JP4102274B2 - Catalyst for urethanization reaction and paint using the same - Google Patents
Catalyst for urethanization reaction and paint using the same Download PDFInfo
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Description
本発明は、新規なウレタン化反応用触媒および同触媒を含む水性二液型ウレタン塗料に関する。 The present invention relates to a novel catalyst for urethanization reaction and an aqueous two-component urethane coating containing the catalyst.
従来の技術としては、例えば有機スズに代表される有機金属化合物は水酸基とイソシアネート基との反応でウレタン結合を形成するような反応の反応触媒として多用されており、例えばポリオール樹脂を塗料成分としポリイソシアネート化合物を硬化剤成分とするような二液型ウレタン塗料組成物などに幅広く用いられている。
一方、近年の環境破壊に対する配慮や法的規制から、従来の有機溶剤を用いた塗料に代わって有機溶剤の環境への排出量の削減を目的とした水性の塗料が多く使用されるようになってきた。
水性塗料に使用される樹脂としては、硬化反応を伴わないような水性樹脂や、硬化剤を使用する場合では水との反応により機能の低下が起こらないような化合物を硬化剤に使用するなどが一般であったが、塗装を行なう直前で塗料と硬化剤とを均一に分散混合するような塗装設備などが開発されたことから、ポリイソシアネート化合物を硬化剤成分に用いる塗料などの応用が可能となり、より耐久性に優れた水性の塗料とポリイソシアネート化合物からなる硬化剤とから構成される二液型ウレタン塗料の使用も検討されている。
二液型ウレタン塗料の利点の一つは、適切なポリオール樹脂からなる塗料とポリイソシアネート化合物を用いれば、耐候性や耐薬品性等の耐久性や機械的特性に優れる硬化物が低温の乾燥で得られる点であり、熱可塑性の汎用プラスチックスのような素材への塗装も可能になる点である。
特に自動車の内外装部品などに使用する塗料では耐候性に優れることも重要であることから、二液型ウレタン塗料では硬化剤として脂肪族系のポリイソシアネート化合物を使用することが一般である。
しかし、脂肪族系のポリイソシアネート化合物と水酸基などの活性水素含有化合物との反応はゆっくりとしたもので、このような塗料組成物を低温条件下、短時間で乾燥する場合には、有効なウレタン化反応用触媒の使用が必須である。
ウレタン化反応用触媒としてはアミン系化合物や有機金属系化合物が有効であるが、有機スズ系化合物の触媒効果は非常に高く、少量の配合で有効に作用することからも、二液型ウレタン塗料の低温短時間硬化には広く有機スズ系化合物が使用されている。
As a conventional technique, for example, an organometallic compound represented by organotin is often used as a reaction catalyst for a reaction in which a urethane bond is formed by a reaction between a hydroxyl group and an isocyanate group. It is widely used in two-component urethane coating compositions that use an isocyanate compound as a curing agent component.
On the other hand, due to recent environmental destruction considerations and legal regulations, water-based paints are often used instead of conventional paints that use organic solvents to reduce emissions of organic solvents into the environment. I came.
Examples of resins used in water-based paints include water-based resins that do not involve a curing reaction, and compounds that do not cause functional deterioration due to reaction with water when a curing agent is used. Although it was common, coating equipment that uniformly disperses and mixes paint and curing agent just before painting has been developed, so it is possible to apply paint that uses polyisocyanate compounds as curing agent components. The use of a two-component urethane paint composed of a water-based paint having higher durability and a curing agent made of a polyisocyanate compound has been studied.
One of the advantages of two-component urethane coatings is that if a coating made of an appropriate polyol resin and a polyisocyanate compound are used, cured products with excellent durability and mechanical properties such as weather resistance and chemical resistance can be dried at low temperatures. This is a point that can be applied to materials such as thermoplastic general-purpose plastics.
In particular, since it is important for paints used for interior and exterior parts of automobiles to have excellent weather resistance, it is common to use an aliphatic polyisocyanate compound as a curing agent in a two-pack type urethane paint.
However, the reaction between an aliphatic polyisocyanate compound and an active hydrogen-containing compound such as a hydroxyl group is slow, and when such a coating composition is dried in a short time under low temperature conditions, it is an effective urethane. It is essential to use a catalyst for the chemical reaction.
Amine-based compounds and organometallic compounds are effective as catalysts for urethanization reactions, but the catalytic effect of organotin-based compounds is very high, and the two-component urethane coatings also work effectively with a small amount of compounding. Organic tin compounds are widely used for low-temperature and short-time curing.
従来の技術にあっては、水性の二液型ウレタン塗料でも低温条件下、短時間の乾燥で硬化させるには有効なウレタン化反応用触媒の使用が必須であることから、有機スズ系化合物を乳化剤を用いて乳化して二液型水性ウレタン塗料中に加えることにより低温条件下、短時間での乾操を達成させることが考えられる。しかし、この場合、液状の有機スズ化合物を乳化剤として用いて水中に分散させたようなウレタン化反応用触媒を用いた場合では水中で有機スズ化合物の分解反応などが起きることに起因して経時的にウレタン化反応用触媒としての活性が低下してしまうという問題があった。
さらに、塗料にそのようなウレタン化反応用触媒を加えた場合では、塗料の保存中に触媒成分が分離する問題も発生しやすく、そのような塗料を塗装した場合には塗膜中にウレタン化反応用触媒が均一に分布しないことから、塗装乾燥後の塗膜の外観に光沢度が高く、鮮映性に優れた仕上がりを求める塗料では、仕上がった塗膜の外観は鮮映性に欠けるといった不具合が生じる。
また、例えば、特開平８−１６５３１８号公報等に開示されているように、有機スズ系触媒の存在下、ポリオール化合物、ポリイソシアネート化合物、イソシアネート基と反応性を有するラジカル重合性モノマー等を水媒体中で重合させて水系のウレタン樹脂を得る方法はあるが、触媒の分解反応に関する安定性に問題がある。なお、本発明におけるようなウレタン化反応に対して活性を有する触媒の存在下、ラジカル重合性モノマーを水媒体中で重合させて得られる乳化された樹脂に担持されたウレタン化反応用触媒や有機金属化合物と高分子化合物の混合物を水中で乳化して得られるウレタン化反応用触媒に関する報告は従来なかった。
In conventional technologies, it is essential to use an effective catalyst for urethanization reaction to cure in a short time under low temperature conditions even with aqueous two-component urethane paints. It is conceivable to achieve drying in a short time under low temperature conditions by emulsifying with an emulsifier and adding it to a two-component aqueous urethane paint. However, in this case, when a catalyst for urethanation reaction in which a liquid organotin compound is used as an emulsifier and dispersed in water is used, the decomposition reaction of the organotin compound occurs in water. However, there is a problem that the activity as a catalyst for urethanization reaction is lowered.
In addition, when such a catalyst for urethanization reaction is added to the paint, the problem of separation of the catalyst component during storage of the paint is likely to occur, and when such paint is applied, urethanization occurs in the coating film. Because the reaction catalyst is not uniformly distributed, the paint film that has a high gloss appearance and a finish that requires excellent finish after painting and drying has a poor appearance. A malfunction occurs.
In addition, as disclosed in, for example, JP-A-8-165318, a polyol compound, a polyisocyanate compound, a radical polymerizable monomer having reactivity with an isocyanate group, and the like in the presence of an organotin catalyst are used as an aqueous medium. Although there is a method for obtaining a water-based urethane resin by polymerization in the inside, there is a problem in stability regarding the decomposition reaction of the catalyst. In the present invention, a catalyst for urethanization reaction or organic supported on an emulsified resin obtained by polymerizing a radical polymerizable monomer in an aqueous medium in the presence of a catalyst having activity for urethanation reaction as in the present invention. There has been no report on a catalyst for urethanization reaction obtained by emulsifying a mixture of a metal compound and a polymer compound in water.
この発明は、このような従来の問題点に着目してなされたものであって、乳化重合することにより微細化した樹脂粒子中にウレタン化反応用触媒としての効果が大きい有機金属化合物を含有させることによって上記問題点の解決に至ったものである。
本発明者らは、乳化重合することにより微細化された樹脂中にウレタン化反応用触媒となりうる有機金属化合物を含有させることにより、単に有機金属化合物を乳化したウレタン化反応用触媒と比べて水分による有機金属化合物の分解や触媒活性の劣化が著しく抑えられ、水中でのウレタン化反応用触媒の効果が長期に亘って持続されることを見出した。
また、本発明者らは、液状の有機金属化合物の乳化物に見られる乳化物のブロッキングなどによる貯蔵安定性に対する問題も、本発明のウレタン化反応用触媒によって回避できることを見出した。
さらに、本発明者らは、乳化重合により得られる樹脂粒子のサイズを重合条件を適切に設定することにより非常に微細に調整することが可能なため、ウレタン化反応を起す組成物中に均一に近い形でウレタン化反応用触媒を分布させることが可能なことから、単に有機金属化合物を乳化したウレタン化反応用触媒と比べ触媒としての活性も高くなることを見出した。
加えて、本発明者らは、塗料用途などにおいて、塗装乾燥後に仕上がった塗膜表面の光沢や鮮映性などの外観を重視する塗料での応用では、ウレタン化反応用触媒を含む微細な樹脂粒子を塗料中に均一に分布させることができることから、極めて平坦性が高く光沢感のある水性の二液型ウレタン塗料を得ることが可能となることを見出した。
The present invention has been made paying attention to such conventional problems, and contains an organometallic compound having a large effect as a catalyst for urethanization reaction in the resin particles refined by emulsion polymerization. As a result, the above problems have been solved.
By including an organometallic compound that can be a catalyst for urethanization reaction in a resin that has been refined by emulsion polymerization, the present inventors have compared with a urethanization reaction catalyst that simply emulsifies an organometallic compound. It has been found that the decomposition of the organometallic compound and the deterioration of the catalytic activity due to the reaction are remarkably suppressed, and the effect of the catalyst for the urethanization reaction in water is sustained for a long time.
Further, the present inventors have found that the problem of storage stability due to blocking of an emulsion found in an emulsion of a liquid organometallic compound can be avoided by the catalyst for urethanization reaction of the present invention.
Furthermore, the present inventors can adjust the size of the resin particles obtained by emulsion polymerization very finely by appropriately setting the polymerization conditions. Since the catalyst for urethanization reaction can be distributed in a close form, it has been found that the activity as a catalyst is higher than that of a catalyst for urethanation reaction simply emulsified with an organometallic compound.
