JP3346929B2 - Aqueous paint for drying at room temperature - Google Patents
Aqueous paint for drying at room temperatureInfo
- Publication number
- JP3346929B2 JP3346929B2 JP33227694A JP33227694A JP3346929B2 JP 3346929 B2 JP3346929 B2 JP 3346929B2 JP 33227694 A JP33227694 A JP 33227694A JP 33227694 A JP33227694 A JP 33227694A JP 3346929 B2 JP3346929 B2 JP 3346929B2
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、常温乾燥用水性塗料に
関する。特に、本塗料は、シーラー塗装工程を省略する
ことが可能で、しかも透湿性、耐候性、耐水性、および
耐久性等を必要とする建築物内外装、の塗装に適する常
温乾燥用水性塗料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous paint for drying at room temperature. In particular, the present invention relates to an aqueous coating for room temperature drying which can omit a sealer coating step and is suitable for coating interior and exterior of buildings requiring moisture permeability, weather resistance, water resistance, and durability. .
【０００２】[0002]
【従来の技術及びその課題】一般に常温乾燥用水性塗料
（以下、常乾用水性塗料という）には、アクリル系共重
合体水分散液が使用されてきている。アクリル系共重合
体水分散液は、塗装後成膜過程でエマルジョン粒子どう
しの融着を必要とする。従って、常乾用水性塗料に用い
られるアクリル系共重合体はその造膜性の関係から、樹
脂のＴｇ（ガラス転移温度）を高くすることが困難であ
り、そのため耐汚染性が低下し、また耐水性等に関して
も脆弱さは否めない。また、セメント系素材に適用する
場合密着性の点から溶剤系および水性系のシーラーが必
要である。一方、市場は、年々、工程の短縮化、機能化
が求められる傾向にあり、要求される機能として、シー
ラーレスがあり、さらに塗膜性能として透湿性、弾性、
強靭性、耐久性および耐汚染性を向上させるニーズも高
まってきている。従来においてもシーラーレスタイプと
して、特殊変性アクリル系共重合体エマルジョン（シロ
キサン基導入）を用いる常乾用塗料があるが、このもの
はセメント系素材との耐水後の２次密着性で、やや不充
分な状況にある。2. Description of the Related Art In general, an aqueous dispersion of an acrylic copolymer has been used as a water-based paint for drying at room temperature (hereinafter referred to as a water-based paint for normal drying). The aqueous dispersion of an acrylic copolymer requires fusion of emulsion particles during the film formation process after coating. Therefore, it is difficult to increase the Tg (glass transition temperature) of the resin due to the film forming property of the acrylic copolymer used for the water-based paint for normal drying, and therefore, the stain resistance is reduced, and Weakness cannot be denied for water resistance and the like. Further, when applied to a cement-based material, a solvent-based and an aqueous-based sealer are required from the viewpoint of adhesion. On the other hand, in the market, there is a tendency for the process to be shortened and functionalized year by year, and there is a sealerless function as a required function.
There is also a growing need to improve toughness, durability and stain resistance. Conventionally, as a sealerless type, there is a paint for normal drying using a specially modified acrylic copolymer emulsion (introducing a siloxane group). However, this paint has a secondary adhesion to a cement material after water resistance and is slightly unsatisfactory. We are in a good situation.
【０００３】[0003]
【課題を解決するための手段】本発明者らは、上記した
常乾用水性塗料における問題点を解決するために鋭意研
究した結果、水性エマルジョン塗料の造膜時の脆弱さを
比較的分子量の小さい架橋剤で補強し、さらにアルコキ
シシリル基含有共重合体水分散液を併用すれば、アクリ
ル系塗料のもつ本来の耐候性を低下させることなく、シ
ーラーレス、透湿性、耐水性、弾性、耐汚染性および耐
久性に優れた常乾用水性塗料が得られることを見出し、
本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems in the water-based paint for normal drying, and as a result, have found that the fragility of the water-based emulsion paint during film formation is relatively small. Reinforcement with a small cross-linking agent and the combined use of an aqueous dispersion of an alkoxysilyl group-containing copolymer, without reducing the original weather resistance of the acrylic paint, sealer-less, moisture permeability, water resistance, elasticity, Finding that a water-based paint for normal drying with excellent stainability and durability can be obtained,
The present invention has been completed.
