JPH07268064A - Water-base resin composition and its production - Google Patents
Water-base resin composition and its productionInfo
- Publication number
- JPH07268064A JPH07268064A JP6499594A JP6499594A JPH07268064A JP H07268064 A JPH07268064 A JP H07268064A JP 6499594 A JP6499594 A JP 6499594A JP 6499594 A JP6499594 A JP 6499594A JP H07268064 A JPH07268064 A JP H07268064A
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- JP
- Japan
- Prior art keywords
- weight
- resin
- parts
- epoxy resin
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、水性樹脂組成物及びそ
の製造法に関し、特に水性液の安定性、消泡性、塗装性
及び塗膜の加工性に優れた金属缶、特に食缶及び飲料缶
の内面塗装に好適な水性エポキシ樹脂組成物及びその製
造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous resin composition and a method for producing the same, and more particularly to metal cans, particularly food cans, which are excellent in stability of aqueous liquid, defoaming property, coatability and processability of coating film. TECHNICAL FIELD The present invention relates to an aqueous epoxy resin composition suitable for coating the inner surface of a beverage can and a method for producing the same.
【0002】[0002]
【従来の技術】金属缶用塗料は、金属缶の加工、流通又
は内容物から受ける諸条件に十分に耐えることが必要で
ある。また作業環境の衛生上及び火災爆発等の防災上の
諸問題への対応が重要であり、特に飲料缶及び食用缶に
ついては食品衛生上の要件を満足させることが必要であ
る。このため、近年、水性塗料が広く使用されるように
なった。2. Description of the Related Art A coating material for a metal can is required to sufficiently withstand various conditions received from processing, distribution or contents of the metal can. In addition, it is important to deal with various problems related to hygiene of work environment and disaster prevention such as fire explosion, and it is particularly necessary to satisfy food hygiene requirements for beverage cans and edible cans. Therefore, in recent years, water-based paints have been widely used.
【0003】このような状況の中で、水性エポキシ樹脂
組成物は、取扱いが容易なため特に注目され、各種の組
成物、製造法が提案されている。例えば、特開昭53−
1228号公報には、ベンゾイルパーオキシドなどの触
媒を用い、エポキシ樹脂の主鎖にカルボキシル基含有モ
ノマーを含むアクリル系モノマーをグラフト重合させ、
得られたグラフト樹脂をアンモニア、アミン等の塩基性
化合物を含む水中に分散させる製造法。特開昭58−1
98513号公報には、エポキシ樹脂にメタクリル酸を
反応させたマクロマーを他の重合性モノマーと共重合さ
せたものを塩基性化合物で水に分散させる製造法。特開
昭56−43362号公報には、エポキシ樹脂とカルキ
シル基含有ポリマーを水性有機溶剤中で部分反応させる
水分散性樹脂組成物の製造法。特開昭56−10924
3号公報には、カルボキシル基過剰のエポキシ樹脂・ア
クリル系樹脂部分反応物をアミンの存在下に水性媒体に
分散させた水性樹脂分散体。特開昭61−268764
号公報には、特定のフェノール樹脂を配合した高酸価ア
クリル樹脂変性エポキシ樹脂水性分散体組成物。特開昭
60−215015号公報には、フェノール樹脂を予備
縮合させたアクリル樹脂変性エポキシ樹脂水性分散体が
開示されている。Under such circumstances, the aqueous epoxy resin composition is particularly noted because it is easy to handle, and various compositions and manufacturing methods have been proposed. For example, JP-A-53-
No. 1228, a catalyst such as benzoyl peroxide is used to graft-polymerize an acrylic monomer containing a carboxyl group-containing monomer on the main chain of an epoxy resin,
A production method in which the obtained graft resin is dispersed in water containing a basic compound such as ammonia and amine. JP 58-1
Japanese Patent Publication No. 98513 discloses a production method in which a macromer obtained by reacting an epoxy resin with methacrylic acid is copolymerized with another polymerizable monomer, and a basic compound is dispersed in water. JP-A-56-43362 discloses a method for producing a water-dispersible resin composition in which an epoxy resin and a polymer containing a carxyl group are partially reacted in an aqueous organic solvent. JP-A-56-10924
In JP-A-3, an aqueous resin dispersion obtained by dispersing an epoxy resin / acrylic resin partial reaction product having an excess of carboxyl groups in an aqueous medium in the presence of an amine. Japanese Patent Laid-Open No. 61-26876
In the publication, a high acid value acrylic resin-modified epoxy resin aqueous dispersion composition containing a specific phenol resin. JP-A-60-215015 discloses an acrylic resin-modified epoxy resin aqueous dispersion prepared by precondensing a phenol resin.
【0004】しかしながら、これら従来の水性エポキシ
樹脂組成物は、一般に分散安定性、消泡性が不良であっ
たり、加工性、耐蝕性、耐溶剤性、フレーバー性が悪か
ったり、塗装を行う場合に塗面の平滑性がでない、ある
いは水及び有機溶剤の突沸等によるワキが発生するとい
う問題があった。However, these conventional water-based epoxy resin compositions are generally poor in dispersion stability and defoaming property, inferior in processability, corrosion resistance, solvent resistance, and flavor property, and are used for coating. There is a problem that the coated surface is not smooth, or cracking occurs due to bumping of water and an organic solvent.
【0005】[0005]
【発明が解決しようとする課題】本発明は、このような
問題を解決するものであり、安定性、消泡性に優れ、塗
面の平滑性がよく、ワキが発生せず、且つその硬化塗膜
が耐熱水性、加工性、耐溶剤性、フレーバー性に優れた
水性樹脂組成物及びその製造法を提供するものである。SUMMARY OF THE INVENTION The present invention is intended to solve such problems and is excellent in stability and defoaming property, has good smoothness of the coated surface, does not cause cracking, and cures the same. It is intended to provide an aqueous resin composition having a coating film excellent in hot water resistance, processability, solvent resistance, and flavor, and a method for producing the same.
【0006】[0006]
【課題を解決するための手段】本発明は、芳香族エポキ
シ樹脂及び/又はフェノキシ樹脂(A)にエチレン性不
飽和脂肪族カルボン酸とこれと共重合性の不飽和単量体
からなる酸価100〜500の単量体混合物(B)をグ
ラフト重合させたカルボン酸変性グラフト化エポキシ樹
脂(C)と、芳香族系エポキシ樹脂(D)との混合物
に、酸価100〜500のカルボキシル基含有アクリル
系樹脂(E)を部分的に結合させた複合樹脂(F)を水
分散又は水溶解させた水性樹脂組成物である。The present invention provides an aromatic epoxy resin and / or a phenoxy resin (A) having an acid value of an ethylenically unsaturated aliphatic carboxylic acid and an unsaturated monomer copolymerizable therewith. A mixture of a carboxylic acid-modified grafted epoxy resin (C) obtained by graft-polymerizing a monomer mixture (B) of 100 to 500 and an aromatic epoxy resin (D) contains a carboxyl group having an acid value of 100 to 500. It is an aqueous resin composition in which a composite resin (F) in which an acrylic resin (E) is partially bonded is dispersed or dissolved in water.
【0007】本発明の水性樹脂組成物は、次の工程を経
て製造される。 芳香族エポキシ樹脂及び/又はフェノキシ樹脂(A)
に、エチレン性不飽和脂肪族カルボン酸とこれと共重合
性の不飽和単量体からなる酸価100〜500の単量体
混合物(B)とをグラフト重合させてカルボン酸変性グ
ラフト化エポキシ樹脂(C)を得、 このカルボン酸変性グラフト化エポキシ樹脂(C)を
芳香族エポキシ樹脂(D)と混合し、 次に、この混合物に酸価100〜500のカルボキシ
ル基含有アクリル系樹脂(E)を反応させて複合樹脂
(F)を得、 この複合樹脂(F)を水分散又は水溶解させる。The aqueous resin composition of the present invention is manufactured through the following steps. Aromatic epoxy resin and / or phenoxy resin (A)
Is graft-polymerized with an ethylenically unsaturated aliphatic carboxylic acid and a monomer mixture (B) having an acid value of 100 to 500 consisting of a copolymerizable unsaturated monomer with the carboxylic acid-modified grafted epoxy resin. (C) is obtained, and the carboxylic acid-modified grafted epoxy resin (C) is mixed with the aromatic epoxy resin (D), and then the mixture is mixed with a carboxyl group-containing acrylic resin (E) having an acid value of 100 to 500. To obtain a composite resin (F), and the composite resin (F) is dispersed or dissolved in water.
【0008】上記芳香族エポキシ樹脂(D)は、芳香族
エポキシ樹脂とフェノキシ樹脂の混合物であってもよ
い。更に、本発明の組成物にはフェノール樹脂及び/又
はアミノ樹脂(G)をさらに混合することができ、これ
らフェノール樹脂及び/又はアミノ樹脂(G)は芳香族
エポキシ樹脂及び/又はフェノキシ樹脂(A)、グラフ
ト化エポキシ樹脂(C)、芳香族エポキシ樹脂又はそれ
とフェノキシ樹脂の混合物、(D)及びアクリル系樹脂
(E)から選ばれる少なくとも一つと予備縮合したもの
であってもよい。The aromatic epoxy resin (D) may be a mixture of an aromatic epoxy resin and a phenoxy resin. Furthermore, the composition of the present invention may further be mixed with a phenol resin and / or an amino resin (G), and these phenol resin and / or amino resin (G) are aromatic epoxy resin and / or phenoxy resin (A). ), A grafted epoxy resin (C), an aromatic epoxy resin or a mixture thereof and a phenoxy resin, (D) and an acrylic resin (E) may be pre-condensed.
【0009】以下、本発明を詳述する。本発明で使用す
る芳香族エポキシ樹脂(A)及び(D)は、ビスフェノ
ールA、F、B又はそれらのハロゲン置換体とエピハロ
ヒドリン又はβ−メチルエピハロヒドリンとの縮合単位
を40%以上、好ましくは60%以上含み、数平均分子
量1,000〜8,000の末端に1個以上のオキシラ
ン環を含む以下のエポキシ樹脂であり、以下の方法で製
造することができる。又、これらの芳香族エポキシ樹脂
は、これらの混合物を使用してもよい。The present invention will be described in detail below. The aromatic epoxy resins (A) and (D) used in the present invention have a condensation unit of bisphenol A, F, B or a halogen substitution product thereof with epihalohydrin or β-methylepihalohydrin of 40% or more, preferably 60%. It is the following epoxy resin containing the above and having at least one oxirane ring at the end and having a number average molecular weight of 1,000 to 8,000, and can be produced by the following method. A mixture of these aromatic epoxy resins may be used.