In addition, the present inventors have applied a fine resin containing a catalyst for urethanization reaction in applications where the emphasis is on the appearance such as gloss and sharpness of the coating film surface that has been finished after coating and drying. since it is possible to uniformly distribute the particles in the coating, we have found that it is possible to obtain a very flatness of high gloss two-component type urethane paint aqueous.
すなわち、本発明の第１は、ウレタン化反応に対して触媒活性のある少なくとも１種類の有機金属化合物の存在下、ラジカル重合性を有するメタクリル酸のエステル、アクリル酸のエステル、およびビニル芳香族化合物を単独もしくは数種類を併用して水中で乳化重合することにより得られることを特徴とするウレタン化反応用触媒を提供する。
本発明の第２は、前記有機金属化合物が少なくとも１種類の有機スズ化合物である上記発明１に記載のウレタン化反応用触媒を提供する。
本発明の第３は、前記有機金属化合物の含有量が１〜２０重量％である上記発明１または２に記載のウレタン化反応用触媒を提供する。
本発明の第４は、前記ラジカル重合性を有するメタクリル酸のエステル、アクリル酸のエステル、およびビニル芳香族化合物が、活性水素を有するメタクリル酸のエステル、アクリル酸のエステル、およびビニル化合物である上記発明１または２に記載のウレタン化反応用触媒を提供する。
本発明の第５は、前記活性水素を有するメタクリル酸のエステル、アクリル酸のエステル、およびビニル芳香族化合物が、活性水素をもった水酸基を有するメタクリル酸のエステル、アクリル酸のエステル、およびビニル芳香族化合物であり、得られる樹脂成分の有する水酸基価が１０〜１００ｍｇＫＯＨ/ｇである上記発明４に記載のウレタン化反応用触媒を提供する。
本発明の第６は、上記発明１〜５のいずれかに記載のウレタン化反応用触媒および水性の硬化性樹脂組成物を主成分とすることを特徴とする水性二液型ウレタン塗料を提供する。
That is, the first of the present invention is a methacrylic acid ester, an acrylic acid ester, and a vinyl aromatic compound having radical polymerizability in the presence of at least one organometallic compound having catalytic activity for the urethanization reaction . It is possible to provide a catalyst for urethanization reaction obtained by emulsion polymerization in water alone or in combination of several kinds .
A second aspect of the present invention provides the catalyst for urethanization reaction according to the first aspect, wherein the organometallic compound is at least one organotin compound.
3rd of this invention provides the catalyst for urethanation reactions of the said invention 1 or 2 whose content of the said organometallic compound is 1-20 weight% .
According to a fourth aspect of the present invention, the methacrylic acid ester, acrylic acid ester, and vinyl aromatic compound having radical polymerization are the methacrylic acid ester, acrylic acid ester, and vinyl compound having active hydrogen. A catalyst for urethanization reaction according to invention 1 or 2 is provided.
According to a fifth aspect of the present invention, the ester of methacrylic acid having an active hydrogen, the ester of acrylic acid, and the vinyl aromatic compound are an ester of methacrylic acid having a hydroxyl group having an active hydrogen, an ester of acrylic acid, and a vinyl aromatic. The catalyst for urethanization reaction of the said invention 4 which is a group compound and the hydroxyl value which the resin component obtained has is 10-100 mgKOH / g .
According to a sixth aspect of the present invention, there is provided an aqueous two-component urethane paint characterized by comprising the urethanization reaction catalyst according to any one of the first to fifth aspects of the invention and an aqueous curable resin composition as main components. .
本発明においては、乳化により微細化した樹脂粒子中にウレタン化反応に対して触媒活性のある有機金属化合物を含有させたウレタン化反応用触媒により、水分による有機金属化合物の分解や触媒活性の劣化を抑えた安定性の良い有機金属系ウレタン化反応用触媒の提供が可能になった。また、この触媒を含むポリウレタン組成物を塗料に応用することにより、硬化性に優れ、かつ、塗膜の平坦性に優れた水性二液型ウレタン塗料を提供することが可能になった。 In the present invention, the decomposition of the organometallic compound or the degradation of the catalytic activity due to moisture is caused by the catalyst for the urethanization reaction containing the organometallic compound having catalytic activity for the urethanization reaction in the resin particles refined by emulsification. It has become possible to provide a highly stable organometallic urethanization catalyst that suppresses the above-mentioned problem. In addition, by applying a polyurethane composition containing this catalyst to a paint, it is possible to provide an aqueous two-component urethane paint having excellent curability and excellent flatness of a coating film.
以下、本発明を詳細に説明する。
本発明のウレタン化反応用触媒に用いる有機金属化合物としては、ウレタン化反応に対して触媒活性のある有機金属化合物であり、例えばナフテン酸コバルト等の有機コバルト化合物、テトラ−ｎ−ブチルスズ、トリメチルスズヒドロキシド、ジメチル二塩化スズ、ジ−ｎ−ブチルスズジラウレート、オクトエ酸スズなどの有機スズ化合物を例示することが出来る。中でも、本発明のウレタン反応触媒が使用される環境は主に水分を含有する系であるため、耐加水分解性に優れているという観点からジ−ｎ−ブチルスズジラウレート、オクトエ酸スズなどが特に好ましい。
これら有機金属化合物の大部分は水中に分散した樹脂粒子をマトリックスとして存在し、有機金属化合物を含む樹脂粒子中の有機金属化合物の割合は、０．２重量％〜２０．０重量％が好ましい。より好ましくは１．０％〜１０．０％である。０．２重量％未満ではウレタン化反応用触媒としての活性が低くなるために好ましくない。また２０．０重量％より多い場合、樹脂粒子中に含まれている分以外に、水中に遊離の状態で存在する有機金属化合物の含有量が増えるために好ましくない。一方、２０．０％より多い場合、乳化重合時の重合安定性も低下するために好ましくない。
このような有機金属化合物とアミン化合物とを併用することによりウレタン化反応の触媒活性はさらに高まることから、例えば、テトラメチルブタンジアミン、１，４−ジアザビシクロ［２，２，２］オクタン、トリエチルアミン、トリエチレンジアミンなどの３級アミン系化合物などを併用することも可能である。
Hereinafter, the present invention will be described in detail.
The organometallic compound used in the catalyst for urethanization reaction of the present invention is an organometallic compound having catalytic activity for the urethanization reaction, for example, an organocobalt compound such as cobalt naphthenate, tetra-n-butyltin, trimethyltin. Examples thereof include organic tin compounds such as hydroxide, dimethyltin dichloride, di-n-butyltin dilaurate and tin octoate. Among them, since the environment in which the urethane reaction catalyst of the present invention is used is a system mainly containing water, di-n-butyltin dilaurate, tin octoate and the like are particularly preferable from the viewpoint of excellent hydrolysis resistance. .
Most of these organometallic compounds are present in the form of resin particles dispersed in water as a matrix, and the ratio of the organometallic compound in the resin particles containing the organometallic compound is preferably 0.2% by weight to 20.0% by weight. More preferably, it is 1.0% to 10.0%. If it is less than 0.2% by weight, the activity as a catalyst for urethanization reaction becomes low, which is not preferable. Moreover, when more than 20.0 weight%, since the content of the organometallic compound which exists in the free state in water other than the part contained in the resin particle increases, it is not preferable. On the other hand, if it is more than 20.0%, the polymerization stability during emulsion polymerization is also lowered, which is not preferable.
Since the catalytic activity of the urethanization reaction is further enhanced by using such an organometallic compound and an amine compound in combination, for example, tetramethylbutanediamine, 1,4-diazabicyclo [2,2,2] octane, triethylamine, A tertiary amine compound such as triethylenediamine may be used in combination.
本発明のウレタン化反応用触媒は、上記有機金属化合物存在下、ラジカル重合性化合物を水中で乳化重合して得られるが、ラジカル重合性化合物としては単独もしくは数種類を併用することができる。ラジカル重合により、有機金属化合物を含む高分子化合物を形成する場合、以下のような化合物が使用できる。
例えば、アクリル酸またはメタクリル酸のエステル、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸ブチル、アクリル酸へキシル、アクリル酸オクチル、アクリル酸ラウリル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸イソプロピル、メタクリル酸ブチル、メタクリル酸へキシル、メタクリル酸オクチル、メタクリル酸ラウリル等のアクリル酸またはメタクリル酸の炭素数１〜１８のアルキルエステル、アクリル酸メトキシブチル、メタクリル酸メトキシブチル、アクリル酸メトキシエチル、メタクリル酸メトキシエチル、アクリル酸エトキシブチル、メタクリル酸エトキシブチル等のアクリル酸またはメタクリル酸の炭素数２〜１８のアルコキシアルキルエステル、アリルアクリレート、アリルメタクリレート等のアクリル酸またはメタクリル酸の炭素数２〜８のアルケニルエステル、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート等のアクリル酸またはメタクリル酸の炭素数２〜８のヒドロキシアルキルエステル、アリルオキシエチルアクリレート、アリルオキシエチルメククリレート等のアクリル酸またはメタクリル酸の炭素数３〜１８のアルケニルオキシアルキルエステル、ビニル芳香族化合物、例えば、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−クロルスチレン、ポリオレフィン系化合物、例えば、ブタジエン、イソプレン、クロロプレン、その他、カプロラクトン変性アクリル酸エステル化合物、カプロラクトン変性メタクリル酸エステル、アクリロニトリル、メタクリロニトリル、メチルイソプロぺニルケトン、酢酸ビニル、ビニルプロピオネート、ビニルピバレート、アクリルアミド、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、Ｎ−メチロールアクリルアミドブチルエーテル、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルメタクリレート、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、アリルアルコール、マレイン酸などを例示することができる。
ラジカル重合性化合物の使用量は水１００重量部に対して５〜５０重量部、好ましくは、１０〜４０重量部、さらに好ましくは、１０〜３０重量部である。５重量部未満では乳化樹脂として得られる触媒の濃度が低くなり、逆に５０重量部を超える場合、原理的に触媒粒子の微分散化を妨げる方向に作用するので、いずれも好ましくない。
The catalyst for urethanization reaction of the present invention can be obtained by emulsion polymerization of a radically polymerizable compound in water in the presence of the organometallic compound, and the radically polymerizable compound can be used alone or in combination of several kinds. When a polymer compound containing an organometallic compound is formed by radical polymerization, the following compounds can be used.