【０００４】本発明は、 「１． カルボニル基含有共重合体水分散液（Ａ）に、
架橋剤として下記式で示されるジヒドラジド化合物
（Ｂ）を、カルボニル基の１モルに対して０．０１〜２
モルを添加し、さらに、アルコキシシリル基含有共重合
体水分散液（Ｃ）を、カルボニル基含有共重合体水分散
液（Ａ）の固形分１００重量部に対して０．５〜５０重
量部（固形分）配合してなる常乾用水性塗料。 Ｈ２Ｎ−ＮＨ−ＣＯ−（ＣｎＨ２ｎ）−ＣＯ−ＮＨ−Ｎ
Ｈ２（ｎ≦８） ２． カルボニル基含有共重合体水分散液（Ａ）が、
（ａ）１分子中に少なくとも１個のカルボニル基を有す
る重合性のカルボニル基含有単量体を０．１〜３０重量
％、（ｂ）３〜５個の炭素原子を有するモノオレフィン
性不飽和カルボン酸、同不飽和カルボン酸アミド、同不
飽和カルボン酸アミドのＮ−アルキルおよび／またはＮ
−アルキロール誘導体、モノオレフィン性不飽和カルボ
ン酸よりなる群から選ばれた単量体を０〜１０重量％、
並びに（ｃ）ビニル芳香族化合物、アクリル酸の炭素数
１〜８個のｎ−アルキルエステル、メタクリル酸の炭素
数１〜８個のｎ−アルキルエステル、飽和カルボン酸の
ビニルエステル、１，３−ジエン、アクリル酸第三級ブ
チル、ハロゲン化ビニル、エチレン、アクリロニトリ
ル、メタクリロニトリルよりなる群から選ばれた単量体
を６０〜９９．９重量％含有する単量体混合物を分散剤
の存在下で乳化重合させることにより得た共重合体分散
液である、１項に記載された常温乾燥用水性塗料。 ３． 単量体（ａ）がダイアセトンアクリルアミド、お
よび／またはダイアセトンメタアクリルアミドである、
１項または２項に記載された常温乾燥用水性塗料。 ４． アルコキシシリル基含有共重合体水分散液（ｃ）
が、アルコキシシリル基ビニルモノマーを酸基を含有す
る不飽和単量体を含有する他の単量体と溶液重合して得
た酸基を有する共重合体をアミン化合物で中和し水に分
散して形成した共重合体分散液である、１項ないし３項
のいずれか１項に記載された常温乾燥用水性塗料。」に
関する。The present invention relates to the following: 1. An aqueous dispersion of a carbonyl group-containing copolymer (A)
A dihydrazide compound (B) represented by the following formula is used as a crosslinking agent in an amount of 0.01 to 2 with respect to 1 mol of a carbonyl group.
Of the alkoxysilyl group-containing copolymer aqueous dispersion (C) in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the solid content of the carbonyl group-containing copolymer aqueous dispersion (A). (Solid content) A water-based paint for normal drying formulated. H 2 N-NH-CO- ( C n H 2n) -CO-NH-N
H 2 (n ≦ 8) 2. The carbonyl group-containing copolymer aqueous dispersion (A) is
(A) 0.1 to 30% by weight of a polymerizable carbonyl group-containing monomer having at least one carbonyl group in one molecule, and (b) monoolefinic unsaturated having 3 to 5 carbon atoms. N-alkyl and / or N-carboxylic acid, unsaturated carboxylic acid amide, and unsaturated carboxylic acid amide
-An alkylol derivative, 0 to 10% by weight of a monomer selected from the group consisting of monoolefinically unsaturated carboxylic acids,
And (c) a vinyl aromatic compound, an n-alkyl ester of acrylic acid having 1 to 8 carbon atoms, an n-alkyl ester of methacrylic acid having 1 to 8 carbon atoms, a vinyl ester of a saturated carboxylic acid, 1,3- A monomer mixture containing 60 to 99.9% by weight of a monomer selected from the group consisting of diene, tertiary butyl acrylate, vinyl halide, ethylene, acrylonitrile and methacrylonitrile is added in the presence of a dispersant. 2. The aqueous coating composition for drying at room temperature according to item 1, which is a copolymer dispersion obtained by emulsion polymerization in step 1. 3. The monomer (a) is diacetone acrylamide and / or diacetone methacrylamide,
Item 3. The aqueous coating composition for drying at room temperature according to Item 1 or 2. 4. Aqueous dispersion of alkoxysilyl group-containing copolymer (c)
However, the copolymer having an acid group obtained by solution polymerization of an alkoxysilyl group vinyl monomer with another monomer containing an unsaturated monomer containing an acid group is neutralized with an amine compound and dispersed in water. Item 4. The aqueous coating composition for drying at room temperature according to any one of Items 1 to 3, which is a copolymer dispersion formed by the above method. About.
【０００５】[0005]
【作用】本発明において使用するカルボニル基を含有す
る共重合体水分散液（Ａ）は、（ａ）１分子中に少なく
とも１個のカルボニル基を有する重合性のカルボニル基
含有単量体を０．１〜３０重量％、（ｂ）３〜５個の炭
素原子を有するモノオレフィン性不飽和カルボン酸、同
不飽和カルボン酸アミド、同不飽和カルボン酸アミドの
Ｎ−アルキルおよび／またはＮ−アルキロール誘導体、
モノオレフィン性不飽和カルボン酸よりなる群から選ば
れた単量体を０〜１０重量％、並びに（ｃ）ビニル芳香
族化合物、アクリル酸の炭素数１〜８個のｎ−アルキル
エステル、メタクリル酸の炭素数１〜８個のｎ−アルキ
ルエステル、飽和カルボン酸のビニルエステル、１，３
−ジエン、アクリル酸第三級ブチル、ハロゲン化ビニ
ル、エチレン、アクリロニトリル、メタクリロニトリル
よりなる群から選ばれた単量体を６０〜９９．９重量％
含有する単量体混合物を分散剤の存在下で乳化重合させ
ることにより容易に得られる。The carbonyl group-containing copolymer aqueous dispersion (A) used in the present invention contains (a) a polymerizable carbonyl group-containing monomer having at least one carbonyl group in one molecule. (B) mono-olefinically unsaturated carboxylic acid having 3 to 5 carbon atoms, unsaturated carboxylic acid amide, N-alkyl and / or N-alkyl of the unsaturated carboxylic acid amide Roll derivatives,
0 to 10% by weight of a monomer selected from the group consisting of monoolefinically unsaturated carboxylic acids, (c) a vinyl aromatic compound, an n-alkyl ester of acrylic acid having 1 to 8 carbon atoms, methacrylic acid N-alkyl esters having 1 to 8 carbon atoms, vinyl esters of saturated carboxylic acids, 1,3
A monomer selected from the group consisting of diene, tertiary butyl acrylate, vinyl halide, ethylene, acrylonitrile and methacrylonitrile at 60 to 99.9% by weight;
It can be easily obtained by subjecting the contained monomer mixture to emulsion polymerization in the presence of a dispersant.
