタノール浸漬部に若干の錆の発生が認められる。
△：エタノール浸漬部の全体に錆の発生が認められる。
[Evaluation of alcohol resistance]
Each test piece was immersed in ethanol at 23 ° C. for 3 minutes, and then subjected to a salt spray tester (35 ° C., salt concentration 5%, spray time 48 hours). Then, each test piece was washed with water, the generation | occurrence | production condition of the rust of the coating-film surface was observed visually, and the following references | standards evaluated.
(Double-circle): Generation | occurrence | production of rust is not recognized at all in the ethanol immersion part.
○: Some rust is observed in the ethanol-immersed part.
(Triangle | delta): Generation | occurrence | production of rust is recognized by the whole ethanol immersion part.
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| US10865326B2 (en) | 2017-09-20 | 2020-12-15 | Ppg Industries Ohio, Inc. | Coating compositions, elastic barrier coatings formed therefrom, and methods of applying such coatings |
| US11015084B2 (en) | 2017-09-20 | 2021-05-25 | Ppg Industries Ohio, Inc. | Coating compositions and elastic barrier coatings formed therefrom |
| US11059993B2 (en) | 2018-09-07 | 2021-07-13 | Ppg Industries Ohio, Inc. | Coating composition exhibiting specific gloss properties for extreme washable coatings |
| US11421130B2 (en) | 2018-09-07 | 2022-08-23 | Ppg Industries Ohio, Inc. | Coating composition for extreme washable coatings comprising self-crosslinkable core-shell particles |
| US11111409B2 (en) | 2019-01-03 | 2021-09-07 | Ppg Industries Ohio, Inc. | Coating composition comprising self-crosslinkable core-shell particles and imparting improved stain resistance |
| US10829664B2 (en) | 2019-03-15 | 2020-11-10 | Ppg Industries Ohio, Inc. | Coating compositions containing polythioethers and elastic barrier coatings formed therefrom |
| US10836924B2 (en) | 2019-03-15 | 2020-11-17 | Ppg Industries Ohio, Inc. | Coating compositions and elastic barrier coatings formed therefrom |
| KR102652729B1 (en) * | 2023-11-21 | 2024-04-01 | (주)새론테크 | Eco-friendly paint composition with excellent carbonation and salt damage prevention functions and construction method using the same |
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