For example, esters of acrylic acid or methacrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, methacryl ethyl, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, alkyl esters having 1 to 18 carbon atoms of acrylic acid or methacrylic acid lauryl methacrylate, methoxybutyl acrylate, methacrylic Of acrylic acid or methacrylic acid such as methoxybutyl acid, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc. C2-C8 alkenyl ester of acrylic acid or methacrylic acid such as koxyalkyl ester, allyl acrylate, allyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate C2-C8 hydroxyalkyl ester of acrylic acid or methacrylic acid, etc., C3-C18 alkenyloxyalkyl ester of acrylic acid or methacrylic acid such as allyloxyethyl acrylate, allyloxyethyl methacrylate, etc., vinyl aroma Group compounds such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, polyolefin compounds, eg For example, butadiene, isoprene, chloroprene, other caprolactone-modified acrylic ester compounds, caprolactone-modified methacrylate esters, acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate, vinyl propionate, vinyl pivalate, acrylamide, N-methylol acrylamide N-methylol methacrylamide, N-methylol acrylamide butyl ether, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, allyl alcohol, maleic acid and the like.
The usage-amount of a radically polymerizable compound is 5-50 weight part with respect to 100 weight part of water, Preferably, it is 10-40 weight part, More preferably, it is 10-30 weight part. If the amount is less than 5 parts by weight, the concentration of the catalyst obtained as an emulsified resin is low. On the other hand, if it exceeds 50 parts by weight, in principle, it acts in the direction of preventing fine dispersion of the catalyst particles, so neither is preferred.
また、本発明のウレタン化反応用触媒を傷付き性や衝撃性に対する耐久性を求められるような水性二液型ウレタン塗料などのウレタン化反応用触媒として用いる場合には、上記ラジカル重合性化合物の成分にイソシアネート基と化学結合をする活性水素を有する官能基をもったラジカル重合性化合物を使用することが好ましい。
この理由は、本発明のウレタン化反応用触媒は樹脂成分を多く含むため、樹脂成分に結合した、活性水素を有する官能基は硬化剤として使用されるイソシアネート化合物と反応し、化学結合を作るために耐久性に優れた硬化組成物が得られるからである。
この活性水素を有する官能基としては、カルボキシル基、アミノ基、チオール基、水酸基などが例示できるが、硬化性組成物の反応性、耐候性、臭気を考えた場合、水酸基であることが好ましい。具体的に好ましい化合物としては、上記ラジカル重合性化合物の中でヒドロキシエチルアクリレート等アクリル酸またはメタクリル酸の炭素数２〜８のヒドロキシアルキルエステルである。
乳化重合して得られる高分子化合物中のこれら化合物の含有量を水酸基価で表すと１０〜１００ｍｇＫＯＨ/ｇ、好ましくは、１０〜８０ｍｇＫＯＨ／ｇ、さらに好ましくは、２０〜６０ｍｇＫＯＨ／ｇである。１０ｍｇＫＯＨ/ｇ未満では硬化性組成物の耐久性の向上への寄与が少ないために好ましくない。一方、１００ｍｇＫＯＨ/ｇを超える場合、樹脂の親水性が高くなるために、樹脂粒子中に含まれる水分が多くなり、結果、樹脂粒子中の有機金属化合物の分解や劣化が起きやすくなるために好ましくない。
In addition, when the urethanization reaction catalyst of the present invention is used as a urethanization reaction catalyst such as an aqueous two-component urethane paint that requires durability against scratching and impact properties, It is preferable to use a radically polymerizable compound having a functional group having an active hydrogen that chemically bonds to an isocyanate group as a component.
This is because the catalyst for urethanization reaction of the present invention contains a large amount of resin components, so that the functional group having active hydrogen bonded to the resin component reacts with an isocyanate compound used as a curing agent to form a chemical bond. This is because a cured composition having excellent durability can be obtained.
Examples of the functional group having active hydrogen include a carboxyl group, an amino group, a thiol group, a hydroxyl group, and the like, but considering the reactivity, weather resistance, and odor of the curable composition, a hydroxyl group is preferable. Specifically preferred compounds are hydroxyalkyl esters of acrylic acid or methacrylic acid having 2 to 8 carbon atoms such as hydroxyethyl acrylate among the above radical polymerizable compounds.
The content of these compounds in the polymer compound obtained by emulsion polymerization is 10 to 100 mgKOH / g, preferably 10 to 80 mgKOH / g, more preferably 20 to 60 mgKOH / g in terms of hydroxyl value. If it is less than 10 mgKOH / g, the contribution to improving the durability of the curable composition is small, such being undesirable. On the other hand, when it exceeds 100 mgKOH / g, the hydrophilicity of the resin is increased, so that the moisture contained in the resin particles is increased, and as a result, decomposition and deterioration of the organometallic compound in the resin particles are likely to occur. Absent.
本発明のウレタン化反応用触媒は、一般的なラジカル重合性化合物の乳化重合処方と同様の方法、条件で得ることができ、そのような合成反応の一例としては、例えば適量のイオン交換水の入っている反応容器を５０℃以上１００℃以下の温度に保ち、別に用意したラジカル重合性化合物と有機金属化合物と水溶性ラジカル重合開始剤とイオン交換水と乳化剤の混合物とからなるプレ乳化物を反応容器内に数時間かけて滴下する乳化重合方法や、前記プレ乳化物の一部をあらかじめイオン交換水と共に反応容器に加え、温度を上げることによって乳化重合におけるシード粒子を得、その後に残りの前記プレ乳化物を数時間に亘って滴下する方法などを例示することができる。なお、前記の例中にある水溶性のラジカル重合開始剤としては、例えばペルオキソ二硫酸アンモニウムやペルオキソ二硫酸カリウムなどの水溶性のラジカル重合開始剤を例示することができる。場合によっては、非水溶性のラジカル重合開始剤を単独で、もしくは前記水溶性のラジカル重合開始剤と併用することも可能である。 The catalyst for urethanization reaction of the present invention can be obtained by the same method and conditions as the emulsion polymerization prescription of a general radical polymerizable compound. As an example of such a synthesis reaction, for example, an appropriate amount of ion-exchanged water is used. A pre-emulsion comprising a mixture of a radically polymerizable compound, an organometallic compound, a water-soluble radical polymerization initiator, ion-exchanged water and an emulsifier prepared separately is maintained at a temperature of 50 ° C. to 100 ° C. An emulsion polymerization method in which the reaction vessel is dropped over several hours, a part of the pre-emulsion is added to the reaction vessel together with ion-exchanged water in advance, and the seed particles in the emulsion polymerization are obtained by raising the temperature. Examples thereof include a method of dripping the pre-emulsion over several hours. Examples of the water-soluble radical polymerization initiator in the above examples include water-soluble radical polymerization initiators such as ammonium peroxodisulfate and potassium peroxodisulfate. In some cases, a water-insoluble radical polymerization initiator can be used alone or in combination with the water-soluble radical polymerization initiator.
乳化重合処方に使用できる乳化剤としては、一般にラジカル重合性単量体の乳化重合で使用されているものが使用でき、例えば、一般に公知のノニオン系、アニオン系、カチオン系の乳化剤、さらに高分子型の乳化剤や反応性の乳化剤も使用することが可能である。しかし、使用する乳化剤の種類や使用量によって、乳化物を処方する時の安定性に影響を及ぼすため、適切な選択が必要である。前記乳化剤として、例えば非イオン型の乳化剤としてはポリオキシエチレンノニルフェニルエーテル系乳化剤、ポリオキシエチレンオクチルフェニルエーテル系乳化剤、ポリオキシエチレン２−へキシルエーテル系乳化剤、ポリオキシエチレンラウリルエーテル系乳化剤、ポリオキシエチレントリデシルエーテル系乳化剤、ポリオキシエチレンヒマシ油エーテル系乳化剤、ポリオキシエチレンセチルエーテル系乳化剤、ポリオキシエチレンステアリルエーテル系乳化剤、ポリオキシエチレンアルキレンアルキル系乳化剤、ポリオキシアルキレングリコール系乳化剤、ポリオキシエチレンオレエート系乳化剤、ポリオキシエチレンアルキルアミン系乳化剤、ポリオキシエチレンソルビタンアルキル系乳化剤、ポリオキシエチレン多環フェニルエーテル系乳化剤、ポリオキシアルキレン多環フェニルエーテル系乳化剤、ポリオキシアルキレンノニルフェニルエーテル系乳化剤等、陰イオン型の乳化剤としては、ドデシルベンゼンスルホン酸アンモニウム塩系乳化剤、ドデシルベンゼンスルホン酸ナトリウム塩系乳化剤、ドデシルベンゼンスルホン酸カルシウム塩系乳化剤、アルキレンジスルホン酸ナトリウム塩系乳化剤、アルキルジフェニルエーテルジスルホン酸塩系乳化剤、ジアルキルサクシネートスルホン酸塩系乳化剤、モノアルキルサクシネートスルホン酸塩系乳化剤、ポリオキシエチレンノニルフェニルエーテル硫酸エステル塩系乳化剤、ポリオキシエチレンアルキルエーテル硫酸エステル塩系乳化剤、ポリオキシエチレンアリルエーテル硫酸エステル塩系乳化剤、ポリオキシエチレンノニルフェニルエーテルりん酸エステル系乳化剤、ポリオキシエチレンアルキルエーテルりん酸エステル系乳化剤等、その他陽イオン型の乳化剤、両性イオン系の乳化剤および高分子型、反応型の乳化剤なども例示することができる。 As emulsifiers which can be used for the emulsion polymerization formulation, General can be used those used in the emulsion polymerization of radically polymerizable monomers in, for example, commonly known nonionic, anionic, cationic emulsifiers, a higher Molecular type emulsifiers and reactive emulsifiers can also be used. However, depending on the type and amount of the emulsifier used, the stability at the time of formulating the emulsion is affected, so an appropriate selection is necessary. As the emulsifier, for example nonionic polyoxyethylene nonylphenyl ether emulsifier as the emulsifier, polyoxyethylene octylphenyl ether emulsifiers, polyoxyethylene to 2 alkoxy Rue ether emulsifiers, polyoxyethylene lauryl ether emulsifier, Polyoxyethylene tridecyl ether emulsifier, polyoxyethylene castor oil ether emulsifier, polyoxyethylene cetyl ether emulsifier, polyoxyethylene stearyl ether emulsifier, polyoxyethylene alkylenealkyl emulsifier, polyoxyalkylene glycol emulsifier, poly Oxyethylene oleate emulsifier, polyoxyethylene alkylamine emulsifier, polyoxyethylene sorbitan alkyl emulsifier, polyoxyethylene polycyclic phenyl ester Ether emulsifiers, polyoxyalkylene polycyclic phenyl ether emulsifiers, polyoxyalkylene nonyl phenyl ether emulsifier. Examples of anionic emulsifiers, ammonium salt emulsifier dodecylbenzenesulfonate, sodium salt emulsifier dodecylbenzenesulfonate, Dodecylbenzene sulfonate calcium salt emulsifier , alkylene disulfonic acid sodium salt emulsifier, alkyl diphenyl ether disulfonate emulsifier, dialkyl succinate sulfonate emulsifier, monoalkyl succinate sulfonate emulsifier, polyoxyethylene nonyl phenyl ether Sulfate ester emulsifier, polyoxyethylene alkyl ether sulfate ester emulsifier, polyoxyethylene allyl ether sulfate ester emulsifier, polyoxy Tylene nonylphenyl ether phosphate ester emulsifiers, polyoxyethylene alkyl ether phosphate ester emulsifiers, and other cationic emulsifiers, zwitterionic emulsifiers and polymer type, reactive emulsifiers and the like can also be exemplified. .