【０００６】単量体（ａ）としては、１分子中に少なく
とも１個のカルボニル基を有する重合可能な二重結合を
有する単量体が用いられる。単量体（ａ）の具体例とし
ては、アクロレイン、ダイアセトンアクリルアミド、ダ
イアセトンメタアクリルアミド、ホルミルスチロール、
４〜７個の炭素原子を有するビニルアルキルケトン（例
えばビニルメチルケトン、ビニルエチルケトン、ビニル
ブチルケトン）等があげられる。特に好ましいのは、ダ
イアセトンアクリルアミド、ダイアセトンメタアクリル
アミドである。As the monomer (a), a monomer having a polymerizable double bond having at least one carbonyl group in one molecule is used. Specific examples of the monomer (a) include acrolein, diacetone acrylamide, diacetone methacrylamide, formylstyrene,
Vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) and the like can be mentioned. Particularly preferred are diacetone acrylamide and diacetone methacrylamide.
【０００７】本発明において使用する架橋剤は下記式で
示されるジヒドラジド化合物（Ｂ）で、ｎは１〜６が好
ましく、特に好ましいのはｎ＝４のアジピン酸ジヒドラ
ジドである。 Ｈ２Ｎ−ＮＨ−ＣＯ−（ＣｎＨ２ｎ）−ＣＯ−ＮＨ−Ｎ
Ｈ２（ｎ≦８） 本発明において、カルボニル基含有共重合体水分散液
（Ａ）と架橋剤であるジヒドラジド化合物（Ｂ）の割合
は、共重合体水分散液中に含まれるカルボニル基１モル
に対して、ヒドラジド化合物が０．０１〜２モル、好ま
しくは０．０５〜１モルになる割合である。０．０１モ
ル以下では造膜時の脆弱さが改善できず２モル以上では
架橋効果のより一層の向上が認められない。The crosslinking agent used in the present invention is a dihydrazide compound (B) represented by the following formula, wherein n is preferably from 1 to 6, and particularly preferably adipic dihydrazide wherein n = 4. H 2 N-NH-CO- ( C n H 2n) -CO-NH-N
H 2 (n ≦ 8) In the present invention, the ratio of the carbonyl group-containing copolymer aqueous dispersion (A) to the dihydrazide compound (B) as a crosslinking agent is such that the carbonyl group contained in the aqueous copolymer dispersion is 1%. The molar ratio of the hydrazide compound is 0.01 to 2 mol, preferably 0.05 to 1 mol, per mol. If it is less than 0.01 mol, the brittleness during film formation cannot be improved, and if it is more than 2 mol, no further improvement in the crosslinking effect can be observed.
【０００８】本発明において、（Ａ）および（Ｂ）を含
む樹脂成分として最も好ましいのは、特開平４−２４９
５８７号に示した組成物である。本発明に用いられるア
ルコキシシリル基含有共重合体水分散液（ｃ）は具体的
には、次のように製造することが出来る。アルコキシシ
リル基含有ビニルモノマーを、酸基を有する不飽和単量
体を必須とするその他の不飽和単量体、例えば（メタ）
アクリル酸、（メタ）アクリル酸のアルキルエステル、
（メタ）アクリルアミド、スチレン、ビニルトルエン等
のビニルモノマーと溶液重合して得られる酸基を有する
共重合体をアミン化合物等で中和し、水に分散すること
によって得られる。この方法で特に好ましいのは、特開
平５−２５３５４号に記載のアルコキシシリル基含有共
重合体水分散液である。また、乳化剤を用いて乳化重合
によって製造することも可能である。この方法において
は、アルコキシシリル基の官能基を水溶液中で、シラノ
ール基として安定化させるために、アルコキシシルリ基
を、エマルジョンのシェル部に分散せしめ、立体的障害
による、シラノール基間の接触を低くさせることが肝要
である。In the present invention, the most preferable resin component containing (A) and (B) is disclosed in JP-A-4-249.
No. 587. The alkoxysilyl group-containing copolymer aqueous dispersion (c) used in the present invention can be specifically produced as follows. The alkoxysilyl group-containing vinyl monomer is replaced with an unsaturated monomer having an unsaturated monomer having an acid group, for example, (meth)
Acrylic acid, alkyl esters of (meth) acrylic acid,
It is obtained by neutralizing a copolymer having an acid group obtained by solution polymerization with a vinyl monomer such as (meth) acrylamide, styrene or vinyltoluene with an amine compound or the like and dispersing it in water. Particularly preferred in this method is an aqueous dispersion of an alkoxysilyl group-containing copolymer described in JP-A-5-25354. Further, it can be produced by emulsion polymerization using an emulsifier. In this method, in order to stabilize a functional group of an alkoxysilyl group as a silanol group in an aqueous solution, an alkoxysilyl group is dispersed in a shell portion of an emulsion, and contact between the silanol groups due to steric hindrance is prevented. It is important to lower it.