【0010】1.ビスフェノールA、F、B又はそれら
のハロゲン置換体とエピハロヒドリン又はβ−メチルエ
ピハロヒドリンとの反応により得られるエポキシ樹脂 2.上記1のエポキシ樹脂と、ビスフェノールA、F、
B又はそれらのハロゲン置換体との反応により得られる
エポキシ樹脂 3.上記1又は2のエポキシ樹脂と、(無水)フタル
酸、(無水)マレイン酸、アジピン酸等の二塩基性酸と
の反応により得られる変性エポキシ樹脂 4.上記1又は2のエポキシ樹脂と、酢酸、酪酸、安息
香酸、ヒマシ油脂肪酸、大豆油脂肪酸、トール油脂肪酸
等の一塩基性酸との反応により得られる変性エポキシ樹
脂 5.上記1又は2のエポキシ樹脂と、(多価)アルコー
ルと(多)塩基性酸より得られるポリエステルポリオー
ルとの反応により得られる変性エポキシ樹脂1. 1. An epoxy resin obtained by reacting bisphenol A, F, B or a halogen-substituted product thereof with epihalohydrin or β-methylepihalohydrin. The epoxy resin of the above 1 and bisphenol A, F,
2. Epoxy resin obtained by reaction with B or a halogen-substituted product thereof. 3. A modified epoxy resin obtained by reacting the epoxy resin of 1 or 2 with a dibasic acid such as (anhydrous) phthalic acid, (anhydrous) maleic acid or adipic acid. 4. A modified epoxy resin obtained by reacting the epoxy resin of 1 or 2 with a monobasic acid such as acetic acid, butyric acid, benzoic acid, castor oil fatty acid, soybean oil fatty acid, tall oil fatty acid. Modified epoxy resin obtained by reaction of the epoxy resin of 1 or 2 with a polyester polyol obtained from a (polyhydric) alcohol and a (poly) basic acid
【0011】ここに、多価アルコールの例としては、
1,6−ヘキサンジオール又はトリメチロールプロパン
等が挙げられる。多塩基性酸の例としては、(無水)フ
タル酸、(無水)マレイン酸、アジピン酸等の二塩基性
酸;無水トリメリット酸、無水ピロメリット酸が挙げら
れる。ビスフェノールA、F、B又はそれらのハロゲン
置換体とエピハロヒドリンとの縮合単位が40%以下で
は耐蝕性が十分でない。また数平均分子量が1,000
未満では、硬化塗膜の加工性及び密着性が低下し、一
方、8,000を超えるとアクリル系樹脂(E)との反
応時にゲル化しやすくなるとともに、塗料の粘度が上が
り、塗料の安定性が低下する傾向にある。これらの特性
の点から、3,000〜7,500が更に好ましい。Here, as an example of the polyhydric alcohol,
1,6-hexanediol, trimethylolpropane, etc. are mentioned. Examples of polybasic acids include dibasic acids such as (anhydrous) phthalic acid, (anhydrous) maleic acid, and adipic acid; trimellitic anhydride, and pyromellitic dianhydride. If the condensation unit of bisphenol A, F, B or a halogen substitution product thereof and epihalohydrin is 40% or less, the corrosion resistance is not sufficient. The number average molecular weight is 1,000.
If it is less than 8,000, the processability and adhesion of the cured coating film will be deteriorated. On the other hand, if it exceeds 8,000, it tends to gel during the reaction with the acrylic resin (E), and the viscosity of the coating composition is increased, resulting in stability of the coating composition. Tends to decrease. From the viewpoint of these characteristics, 3,000 to 7,500 is more preferable.
【0012】本発明で使用するフェノキシ樹脂(A)及
び(D)は、上記エポキシ樹脂(A)、(D)より更に
高分子量のものであり、数平均分子量8,000〜5
0,000のものである。ユニオンカーバイト社製のP
KHC、PKHH、PKHJ及び東都化成社製のYP−
50、YP−50Sなどが使用できる。The phenoxy resins (A) and (D) used in the present invention have a higher molecular weight than the above epoxy resins (A) and (D) and have a number average molecular weight of 8,000 to 5.
It is 50,000. Union Carbide P
KHC, PKHH, PKHJ and YP-made by Tohto Kasei Co.
50, YP-50S, etc. can be used.
【0013】本発明で芳香族エポキシ樹脂及び/又はフ
ェノキシ樹脂(A)に反応させるエチレン性不飽和脂肪
族カルボン酸としては、アクリル酸、メタクリル酸、マ
レイン酸、イタコン酸などのα,β−エチレン性不飽和
カルボン酸であり、これと共重合性の不飽和単量体とし
ては、アクリル酸メチル、アクリル酸エチル、アクリル
酸n−ブチル、アクリル酸2−エチルヘキシル、メタク
リル酸メチル、メタクリル酸エチル、メタクリル酸n−
ブチル、メタクリル酸2−エチルヘキシルなどのα,β
−エチレン性不飽和脂肪族カルボン酸のアルキルエステ
ル;アクリル酸2−ヒドロキシエチル、アクリル酸2−
ヒドロキシプロピル、メタクリル酸2−ヒドロキシエチ
ル、メタクリル酸2−ヒドロキシプロピルなどのヒドロ
キシル基を有するα,β−エチレン性不飽和脂肪族カル
ボン酸;アクリルアミド、メタクリルアミド、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、ジアセトンアクリルアミドなどのアクリルアミド誘
導体;アクリル酸グリシジル、メタクリル酸グリシジル
などのα,β−エチレン性不飽和脂肪族カルボン酸のグ
リシジルエステル;酢酸ビニル、プロピオン酸ビニルな
どの飽和脂肪族カルボン酸のビニルエステル;スチレ
ン、α−メチルスチレン、ビニルトルエンなどのスチレ
ン系単量体などである。単量体混合物(B)の酸価は1
00〜500であるが、更に好ましくは200〜400
である。酸価が100未満では分散安定性が低下した
り、塗膜とした時の光沢が低下し、酸価が500を超え
ると塗膜の加工性、耐水性等が劣る。The ethylenically unsaturated aliphatic carboxylic acid to be reacted with the aromatic epoxy resin and / or the phenoxy resin (A) in the present invention includes α, β-ethylene such as acrylic acid, methacrylic acid, maleic acid and itaconic acid. Unsaturated carboxylic acid, and as the unsaturated monomer copolymerizable therewith, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Methacrylic acid n-
Α, β such as butyl and 2-ethylhexyl methacrylate
-Alkyl esters of ethylenically unsaturated aliphatic carboxylic acids; 2-hydroxyethyl acrylate, 2-acrylic acid
Α, β-ethylenically unsaturated aliphatic carboxylic acid having a hydroxyl group such as hydroxypropyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide , Acrylamide derivatives such as diacetone acrylamide; glycidyl esters of α, β-ethylenically unsaturated aliphatic carboxylic acids such as glycidyl acrylate and glycidyl methacrylate; vinyl esters of saturated aliphatic carboxylic acids such as vinyl acetate and vinyl propionate Styrene-based monomers such as styrene, α-methylstyrene and vinyltoluene. The acid value of the monomer mixture (B) is 1
0 to 500, more preferably 200 to 400
Is. When the acid value is less than 100, the dispersion stability is lowered or the gloss when formed into a coating film is lowered, and when the acid value is more than 500, the workability and water resistance of the coating film are deteriorated.
【0014】カルボン酸変性グラフト化エポキシ樹脂
(C)を得るには、芳香族エポキシ樹脂及び/又はフエ
ノキシ樹脂(A)に上記単量体混合物(B)を、アゾビ
スイソブチロニトリル、t−ブチルパーオキシベンゾエ
ート、ベンゾイルパーオキシド、ジt−ブチルパーオキ
シド、クメンヒドロパーオキシドなどのフリーラジカル
発生剤の存在下に、80〜130℃に加熱して行うこと
ができる。カルボン酸変性グラフト化エポキシ樹脂
(C)のグラフト化効率を高めるために、フリーラジカ
ル発生剤は、単量体混合物(B)に対して4重量%以
上、好ましくは6〜15重量%、更に好ましくは7〜1
2重量%の範囲で使用することが望ましい。To obtain the carboxylic acid-modified grafted epoxy resin (C), the above-mentioned monomer mixture (B) is added to the aromatic epoxy resin and / or phenoxy resin (A), azobisisobutyronitrile, t- It can be carried out by heating to 80 to 130 ° C. in the presence of a free radical generator such as butyl peroxybenzoate, benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide. In order to enhance the grafting efficiency of the carboxylic acid-modified grafted epoxy resin (C), the free radical generator is contained in an amount of 4% by weight or more, preferably 6 to 15% by weight, more preferably 6 to 15% by weight, based on the monomer mixture (B). Is 7-1
It is desirable to use in the range of 2% by weight.
【0015】芳香族エポキシ樹脂とフェノキシ樹脂との
混合物(D)の両者の固形分重量比は、40〜100/
60〜0が好ましく、フェノキシ樹脂の重量比が60を
超えると分散性が低下する。アクリル系樹脂(E)は、
上記単量体混合物(B)と同様の単量体を共重合させた
ものである。該共重合は、アゾビスイソブチロニトリ
ル、t−ブチルパーオキシベンゾエート、ベンゾイルパ
ーオキシド、ジt−ブチルパーオキシド、クメンヒドロ
パーオキシドなどのフリーラジカル発生剤の存在下に、
80〜130℃に加熱して行うことができる。アクリル
系樹脂(E)は、酸価100〜500、好ましくは20
0〜320に調整されることが好ましい。酸価が100
未満であるとグラフト化エポキシ樹脂(C)及び/又は
芳香族エポキシ樹脂又はそれとフェノキシ樹脂との混合
物(D)との反応後に得られる複合樹脂(F)の水溶性
又は水分散性が劣る。また酸価が500を超えると塗膜
特性(特に耐温水性)が低下する。また反応時に生成物
はゲル化しやすい。アクリル系樹脂(E)の数平均分子
量は3,000〜12,000であり、4,000〜1
1,000がより好ましい。数平均分子量が3,000
未満では塗膜の耐温水性、加工性、耐溶剤性に劣り、1
2,000を超えると最終製品の粘度が高くなり、好ま
しくない。The solid content weight ratio of both the mixture (D) of the aromatic epoxy resin and the phenoxy resin is 40 to 100 /.