乳化剤の添加量は使用するラジカル重合性化合物に対して多くなるほど粒子径の小さいウレタン化反応用触媒が得られ、また乳化重合におけるモノマー混合物のプレ乳化物の濃度は低いほど粒子径の小さいウレタン化反応用触媒が得られる。これは本発明の関与する処方の原理から、有機金属触媒を含むプレ乳化物の粒子径が小さいほど生成するウレタン化反応用触媒の粒子径が小さくなるからである。よって、プレ乳化物の粒子径を小さく設定するほど微細に分散したウレタン化反応用触媒が得られ、その結果、触媒効力などに優れたウレタン化反応用触媒が得られる。
しかし使用する乳化剤の量は、ラジカル重合性化合物の１００重量部に対して２〜２０重量部、好ましくは３〜１５重量部、さらに好ましくは５〜１０重量部の乳化剤を使用するのが一般である。２重量部より少ないと、乳化重合が不安定となり、２０重量部より多いと、触媒中に含まれる乳化剤が多く存在することから、本触媒を用いたコーティング剤や接着剤の耐水性などの耐久性を低下させるので、いずれも好ましくない。
しかしながら、極めて微粒子化された触媒を得る必要があるときは、２０重量部以上の乳化剤の使用も可能であり、この場合はラジカル重合性の乳化剤の使用、もしくはラジカル重合性の乳化剤と一般の乳化剤を併用することにより前記問題点は軽減される。
As the amount of emulsifier added increases with respect to the radical polymerizable compound used, a catalyst for urethanization reaction with a smaller particle size is obtained. Also, the lower the concentration of the pre-emulsion of the monomer mixture in emulsion polymerization, the smaller the particle size urethanization. A reaction catalyst is obtained. This is because, based on the principle of the formulation involved in the present invention, the smaller the particle size of the pre-emulsion containing the organometallic catalyst, the smaller the particle size of the urethanization reaction catalyst that is generated. Therefore, a urethanization reaction catalyst that is finely dispersed as the particle size of the pre-emulsion is set smaller is obtained, and as a result, a urethanization reaction catalyst having excellent catalytic efficacy and the like is obtained.
However, the amount of the emulsifier to be used is generally 2 to 20 parts by weight, preferably 3 to 15 parts by weight, more preferably 5 to 10 parts by weight, based on 100 parts by weight of the radical polymerizable compound. is there. If the amount is less than 2 parts by weight, the emulsion polymerization becomes unstable. If the amount is more than 20 parts by weight, since there are many emulsifiers contained in the catalyst, durability such as water resistance of a coating agent and an adhesive using the catalyst is present. Neither is preferred because it reduces the properties.
However, when it is necessary to obtain an extremely finely divided catalyst, it is possible to use 20 parts by weight or more of an emulsifier. In this case, use of a radical polymerizable emulsifier or a radical polymerizable emulsifier and a general emulsifier The above problems are alleviated by using together.
本発明における調製方法により得られるウレタン化反応用触媒の成分の構成は原理的に、有機金属化合物と乳化剤から構成される粒子、有機金属化合物を含有する樹脂粒子、有機金属化合物を含有しない樹脂粒子の、３種類の成分からなる粒子混合物として得られる。 In principle, the components of the catalyst for urethanization reaction obtained by the preparation method of the present invention are particles composed of an organometallic compound and an emulsifier, resin particles containing an organometallic compound, and resin particles not containing an organometallic compound. Obtained as a particle mixture composed of three kinds of components.
重要となるのは有機金属化合物を含有する粒子であり、この粒子についての大きさについて言及すれば、特に乳化重合により得られる触媒を含有する樹脂粒子のサイズは通常、０．０２〜１．０μｍ、好ましくは、０．０２〜０．５μｍ、さらに好ましくは、０．０２〜０．２μｍである。樹脂粒子のサイズが０．０２μｍ未満では、原理的にさまざまな問題が生じるために好ましくない。この問題について説明すると、本発明の触媒製造の原理を考えた場合、例えば体積として１％の有機金属化合物を含有するようなラジカル重合性化合物と有機金属化合物の混合物を例にすると、この混合物からなるプレ乳化物の直径が０．１μｍであったと仮定すれば、乳化重合が進むに従ってプレ乳化物中のラジカル重合性化合物は消費されその粒子径は小さくなっていく。仮にこの乳化重合が乳化重合理論の仮定に従い重合はポリマーミセル中のみで進行してモノマー粒子中では起こらないと仮定するならば、生成する金属粒子の直径は初期のプレ乳化物粒子の体積の１００分の１になる。よって直径は約４．６５分の１となるのでおよそ０．０２μｍ程度の有機金属化合物を有する粒子が得られることになる。
このことを鑑みると、プレ乳化物の直径を０．１μｍ以下にすることは非常に強力な機械的な乳化と多量の乳化剤を必要とすることから経済的でない。プレ乳化物中に含まれる有機金属化合物の体積を１％以下に抑えることによっても粒子径の小さな触媒を得ることは可能であるが、この場合はウレタン化反応用触媒としての有機金属化合物の含有量が極端に少なくなることから、触媒としての機能が十分に発揮されないために好ましくない。
また、１．０μｍより大きいと、本発明の触媒を含む水性のポリウレタン組成物をコーティング剤などに応用した場合に、触媒は十分均一に分散した状態ではないために、十分な触媒効果が得られない等の問題が生じるため、好ましくない。
What is important is a particle containing an organometallic compound. When referring to the size of this particle, the size of the resin particle containing a catalyst obtained by emulsion polymerization is usually 0.02 to 1.0 μm. m , preferably 0.02 to 0.5 μm, more preferably 0.02 to 0.2 μm. If the size of the resin particles is less than 0.02 μm, various problems arise in principle, which is not preferable. This problem will be described. When the principle of the catalyst production of the present invention is considered, for example, a mixture of a radical polymerizable compound and an organometallic compound containing 1% by volume of an organometallic compound is taken as an example. Assuming that the diameter of the resulting pre-emulsion is 0.1 μm, the radical polymerizable compound in the pre-emulsion is consumed and the particle diameter becomes smaller as the emulsion polymerization proceeds. If this emulsion polymerization assumes that the polymerization proceeds only in the polymer micelles and does not occur in the monomer particles according to the assumption of the emulsion polymerization theory, the diameter of the resulting metal particles is 100 times the volume of the initial pre-emulsion particles. It will be a fraction. Accordingly, since the diameter is about 1.65, particles having an organometallic compound of about 0.02 μm are obtained.
In view of this, it is not economical to reduce the diameter of the pre-emulsion to 0.1 μm or less because it requires very strong mechanical emulsification and a large amount of emulsifier. Although it is possible to obtain a catalyst having a small particle size by suppressing the volume of the organometallic compound contained in the pre-emulsion to 1% or less, in this case, the inclusion of the organometallic compound as a catalyst for the urethanization reaction Since the amount becomes extremely small, the function as a catalyst is not sufficiently exhibited, which is not preferable.
On the other hand, if it is larger than 1.0 μm, when the aqueous polyurethane composition containing the catalyst of the present invention is applied to a coating agent or the like, the catalyst is not sufficiently uniformly dispersed, so that a sufficient catalytic effect is obtained. This is not preferable because it causes problems such as absence.
本発明のウレタン化反応用触媒は上記乳化重合法を用いて製造する以外に、上記有機金属化合物と有機溶剤に可溶な高分子化合物、および必要に応じて有機溶剤との混合物を乳化剤と共に水中で機械的なせん断力を加えて強制乳化を行い、その後に含有する有機溶剤等の揮発成分を加熱などの方法により脱溶剤をすることによっても得られる。
有機溶剤に可溶な高分子化合物の１００重量部に対する有機金属化合物の使用量は０．２〜２０．０重量部、好ましくは、０．５〜１０．０重量部、さらに好ましくは、１．０〜５．０重量部である。使用量が０．２重量部未満では、触媒としての効果が小さくなり、２０．０重量部を超える場合、本触媒を使用する組成物中での触媒の分布が不均一となるため触媒効果が小さくなり、いずれも好ましくない。
有機溶剤を使用する場合、その使用量は有機溶剤に可溶な高分子化合物の１００重量部に対して１０〜１０００重量部、好ましくは、５０〜５００重量部、さらに好ましくは、１００〜３００重量部である。１０重量部より少ないと、触媒を含有する粒子の粒子径を小さくすることが困難となり、１０００重量部より多いと、粒子調製後の有機溶剤の除去に多大なコストがかかるので、いずれも好ましくない。
有機溶剤に可溶な高分子化合物としては、前記各種のラジカル重合性化合物をモノマー成分とするアクリル樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート、グリコールのアジペートのようなポリエステル樹脂、ポリエーテル型ウレタン、ポリエステル型ウレタン、エポキシウレタンのようなポリウレタン樹脂、ビスフェノールＡ型エポキシ樹脂、ノボラック型エポキシ樹脂のようなエポキシ樹脂、溶剤可溶型のポリプロピレン樹脂などが例示できるが、樹脂成分の選択はウレタン化反応用触媒を使用する水性組成物の特性や用途によって選ばれるものであり、これらに限定されるものではない。
また乳化剤としては、前記のような一般に公知のノニオン系、アニオン系、カチオン系の乳化剤を使用することができ、さらに高分子型の乳化剤や反応性の乳化剤も使用することが可能である。乳化剤の添加量は通常前記の通りである。
The catalyst for urethanization reaction of the present invention is produced using the above emulsion polymerization method, and a mixture of the above organic metal compound and an organic solvent soluble in an organic solvent and, if necessary, a mixture of an organic solvent together with an emulsifier in water. It can also be obtained by forcibly emulsifying by applying mechanical shearing force and then removing the volatile components such as organic solvent contained by a method such as heating.
The amount of the organometallic compound used relative to 100 parts by weight of the polymer compound soluble in the organic solvent is 0.2 to 20.0 parts by weight, preferably 0.5 to 10.0 parts by weight, more preferably 1. 0 to 5.0 parts by weight. If the amount used is less than 0.2 parts by weight, the effect as a catalyst is reduced, and if it exceeds 20.0 parts by weight, the catalyst distribution becomes uneven in the composition using the present catalyst, resulting in a catalyst effect. Neither is preferred.