【０００９】上記したアルコキシシリル基含有共重合体
水分散液の製造に用いる、アルコキシシリル基を有する
ビニルモノマーまたは重合性オリゴマーの具体例として
は、ビニルシラン（例えばビニルメチルジメトキシシラ
ン、ビニルトリメトキシシラン、ビニルトリエトキシシ
ラン、ビニルトリス（β−メトキシエトキシ）シランな
ど）；（メタ）アクリロキシアルキルシラン（例えば、
γ−メタクリロキシプロピルトリメトキシシラン、γ−
メタクリロキシプロピルメチルジメトキシシラン、γ−
アクリロキシプロピルトリメトキシシラン、γ−メタク
リロキシプロピルメチルジエトキシシラン、γ−アクリ
ロキシプロピルトリエトキシシランなど）；アルコキシ
シリル基を有する重合性オリゴマー；（例えば、１個以
上のビニル基とアルコキシシリル基を有するポリウレタ
ンオリゴマー、ポリエーテルオリゴマー、ポリアミドオ
リゴマー、エポキシオリゴマー、ポリエステルオリゴマ
ーなど）を挙げることが出来る。Specific examples of the vinyl monomer or polymerizable oligomer having an alkoxysilyl group used in the production of the above-mentioned aqueous dispersion of an alkoxysilyl group-containing copolymer include vinylsilane (for example, vinylmethyldimethoxysilane, vinyltrimethoxysilane, and vinyltrimethoxysilane). Vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, etc.); (meth) acryloxyalkylsilane (for example,
γ-methacryloxypropyltrimethoxysilane, γ-
Methacryloxypropylmethyldimethoxysilane, γ-
Acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltriethoxysilane, etc.); a polymerizable oligomer having an alkoxysilyl group; (for example, one or more vinyl group and alkoxysilyl group) (Polyurethane oligomer, polyether oligomer, polyamide oligomer, epoxy oligomer, polyester oligomer, etc.)
【００１０】本発明において、カルボニル基含有共重合
体水分散液（Ａ）とアルコキシシリル基含有共重合体水
分散液（Ｃ）の配合比は、カルボニル基含有共重合体水
分散液（Ａ）の固形分１００重量部に対して０．５〜５
０重量部、好ましくは２〜２０重量部である。０．５重
量部未満では、セメント系素地面への付着性が乏しく。
５０重量部を越えると耐汚染性、弾性が低下し、しかも
コスト高となる。In the present invention, the mixing ratio of the carbonyl group-containing copolymer aqueous dispersion (A) and the alkoxysilyl group-containing copolymer aqueous dispersion (C) is such that the carbonyl group-containing copolymer aqueous dispersion (A) 0.5 to 5 with respect to 100 parts by weight of the solid content of
0 parts by weight, preferably 2 to 20 parts by weight. If the amount is less than 0.5 parts by weight, adhesion to a cement-based base is poor.
If the amount exceeds 50 parts by weight, stain resistance and elasticity decrease, and the cost increases.
【００１１】本発明において、カルボニル基含有共重合
体水分散液（Ａ）のポリマー分子末端のカルボニル基と
比較的低分子のジヒドラジド化合物（Ｂ）とが造膜時に
反応して弾性、強靭性、耐候性などに優れた塗膜を付与
する。それと同時にアルコキシシリル基含有共重合体水
分散液（Ｃ）中のアルコキシシリル基または、シラノー
ル基が造膜時に縮合してシロキサン結合を形成し、セメ
ント素地面との密着性、造膜の耐水性および透湿性を向
上させる。本発明の水性塗料を製造するにあたっては、
適宜、顔料、充填剤、骨材、顔料分散剤、湿潤剤、増粘
剤、消泡剤、可塑剤、造膜助剤、有機溶剤、防腐剤、防
黴剤、ｐＨ調整剤、防錆剤など、それぞれの目的に応じ
て選択、組み合わされ、通常の方法で行うことができ
る。In the present invention, the carbonyl group at the polymer molecule terminal of the aqueous carbonyl group-containing copolymer aqueous dispersion (A) reacts with a relatively low molecular weight dihydrazide compound (B) during film formation to provide elasticity, toughness, Provides a coating film with excellent weather resistance and the like. At the same time, the alkoxysilyl groups or silanol groups in the alkoxysilyl group-containing copolymer aqueous dispersion (C) condense during the film formation to form siloxane bonds, and provide adhesion to the cement base and water resistance of the film. And improve moisture permeability. In producing the water-based paint of the present invention,
As appropriate, pigments, fillers, aggregates, pigment dispersants, wetting agents, thickeners, defoamers, plasticizers, film-forming aids, organic solvents, preservatives, fungicides, pH adjusters, rust inhibitors For example, they can be selected and combined according to each purpose, and can be performed by a usual method.
【００１２】本発明の水性塗料は、シーラーレスで塗装
が可能であり、耐候性、透湿性、耐水性、弾性、強靭
性、および耐汚染性、耐久性に優れることから、建築物
内外装、の塗装に適している。The water-based paint of the present invention can be applied without a sealer and has excellent weather resistance, moisture permeability, water resistance, elasticity, toughness, stain resistance, and durability. Suitable for painting.
【００１３】[0013]
【実施例】以下、本発明を実施例により、さらに詳細に
説明する。The present invention will be described below in more detail with reference to examples.
【００１４】カルボニル基含有共重合体水分散液の製造 製造例１ ２リットルの４つ口フラスコに脱イオン水３１２重量
部、Ｎｅｗｃｏｌ ７０７ＳＦ（日本乳化剤製、固形分
３０重量％）２．３重量部を加え、窒素置換後、８０℃
に保つ。下記組成のプレエマルジョンを滴下する直前に
０．７重量部の過硫酸アンモニウムを加え、プレエマル
ジョンを３時間にわたって滴下した。 脱イオン水 ３３８重量部 ダイアセトンアクリルアミド ３２重量部 アクリル酸 ３．２重量部 スチレン ９７重量部 メチルメタクリレート ２６０重量部 ２−エチルヘキシルアクリレート １００重量部 ｎ−ブチルアクリレート １５０重量部 Ｎｅｗｃｏｌ ７０７ＳＦ ６２重量部 過硫酸アンモニウム １．２重量部 滴下終了後３０分より、３０分間０．７重量部の過硫酸
アンモニウムを７重量部の脱イオン水に溶かした溶液を
滴下し、さらに２時間８０℃に保持し、その後約４０〜
６０℃に降温した後、アンモニア水でｐＨを８〜９に調
整し、固形分５１．２重量％及び粒径０．１６μｍのエ
マルジョンＡ−１を得た。Production of carbonyl group-containing copolymer aqueous dispersion Production Example 1 312 parts by weight of deionized water and 2.3 parts by weight of Newcol 707SF (manufactured by Nippon Emulsifier, solid content 30% by weight) in a two-liter four-necked flask. At 80 ° C after purging with nitrogen.