60 to 0 is preferable, and if the weight ratio of the phenoxy resin exceeds 60, the dispersibility decreases. Acrylic resin (E) is
It is obtained by copolymerizing the same monomer as the monomer mixture (B). The copolymerization is carried out in the presence of a free radical generator such as azobisisobutyronitrile, t-butylperoxybenzoate, benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide,
It can be performed by heating to 80 to 130 ° C. The acrylic resin (E) has an acid value of 100 to 500, preferably 20.
It is preferably adjusted to 0 to 320. Acid value is 100
When it is less than the above range, the water solubility or water dispersibility of the composite resin (F) obtained after the reaction with the grafted epoxy resin (C) and / or the aromatic epoxy resin or the mixture thereof (D) with the phenoxy resin is poor. Further, when the acid value exceeds 500, coating film characteristics (particularly hot water resistance) are deteriorated. In addition, the product tends to gel during the reaction. The number average molecular weight of the acrylic resin (E) is 3,000 to 12,000 and 4,000 to 1
1,000 is more preferable. Number average molecular weight of 3,000
If it is less than 1, the water resistance of the coating film, processability and solvent resistance are poor, and 1
When it exceeds 2,000, the viscosity of the final product becomes high, which is not preferable.
【0016】複合樹脂(F)を構成する芳香族エポキシ
樹脂及び/又はフェノキシ樹脂(A):単量体混合物
(B)の固形分重量比は10〜95:5〜90、好まし
くは30〜90:10〜70、更に好ましくは50〜8
5:15〜50であり、芳香族エポキシ樹脂及び/又は
フェノキシ樹脂(A)の使用比が95を超えると塗膜の
耐溶剤性、フレーバー性が劣り、10未満では水性樹脂
組成物の粘度が高くなる傾向がある。単量体混合物
(B)の使用比が90を超えると塗膜の耐溶剤性、フレ
ーバー性が劣り、5未満では水性樹脂組成物の分散性が
劣る。カルボン酸変性グラフト化エポキシ樹脂(C=A
+B):芳香族エポキシ樹脂又はそれとフェノキシ樹脂
との混合物(D):アクリル系樹脂(E)の固形分重量
比は、10〜80:10〜80:5〜70、好ましくは
30〜70:20〜60:10〜50、更に好ましくは
40〜60:30〜50:10〜30であり、芳香族エ
ポキシ樹脂又はそれとフェノキシ樹脂との混合物(D)
の使用比が80を超えると水性樹脂組成物の分散性が劣
り、10未満では塗膜の耐溶剤性、フレーバー性が劣
る。アクリル系樹脂(E)の使用比が70を超えると、
水性樹脂組成物の粘度が高くなる傾向があり、5未満で
は塗膜の耐溶剤性、フレーバー性が劣る。Aromatic epoxy resin and / or phenoxy resin (A): monomer mixture (B) constituting the composite resin (F) has a solid content weight ratio of 10 to 95: 5 to 90, preferably 30 to 90. : 10 to 70, more preferably 50 to 8
It is 5:15 to 50, and when the use ratio of the aromatic epoxy resin and / or the phenoxy resin (A) exceeds 95, the solvent resistance and the flavor property of the coating film are poor, and when it is less than 10, the viscosity of the aqueous resin composition is low. Tends to be high. If the use ratio of the monomer mixture (B) exceeds 90, the solvent resistance and flavor of the coating film are poor, and if it is less than 5, the dispersibility of the aqueous resin composition is poor. Carboxylic acid modified grafted epoxy resin (C = A
+ B): Aromatic epoxy resin or a mixture thereof and a phenoxy resin (D): acrylic resin (E), the solid content weight ratio is 10 to 80:10 to 80: 5 to 70, preferably 30 to 70:20. To 60:10 to 50, and more preferably 40 to 60:30 to 50:10 to 30, and an aromatic epoxy resin or a mixture thereof (D) with a phenoxy resin.
If the use ratio exceeds 80, the dispersibility of the aqueous resin composition is poor, and if it is less than 10, the solvent resistance and flavor of the coating film are poor. If the usage ratio of the acrylic resin (E) exceeds 70,
The viscosity of the aqueous resin composition tends to increase, and if it is less than 5, the solvent resistance and flavor of the coating film are poor.
【0017】カルボン酸変性グラフト化エポキシ樹脂
(C)と芳香族エポキシ樹脂又はそれとフェノキシ樹脂
との混合物(D)との混合物に、アクリル系樹脂(E)
を部分的に結合させるには、無触媒又はアミン等の塩基
を触媒にして行うことができる。無触媒で行う場合は、
有機溶剤中で100〜150℃に1〜20時間保温する
ことにより行うことができる。アミン等の塩基を触媒に
して行う場合は、有機溶剤又は有機溶剤に水を加えた水
性溶剤中で50〜100℃に10分〜3時間保温するこ
とにより行うことができる。得られる複合樹脂(F)の
固形分酸価は15〜50である。A mixture of a carboxylic acid-modified grafted epoxy resin (C) and an aromatic epoxy resin or a mixture thereof (D) with an acrylic resin (E).
Can be partially bound by using no catalyst or a base such as amine as a catalyst. When performing without catalyst,
It can be carried out by keeping the temperature in an organic solvent at 100 to 150 ° C. for 1 to 20 hours. When using a base such as an amine as a catalyst, the reaction can be carried out by keeping the temperature at 50 to 100 ° C. for 10 minutes to 3 hours in an organic solvent or an aqueous solvent prepared by adding water to the organic solvent. The solid acid value of the obtained composite resin (F) is 15 to 50.
【0018】本発明で使用するフェノール樹脂(G)と
しては、フェノール、炭素数1〜12のアルキル置換基
を有するフェノール又はビスフェノールA、F、B等と
ホルムアルデヒドをアルカリ触媒で反応させて得られる
レゾール型フェノール樹脂、又は酸触媒を反応させて得
られるノボラック型フェノール樹脂が挙げられる。ま
た、アミノ樹脂(G)としては部分又は完全メチル化メ
ラミン樹脂、部分又は完全ブチル化メラミン樹脂等のメ
ラミン樹脂;部分又は完全メチル化ベンゾグアナミン樹
脂、部分又は完全メチル化ブチル化ベンゾグアナミン樹
脂等のベンゾグアナミン樹脂;部分又は完全メチル化尿
素樹脂等の尿素樹脂が挙げられる。本発明におけるフェ
ノール樹脂及び/又はアミノ樹脂(G)は複合樹脂
(F)を水分散又は水溶解する前に加えるか、水分散又
は水溶解した後に加えることができる。The phenolic resin (G) used in the present invention is a resol obtained by reacting phenol, phenol having an alkyl substituent having 1 to 12 carbon atoms or bisphenol A, F, B or the like with formaldehyde with an alkali catalyst. Type phenolic resin or a novolac type phenolic resin obtained by reacting an acid catalyst. Further, as the amino resin (G), a melamine resin such as a partially or completely methylated melamine resin, a partially or completely butylated melamine resin; a partially or fully methylated benzoguanamine resin, a partially or completely methylated butylated benzoguanamine resin or the like benzoguanamine resin A urea resin such as a partially or fully methylated urea resin. The phenol resin and / or amino resin (G) in the present invention can be added before the composite resin (F) is dispersed or dissolved in water, or can be added after the dispersion or dissolution in water.
【0019】フェノール樹脂及び/又はアミノ樹脂
(G)と、芳香族エポキシ樹脂及び/又はフェノキシ樹
脂(A)、カルボン酸変性グラフト化エポキシ樹脂
(C)、芳香族エポキシ樹脂又はそれとフェノキシ樹脂
(D)及びアクリル系樹脂(E)から選ばれる少なくと
も一つとの予備縮合は、好ましくは親水性溶剤中で50
℃乃至150℃で10分間ないし3時間反応させること
により行うことができる。最終水性樹脂組成物中におけ
るフェノール樹脂及び/又はアミノ樹脂(G)の量は固
形分換算で水性樹脂組成物に対して1〜40重量%、好
ましくは1〜20重量%、更に好ましくは2〜10重量
%であり、1重量%未満では塗膜の硬化速度に対する寄
与が不十分であり、また40重量%を超えると塗膜の加
工性、フレーバー性などの物性が低下する傾向がある。Phenolic resin and / or amino resin (G), aromatic epoxy resin and / or phenoxy resin (A), carboxylic acid modified grafted epoxy resin (C), aromatic epoxy resin or phenoxy resin (D) And the precondensation with at least one selected from the acrylic resin (E) is preferably 50 in a hydrophilic solvent.
It can be performed by reacting at 10 to 150 ° C. for 10 minutes to 3 hours. The amount of phenol resin and / or amino resin (G) in the final aqueous resin composition is 1 to 40% by weight, preferably 1 to 20% by weight, more preferably 2 to 40% by weight based on the solid content of the aqueous resin composition. It is 10% by weight, and if it is less than 1% by weight, the contribution to the curing rate of the coating film is insufficient, and if it exceeds 40% by weight, physical properties such as processability and flavor property of the coating film tend to be deteriorated.
【0020】本発明において、水性樹脂組成物を製造す
るには、複合樹脂(F)の酸基の40%ないし130%
を中和するのに必要なアンモニアもしくはアミンを加え
た水性媒体中に分散又は溶解すればよい。上記アミンと
しては、モノプロピルアミン、モノブチルアミン、ジエ
チルアミン、ジブチルアミン、トリエチルアミン、トリ
ブチルアミン、モノエタノールアミン、エチルアミノモ
ノエタノール、ジメチルアミノエタノール、2−アミノ
−2−メチル−1−プロパノール、シクロヘキシルアミ
ン、モルホリン、ピペリジンのような第一級、第二級又
は第三級のアミンが使用できる。中和率が40%未満で
は水分散性あるいは水溶解性に劣る傾向があり、130
%を超えると粘度が高くなりすぎる。In the present invention, in order to produce an aqueous resin composition, 40% to 130% of the acid groups of the composite resin (F) are used.
It may be dispersed or dissolved in an aqueous medium to which ammonia or amine necessary for neutralizing the is added. Examples of the amine include monopropylamine, monobutylamine, diethylamine, dibutylamine, triethylamine, tributylamine, monoethanolamine, ethylaminomonoethanol, dimethylaminoethanol, 2-amino-2-methyl-1-propanol, cyclohexylamine, Primary, secondary or tertiary amines such as morpholine, piperidine can be used. If the neutralization rate is less than 40%, the water dispersibility or water solubility tends to be poor.
If it exceeds%, the viscosity becomes too high.