When an organic solvent is used, the amount used is 10 to 1000 parts by weight, preferably 50 to 500 parts by weight, more preferably 100 to 300 parts by weight, based on 100 parts by weight of the polymer compound soluble in the organic solvent. Part. If the amount is less than 10 parts by weight, it is difficult to reduce the particle size of the particles containing the catalyst. If the amount is more than 1000 parts by weight, the removal of the organic solvent after the preparation of the particles requires a great deal of cost. .
Polymer compounds soluble in organic solvents include acrylic resins, polyethylene terephthalate, polybutylene terephthalate, glycol resins such as glycol adipate, polyether type urethane, polyester type, which contain the above various radical polymerizable compounds as monomer components. Examples include polyurethane resins such as urethane and epoxy urethane, epoxy resins such as bisphenol A type epoxy resins and novolac type epoxy resins, solvent soluble type polypropylene resins, etc. It is selected according to the characteristics and application of the aqueous composition to be used, and is not limited thereto.
As the emulsifier, generally known nonionic, anionic, and cationic emulsifiers as described above can be used, and a polymer type emulsifier and a reactive emulsifier can also be used. The amount of the emulsifier is usually as described above.
また、本発明のウレタン化反応用触媒の製造方法としては、一般的に有機溶剤系の溶媒に溶解している高分子化合物や比較的低融点の高分子化合物の水性乳化に用いられている処方を使用することができる。例えば溶融状態の樹脂を乳化剤と水と共に撹拌して乳化を行なうような転相乳化法や、水中に炭化水素系の有機溶剤等により溶解している状態の樹脂化合物を加えて、乳化剤と共に強力な撹拌を行なうことによって乳化物を得、その後得られた乳化物を加熱、共沸蒸留等により、含有する有機溶剤成分を取り除く等の乳化処方を例示することができる。乳化する際の温度は前記と同様、５０℃以上１００℃程度である。 In addition, as a method for producing a catalyst for urethanization reaction of the present invention, a formulation generally used for aqueous emulsification of a polymer compound dissolved in an organic solvent solvent or a polymer compound having a relatively low melting point Can be used. For example, a phase inversion emulsification method in which a molten resin is agitated with an emulsifier and water to emulsify, or a resin compound in a state dissolved in water with a hydrocarbon-based organic solvent is added to provide a powerful combination with the emulsifier. Examples of the emulsified formulation include obtaining an emulsion by stirring and then removing the organic solvent component contained in the obtained emulsion by heating, azeotropic distillation, or the like. The temperature during emulsification is about 50 ° C. or more and about 100 ° C. as described above.
以上述べてきたウレタン化反応用触媒は水中で乳化された樹脂粒子中に分散されている状態で、水性塗料や水性接着剤などに使用するものである。
例えば水性二液型ウレタン塗料では、水酸基を有する高分子化合物を樹脂成分として含むエマルジョン樹脂を使用した塗料中に、本発明のウレタン化反応用触媒を水酸基を有する高分子化合物との組成物中、０．１〜５０．０重量％、好ましくは、０．５〜２０．０重量％、さらに好ましくは、１．０〜１０．０重量％加えた組成物を塗料主剤とし（いずれも固形分換算）、塗装直前にアセトンのような水溶性有機溶剤などで稀釈したイソシアネート化合物を塗料主剤中に分散して水性二液型ウレタン硬化性組成物として使用できる。本発明のウレタン化反応用触媒の使用量が０．１重量％未満では、触媒としての効果が小さくなり、５０．０重量％を超えると、反応が早過ぎる場合があり、外観的な不具合を生じ、いずれも好ましくない。
本発明の水性二液型ウレタン塗料を塗布するには、乳化されたウレタン化反応用触媒と塗料成分を塗装前に混合して通常の刷毛塗り、スプレー塗り、カーテン塗り、ロールコート等が適用できる。
本発明の水性二液型ウレタン塗料には、必要に応じて、通常の塗料に添加できる各種添加剤や顔料、例えばレベリング剤、流動性改良剤、酸化防止剤、光安定剤、紫外線吸収剤、スリップ剤、体質顔料、着色顔料、染料等の添加剤や顔料を加えることができる。
本発明の水性二液型ウレタン塗料は、ポリカーボネート樹脂、ＡＢＳ樹脂、アクリル樹脂、塩化ビニル樹脂、ポリアミド系樹脂、ポリフェニレンオキサイド樹脂またはこれらを含有する樹脂アロイからなる成形品の塗料として使用することができる。成形品としては、射出成形品、押出成形品、圧縮成形品等の各種成形品が挙げられる。
The catalyst for urethanization reaction described above is used in water-based paints and water-based adhesives in a state where it is dispersed in resin particles emulsified in water.
For example, in an aqueous two-component urethane paint, in a paint using an emulsion resin containing a polymer compound having a hydroxyl group as a resin component, the catalyst for urethanization reaction of the present invention in a composition with a polymer compound having a hydroxyl group, A composition containing 0.1 to 50.0% by weight, preferably 0.5 to 20.0% by weight, and more preferably 1.0 to 10.0% by weight is used as a coating material (all in terms of solid content) ), An isocyanate compound diluted with a water-soluble organic solvent such as acetone just before coating can be dispersed in a paint base and used as an aqueous two-component urethane curable composition. If the amount of the catalyst for urethanization reaction of the present invention is less than 0.1% by weight, the effect as a catalyst is reduced, and if it exceeds 50.0% by weight, the reaction may be too early, resulting in an appearance defect. Both are unfavorable.
In order to apply the aqueous two-component urethane paint of the present invention, an emulsified catalyst for urethanization reaction and a paint component are mixed before painting, and ordinary brush coating, spray coating, curtain coating, roll coating, etc. can be applied. .
In the aqueous two-component urethane paint of the present invention, if necessary, various additives and pigments that can be added to a normal paint, such as a leveling agent, a fluidity improver, an antioxidant, a light stabilizer, an ultraviolet absorber, Additives and pigments such as slip agents, extender pigments, color pigments and dyes can be added.
The aqueous two-component urethane paint of the present invention can be used as a paint for molded products made of polycarbonate resin, ABS resin, acrylic resin, vinyl chloride resin, polyamide resin, polyphenylene oxide resin, or resin alloy containing these. . Examples of the molded product include various molded products such as injection molded products, extrusion molded products, and compression molded products.
（実施例）
以下、本発明を実施例および比較例を用いて説明するが、これらによって本発明が限定されるものではない。なお、例中の％はいずれも重量％を示す。
(Example)
EXAMPLES Hereinafter, although this invention is demonstrated using an Example and a comparative example, this invention is not limited by these. In the examples, “%” represents “% by weight”.
＜実施例１＞
（ウレタン化反応用触媒の製造−１）
窒素導入管、温度計、冷却管、滴下ロート、撹拌装置を備えた１リットルの丸底四つ口フラスコに、イオン交換水２５３．０ｇとニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１０．０ｇを加えた。別の容器に、メタクリル酸ノルマルブチル１０．０ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１．５ｇ、過硫酸アンモニウム１０％水溶液０．５ｇ、イオン交換水５．０ｇの混合物を仕込んだ後、高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ａを１６．５ｇ得た。フラスコ内の温度を８０℃に昇温した後撹拌しながら３０分間でプレ乳化物Ａをフラスコ内に滴下し、その後３０分間、撹拌しながらフラスコ内温度を８０℃に保った。
さらに、別の容器に、メタクリル酸ノルマルブチル１３９．７ｇ、ジ−ｎ−ブチルスズジラウレート０．３ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］２０．０ｇ、過硫酸アンモニウム１０％水溶液１０．０ｇ、イオン交換水５０．０ｇの混合物を仕込んだ後、高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ｂを２２０．０ｇ得た。
フラスコ温度を８０℃に保ちながらプレ乳化物Ｂをフラスコ内に３時間で滴下し、１時間撹拌をした後に過硫酸アンモニウム１０％水溶液５．０ｇを加え、フラスコ内温度を８０℃に６時間保った後、フラスコを常温まで冷却して反応を終了した。
本実施例で得られた乳化物であるウレタン化反応用触媒（触媒１と称する）中の固形分は３０％であり、固形分中に含まれる有機金属化合物は０．２％である。
<Example 1>
(Production of catalyst for urethanization reaction-1)
In a 1 liter round bottom four-necked flask equipped with a nitrogen inlet tube, thermometer, condenser, dropping funnel and stirring device, 253.0 g of ion-exchanged water and New Coal 707SF [anionic emulsifier manufactured by Nippon Emulsifier Co., Ltd.] 10.0 g was added. In a separate container, a mixture of normal butyl methacrylate 10.0 g, New Coal 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier] 1.5 g, ammonium persulfate 10% aqueous solution 0.5 g, ion-exchanged water 5.0 g. After charging, 16.5 g of pre-emulsion A was obtained by vigorously stirring using a high-speed stirrer. After raising the temperature in the flask to 80 ° C., the pre-emulsion A was dropped into the flask in 30 minutes with stirring, and then the temperature in the flask was kept at 80 ° C. with stirring for 30 minutes.
Further, in another container, 139.7 g of normal butyl methacrylate, 0.3 g of di-n-butyltin dilaurate, 20.0 g of New Coal 707SF [anionic emulsifier manufactured by Nippon Emulsifier Co., Ltd.], 10% aqueous solution of ammonium persulfate 10% After preparing a mixture of 0.0 g and ion-exchanged water 50.0 g, 220.0 g of pre-emulsion B was obtained by vigorously stirring using a high-speed stirrer.
While maintaining the flask temperature at 80 ° C., the pre-emulsion B was dropped into the flask over 3 hours. After stirring for 1 hour, 5.0 g of 10% ammonium persulfate aqueous solution was added, and the temperature in the flask was maintained at 80 ° C. for 6 hours. Then, the flask was cooled to room temperature to complete the reaction.
The solid content in the catalyst for urethanization reaction (referred to as catalyst 1), which is the emulsion obtained in this example, is 30%, and the organometallic compound contained in the solid content is 0.2%.