To keep. Immediately before dropping the pre-emulsion having the following composition, 0.7 parts by weight of ammonium persulfate was added, and the pre-emulsion was dropped over 3 hours. Deionized water 338 parts by weight Diacetone acrylamide 32 parts by weight Acrylic acid 3.2 parts by weight Styrene 97 parts by weight Methyl methacrylate 260 parts by weight 2-ethylhexyl acrylate 100 parts by weight n-butyl acrylate 150 parts by weight Newcol 707SF 62 parts by weight Ammonium persulfate 1 .2 parts by weight From 30 minutes after the completion of the dropping, a solution prepared by dissolving 0.7 parts by weight of ammonium persulfate in 7 parts by weight of deionized water was added dropwise for 30 minutes, and kept at 80 ° C. for another 2 hours.
After the temperature was lowered to 60 ° C., the pH was adjusted to 8 to 9 with aqueous ammonia to obtain an emulsion A-1 having a solid content of 51.2% by weight and a particle size of 0.16 μm.
【００１５】アルコキシシリル基含有共重合体水分散液
の製造 製造例１ ２リットルの４つ口フラスコに脱イオン水２７０重量
部、Ｎｅｗｃｏｌ ７０７ＳＦ１．８重量部を加え、窒
素置換後、８０℃に保つ。下記組成のプレエマルジョン
を滴下する直前に０．６重量部の過硫酸アンモニウムを
加え、プレエマルジョンを２時間にわたって滴下した。 脱イオン水 ２１０重量部 メチルメタクリレート １２８重量部 エチルアクリレート ９６重量部 ｎ−ブチルアクリレート ７８．４重量部 ２−ヒドロキシエチルメタクリレート １６重量部 アクリル酸 １．６重量部 Ｎｅｗｃｏｌ ７０７ＳＦ ３１重量部 過硫酸アンモニウム ０．７重量部 滴下終了後３０分より、さらに、下記組成のプレエマル
ジョンを１．５時間にわたって滴下した。 脱イオン水 １２８重量部 スチレン ３８．４重量部 ｎ−ブチルアクリレート ７６．８重量部 γ−メタクリロキシプロピルトリメトキシシラン ７６．８重量部 Ｎｅｗｃｏｌ ７０７ＳＦ １８．５重量部 過硫酸アンモニウム ０．３重量部 滴下終了後３０分より、３０分間０．６重量部の過硫酸
アンモニウムを７重量部の脱イオン水に溶かした溶液を
滴下し、さらに２時間８０℃に保持し、その後約４０℃
に降温した後、アンモニア水でｐＨを８〜９に調整し、
固形分４４．７重量％、粒径０．１７μｍのエマルジョ
ンＡ−２を得た。Preparation of Aqueous Dispersion of Alkoxysilyl Group-Containing Copolymer Preparation Example 1 270 parts by weight of deionized water and 1.8 parts by weight of Newcol 707SF were added to a 2 liter four-necked flask, and kept at 80 ° C. after purging with nitrogen. . Immediately before dropping the pre-emulsion having the following composition, 0.6 parts by weight of ammonium persulfate was added, and the pre-emulsion was dropped over 2 hours. Deionized water 210 parts by weight Methyl methacrylate 128 parts by weight Ethyl acrylate 96 parts by weight n-butyl acrylate 78.4 parts by weight 2-hydroxyethyl methacrylate 16 parts by weight Acrylic acid 1.6 parts by weight Newcol 707SF 31 parts by weight Ammonium persulfate 0.7 30 parts after the completion of the dropwise addition, a pre-emulsion having the following composition was further added dropwise over 1.5 hours. Deionized water 128 parts by weight Styrene 38.4 parts by weight n-butyl acrylate 76.8 parts by weight γ-methacryloxypropyltrimethoxysilane 76.8 parts by weight Newcol 707SF 18.5 parts by weight Ammonium persulfate 0.3 part by weight Drip end After 30 minutes, a solution prepared by dissolving 0.6 parts by weight of ammonium persulfate in 7 parts by weight of deionized water was added dropwise for 30 minutes, kept at 80 ° C. for further 2 hours, and then kept at about 40 ° C.
After the temperature is lowered to pH 8 to 9 with aqueous ammonia,
Emulsion A-2 having a solid content of 44.7% by weight and a particle size of 0.17 μm was obtained.