【0021】本発明の水性樹脂組成物の製造において、
芳香族エポキシ樹脂及び/又はフェノキシ樹脂(A)、
カルボン酸変性グラフト化エポキシ樹脂(C)、芳香族
エポキシ樹脂又はそれとフェノキシ樹脂(D)、アクリ
ル系樹脂(E)、複合樹脂(F)、フェノール樹脂及び
/又はアミノ樹脂(G)を溶解することのできる有機溶
剤を使用することができる。通常、使用できる溶剤の例
としては、イソプロパノール、メタノール、エタノー
ル、2−エチルヘキサノール、シクロヘキサノール等の
アルコール類;メチルセロソルブ、エチルセロソルブ、
ブチルセロソルブ等のエーテルアルコール類;エチレン
グリコール、ジエチレングリコール等のグリコール類;
メチルカルビトール、エチルカルビトール、ブチルカル
ビトール等のジグリコール類;メチルエチルケトン、イ
ソブチルケトン、シクロヘキサノン等のケトン類;トル
エン、キシレン等の芳香族炭化水素類;その他ジアセト
ンアルコール、3−メトキシ−3−メチルブタン−1−
オール等が使用できる。しかしながら、これらの有機溶
剤は、取扱作業に支障のない範囲で少ないほど好まし
い。必要ならば、水性樹脂組成物から常圧又は減圧にて
脱溶剤してもよい。水性樹脂組成物の最終有機溶剤含有
量は20重量%以下が望ましい。In the production of the aqueous resin composition of the present invention,
Aromatic epoxy resin and / or phenoxy resin (A),
Dissolving a carboxylic acid-modified grafted epoxy resin (C), an aromatic epoxy resin or a phenoxy resin (D), an acrylic resin (E), a composite resin (F), a phenol resin and / or an amino resin (G). An organic solvent that can be used can be used. Usually, examples of the solvent that can be used include alcohols such as isopropanol, methanol, ethanol, 2-ethylhexanol and cyclohexanol; methyl cellosolve, ethyl cellosolve,
Ether alcohols such as butyl cellosolve; glycols such as ethylene glycol and diethylene glycol;
Diglycols such as methyl carbitol, ethyl carbitol and butyl carbitol; ketones such as methyl ethyl ketone, isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; other diacetone alcohol, 3-methoxy-3- Methylbutane-1-
All can be used. However, it is preferable that the amount of these organic solvents is as small as possible within a range that does not hinder the handling work. If necessary, the solvent may be removed from the aqueous resin composition under normal pressure or reduced pressure. The final organic solvent content of the aqueous resin composition is preferably 20% by weight or less.
【0022】また、本発明の水性樹脂組成物には、塩
酸、リン酸等の無機酸、パラトルエンスルホン酸等の有
機酸などの触媒を添加してもよい。使用量は水性樹脂組
成物の固形分100重量部に対して1重量部以下が好ま
しい。本発明の水性樹脂組成物は、目的に応じて顔料、
防錆剤、その他の水溶性樹脂、添加剤等を配合して、防
錆プライマー、防錆塗料等の水性塗料組成物又は水性印
刷インキ等としても使用できる。Further, a catalyst such as an inorganic acid such as hydrochloric acid or phosphoric acid, an organic acid such as paratoluenesulfonic acid or the like may be added to the aqueous resin composition of the present invention. The amount used is preferably 1 part by weight or less based on 100 parts by weight of the solid content of the aqueous resin composition. The aqueous resin composition of the present invention is a pigment depending on the purpose,
A rust preventive agent, other water-soluble resin, an additive, etc. may be blended to be used as a water-based coating composition such as a rust-preventive primer or rust-preventive paint, or a water-based printing ink.
【0023】本発明の水性樹脂組成物は、金属、例えば
鉄鋼板、アルミニウム板又は鉄鋼板の表面に亜鉛、ス
ズ、クロム、ニッケル、アルミニウム等の単独又は複数
金属をメッキ処理したメッキ鋼板、あるいはこれらの表
面をクロム酸、リン酸等で化学処理又は電解処理したも
の、更には紙、木材等の基材への塗装に有用である。塗
装方法としては、スプレー塗装、ロールコーター塗装、
電着塗装、浸漬塗装、刷毛塗り等の公知の方法が採用で
きる。硬化条件としては、常温乾燥も可能であるが、8
0〜350℃の温度範囲で10秒〜30分の強制乾燥が
好ましい。The aqueous resin composition of the present invention is a plated steel plate obtained by plating a metal such as a steel plate, an aluminum plate or a steel plate with a single or multiple metals such as zinc, tin, chromium, nickel and aluminum, or these. It is useful for coating the surface of which is chemically or electrolytically treated with chromic acid, phosphoric acid or the like, and further to a substrate such as paper or wood. As the coating method, spray coating, roll coater coating,
Known methods such as electrodeposition coating, dip coating and brush coating can be adopted. As the curing conditions, it is possible to dry at room temperature, but
Forced drying in the temperature range of 0 to 350 ° C. for 10 seconds to 30 minutes is preferable.
【0024】[0024]
【実施例】以下実施例によって本発明を具体的に説明す
る。The present invention will be specifically described with reference to the following examples.
【0025】合成例1.アクリル系樹脂(E)の合成 撹拌機、還流冷却器、温度計、不活性ガス注入口を備え
たフラスコにブチルセロソルブ35重量部及びn−ブタ
ノール20重量部を仕込み、130℃まで昇温する。こ
れに同温度でスチレン28重量部、アクリル酸2−ヒド
ロキシエチル26重量部、メタクリル酸46重量部及び
t−ブチルパーオキシベンゾエート0.6重量部からな
る単量体混合液を3時間かけてフラスコに徐々に滴下し
た。その後、ブチルセロソルブ5重量部及びn−ブタノ
ール23重量部を20分間で滴下し、その後2時間保温
し、固形分55%、固形分酸価300、数平均分子量
9,700のアクリル系樹脂溶液を得た。Synthesis Example 1. Synthesis of acrylic resin (E) A flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet is charged with 35 parts by weight of butyl cellosolve and 20 parts by weight of n-butanol, and heated to 130 ° C. At the same temperature, a monomer mixture liquid consisting of 28 parts by weight of styrene, 26 parts by weight of 2-hydroxyethyl acrylate, 46 parts by weight of methacrylic acid and 0.6 part by weight of t-butylperoxybenzoate was added to the flask over 3 hours. Was gradually added dropwise. Then, 5 parts by weight of butyl cellosolve and 23 parts by weight of n-butanol were added dropwise over 20 minutes and then kept warm for 2 hours to obtain an acrylic resin solution having a solid content of 55%, a solid acid value of 300, and a number average molecular weight of 9,700. It was
【0026】合成例2.アクリル樹脂(E)の合成 単量体混合液(B)として、スチレン32重量部、アク
リル酸エチル30重量部、メタクリル酸38重量部及び
t−ブチルパーオキシベンゾエート0.6重量部を用い
た以外は合成例1と同様に合成して、固形分55%、固
形分酸価250、数平均分子量9,500のアクリル系
樹脂溶液を得た。Synthesis Example 2. Synthesis of Acrylic Resin (E) Except that 32 parts by weight of styrene, 30 parts by weight of ethyl acrylate, 38 parts by weight of methacrylic acid and 0.6 part by weight of t-butylperoxybenzoate were used as the monomer mixture liquid (B). Was synthesized in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution having a solid content of 55%, a solid content acid value of 250, and a number average molecular weight of 9,500.
【0027】合成例3.アクリル系樹脂(E)の合成 単量体混合液として、スチレン10.0重量部、アクリ
ル酸エチル28.5重量部、メタクリル酸61.5重量
部及びt−ブチルパーオキシベンゾエート0.6重量部
を用いた以外は、合成例1と同様に合成して、固形分5
5%、固形分酸価400、数平均分子量10,500の
アクリル系樹脂溶液を得た。Synthesis Example 3. Synthesis of acrylic resin (E) As a monomer mixture, 10.0 parts by weight of styrene, 28.5 parts by weight of ethyl acrylate, 61.5 parts by weight of methacrylic acid and 0.6 part by weight of t-butylperoxybenzoate. Except that the same procedure as in Synthesis Example 1 was conducted except that the solid content was 5
An acrylic resin solution having a solid content of 5%, an acid value of 400, and a number average molecular weight of 10,500 was obtained.
【0028】合成例4.アクリル系樹脂(E)の合成 単量体混合液として、スチレン42.4重量部、アクリ
ル酸エチル42.3重量部、メタクリル酸15.3重量
部及びt−ブチルパーオキシベンゾエート0.6重量部
を用いた以外は、合成例1と同様に合成して、固形分5
5%、固形分酸価100、数平均分子量7,500のア
クリル系樹脂溶液を得た。Synthesis Example 4. Synthesis of acrylic resin (E) As a monomer mixture, 42.4 parts by weight of styrene, 42.3 parts by weight of ethyl acrylate, 15.3 parts by weight of methacrylic acid and 0.6 part by weight of t-butylperoxybenzoate. Except that the same procedure as in Synthesis Example 1 was conducted except that the solid content was 5
An acrylic resin solution having a solid content of 5%, an acid value of 100, and a number average molecular weight of 7,500 was obtained.
【0029】合成例5.芳香族エポキシ樹脂(A)の合
成 撹拌機、還流冷却器、温度計、不活性ガス注入口を備え
たフラスコにエピコート1007(シェル化学社製、エ
ポキシ樹脂)500重量部、アジピン酸7.6重量部、
トリ(n−ブチル)アミン1重量部及びセロソルブアセ
テート338重量部を仕込み、120℃で5時間反応さ
せ、固形分60%、固形分酸価0.2のエポキシ樹脂溶
液を得た。Synthesis Example 5. Synthesis of aromatic epoxy resin (A) In a flask equipped with a stirrer, a reflux condenser, a thermometer, an inert gas inlet, 500 parts by weight of Epicoat 1007 (epoxy resin manufactured by Shell Chemical Co., Ltd.), 7.6 parts by weight of adipic acid. Department,
1 part by weight of tri (n-butyl) amine and 338 parts by weight of cellosolve acetate were charged and reacted at 120 ° C. for 5 hours to obtain an epoxy resin solution having a solid content of 60% and a solid acid value of 0.2.
【0030】合成例6.フェノール樹脂(G)の合成 撹拌機、還流冷却器、温度計、不活性ガス注入口を備え
たフラスコに石炭酸94重量部、37%ホルマリン28
0重量部及び25%水酸化ナトリウム水溶液48重量部
を仕込み、50℃で2時間反応させた。これを塩酸で中
和後、酢酸エチル/n−ブタノール=1/1の混合溶剤
で抽出して、固形分80%のレゾール型フェノール樹脂
溶液を得た。Synthesis Example 6. Synthesis of Phenolic Resin (G) 94 parts by weight of carboxylic acid, 37% formalin 28 in a flask equipped with a stirrer, reflux condenser, thermometer, and inert gas inlet.