＜実施例２＞
（ウレタン化反応触媒の製造−２）
実施例１と同様のフラスコ内にイオン交換水２５３．０ｇとニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１０．０ｇ、を加えた。別の容器に、メタクリル酸ノルマルブチル１０．０ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１．５ｇ、過硫酸アンモニウム１０％水溶液０．５ｇ、イオン交換水５．０ｇの混合物を仕込んだ後、高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ａを１６．５ｇ得た。フラスコ内の温度を８０℃に昇温した後攪拌しながら３０分間でプレ乳化物Ａをフラスコ内に滴下し、その後３０分間、攪拌しながらフラスコ内温度を８０℃に保った。別の容器に、メタクリル酸ノルマルブチル１３８．５ｇ、ジ−ｎ−ブチルスズジラウレート１．５ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］２０．０ｇ、過硫酸アンモニウム１０％水溶液１０．０ｇ、イオン交換水５０．０ｇの混合物を仕込んだ後、高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ｃを２２０．０ｇ得た。
フラスコ温度を８０℃に保ちながらプレ乳化物Ｃをフラスコ内に３時間で滴下し、１時間撹拌をした後に過硫酸アンモニウム１０％水溶液５．０ｇを加え、フラスコ内温度を８０℃に６時間保った後フラスコを常温まで冷却して反応を終了した。
本実施例で得られた乳化物であるウレタン化反応用触媒（触媒２と称する）中の固形分は３０％であり、固形分中に含まれる有機金属化合物は１．０％である。
<Example 2>
(Production of Urethane Reaction Catalyst-2)
In the same flask as in Example 1, 253.0 g of ion-exchanged water and 10.0 g of Neucor 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier] were added. In a separate container, a mixture of normal butyl methacrylate 10.0 g, New Coal 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier] 1.5 g, ammonium persulfate 10% aqueous solution 0.5 g, ion-exchanged water 5.0 g. After charging, 16.5 g of pre-emulsion A was obtained by vigorously stirring using a high-speed stirrer. After raising the temperature in the flask to 80 ° C., the pre-emulsion A was dropped into the flask in 30 minutes with stirring, and then the temperature in the flask was kept at 80 ° C. with stirring for 30 minutes. In a separate container, 138.5 g of normal butyl methacrylate, 1.5 g of di-n-butyltin dilaurate, 20.0 g of New Coal 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier], 10.0 g of ammonium persulfate 10% aqueous solution 10.0 g After charging a mixture of 50.0 g of ion exchange water, 220.0 g of pre-emulsion C was obtained by vigorously stirring using a high-speed stirrer.
While maintaining the flask temperature at 80 ° C., the pre-emulsion C was dropped into the flask over 3 hours. After stirring for 1 hour, 5.0 g of 10% aqueous solution of ammonium persulfate was added, and the temperature in the flask was maintained at 80 ° C. for 6 hours. Thereafter, the flask was cooled to room temperature to complete the reaction.
The solid content in the catalyst for urethanization reaction (referred to as catalyst 2), which is the emulsion obtained in this example, is 30%, and the organometallic compound contained in the solid content is 1.0%.
＜実施例３＞
（ウレタン化反応触媒の製造−３）
実施例１と同様のフラスコ内にイオン交換水２５３．０ｇとニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１０．０ｇ、を加えた。別に、メタクリル酸ノルマルブチル１０．０ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１．５ｇ、過硫酸アンモニウム１０%水溶液０．５ｇ、イオン交換水５．０ｇの混合物を仕込んだ後、高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ａを１６．５ｇ得た。フラスコ内の温度を８０℃に昇温した後攪拌しながら３０分間でプレ乳化物Ａをフラスコ内に滴下し、その後３０分間、攪拌しながらフラスコ内温度を８０℃に保った。別の容器に、メタクリル酸ノルマルブチル１３２．５ｇ、ジ−ｎ−ブチルスズジラウレート７．５ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］２０．０ｇ、過硫酸アンモニウム１０％水溶液１０．０ｇ、イオン交換水５０．０ｇの混合物を仕込んだ後、高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ｄを２２０．０ｇ得た。
フラスコ温度を８０℃に保ちながらプレ乳化物Ｄをフラスコ内に３時間で滴下し、１時間撹拌をした後に過硫酸アンモニウム１０％水溶液５．０ｇを加え、フラスコ内温度を８０℃に６時間保った後フラスコを常温まで冷却して反応を終了した。
本実施例で得られた乳化物であるウレタン化反応用触媒（触媒３と称する）中の固形分は３０％であり、固形分中に含まれる有機金属化合物は５．０％である。
<Example 3>
(Production of Urethane Reaction Catalyst-3)
In the same flask as in Example 1, 253.0 g of ion-exchanged water and 10.0 g of Neucor 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier] were added. Separately, after charging a mixture of 10.0 g of normal butyl methacrylate, 1.5 g of New Coal 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier], 0.5 g of 10% aqueous solution of ammonium persulfate, and 5.0 g of ion-exchanged water. 16.5 g of pre-emulsion A was obtained by vigorously stirring using a high-speed stirrer. After raising the temperature in the flask to 80 ° C., the pre-emulsion A was dropped into the flask in 30 minutes with stirring, and then the temperature in the flask was kept at 80 ° C. with stirring for 30 minutes. In a separate container, 132.5 g of normal butyl methacrylate, 7.5 g of di-n-butyltin dilaurate, 20.0 g of New Coal 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier], 10.0 g of 10% aqueous solution of ammonium persulfate After charging a mixture of 50.0 g of ion-exchanged water, 220.0 g of pre-emulsion D was obtained by vigorously stirring using a high-speed stirrer.
While maintaining the flask temperature at 80 ° C., the pre-emulsion D was dropped into the flask over 3 hours. After stirring for 1 hour, 5.0 g of 10% ammonium persulfate aqueous solution was added, and the temperature in the flask was maintained at 80 ° C. for 6 hours. Thereafter, the flask was cooled to room temperature to complete the reaction.
The solid content in the catalyst for urethanization reaction (referred to as catalyst 3), which is the emulsion obtained in this example, is 30%, and the organometallic compound contained in the solid content is 5.0%.
＜実施例４＞
（ウレタン化反応触媒の製造−４）
実施例１と同様のフラスコ内にイオン交換水２５３．０ｇとニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１０．０ｇ、を加えた。別の容器に、メタクリル酸ノルマルブチル１０．０ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１．５ｇ、過硫酸アンモニウム１０％水溶液０．５ｇ、イオン交換水５．０ｇの混合物を仕込んだ後、高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ａを１６．５ｇ得た。フラスコ内の温度を８０℃に昇温した後攪拌しながら３０分間でプレ乳化物Ａをフラスコ内に滴下し、その後３０分間、攪拌しながらフラスコ内温度を８０℃に保った。別の容器に、メタクリル酸ノルマルブチル１１０．０ｇ、ジ−ｎ−ブチルスズジラウレート３０．０ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］２０．０ｇ、過硫酸アンモニウム１０％水溶液１０．０ｇ、イオン交換水５０．０ｇの混合物を仕込んだ後、高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ｅを２２０．０ｇ得た。
フラスコ温度を８０℃に保ちながらプレ乳化物Ｅをフラスコ内に３時間で滴下し、１時間撹拌をした後に過硫酸アンモニウム１０％水溶液５．０ｇを加え、フラスコ内温度を８０℃に６時間保った後フラスコを常温まで冷却して反応を終了した。
本実施例で得られた乳化物であるウレタン化反応用触媒（触媒４と称する）中の固形分は３０％であり、固形分中に含まれる有機金属化合物は２０．０％である。
<Example 4>
(Production of Urethane Reaction Catalyst-4)
In the same flask as in Example 1, 253.0 g of ion-exchanged water and 10.0 g of Neucor 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier] were added. In a separate container, a mixture of normal butyl methacrylate 10.0 g, New Coal 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier] 1.5 g, ammonium persulfate 10% aqueous solution 0.5 g, ion-exchanged water 5.0 g. After charging, 16.5 g of pre-emulsion A was obtained by vigorously stirring using a high-speed stirrer. After raising the temperature in the flask to 80 ° C., the pre-emulsion A was dropped into the flask in 30 minutes with stirring, and then the temperature in the flask was kept at 80 ° C. with stirring for 30 minutes. In a separate container, 110.0 g of normal butyl methacrylate, 30.0 g of di-n-butyltin dilaurate, 20.0 g of New Coal 707SF [anionic emulsifier manufactured by Nippon Emulsifier Co., Ltd.], 10.0 g of ammonium persulfate 10% aqueous solution After charging a mixture of 50.0 g of ion-exchanged water, 220.0 g of pre-emulsion E was obtained by vigorously stirring using a high-speed stirrer.
While maintaining the flask temperature at 80 ° C., the pre-emulsion E was dropped into the flask over 3 hours. After stirring for 1 hour, 5.0 g of 10% aqueous solution of ammonium persulfate was added, and the temperature in the flask was maintained at 80 ° C. for 6 hours. Thereafter, the flask was cooled to room temperature to complete the reaction.
The solid content in the catalyst for urethanization reaction (referred to as catalyst 4), which is the emulsion obtained in this example, is 30%, and the organometallic compound contained in the solid content is 20.0%.
＜実施例５＞
（ウレタン化反応触媒の製造−５）
実施例１と同様のフラスコ内にイオン交換水２５３．０ｇとニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１０．０ｇ、を加えた。別に、メタクリル酸ノルマルブチル１０．０９、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１．５ｇ、過硫酸アンモニウム１０％水溶液０．５ｇ、イオン交換水５．０ｇの混合物を高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ａを１６．５ｇ得た。フラスコ内の温度を８０℃に昇温した後、攪拌しながら３０分間でプレ乳化物Ａをフラスコ内に滴下し、その後３０分間、攪拌しながらラスコ内温度を８０℃に保った。別の容器に、メタクリル酸ノルマルブチル１３７．０ｇ、ジ−ｎ−ブチルスズジラウレート１．５ｇ、テトラメチルブタンジアミン１．５ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］２０．０ｇ、過硫酸アンモニウム１０％水溶液１０．０ｇ、イオン交換水５０．０ｇの混合物を仕込んだ後、高速撹拌機を用いて独力に撹拌を行うことによりプレ乳化物Ｆを２２０．０ｇ得た。
フラスコ温度を８０℃に保ちながらプレ乳化物Ｆをフラスコ内に３時間で滴下し、１時間撹拌をした後に過硫酸アンモニウム１０％水溶液５．０ｇを加え、フラスコ内温度を８０℃に６時間保った後フラスコを常混まで冷却して反応を終了した。
本実施例で得られた乳化物であるウレタン化反応用触媒（触媒５と称する）中の固形分は３０％であり、固形分中に含まれる有機金属化合物は１．０％である。
<Example 5>
(Production of Urethane Reaction Catalyst-5)
In the same flask as in Example 1, 253.0 g of ion-exchanged water and 10.0 g of Neucor 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier] were added. Separately, a mixture of normal butyl methacrylate 10.09, New Coal 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier] 1.5 g ammonium persulfate 10% aqueous solution 0.5 g, ion-exchanged water 5.0 g mixture 16.5 g of pre-emulsion A was obtained by vigorously stirring the mixture. After raising the temperature in the flask to 80 ° C., the pre-emulsion A was dropped into the flask in 30 minutes with stirring, and then the temperature in Lasco was kept at 80 ° C. with stirring for 30 minutes. In another container, 137.0 g of normal butyl methacrylate, 1.5 g of di-n-butyltin dilaurate, 1.5 g of tetramethylbutanediamine, 20.0 g of New Coal 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier], A mixture of 10.0 g of 10% ammonium persulfate aqueous solution and 50.0 g of ion-exchanged water was charged, and then the mixture was stirred independently using a high-speed stirrer to obtain 220.0 g of pre-emulsion F.