【００１６】樹脂混合液の調製 １リットルのステンレス容器に、エマルジョンＡ−１を
５１３重量部、アジピン酸ジヒドラジドを７．６５重量
部、３５重量％グラスコールＳＷ−１３５（三洋化成社
製 アルコキシシリル基含有共重合体水分散液、Ｓｉ含
有量１．４５重量％）を３７．５重量部入れ撹拌して樹
脂混液Ｄ−１を得た。同様にして、表１の配合に基づい
て樹脂混液Ｄ−２〜Ｄ−８を得た。Preparation of Resin Mixture In a 1-liter stainless steel container, 513 parts by weight of emulsion A-1, 7.65 parts by weight of adipic dihydrazide, and 35% by weight of glasscol SW-135 (alkoxysilyl group manufactured by Sanyo Chemical Co., Ltd.) 37.5 parts by weight of a water-containing copolymer aqueous dispersion (Si content: 1.45% by weight) was stirred to obtain a resin mixture D-1. Similarly, resin mixtures D-2 to D-8 were obtained based on the formulations in Table 1.
【００１７】[0017]
【表１】 [Table 1]
【００１８】実施例１ １リットルのステンレス容器に、下記表２に示す顔料ペ
ースト配合を入れ、ディスパーで３０分間撹拌し顔料ペ
ーストを作り、次にレットダウン工程で、樹脂液Ｄ−１
５５８．２重量部、テキサノール３８重量部、ＳＮデ
フォーマーＡ−６３を７重量部、プライマールＴＴ−６
３５を６重量部、アンモニア水１重量部及びミネラルス
ピリット２０重量部を入れて２０分間撹拌して、水性塗
料を得た。Example 1 A 1 liter stainless steel container was charged with the pigment paste composition shown in Table 2 below, and stirred for 30 minutes with a disper to form a pigment paste.
558.2 parts by weight, Texanol 38 parts by weight, SN deformer A-63 7 parts by weight, Primal TT-6
35 parts by weight, 1 part by weight of aqueous ammonia and 20 parts by weight of mineral spirit were added and stirred for 20 minutes to obtain an aqueous paint.
【００１９】[0019]
【表２】 [Table 2]
【００２０】（註） 配合量は全て重量部である。 ＊１ サンノプコ株式会社製 顔料分散剤 ＊２ 旭電化株式会社製 増粘剤 ＊３ サンノプコ株式会社製 消泡剤 ＊４ 武田薬品工業株式会社製 防腐剤 ＊５ テイカ株式会社製 白色顔料 ＊６ ローム＆ハウス株式会社製 増粘剤(Note) All amounts are parts by weight. * 1 Pigment dispersant manufactured by San Nopco Co., Ltd. * 2 Thickener manufactured by Asahi Denka Co., Ltd. * 3 Antifoaming agent manufactured by San Nopco Co., Ltd. * 4 Preservative manufactured by Takeda Pharmaceutical Co., Ltd. * 5 White pigment manufactured by Teica Co., Ltd. * 6 ROHM & House Co., Ltd. Thickener
【００２１】実施例２〜５、比較例１〜３ 表３に示す配合に基づき実施例１と同様にして水性塗料
を得た。実施例１〜５および比較例１〜３で得た塗料Ｅ
−１〜Ｅ−８を上水で希釈して１００ｍｍ×３００ｍｍ
×３ｍｍスレート板にウエット膜厚１ｍｍになるように
ドクターブレードで塗装し塗板を２０℃、６５重量％Ｒ
Ｈ下で１４日間放置した。得られた試験板について以下
の試験を行った。その結果を表３に示す。Examples 2 to 5 and Comparative Examples 1 to 3 Water-based paints were obtained in the same manner as in Example 1 based on the formulations shown in Table 3. Paint E obtained in Examples 1 to 5 and Comparative Examples 1 to 3
-1 to E-8 are diluted with tap water to 100 mm x 300 mm
× 3 mm slate plate is coated with a doctor blade so as to have a wet film thickness of 1 mm.
It was left under H for 14 days. The following tests were performed on the obtained test plates. Table 3 shows the results.
【００２２】[0022]
【表３】 [Table 3]
【００２３】（１） 初期付着性 ＮＴカッターで６０°角度に塗膜に傷を入れ、ガムテー
プを貼り付けて、急速の速さでガムテープをはがす。塗
面を目視で評価した。 ◎ ： 全くはがれが認められない。 ○ ： カッターの傷の塗膜の一部にはがれが認められ
る。 △ ： １０〜２５％塗膜のはがれが認められる。 × ： ２５％以上塗膜のはがれが認められる。(1) Initial Adhesion The coating film is scratched at an angle of 60 ° with an NT cutter, a gum tape is attached, and the gum tape is peeled off at a rapid speed. The painted surface was evaluated visually. ◎: No peeling was observed. : Peeling is observed in a part of the coating film of the cutter scratch. B: 10% to 25% peeling of the coating film is observed. ×: Peeling of the coating film is observed 25% or more.
【００２４】（２） 耐水試験 前記試験板を、流水中の上水に半分浸漬し、７日後に試
験板を引き上げて、塗面を目視で評価した。 ◎ ： 全く変化なし ○ ： 部分的なフクレ × ： 全面的なフクレ 評価後、２０℃６５％ＲＨ下で１日間乾燥後（１）の初
期付着性試験を再び行った。(2) Water resistance test The test plate was half immersed in running water of running water, and after 7 days, the test plate was pulled up and the coated surface was visually evaluated. ◎: No change at all ○: Partial swelling X: Full swelling After the evaluation, drying was performed at 20 ° C. and 65% RH for 1 day, and the initial adhesion test (1) was performed again.
【００２５】（３） 透水性試験 前記試験板を使用して、ＪＩＳＡ−６９１０の透水性試
験を行った。(3) Water permeability test A water permeability test according to JISA-6910 was performed using the test plate.