0 parts by weight and 48 parts by weight of a 25% aqueous sodium hydroxide solution were charged and reacted at 50 ° C. for 2 hours. This was neutralized with hydrochloric acid and then extracted with a mixed solvent of ethyl acetate / n-butanol = 1/1 to obtain a resol type phenol resin solution having a solid content of 80%.
【0031】合成例7.フェノール樹脂(G)の合成 合成例6と同一の配合で、同様に反応させた後、アリル
クロライド80重量部を加えて同温度で1時間反応さ
せ、合成例6と同様に処理して、固形分80%のアリル
化レゾール型フェノール樹脂溶液を得た。Synthesis Example 7. Synthesis of Phenolic Resin (G) The same formulation as in Synthesis Example 6 was used, the same reaction was performed, 80 parts by weight of allyl chloride was added, and the mixture was reacted at the same temperature for 1 hour, treated in the same manner as in Synthesis Example 6, and solidified. An allylated resol type phenolic resin solution having a content of 80% was obtained.
【0032】合成例8.9.10.11.12.13.
アクリル系樹脂(E)の合成 単量体混合物(B)を表1に示す組成にした以外は、合
成例1と同様にして、アクリル系樹脂溶液を得た。それ
ぞれの固形分酸価、数平均分子量も表1に示す。Synthesis Example 8.9.10.11.12.13.
Synthesis of acrylic resin (E) An acrylic resin solution was obtained in the same manner as in Synthesis Example 1, except that the composition of the monomer mixture (B) was as shown in Table 1. The solid acid value and the number average molecular weight of each are also shown in Table 1.
【0033】[0033]
【表1】 [Table 1]
【0034】合成例14.15.16.17.アクリル
系樹脂(E)の合成 t−ブチルパーオキシベンゾエートを表2に示す量にし
た以外は、合成例1と同様にして、アクリル系樹脂溶液
を得た。それぞれの数平均分子量も表2に示す。Synthesis Example 14.15.16.17. Synthesis of acrylic resin (E) An acrylic resin solution was obtained in the same manner as in Synthesis Example 1 except that the amount of t-butylperoxybenzoate shown in Table 2 was used. The number average molecular weight of each is also shown in Table 2.
【0035】[0035]
【表2】 [Table 2]
【0036】実施例1.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
90重量部、n−ブタノール225重量部及びフェノト
ートYP−50(A)(東都化成社製、フェノキシ樹
脂)203重量部を仕込み、加熱した。130℃まで昇
温し完全に溶解後、100℃に降温し、これにスチレン
16.6重量部、アクリル酸エチル15.7重量部、メ
タクリル酸22.7重量部及びベンゾイルパーオキシド
4.2重量部からなる単量体混合溶液(B)を3時間か
けてフラスコに徐々に滴下した。同温度に30分保温し
た後、ブチルセロソルブ5重量部、n−ブタノール23
重量部及びベンゾイルパーオキシド0.7重量部からな
る混合液を20分間で滴下、更に2時間保温し、カルボ
ン酸変性グラフト化エポキシ樹脂(C)を得た。その
後、エピコート1010(D)(シェル化学社製、芳香
族エポキシ樹脂)135重量部をフラスコ内に添加し溶
解後、合成例1で得たアクリル系樹脂(E)溶液128
重量部、ジメチルエタノールアミン36重量部及び脱イ
オン水40重量部の混合液を添加し、80〜85℃で1
時間撹拌して反応させ複合樹脂(F)を得た。この複合
樹脂の固形分酸価は31であった。その後、脱イオン水
950重量部を1時間30分かけて徐々に滴下し、白色
の水分散体を得た。これを固形分が35%になるように
減圧下で過剰の溶剤を留去した。このときの粘度は15
00cps (B型粘度計6rpm )であった。これを厚さ
0.30mmのアルミニウム板の片面、及び両面に乾燥塗
布量120mg/dm2となるようにバーコーターで塗布し、
いずれも250℃で30秒焼き付けた。水性樹脂組成物
の安定性、片面塗装板で塗膜表面のワキ、耐加工性、耐
蝕性、耐レトルト性、MEK抽出率を、両面塗装板でフ
レーバー性を下記の試験法によって評価した。結果を表
3に示す。Example 1. Stirrer, reflux condenser, thermometer,
A flask equipped with an inert gas inlet was charged with 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, and 203 parts by weight of Phenothote YP-50 (A) (phenoxy resin manufactured by Toto Kasei Co., Ltd.) and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide. The monomer mixed solution (B) consisting of 10 parts was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, 5 parts by weight of butyl cellosolve, n-butanol 23
A mixed solution of 1 part by weight and 0.7 part by weight of benzoyl peroxide was added dropwise over 20 minutes and the temperature was kept for 2 hours to obtain a carboxylic acid-modified grafted epoxy resin (C). Then, 135 parts by weight of Epicoat 1010 (D) (Aromatic epoxy resin manufactured by Shell Chemical Co., Ltd.) was added to the flask and dissolved, and then the acrylic resin (E) solution 128 obtained in Synthesis Example 1 was added.
Add a mixed solution of 40 parts by weight of dimethylethanolamine and 40 parts by weight of deionized water, and add 1 part at 80 to 85 ° C.
The mixture was stirred for reaction to obtain a composite resin (F). The solid acid value of this composite resin was 31. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is 15
It was 00 cps (B-type viscometer 6 rpm). This is applied to one side and both sides of a 0.30 mm thick aluminum plate with a bar coater so that the dry coating amount is 120 mg / dm 2 .
Both were baked at 250 ° C. for 30 seconds. The stability of the aqueous resin composition, the surface of the coating film on one-sided coated plate, the workability, the corrosion resistance, the retort resistance, and the MEK extraction rate were evaluated, and the flavor property on the two-sided coated plate was evaluated by the following test methods. The results are shown in Table 3.
【0037】水性樹脂組成物の安定性:10倍量の脱イ
オン水で希釈して、25℃で24時間放置後沈降の有無
をみた。 ○ : 沈降なし △ : 若干の沈降あり × : かなりの沈降あり 塗膜試験方法 ワキ : 目視でワキの発生状態をみた。 ○ : ワキなし △ : 若干のワキあり × : かなりのワキあり 耐加工性 : 試験片に同じ板厚のアルミニウム板を2
枚挟み、バイスで締める。50倍のルーペで加工部のワ
レ程度を判定した。 ○ : ワレなし △ : 若干のワレあり × : かなりのワレありStability of Aqueous Resin Composition: Diluted with 10 times amount of deionized water and allowed to stand at 25 ° C. for 24 hours, and then it was observed whether or not there was sedimentation. ◯: No sedimentation Δ: Slight sedimentation X: Significant sedimentation Coating film test method Waki: The appearance of wrinkles was visually observed. ○: No cracking △: Slight cracking ×: Significant cracking Machining resistance: Two aluminum plates of the same thickness were used as test pieces.
Insert the sheets and tighten with a vise. The degree of cracking of the processed portion was judged with a 50 times magnifying glass. ○: No cracks △: Some cracks ×: Significant cracks
【0038】耐蝕性 : 裏面をポリエステルテープ
でシールした試験片を沸騰した3%食塩水に1時間浸漬
して、塗面の腐食程度を判定した。 ○ : 腐食なし △ : 若干の腐食あり × : かなりの腐食あり 耐レトルト性 : オートクレーブにイオン交換水を入
れ、試験片を浸漬、125℃で30分間処理して、塗膜
の白化の程度を判定した。 ○ : 白化なし △ : 若干の白化あり × : かなりの白化ありCorrosion resistance: A test piece whose back surface was sealed with a polyester tape was immersed in boiling 3% saline for 1 hour to determine the degree of corrosion of the coated surface. ○: No corrosion △: Slight corrosion ×: Significant corrosion Retort resistance: Ion-exchanged water was put into the autoclave, the test piece was dipped and treated at 125 ° C for 30 minutes to judge the degree of whitening of the coating film. did. ○: No whitening △: Slight whitening ×: Significant whitening
【0039】MEK抽出率 : 試験片を沸騰したメチ
ルエチルケトンに1時間浸漬して、塗膜の減量を測定し
た。MEK抽出率30%以上は架橋度が不充分であっ
た。 フレーバー性 : 10cm×10cmの試験片を清浄な耐
圧ガラス瓶に入れ、200mlのイオン交換蒸留水を入
れ、100℃で30分間の殺菌処理を行った後、更に5
0℃で6ヶ月保存した内容液を、試験片を入れないで同
様に行った内容液と比較した。 ○ : 全く差なし △ : 若干の差あり × : かなりの差ありMEK extraction rate: The test piece was immersed in boiling methyl ethyl ketone for 1 hour, and the weight loss of the coating film was measured. When the MEK extraction rate was 30% or more, the degree of crosslinking was insufficient. Flavorability: A 10 cm × 10 cm test piece was placed in a clean pressure-resistant glass bottle, 200 ml of ion-exchanged distilled water was added, and sterilization treatment was performed at 100 ° C. for 30 minutes, and then 5
The content solution stored at 0 ° C. for 6 months was compared with the content solution prepared in the same manner without the test piece. ○: There is no difference △: There is a slight difference ×: There is a considerable difference
【0040】[0040]
【表3】 [Table 3]
【0041】実施例2.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
22重量部、n−ブタノール56重量部及びフェノトー
トYP−50(A)(前出フェノキシ樹脂)50重量部
を仕込み、加熱した。130℃まで昇温し完全に溶解
後、100℃に降温し、これにスチレン18.6重量
部、アクリル酸エチル14.3重量部、アクリル酸1
7.2重量部及びベンゾイルパーオキシド3.8重量部
からなる単量体混合溶液(B)を3時間かけてフラスコ
に徐々に滴下した。同温度に30分保温した後、ブチル
セロソルブ5重量部、n−ブタノール23重量部及びベ
ンゾイルパーオキシド0.64重量部からなる混合液を
20分間で滴下、更に2時間保温し、カルボン酸変性グ
ラフト化エポキシ樹脂(C)を得た。その後、エピコー
ト1010(D)(前出エポキシ樹脂)350重量部を
フラスコ内に添加し溶解後、合成例1で得たアクリル系
樹脂溶液(E)91重量部、ジメチルエタノールアミン
30重量部及び脱イオン水40重量部の混合液を添加
し、80〜85℃で1時間撹拌し反応させ複合樹脂
(F)を得た。この樹脂の固形分酸価は20であった。
その後、脱イオン水950重量部を1時間30分かけて
徐々に滴下し、白色の水分散体を得た。これを固形分が
35%になるように減圧下で過剰の溶剤を留去した。こ
のときの粘度は2500cps (B型粘度計6rpm )であ
った。これを実施例1と同様の方法で塗膜を作成、塗膜
物性試験を行った。水性樹脂組成物の安定性と塗膜物性
試験結果を表3に示す。Example 2. Stirrer, reflux condenser, thermometer,
A flask equipped with an inert gas inlet was charged with 22 parts by weight of butyl cellosolve, 56 parts by weight of n-butanol and 50 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 18.6 parts by weight of styrene, 14.3 parts by weight of ethyl acrylate, 1 part of acrylic acid
A monomer mixed solution (B) composed of 7.2 parts by weight and 3.8 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, a mixed solution consisting of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.64 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the temperature was maintained for another 2 hours to carry out carboxylic acid-modified grafting. An epoxy resin (C) was obtained. Thereafter, 350 parts by weight of Epicoat 1010 (D) (epoxy resin described above) was added into the flask and dissolved, and then 91 parts by weight of the acrylic resin solution (E) obtained in Synthesis Example 1, 30 parts by weight of dimethylethanolamine, and desorption. A mixed solution of 40 parts by weight of deionized water was added, and the mixture was stirred and reacted at 80 to 85 ° C for 1 hour to obtain a composite resin (F). The acid value of the solid content of this resin was 20.
Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. At this time, the viscosity was 2500 cps (B type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the stability of the aqueous resin composition and the results of the coating film physical property test.
【0042】実施例3.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
155重量部、n−ブタノール388重量部及びフェノ
トートYP−50(A)(前出フェノキシ樹脂)400
重量部を仕込み、加熱した。130℃まで昇温し完全に
溶解後、100℃に降温し、これにスチレン15.2重
量部、アクリル酸エチル14.3重量部、メタクリル酸
20.6重量部及びベンゾイルパーオキシド3.8重量
部からなる単量体混合溶液(B)を3時間かけてフラス
コに徐々に滴下した。同温度に30分保温した後、ブチ
ルセロソルブ5重量部、n−ブタノール23重量部及び
ベンゾイルパーオキシド0.63重量部からなる混合液
を20分間で滴下、更に2時間保温し、カルボン酸変性
グラフト化エポキシ樹脂(C)を得た。その後、エピコ
ート1010(D)(前出エポキシ樹脂)50重量部を
フラスコ内に添加し溶解後、合成例1で得たアクリル系
樹脂溶液(E)91重量部、ジメチルエタノールアミン
30重量部及び脱イオン水40重量部の混合液を添加
し、80〜85℃で1時間撹拌し反応させ複合樹脂
(F)を得た。この樹脂の固形分酸価は25であった。
その後、脱イオン水950重量部を1時間30分かけて
徐々に滴下し、白色の水分散体を得た。これを固形分が
35%になるように減圧下で過剰の溶剤を留去した。こ
のときの粘度は1100cps (B型粘度計6rpm )であ
った。これを実施例1と同様の方法で塗膜を作成、塗膜
物性試験を行った。水性樹脂組成物の安定性と塗膜物性
試験結果を表3に示す。Example 3. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 155 parts by weight of butyl cellosolve, 388 parts by weight of n-butanol and 400 Phenototo YP-50 (A) (phenoxy resin described above) were added.
Part by weight was charged and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 15.2 parts by weight of styrene, 14.3 parts by weight of ethyl acrylate, 20.6 parts by weight of methacrylic acid and 3.8 parts by weight of benzoyl peroxide were added. The monomer mixed solution (B) consisting of 10 parts was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, a mixed solution consisting of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.63 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the temperature was kept for 2 hours for grafting with carboxylic acid modification. An epoxy resin (C) was obtained. Then, 50 parts by weight of Epicoat 1010 (D) (epoxy resin) was added to the flask and dissolved, then 91 parts by weight of the acrylic resin solution (E) obtained in Synthesis Example 1, 30 parts by weight of dimethylethanolamine, and A mixed solution of 40 parts by weight of deionized water was added, and the mixture was stirred and reacted at 80 to 85 ° C for 1 hour to obtain a composite resin (F). The acid value of the solid content of this resin was 25.
Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. At this time, the viscosity was 1100 cps (B-type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the stability of the aqueous resin composition and the results of the coating film physical property test.
【0043】実施例4.フェノトートYP−50(A)
203重量部の代わりに合成例5のエポキシ樹脂(A)
溶液338重量部、及び合成例1のアクリル系樹脂溶液
(E)128重量部の代わりに合成例2のアクリル系樹
脂(E)溶液154重量部を用いた以外は、実施例1と
同様にして固形分35%、粘度2100cps (B型粘度
計6rpm)の水性樹脂組成物を得た。これを実施例1と
同様の方法で塗膜を作成、塗膜物性試験を行った。水性
樹脂組成物の安定性と塗膜物性試験結果を表3に示す。Example 4. Phenothote YP-50 (A)
Epoxy resin (A) of Synthesis Example 5 instead of 203 parts by weight
The procedure of Example 1 was repeated, except that 338 parts by weight of the solution and 154 parts by weight of the acrylic resin (E) solution of Synthesis Example 2 were used instead of 128 parts by weight of the acrylic resin solution (E) of Synthesis Example 1. An aqueous resin composition having a solid content of 35% and a viscosity of 2100 cps (B type viscometer 6 rpm) was obtained. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the stability of the aqueous resin composition and the results of the coating film physical property test.
【0044】実施例5.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
90重量部、n−ブタノール225重量部及びフェノト
ートYP−50S(A)(東都化成社製、フェノキシ樹
脂)203重量部を仕込み、加熱した。130℃まで昇
温し完全に溶解後、100℃に降温し、これにスチレン
16.6重量部、アクリル酸エチル15.7重量部、メ
タクリル酸22.7重量部及びベンゾイルパーオキシド
4.2重量部からなる単量体混合溶液(B)を3時間か
けてフラスコに徐々に滴下した。同温度に30分保温し
た後、ブチルセロソルブ5重量部、n−ブタノール23
重量部及びベンゾイルパーオキシド0.7重量部からな
る混合液を20分間で滴下、更に2時間保温し、カルボ
ン酸変性グラフト化エポキシ樹脂(C)を得た。その
後、エピコート1007(D)(前出エポキシ樹脂)1
35重量部をフラスコ内に添加し溶解後、合成例4で得
たアクリル系樹脂(E)溶液50重量部、ジメチルエタ
ノールアミン3重量部及び脱イオン水21重量部の混合
液を添加した。その後、80〜85℃で1時間撹拌し反
応させた。更に、予め合成例3で得たアクリル系樹脂
(E)溶液84重量部、ジメチルエタノールアミン37
重量部及び脱イオン水20重量部の混合溶液を作成し、
それを全量添加した。その後、80〜85℃で1時間撹
拌し反応させ複合樹脂(F)を得た。この樹脂の固形分
酸価は36であった。その後脱イオン水950重量部を
1時間30分かけて徐々に滴下し、白色の水分散体を得
た。これを固形分が35%になるように減圧下で過剰の
溶剤を留去した。このときの粘度は800cps(B型粘
度計6rpm )であった。これを実施例1と同様の方法で
塗膜を作成、塗膜物性試験を行った。水性樹脂組成物の
安定性と塗膜物性試験結果を表3に示す。Example 5. Stirrer, reflux condenser, thermometer,
A flask equipped with an inert gas inlet was charged with 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, and 203 parts by weight of Phenothote YP-50S (A) (phenoxy resin manufactured by Toto Kasei Co., Ltd.) and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide. The monomer mixed solution (B) consisting of 10 parts was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, 5 parts by weight of butyl cellosolve, n-butanol 23
A mixed solution of 1 part by weight and 0.7 part by weight of benzoyl peroxide was added dropwise over 20 minutes and the temperature was kept for 2 hours to obtain a carboxylic acid-modified grafted epoxy resin (C). After that, Epicoat 1007 (D) (epoxy resin described above) 1
After adding 35 parts by weight into the flask and dissolving, 50 parts by weight of the acrylic resin (E) solution obtained in Synthesis Example 4, 3 parts by weight of dimethylethanolamine, and 21 parts by weight of deionized water were added. Then, the mixture was stirred at 80 to 85 ° C. for 1 hour for reaction. Furthermore, 84 parts by weight of the acrylic resin (E) solution previously obtained in Synthesis Example 3 and dimethylethanolamine 37
A mixed solution of 20 parts by weight of deionized water and 20 parts by weight of deionized water is prepared,
The whole amount was added. Then, it stirred at 80-85 degreeC for 1 hour, and was made to react, and the composite resin (F) was obtained. The solid acid value of this resin was 36. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. At this time, the viscosity was 800 cps (B-type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the stability of the aqueous resin composition and the results of the coating film physical property test.
【0045】実施例6.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
90重量部、n−ブタノール225重量部、フェノトー
トYP−50S(A)(前出フェノキシ樹脂)100重
量部及びエピコート1010(A)(前出エポキシ樹
脂)100重量部を仕込み、加熱した。130℃まで昇
温し完全に溶解後、100℃に降温し、これにスチレン
16.6重量部、アクリル酸エチル15.7重量部、メ
タクリル酸22.7重量部及びベンゾイルパーオキシド
4.2重量部からなる単量体混合溶液(B)を3時間か
けてフラスコに徐々に滴下した。同温度に30分保温し
た後、ブチルセロソルブ5重量部、n−ブタノール23
重量部及びベンゾイルパーオキシド0.7重量部からな
る混合液を20分間で滴下、更に2時間保温し、カルボ
ン酸変性グラフト化エポキシ樹脂(C)を得た。その
後、エピコート1010(D)(前出エポキシ樹脂)1
35重量部及びフェノトートYP−50(D)(前出フ
ェノキシ樹脂)10重量部をフラスコ内に添加し溶解
後、合成例1で得たアクリル系樹脂(E)溶液128重
量部、ジメチルエタノールアミン36重量部及び脱イオ
ン水40重量部の混合液を添加した。その後、80〜8
5℃で1時間撹拌し反応させ、複合樹脂(F)を得た。
この樹脂の固形分酸価は18であった。その後、脱イオ
ン水950重量部を1時間30分かけて徐々に滴下し、
白色の水分散体を得た。これを固形分が35%になるよ
うに減圧下で過剰の溶剤を留去した。このときの粘度は
1600cps (B型粘度計6rpm )であった。これを実
施例1と同様の方法で塗膜を作成、塗膜物性試験を行っ
た。水性樹脂組成物の安定性と塗膜物性試験結果を表3
に示す。Example 6. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, 100 parts by weight of Phenothote YP-50S (A) (phenoxy resin described above) and Epicoat 1010 (A) (epoxy resin described above). ) 100 parts by weight were charged and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide. The monomer mixed solution (B) consisting of 10 parts was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, 5 parts by weight of butyl cellosolve, n-butanol 23
A mixed solution of 1 part by weight and 0.7 part by weight of benzoyl peroxide was added dropwise over 20 minutes and the temperature was kept for 2 hours to obtain a carboxylic acid-modified grafted epoxy resin (C). Then, Epicoat 1010 (D) (epoxy resin described above) 1
35 parts by weight and 10 parts by weight of Phenothote YP-50 (D) (phenoxy resin described above) were added to the flask and dissolved, and then 128 parts by weight of the acrylic resin (E) solution obtained in Synthesis Example 1 and dimethylethanolamine. A mixture of 36 parts by weight and 40 parts by weight of deionized water was added. Then 80-8
The mixture was stirred at 5 ° C. for 1 hour and reacted to obtain a composite resin (F).