While maintaining the flask temperature at 80 ° C., the pre-emulsion F was dropped into the flask over 3 hours. After stirring for 1 hour, 5.0 g of 10% aqueous solution of ammonium persulfate was added, and the temperature in the flask was maintained at 80 ° C. for 6 hours. Thereafter, the flask was cooled to normal mixing to complete the reaction.
The solid content in the catalyst for urethanization reaction (referred to as catalyst 5), which is the emulsion obtained in this example, is 30%, and the organometallic compound contained in the solid content is 1.0%.
＜実施例６＞
（ウレタン化反応触媒の製造−６）
実施例１と同様のフラスコ内にイオン交換水２５３．０ｇとニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１０．０ｇ、を加えた。別に、メタクリル酸ノルマルブチル１０．０ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１．５ｇ、過硫酸アンモニウム１０％水溶液０．５ｇ、イオン交換水５．０ｇの混合物を仕込んだ後、高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ａを１６．５ｇ得た。フラスコ内の温度を８０℃に昇温した後攪拌しながら３０分間でプレ乳化物Ａをフラスコ内に滴下し、その後３０分間、攪拌しながらフラスコ内温度を８０℃に保った。別の容器に、メタクリル酸ノルマルブチル１１６ｇ、メタクリル酸２−ヒドロキシエチル２２．５ｇ、ジ−ｎ−ブチルスズジラウレート１．５ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］２０．０ｇ、過硫酸アンモニウム１０％水溶液１０．０ｇ、イオン交換水５０．０ｇの混合物を仕込んだ後、高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ｇを２２０．０ｇ得た。
フラスコ温度を８０℃に保ちながらプレ乳化物Ｇをフラスコ内に３時間で滴下し、１時間撹拌をした後に過硫酸アンモニウム１０％水溶液５．０ｇを加え、フラスコ内温度を８０℃に６時間保った後フラスコを常温まで冷却して反応を終了した。
本実施例で得られた乳化物であるウレタン化反応用触媒（触媒６と称する）中の固形分は３０％であり、固形分中に含まれる有機金属化合物は１．０％である。
乳化重合樹脂は水酸基を有しており、その水酸基価は６４ｍｇＫＯＨ／ｇである。
<Example 6>
(Production of Urethane Reaction Catalyst-6)
In the same flask as in Example 1, 253.0 g of ion-exchanged water and 10.0 g of Neucor 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier] were added. Separately, 10.0 g of normal butyl methacrylate, 1.5 g of New Coal 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier], 0.5 g of 10% aqueous solution of ammonium persulfate, and 5.0 g of ion-exchanged water were charged. 16.5 g of pre-emulsion A was obtained by vigorously stirring using a high-speed stirrer. After raising the temperature in the flask to 80 ° C., the pre-emulsion A was dropped into the flask in 30 minutes with stirring, and then the temperature in the flask was kept at 80 ° C. with stirring for 30 minutes. In another container, 116 g of normal butyl methacrylate, 22.5 g of 2-hydroxyethyl methacrylate, 1.5 g of di-n-butyltin dilaurate, 20.0 g of New Coal 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier], A mixture of 10.0 g of 10% ammonium persulfate aqueous solution and 50.0 g of ion-exchanged water was charged and then vigorously stirred using a high-speed stirrer to obtain 220.0 g of pre-emulsion G.
While maintaining the flask temperature at 80 ° C., the pre-emulsion G was dropped into the flask over 3 hours. After stirring for 1 hour, 5.0 g of 10% ammonium persulfate aqueous solution was added, and the temperature in the flask was maintained at 80 ° C. for 6 hours. Thereafter, the flask was cooled to room temperature to complete the reaction.
The solid content in the catalyst for urethanization reaction (referred to as catalyst 6), which is the emulsion obtained in this example, is 30%, and the organometallic compound contained in the solid content is 1.0%.
The emulsion polymerization resin has a hydroxyl group, and the hydroxyl value is 64 mgKOH / g.
＜実施例７＞
（ウレタン化反応触媒の製造−７）
窒素導入管、温度計、冷却管、滴下ロート、撹拌装置を備えた１リットルの丸底四つ口フラスコにトルエン５６０．０ｇ、メタクリル酸ノルマルブチル２３７．６ｇ、ジ−ｎ−ブチルスズジラウレート２．４ｇを加えて９０℃に加熱した。フラスコ内温度が９０℃に達した時点で、カヤエステルＯ［化薬アクゾ(株)製過酸化物系化合物］のトルエン２０％稀釈溶液を３．０ｇを加えた。その後３０分毎に合計５回、カヤエステルＯの２０％トルエン稀釈溶液３．０ｇずつを加えた。その後３時間フラスコ温度を９０℃に保った後に常温まで冷却して反応を終了し、固形分３０％のポリマー溶液Ａを得た。
次にポリマー溶液Ａ５０％とトルエン５０％とからなる樹脂溶液１００．０ｇとニューコール７４０ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］２０．０ｇ、イオン交換水３００ｇを混合し、高速撹拌機を使用して十分に撹拌することにより乳化物Ａを得た。
乳化物Ａには有機溶剤としてトルエンが含まれるため、加熱し共沸蒸留を行うことにより乳化物に含まれる有機溶剤成分を留去し、さらに固形分が３０％になるまで蒸留を続けて実施例７のウレタン反応触媒を得た。
本実施例で得られた乳化物であるウレタン化反応用触媒（触媒７と称する）中の固形分は３０％であり、固形分中に含まれる有機金属化合物は１．０％である。
<Example 7>
(Production of Urethane Reaction Catalyst-7)
In a 1 liter round bottom four-necked flask equipped with a nitrogen introduction tube, thermometer, cooling tube, dropping funnel and stirring device, 560.0 g of toluene, 237.6 g of normal butyl methacrylate, 2.4 g of di-n-butyltin dilaurate And heated to 90 ° C. When the temperature in the flask reached 90 ° C., 3.0 g of a 20% toluene diluted solution of Kayaester O [a peroxide compound manufactured by Kayaku Akzo Co., Ltd.] was added. Thereafter, 3.0 g of a 20% toluene diluted solution of Kayaester O was added 5 times every 30 minutes. Thereafter, the flask temperature was maintained at 90 ° C. for 3 hours, and then the reaction was terminated by cooling to room temperature to obtain a polymer solution A having a solid content of 30%.
Next, 100.0 g of a resin solution composed of 50% of polymer solution A and 50% of toluene, 20.0 g of New Coal 740SF [Nippon Emulsifier Co., Ltd. anionic emulsifier] and 300 g of ion-exchanged water were mixed together, An emulsion A was obtained by using and stirring well.
Since the emulsion A contains toluene as an organic solvent, the organic solvent component contained in the emulsion is distilled off by heating and azeotropic distillation, and the distillation is continued until the solid content reaches 30%. The urethane reaction catalyst of Example 7 was obtained.
The solid content in the catalyst for urethanization reaction (referred to as catalyst 7), which is the emulsion obtained in this example, is 30%, and the organometallic compound contained in the solid content is 1.0%.
＜実施例８＞
（ウレタン化反応触媒の製造−８）
実施例１と同様のフラスコ内にイオン交換水２５３．０ｇとニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１０．０ｇ、を加えた。別に、メタクリル酸ノルマルブチル１０．０ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］１．５ｇ、過硫酸アンモニウム１０％水溶液０．５ｇ、イオン交換水５．０ｇの混合物を仕込んだ後、高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ａを１６．５ｇ得た。フラスコ内の温度を８０℃に昇温した後、攪拌しながら３０分間でプレ乳化物Ａをフラスコ内に滴下し、その後３０分間、攪拌しながらフラスコ内温度を８０℃に保った。別の容器に、メタクリル酸ノルマルブチル１１６ｇ、メタクリル酸２−ヒドロキシエチル２２．５ｇ、ジ−ｎ−オクチルスズジラウレート１．５ｇ、ニューコール７０７ＳＦ［日本乳化剤（株）製陰イオン系乳化剤］２０．０ｇ、過硫酸アンモニウム１０％水溶液１０．０ｇ、イオン交換水５０．０ｇの混合物を仕込んだ後、高速撹拌機を用いて強力に撹拌を行うことによりプレ乳化物Ｇを２２０．０ｇ得た。
フラスコ温度を８０℃に保ちながらプレ乳化物Ｇをフラスコ内に３時間で滴下し、１時間撹拌をした後に過硫酸アンモニウム１０％水溶液５．０ｇを加え、フラスコ内温度を８０℃に６時間保った後フラスコを常温まで冷却して反応を終了した。
本実施例で得られた乳化物であるウレタン化反応用触媒（触媒８と称する）中の固形分は３０％であり、固形分中に含まれる有機金属化合物は１．０％である。
乳化重合樹脂は水酸基を有しており、その水酸基価は６４ｍｇＫＯＨ／ｇである。
<Example 8>
(Production of Urethane Reaction Catalyst-8)
In the same flask as in Example 1, 253.0 g of ion-exchanged water and 10.0 g of Neucor 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier] were added. Separately, 10.0 g of normal butyl methacrylate, 1.5 g of New Coal 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier], 0.5 g of 10% aqueous solution of ammonium persulfate, and 5.0 g of ion-exchanged water were charged. 16.5 g of pre-emulsion A was obtained by vigorously stirring using a high-speed stirrer. After raising the temperature in the flask to 80 ° C., the pre-emulsion A was dropped into the flask in 30 minutes with stirring, and then the temperature in the flask was kept at 80 ° C. with stirring for 30 minutes. In a separate container, 116 g of normal butyl methacrylate, 22.5 g of 2-hydroxyethyl methacrylate, 1.5 g of di-n-octyltin dilaurate, Newcor 707SF [Nippon Emulsifier Co., Ltd. anionic emulsifier] 20.0 g Then, 10.0 g of a 10% aqueous solution of ammonium persulfate and 50.0 g of ion-exchanged water were charged, and then the mixture was vigorously stirred using a high-speed stirrer to obtain 220.0 g of pre-emulsion G.