【００２６】（４） 付着の強さ（標準時、浸水後） ＪＩＳＡ−６９１０による。試験板は７０×７０×２０
ｍ／ｍモルタル板に、シーラーなしで、直接Ｅ−１〜Ｅ
−８を１ｍ／ｍ厚の型枠内に塗付した。(4) Adhesion strength (standard time, after immersion) According to JISA-6910. Test plate is 70 × 70 × 20
E-1 to E directly on m / m mortar plate without sealer
-8 was applied in a 1 m / m thick mold.
【００２７】（５） 温冷繰り返し試験：ＪＩＳＡ−６
９１０による。（４）の付着の強さと同様に試験板を作
成。(5) Hot / cold repetition test: JISA-6
910. A test plate was prepared in the same manner as in (4).
【００２８】（６） 透湿性試験 離型紙に１ｍｍのドクターブレードでＥ−１〜Ｅ−８を
それぞれひき塗りし、２０℃６５％ＲＨ下で７日間乾燥
した後塗膜をはがして、表面を裏面にひっくり返して、
再び７日間乾燥後ＪＩＳＺ−０２０８−７６のカップ法
で透湿性試験を行った。(6) Moisture Permeability Test E-1 to E-8 were each applied to a release paper with a 1 mm doctor blade, dried at 20 ° C. and 65% RH for 7 days. Turn it over on the back,
After drying again for 7 days, a moisture permeability test was conducted by the cup method of JISZ-0208-76.
【００２９】（７） ゼロスパン試験 ７０×１５０×５ｍｍのフレキシブル板の下面に深さ
２．５ｍｍ、巾３ｍｍの溝を設け、溝の反対側に１ｍｍ
のドクターブレードでＥ−１〜Ｅ−８をそれぞれひき塗
りし、２０℃６５％ＲＨで１４日間乾燥した後、溝の中
間でフレキシブル板を２つに切断して試験に供した。試
験機の引張り速度は５ｍｍ／分で行い、塗面表面にクラ
ック発生時の伸びをゼロスパン値（ｍｍ）とする。(7) Zero span test A groove having a depth of 2.5 mm and a width of 3 mm is provided on the lower surface of a 70 × 150 × 5 mm flexible plate, and 1 mm is provided on the opposite side of the groove.
Each of E-1 to E-8 was applied with a doctor blade and dried at 20 ° C. and 65% RH for 14 days, and then the flexible plate was cut into two pieces in the middle of the groove to be subjected to the test. The tensile speed of the tester is set at 5 mm / min, and the elongation at the time of occurrence of cracks on the coated surface is defined as the zero span value (mm).
【００３０】（８） 耐候性試験 試験板を、南面３５°屋外バクロ試験台に取り付け、３
年間バクロした後、水洗いした後目視で塗面を評価し
た。 ◎ ： 全く変化なし ○ ： 汚れが僅かで、光沢低下が認められない。 △ ： 汚れまたは光沢低下が認められる。 × ： 汚れまたは光沢低下が著しい。(8) Weather resistance test The test plate was mounted on a 35 ° outdoor bacground test stand on the south side.
After backwashing for a year, the coated surface was visually evaluated after washing with water. ◎: No change: Slight stain, no decrease in gloss. Δ: Stain or decrease in gloss is observed. ×: Stain or gloss is remarkably reduced.
【００３１】[0031]
【発明の効果】表３からわかるように、本発明の常乾用
水性塗料は、本発明要件を満たしていない水性塗料（比
較例１〜３）に比較して、耐水試験後の２次付着性、透
水性、付着の強さ、温冷繰り返し性、透湿性、ゼロスパ
ンおよび屋外耐候性について、バランス良く、しかも優
れている。比較例では、カルボニル基含有共重合体水液
とジヒドラジド化合物との組成（比較例１）およびカル
ボニル基含有共重合体水溶液とアルコキシシリル基含有
共重合体水分散液との組成（比較例２）の２成分系は、
いずれも耐水後の２次付着性が劣ることからも本発明の
効果が優れていることがわかる。As can be seen from Table 3, the water-based paint for normal drying of the present invention has a lower secondary adhesion after the water resistance test than the water-based paint which does not satisfy the requirements of the present invention (Comparative Examples 1 to 3). The properties, water permeability, adhesion strength, repetition of heating and cooling, moisture permeability, zero span and outdoor weather resistance are well-balanced and excellent. In Comparative Examples, the composition of a carbonyl group-containing copolymer aqueous solution and a dihydrazide compound (Comparative Example 1) and the composition of a carbonyl group-containing copolymer aqueous solution and an alkoxysilyl group-containing copolymer aqueous dispersion (Comparative Example 2) The two-component system of
In each case, the secondary adhesion after water resistance is inferior, indicating that the effect of the present invention is excellent.
フロントページの続き (56)参考文献 特開 平６−190332（ＪＰ，Ａ) 特開 平４−214747（ＪＰ，Ａ) 特開 平３−70763（ＪＰ，Ａ) 特開 昭63−370（ＪＰ，Ａ) 特開 昭56−57860（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C09D 5/00 - 201/10 Continuation of the front page (56) References JP-A-6-190332 (JP, A) JP-A-4-214747 (JP, A) JP-A-3-70763 (JP, A) JP-A-63-370 (JP) , A) JP-A-56-57860 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C09D 5/00-201/10
Claims (4)
（Ａ）に、架橋剤として下記式で示されるジヒドラジド
化合物（Ｂ）を、カルボニル基の１モルに対して０．０
１〜２モルを添加し、さらに、アルコキシシリル基含有
共重合体水分散液（Ｃ）を、カルボニル基含有共重合体
水分散液（Ａ）の固形分１００重量部に対し０．５〜５
０重量部（固形分）配合してなる常温乾燥用水性塗料。 Ｈ２Ｎ−ＮＨ−ＣＯ−（ＣｎＨ２ｎ）−ＣＯ−ＮＨ−Ｎ
Ｈ２（ｎ≦８）1. A dihydrazide compound (B) represented by the following formula as a crosslinking agent is added to an aqueous dispersion of a carbonyl group-containing copolymer (A) in an amount of 0.0
1 to 2 mol, and further, the alkoxysilyl group-containing copolymer aqueous dispersion (C) was added to the carbonyl group-containing copolymer aqueous dispersion (A) in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the solid content.