The solid acid value of this resin was 18. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes,
A white aqueous dispersion was obtained. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. At this time, the viscosity was 1600 cps (B-type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the stability of the aqueous resin composition and the test results of coating film physical properties.
Shown in.
【0046】実施例7.実施例1で得た水性樹脂組成物
500重量部に、ディスパーで撹拌しながら合成例6の
フェノール樹脂(G)15重量部を徐々に加えてフェノ
ール樹脂配合の水性樹脂組成物を得た。これを実施例1
と同様の方法で塗膜を作成、塗膜物性試験を行った。試
験結果を表3に示す。Example 7. To 500 parts by weight of the aqueous resin composition obtained in Example 1, 15 parts by weight of the phenol resin (G) of Synthesis Example 6 was gradually added while stirring with a disper to obtain an aqueous resin composition containing a phenol resin. This is Example 1
A coating film was prepared by the same method as described above, and the physical properties of the coating film were tested. The test results are shown in Table 3.
【0047】実施例8.実施例2で得られた水性樹脂組
成物500重量部に、ディスパーで撹拌しながら合成例
7のフェノール樹脂10重量部及びサイメル303
(G)(三井サイアナミド社製、メラミン樹脂)5重量
部を徐々に加えてフェノール樹脂及びメラミン樹脂配合
の水性樹脂組成物を得た。これを実施例1と同様の方法
で塗膜を作成、塗膜物性試験を行った。試験結果を表3
に示す。Example 8. To 500 parts by weight of the aqueous resin composition obtained in Example 2, 10 parts by weight of the phenol resin of Synthesis Example 7 and Cymel 303 were stirred with a disper.
(G) (Mitsui Cyanamide Co., Ltd., melamine resin) 5 parts by weight was gradually added to obtain an aqueous resin composition containing a phenol resin and a melamine resin. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the test results
Shown in.
【0048】実施例9.実施例3で得られた水性樹脂組
成物500重量部に、ディスパーで撹拌しながらサイメ
ル303(G)(前出メラミン樹脂)10重量部を徐々
に加えてメラミン樹脂配合の水性樹脂組成物を得た。こ
れを実施例1と同様の方法で塗膜を作成、塗膜物性試験
を行った。試験結果を表3に示す。Example 9. To 500 parts by weight of the aqueous resin composition obtained in Example 3, 10 parts by weight of Cymel 303 (G) (previously described melamine resin) was gradually added while stirring with a disper to obtain an aqueous resin composition containing a melamine resin. It was A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. The test results are shown in Table 3.
【0049】実施例10.撹拌機、還流冷却器、温度
計、不活性ガス注入口を備えたフラスコにブチルセロソ
ルブ90重量部、n−ブタノール225重量部、PKH
H(A)(ユニオンカーバイト社製、フェノキシ樹脂)
122重量部及びエピコート1010(A)(前出エポ
キシ樹脂)81重量部を仕込み、130℃まで昇温し完
全に溶解後、120℃に降温し、合成例6のフェノール
樹脂(G)15重量部を入れ、2時間同温度で撹拌し
た。GPCによる分子量測定により、フェノール樹脂が
フェノキシ樹脂及び/又はエポキシ樹脂に予備縮合され
ていることが確認できた。更に100℃に降温し、これ
にスチレン16.6重量部、アクリル酸エチル15.7
重量部、メタクリル酸22.7重量部及びベンゾイルパ
ーオキシド4.2重量部からなる単量体混合溶液(B)
を3時間かけてフラスコに徐々に滴下した。同温度に3
0分保温した後、ブチルセロソルブ5重量部、n−ブタ
ノール23重量部及びベンゾイルパーオキシド0.7重
量部からなる混合液を20分間で滴下、更に2時間保温
し、カルボン酸変性グラフト化エポキシ樹脂(C)を得
た。その後、エピコート1010(D)(前出エポキシ
樹脂)135重量部をフラスコ内に添加し溶解後、合成
例1で得たアクリル系樹脂(E)128重量部、ジメチ
ルエタノールアミン36重量部及び脱イオン水40重量
部の混合液を添加した。その後、80〜85℃で1時間
撹拌し反応させ複合樹脂(F)を得た。この樹脂の固形
分酸価は20であった。その後、脱イオン水950重量
部を1時間30分かけて徐々に滴下し、白色の水分散体
を得た。これを固形分が35%になるように減圧下で過
剰の溶剤を留去した。このときの粘度は1800cps
(B型粘度計6rpm)であった。これを実施例1と同様
の方法で塗膜を作成、塗膜物性試験を行った。試験結果
を表3に示す。Example 10. 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, PKH in a flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet.
H (A) (Phenoxy resin manufactured by Union Carbide)
122 parts by weight and 81 parts by weight of Epicoat 1010 (A) (epoxy resin) were charged, heated to 130 ° C. and completely dissolved, and then cooled to 120 ° C., and 15 parts by weight of the phenolic resin (G) of Synthesis Example 6. Was charged and stirred for 2 hours at the same temperature. By the molecular weight measurement by GPC, it was confirmed that the phenol resin was precondensed with the phenoxy resin and / or the epoxy resin. The temperature was further lowered to 100 ° C., and 16.6 parts by weight of styrene and 15.7 of ethyl acrylate were added.
Part by weight, monomer mixture solution (B) consisting of 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide
Was gradually added dropwise to the flask over 3 hours. 3 at the same temperature
After keeping the temperature for 0 minutes, a mixed solution of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the temperature was kept for 2 hours, and the carboxylic acid-modified grafted epoxy resin ( C) was obtained. Then, 135 parts by weight of Epicoat 1010 (D) (epoxy resin described above) was added into the flask and dissolved, and then 128 parts by weight of the acrylic resin (E) obtained in Synthesis Example 1, 36 parts by weight of dimethylethanolamine and deionized. A mixture of 40 parts by weight of water was added. Then, it stirred at 80-85 degreeC for 1 hour, and was made to react, and the composite resin (F) was obtained. The acid value of the solid content of this resin was 20. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is 1800 cps
(B type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. The test results are shown in Table 3.
【0050】実施例11.撹拌機、還流冷却器、温度
計、不活性ガス注入口を備えたフラスコにブチルセロソ
ルブ90重量部、n−ブタノール225重量部及びフェ
ノトートYP−50(A)(前出フェノキシ樹脂)20
3重量部を仕込み、加熱した。130℃まで昇温し完全
に溶解後、100℃に降温し、これにスチレン16.6
重量部、アクリル酸エチル15.7重量部、メタクリル
酸22.7重量部及びベンゾイルパーオキシド4.2重
量部からなる単量体混合溶液(B)を3時間かけてフラ
スコに徐々に滴下した。同温度に30分保温した後、ブ
チルセロソルブ5重量部、ブタノール23重量部及びベ
ンゾイルパーオキシド0.7重量部からなる混合液を2
0分間で滴下、更に2時間保温し、カルボン酸変性グラ
フト化エポキシ樹脂(C)を得た。一方、別の撹拌機、
還流冷却器、温度計、不活性ガス注入口を備えたフラス
コにメチルエチルケトン50重量部、n−ブタノール4
0重量部及びエポトートYD−20H(D)(東都化成
社製、エポキシ樹脂)135重量部を仕込み、130℃
まで昇温し完全に溶解後、120℃に降温し、合成例7
のフェノール樹脂(G)15重量部を入れ、2時間同温
度で撹拌した。GPCによる分子量測定により、フェノ
ール樹脂がエポキシ樹脂に予備縮合されていることが確
認できた。これの全量及び合成例1で得たアクリル系樹
脂(E)128重量部及びジメチルエタノールアミン3
6重量部と脱イオン水40重量部の混合液を上記フラス
コに添加した。その後、80〜85℃で1時間撹拌し反
応させ複合樹脂(F)を得た。この樹脂の固形分酸価は
32であった。その後、脱イオン水950重量部を1時
間30分かけて徐々に滴下し、白色の水分散体を得た。
これを固形分が35%になるように減圧下で過剰の溶剤
を留去した。このときの粘度は1400cps (B型粘度
計6rpm )であった。これを実施例1と同様の方法で塗
膜を作成、塗膜物性試験を行った。試験結果を表3に示
す。Example 11. 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, and Phenothote YP-50 (A) (phenoxy resin described above) were placed in a flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet.
3 parts by weight were charged and heated. After the temperature was raised to 130 ° C and it was completely dissolved, the temperature was lowered to 100 ° C.
The monomer mixed solution (B) consisting of 1 part by weight, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After keeping the same temperature for 30 minutes, 2 parts by weight of a mixed solution of 5 parts by weight of butyl cellosolve, 23 parts by weight of butanol and 0.7 parts by weight of benzoyl peroxide was added.
The mixture was added dropwise over 0 minutes and kept warm for 2 hours to obtain a carboxylic acid-modified grafted epoxy resin (C). Meanwhile, another stirrer,
In a flask equipped with a reflux condenser, a thermometer, and an inert gas inlet, 50 parts by weight of methyl ethyl ketone and 4 parts of n-butanol.
Charge 0 parts by weight and 135 parts by weight of Epototo YD-20H (D) (Epoxy resin manufactured by Tohto Kasei Co., Ltd.), and 130 ° C.
The temperature was raised to 120 ° C. and the temperature was lowered to 120 ° C.