While maintaining the flask temperature at 80 ° C., the pre-emulsion G was dropped into the flask over 3 hours. After stirring for 1 hour, 5.0 g of 10% ammonium persulfate aqueous solution was added, and the temperature in the flask was maintained at 80 ° C. for 6 hours. Thereafter, the flask was cooled to room temperature to complete the reaction.
The solid content in the catalyst for urethanization reaction (referred to as catalyst 8), which is the emulsion obtained in this example, is 30%, and the organometallic compound contained in the solid content is 1.0%.
The emulsion polymerization resin has a hydroxyl group, and the hydroxyl value is 64 mgKOH / g.
＜比較例１＞
（樹脂成分を含まないウレタン化反応触媒の製造）
２００ｃｃの高速撹拌用金属製コップにジ−ｎ−ブチルスズジラウレート３０．０ｇ、レオドールＴＷ−０１０６Ｖ［花王株式会社製乳化剤］２０．０ｇ、イオン交換水５０．０ｇを加え、高速撹拌をすることによりジ−１−ブチルスズジラウレートの乳化物（触媒Ｒと称する）を得た。
<Comparative Example 1>
(Manufacture of urethanization reaction catalyst without resin component)
Di-n-butyltin dilaurate 30.0g, Rheodor TW-0106V [Emulsifier manufactured by Kao Corporation] 20.0g, and ion-exchanged water 50.0g were added to a 200cc metal cup for high-speed stirring, and the mixture was stirred at high speed. An emulsion (referred to as catalyst R) of -1-butyltin dilaurate was obtained.
＜応用例１〜９＞
［ウレタン化反応用触媒の評価］
実施例１〜８と比較例１で製造したウレタン化反応用触媒の有効性評価は、水性の二液型ウレタン塗料用組成物として下記の特性を比較することにより行なった。
バイヒドールＶＰＬＳ２０５８［住友バイエルウレタン（株）製水性ポリオールディスパージョン樹脂］対して当量比（イソシアネート基／水酸基）を１．５に相当するデュラネートＷＢ４０−８０Ｄ［旭化成（株）製イソシアネートプレポリマー］、およびジ−ｎ−ブチルスズジラウレートの含有量が０．２％となるように実施例１〜８および比較例１で得られたウレタン化反応用触媒を加えて高速撹拌して、水性の硬化性組成物を得た。
これらの硬化性組成物をイオン交換水を用いてエアースプレー塗装可能な粘度まで稀釈したものをＡＢＳ板に塗装してそれぞれの評価を行なった。
<Application examples 1 to 9>
[Evaluation of catalyst for urethanization reaction]
The effectiveness evaluation of the catalysts for urethanization reaction produced in Examples 1 to 8 and Comparative Example 1 was carried out by comparing the following characteristics as an aqueous two-component urethane coating composition.
Duranate WB40-80D [isocyanate prepolymer manufactured by Asahi Kasei Co., Ltd.] having an equivalent ratio (isocyanate group / hydroxyl group) of 1.5 with respect to Bihydrol VPLS2058 [aqueous polyol dispersion resin manufactured by Sumitomo Bayer Urethane Co., Ltd.], and di The catalyst for urethanization reaction obtained in Examples 1 to 8 and Comparative Example 1 was added so that the content of n-butyltin dilaurate was 0.2%, and the mixture was stirred at a high speed to obtain an aqueous curable composition. Obtained.
Each of these curable compositions diluted to a viscosity capable of air spray coating using ion-exchanged water was applied to an ABS plate and evaluated.
(1)乾燥性：各実施例および比較例１で得られたウレタン化反応用触媒を含む乳化物と硬化性樹脂成分を含む硬化性組成物を塗装した試験板を、７０℃のボックス型乾燥炉で３０分間加熱した後の塗膜の指触乾燥状態により下記の基準で相対的に評価した。
◎：ベタつきを全く感じない。
○：ベタつきを感じない。
△：ベタつきを感じるが、使用可能範囲である。
×：ベタつきを感じる。
(2)塗膜外観：７０℃での乾燥後、さらに３日間室内放置した後の塗膜表面の状態を下記の基準で目視評価した。
◎：光沢感に優れ、有機溶剤型ハイソリッド系トップコート仕上げと同等の外観。
○：光沢感には優れるが、僅かに鮮映性に欠ける。
△：光沢感、鮮映性とも欠けるが、塗装部位によっては使用可能。
×：光沢塗料としての使用不可。
(3)耐水性：７０℃での乾燥後さらに３日間室内放置した後に塗膜を４０℃の温水に１０日間浸漬し塗膜の状態を下記の基準で目視評価した。
◎：透明性に変化なし。膨潤や剥離はなし。
○：わずかに白化が観察されるが、膨潤や剥離はなし。
△：わずかに白化や剥離が観察される。
×：全面的に白化し、膨潤や剥離が観察される。
(4)貯蔵安定性：水性ポリオール樹脂と各実施例および比較例１で得られたウレタン化反応用触媒のみからなる組成物を密封状態で４０℃で３０日保存した後の組成物の状態およびそれを塗装した場合の塗膜表面の状態を目視で観察して下記の基準で相対的に評価した。
◎：塗料粘度変化は少なく分離沈殿は認められない。塗膜の表面状態にも大きな変化無し。
○：塗料粘度変化は少ないがやや沈殿や分離傾向が見られる。沈殿は攪拌すれば戻り、ハードケーキにはなっていない。塗膜の表面状態にも大きな変化なし。
△：塗料の粘度変化や沈殿がみられるものの、攪拌により実際の使用は可能。塗膜状態はやや平坦さを欠く傾向にあるが使用可能。
×：粘度変化が大きく、沈殿やゲル化により使用不可。
評価結果を下記表１に示す。
(1) Drying property: A test plate coated with an emulsion containing a catalyst for urethanization reaction obtained in each Example and Comparative Example 1 and a curable composition containing a curable resin component was dried at 70 ° C. in a box shape. Relative evaluation was performed based on the following criteria according to the dry touch state of the coating film after heating in an oven for 30 minutes.
A: There is no stickiness at all.
○: There is no stickiness.
Δ: Stickiness is felt, but within the usable range.
X: Feels sticky.
(2) Appearance of coating film: After drying at 70 ° C., the condition of the coating film surface after standing for 3 days in the room was visually evaluated according to the following criteria.
A: Excellent gloss and appearance equivalent to organic solvent type high solid topcoat finish.
○: Excellent glossiness, but slightly lacks clarity.
△: Glossiness and sharpness are lacking, but it can be used depending on the painted part.
X: Cannot be used as a gloss paint.
(3) Water resistance: After drying at 70 ° C. and standing for 3 days, the coating film was immersed in warm water at 40 ° C. for 10 days, and the state of the coating film was visually evaluated according to the following criteria.
A: No change in transparency. No swelling or peeling.
○: Slight whitening is observed, but there is no swelling or peeling.
Δ: Slight whitening or peeling is observed.
X: It whitens entirely and swelling and peeling are observed.
(4) Storage stability: the composition comprising only the aqueous polyol resin and the catalyst for urethanization reaction obtained in each Example and Comparative Example 1 was stored in a sealed state at 40 ° C. for 30 days, and The state of the coating film surface when it was applied was visually observed and relatively evaluated according to the following criteria.
A: The change in the viscosity of the paint is small and no separation / precipitation is observed. There is no significant change in the surface condition of the paint film.
○: Little change in paint viscosity but slight precipitation and tendency to separate. Precipitation returns if the stirring, not in a hard cake. There is no significant change in the surface condition of the coating film.
Δ: Changes in viscosity and precipitation of paint are observed, but actual use is possible by stirring. The coating state tends to lack a little flatness but can be used.
X: Viscosity change is large and cannot be used due to precipitation or gelation.
The evaluation results are shown in Table 1 below.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003311756A JP4102274B2 (en) | 2003-09-03 | 2003-09-03 | Catalyst for urethanization reaction and paint using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003311756A JP4102274B2 (en) | 2003-09-03 | 2003-09-03 | Catalyst for urethanization reaction and paint using the same |
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| Publication Number | Publication Date |
|---|---|
| JP2005076011A JP2005076011A (en) | 2005-03-24 |
| JP4102274B2 true JP4102274B2 (en) | 2008-06-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2003311756A Expired - Fee Related JP4102274B2 (en) | 2003-09-03 | 2003-09-03 | Catalyst for urethanization reaction and paint using the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9018327B1 (en) | 2013-11-08 | 2015-04-28 | Ppg Industries Ohio, Inc. | Catalyst compositions and methods of preparing them |
| US10221315B2 (en) | 2013-11-08 | 2019-03-05 | Ppg Industries Ohio, Inc. | Curable film-forming composition comprising catalyst associated with a carrier |
| US11555127B2 (en) | 2013-11-08 | 2023-01-17 | Ppg Industries Ohio, Inc. | Curable film-forming compositions comprising catalyst associated with a carrier and methods for coating a substrate |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007091782A (en) * | 2005-09-27 | 2007-04-12 | Asahi Kasei Chemicals Corp | Cross-linkable water-based coating composition |
| JP2007186582A (en) * | 2006-01-12 | 2007-07-26 | Asahi Kasei Chemicals Corp | Cross-linkable aqueous coating composition |
| JP5500330B2 (en) * | 2006-10-31 | 2014-05-21 | Ｄｉｃ株式会社 | Resin composition for water-based paint |
| DE102019127885A1 (en) * | 2018-10-26 | 2020-04-30 | Toyota Jidosha Kabushiki Kaisha | WATER-BASED COATING COMPOSITION AND PRODUCTION METHOD THEREOF |
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2003
- 2003-09-03 JP JP2003311756A patent/JP4102274B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9018327B1 (en) | 2013-11-08 | 2015-04-28 | Ppg Industries Ohio, Inc. | Catalyst compositions and methods of preparing them |
| US10221315B2 (en) | 2013-11-08 | 2019-03-05 | Ppg Industries Ohio, Inc. | Curable film-forming composition comprising catalyst associated with a carrier |
| US11555127B2 (en) | 2013-11-08 | 2023-01-17 | Ppg Industries Ohio, Inc. | Curable film-forming compositions comprising catalyst associated with a carrier and methods for coating a substrate |
| US11981832B2 (en) | 2013-11-08 | 2024-05-14 | Ppg Industries Ohio, Inc. | Curable film-forming compositions comprising catalyst associated with a carrier and methods for coating a substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005076011A (en) | 2005-03-24 |
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