A water-based paint for drying at room temperature, containing 0 parts by weight (solid content). H 2 N-NH-CO- ( C n H 2n) -CO-NH-N
H 2 (n ≦ 8)
（Ａ）が、（ａ）１分子中に少なくとも１個のカルボニ
ル基を有する重合性のカルボニル基含有単量体を０．１
〜３０重量％、（ｂ）３〜５個の炭素原子を有するモノ
オレフィン性不飽和カルボン酸、同不飽和カルボン酸ア
ミド、同不飽和カルボン酸アミドのＮ−アルキルおよび
／またはＮ−アルキロール誘導体、モノオレフィン性不
飽和カルボン酸よりなる群から選ばれた単量体を０〜１
０重量％、並びに（ｃ）ビニル芳香族化合物、アクリル
酸の炭素数１〜８個のｎ−アルキルエステル、メタクリ
ル酸の炭素数１〜８個のｎ−アルキルエステル、飽和カ
ルボン酸のビニルエステル、１，３−ジエン、アクリル
酸第三級ブチル、ハロゲン化ビニル、エチレン、アクリ
ロニトリル、メタクリロニトリルよりなる群から選ばれ
た単量体を６０〜９９．９重量％含有する単量体混合物
を分散剤の存在下で乳化重合させることにより得た共重
合体分散液である、請求項１に記載された常温乾燥用水
性塗料。2. An aqueous dispersion of a carbonyl group-containing copolymer (A) contains (a) 0.1% of a polymerizable carbonyl group-containing monomer having at least one carbonyl group in one molecule.
(B) a monoolefinically unsaturated carboxylic acid having 3 to 5 carbon atoms, an unsaturated carboxylic acid amide, an N-alkyl and / or N-alkylol derivative of the unsaturated carboxylic acid amide A monomer selected from the group consisting of monoolefinically unsaturated carboxylic acids,
0% by weight, and (c) a vinyl aromatic compound, an n-alkyl ester of acrylic acid having 1 to 8 carbon atoms, an n-alkyl ester of methacrylic acid having 1 to 8 carbon atoms, a vinyl ester of a saturated carboxylic acid, A monomer mixture containing 60 to 99.9% by weight of a monomer selected from the group consisting of 1,3-diene, tertiary butyl acrylate, vinyl halide, ethylene, acrylonitrile, and methacrylonitrile is dispersed. The aqueous coating composition for drying at room temperature according to claim 1, which is a copolymer dispersion obtained by emulsion polymerization in the presence of an agent.
ミド、および／またはダイアセトンメタアクリルアミド
である、請求項１または２に記載された常温乾燥用水性
塗料。3. The aqueous coating composition for drying at room temperature according to claim 1, wherein the monomer (a) is diacetone acrylamide and / or diacetone methacrylamide.
液（ｃ）が、アルコキシシリル基ビニルモノマーを酸基
を有する不飽和単量体を含有する他の単量体と溶液重合
して得た酸基を有する共重合体をアミン化合物で中和し
水に分散して形成した共重合体分散液である、請求項１
ないし３のいずれか１項に記載された常温乾燥用水性塗
料。4. An alkoxysilyl group-containing copolymer aqueous dispersion (c) obtained by solution polymerization of an alkoxysilyl group vinyl monomer with another monomer containing an unsaturated monomer having an acid group. 2. A copolymer dispersion formed by neutralizing a copolymer having an acid group with an amine compound and dispersing the copolymer in water.
4. The aqueous coating composition for drying at room temperature according to any one of items 3 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33227694A JP3346929B2 (en) | 1994-12-02 | 1994-12-02 | Aqueous paint for drying at room temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33227694A JP3346929B2 (en) | 1994-12-02 | 1994-12-02 | Aqueous paint for drying at room temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08157775A JPH08157775A (en) | 1996-06-18 |
| JP3346929B2 true JP3346929B2 (en) | 2002-11-18 |
Family
ID=18253141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33227694A Expired - Fee Related JP3346929B2 (en) | 1994-12-02 | 1994-12-02 | Aqueous paint for drying at room temperature |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3346929B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000169785A (en) * | 1998-12-04 | 2000-06-20 | Mitsubishi Kagaku Basf Kk | Composition for crosslinkable water-base paint |
| JP3901500B2 (en) * | 2001-11-30 | 2007-04-04 | 日本カーバイド工業株式会社 | Cross-linked resin aqueous composition for fiber processing |
| JP5622504B2 (en) * | 2010-09-24 | 2014-11-12 | 関西ペイント株式会社 | Multi-layer coating formation method |
| CN104194440A (en) * | 2014-08-25 | 2014-12-10 | 安徽梁溪环保新材料有限公司 | Waterproof coating capable of being cured at normal temperature |
| JP6674558B2 (en) | 2016-04-20 | 2020-04-01 | ダウ シリコーンズ コーポレーション | Lithium alkylsiliconate composition, coating film, and method for producing the same |
-
1994
- 1994-12-02 JP JP33227694A patent/JP3346929B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08157775A (en) | 1996-06-18 |
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