15 parts by weight of the phenol resin (G) was added and stirred at the same temperature for 2 hours. By the molecular weight measurement by GPC, it was confirmed that the phenol resin was precondensed with the epoxy resin. The total amount of this, 128 parts by weight of the acrylic resin (E) obtained in Synthesis Example 1, and dimethylethanolamine 3
A mixture of 6 parts by weight and 40 parts by weight of deionized water was added to the flask. Then, it stirred at 80-85 degreeC for 1 hour, and was made to react, and composite resin (F) was obtained. The acid value of the solid content of this resin was 32. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion.
The excess solvent was distilled off under reduced pressure so that the solid content was 35%. At this time, the viscosity was 1400 cps (B-type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. The test results are shown in Table 3.
【0051】実施例12.撹拌機、還流冷却器、温度
計、不活性ガス注入口を備えたフラスコにブチルセロソ
ルブ90重量部、n−ブタノール225重量部及びPK
HH(A)(前出フェノキシ樹脂)203重量部を仕込
み、加熱した。130℃まで昇温し完全に溶解後、10
0℃に降温し、これにスチレン16.6重量部、アクリ
ル酸エチル15.7重量部、メタクリル酸22.7重量
部及びベンゾイルパーオキシド4.2重量部からなる単
量体混合溶液(B)を3時間かけてフラスコに徐々に滴
下した。同温度に30分保温した後、ブチルセロソルブ
5重量部、n−ブタノール23重量部及びベンゾイルパ
ーオキシド0.7重量部からなる混合液を20分間で滴
下、更に2時間保温し、カルボン酸変性グラフト化エポ
キシ樹脂(C)を得た。その後、エポトートYD−20
H(D)(前出エポキシ樹脂)135重量部を仕込み、
130℃まで昇温し完全に溶解する。一方、別の撹拌
機、還流冷却器、温度計、不活性ガス注入口を備えたフ
ラスコに合成例1で得たアクリル系樹脂(E)128重
量部及びサイメル303(G)(前出メラミン樹脂)1
0重量部を入れ、100℃で1時間撹拌する。GPCに
よる分子量測定により、メラミン樹脂(G)がアクリル
系樹脂(E)に予備縮合されていることが確認できた。
これの全量及びジメチルエタノールアミン1重量部を添
加した。その後、100℃で1時間撹拌し反応をさせ複
合樹脂(F)を得た。この樹脂の固形分酸価は31であ
った。その後、脱イオン水950重量部とジメチルエタ
ノールアミン35重量部の混合液を1時間30分かけて
徐々に滴下し、白色の水分散体を得た。これを固形分が
35%になるように減圧下で過剰の溶剤を留去した。こ
のときの粘度は870cps (B型粘度計6rpm )であっ
た。これを実施例1と同様の方法で塗膜を作成、塗膜物
性試験を行った。試験結果を表3に示す。Example 12 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, and PK in a flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet.
203 parts by weight of HH (A) (phenoxy resin described above) were charged and heated. After heating up to 130 ℃ and completely dissolving, 10
The temperature was lowered to 0 ° C., and a monomer mixed solution (B) containing 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide was added. Was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, a mixed solution consisting of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the temperature was further maintained for 2 hours for grafting with carboxylic acid. An epoxy resin (C) was obtained. After that, Epototo YD-20
Charge 135 parts by weight of H (D) (epoxy resin),
The temperature is raised to 130 ° C. and completely dissolved. On the other hand, 128 parts by weight of the acrylic resin (E) obtained in Synthesis Example 1 and Cymel 303 (G) (the above-mentioned melamine resin) were placed in a flask equipped with another stirrer, a reflux condenser, a thermometer, and an inert gas inlet. ) 1
Add 0 parts by weight and stir at 100 ° C. for 1 hour. It was confirmed by the molecular weight measurement by GPC that the melamine resin (G) was precondensed with the acrylic resin (E).
The total amount of this and 1 part by weight of dimethylethanolamine were added. Then, it stirred at 100 degreeC for 1 hour, and was made to react, and the composite resin (F) was obtained. The solid acid value of this resin was 31. Then, a mixed solution of 950 parts by weight of deionized water and 35 parts by weight of dimethylethanolamine was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. At this time, the viscosity was 870 cps (B type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. The test results are shown in Table 3.
【0052】実施例13.撹拌機、還流冷却器、温度
計、不活性ガス注入口を備えたフラスコにブチルセロソ
ルブ90重量部、n−ブタノール225重量部及びエピ
コート1010(A)(前出エポキシ樹脂)203重量
部を仕込み、130℃まで昇温し完全に溶解後、100
℃に降温し、これにスチレン16.6重量部、アクリル
酸エチル15.7重量部、メタクリル酸22.7重量部
及びベンゾイルパーオキシド4.2重量部からなる単量
体混合溶液(B)を3時間かけてフラスコに徐々に滴下
した。同温度に30分保温した後、ブチルセロソルブ5
重量部、n−ブタノール23重量部及びベンゾイルパー
オキシド0.7重量部からなる混合液を20分間で滴
下、更に2時間保温し、カルボン酸変性グラフト化エポ
キシ樹脂(C)を得た。その後、エポトートYD−20
H(D)(前出エポキシ樹脂)135重量部をフラスコ
内に添加し溶解後、合成例1で得たアクリル系樹脂
(E)128重量部を添加した。その後、130℃で2
0時間撹拌し反応させ複合樹脂(F)を得た。この樹脂
の固形分酸価は24であった。その後、ジメチルエタノ
ールアミン36重量部と脱イオン水990重量部の混合
液を1時間30分かけて徐々に滴下し、白色の水分散体
を得た。これを固形分が35%になるように減圧下で過
剰の溶剤を留去した。このときの粘度は800cps (B
型粘度計6rpm )であった。これを実施例1と同様の方
法で塗膜を作成、塗膜物性試験を行った。試験結果を表
3に示す。Example 13. A flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet was charged with 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, and 203 parts by weight of Epicoat 1010 (A) (epoxy resin). After the temperature was raised to ℃ and completely dissolved, 100
The temperature was lowered to ℃, and a monomer mixture solution (B) consisting of 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide was added. It was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, butyl cellosolve 5
By weight, a mixed solution of 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the mixture was kept warm for 2 hours to obtain a carboxylic acid-modified grafted epoxy resin (C). After that, Epototo YD-20
135 parts by weight of H (D) (epoxy resin) was added to the flask and dissolved, and then 128 parts by weight of the acrylic resin (E) obtained in Synthesis Example 1 was added. Then, at 130 ℃ 2
The mixture was stirred and reacted for 0 hour to obtain a composite resin (F). The acid value of the solid content of this resin was 24. Then, a mixed solution of 36 parts by weight of dimethylethanolamine and 990 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is 800 cps (B
Type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. The test results are shown in Table 3.
【0053】実施例14.撹拌機、還流冷却器、温度
計、不活性ガス注入口を備えたフラスコにブチルセロソ
ルブ11重量部、n−ブタノール28重量部及びフェノ
トートYP−50(A)(前出フェノキシ樹脂)25重
量部を仕込み、加熱した。130℃まで昇温し完全に溶
解後、100℃に降温し、これにスチレン7.5重量
部、アクリル酸エチル7重量部、メタクリル酸10.5
重量部及びベンゾイルパーオキシド1.9重量部からな
る単量体混合溶液(B)を3時間かけてフラスコに徐々
に滴下した。同温度に30分保温した後、ブチルセロソ
ルブ5重量部、n−ブタノール23重量部及びベンゾイ
ルパーオキシド0.32重量部からなる混合液を20分
間で滴下、更に2時間保温し、カルボン酸変性グラフト
化エポキシ樹脂(C)を得た。その後、エピコート10
10(前出エポキシ樹脂)350重量部をフラスコ内に
添加し溶解後、合成例1で得たアクリル系樹脂(E)溶
液182重量部、ジメチルエタノールアミン38重量部
及び脱イオン水40重量部の混合液を添加し、80〜8
5℃で1時間撹拌し反応させ複合樹脂(F)を得た。こ
の樹脂の固形分酸価は27であった。その後、脱イオン
水950重量部を1時間30分かけて徐々に滴下し、白
色の水分散体を得た。これを固形分が35%になるよう
に減圧下で過剰の溶剤を留去した。このときの粘度は9
50cps (B型粘度計6rpm )であった。これを実施例
1と同様の方法で塗膜を作成、塗膜物性試験を行った。
試験結果を表3に示す。Example 14 A flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet was charged with 11 parts by weight of butyl cellosolve, 28 parts by weight of n-butanol, and 25 parts by weight of Phenothote YP-50 (A) (phenoxy resin). Charged and heated. After the temperature was raised to 130 ° C and completely dissolved, the temperature was lowered to 100 ° C, and 7.5 parts by weight of styrene, 7 parts by weight of ethyl acrylate and 10.5 of methacrylic acid were added.
The monomer mixed solution (B) consisting of 1 part by weight and 1.9 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, a mixed solution consisting of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.32 part by weight of benzoyl peroxide was added dropwise over 20 minutes, and the mixture was further maintained for 2 hours and grafted with carboxylic acid. An epoxy resin (C) was obtained. Then Epicote 10
After adding 350 parts by weight of 10 (epoxy resin) to the flask and dissolving, 182 parts by weight of the acrylic resin (E) solution obtained in Synthesis Example 1, 38 parts by weight of dimethylethanolamine and 40 parts by weight of deionized water were added. Add the mixture, 80-8
The mixture was stirred at 5 ° C. for 1 hour and reacted to obtain a composite resin (F). The acid value of the solid content of this resin was 27. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is 9
It was 50 cps (B-type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested.
The test results are shown in Table 3.
【0054】実施例15.撹拌機、還流冷却器、温度
計、不活性ガス注入口を備えたフラスコにブチルセロソ
ルブ155重量部、n−ブタノール390重量部及びフ
ェノトートYP−50(A)(前出フェノキシ樹脂)3
50重量部を仕込み、加熱した。130℃まで昇温し完
全に溶解後、100℃に降温し、これにスチレン30重
量部、アクリル酸エチル29重量部、メタクリル酸41
重量部及びベンゾイルパーオキシド7.6重量部からな
る単量体混合溶液(B)を3時間かけてフラスコに徐々
に滴下した。同温度に30分保温した後、ブチルセロソ
ルブ5重量部、n−ブタノール23重量部及びベンゾイ
ルパーオキシド1.3重量部からなる混合液を20分間
で滴下、更に2時間保温し、カルボン酸変性グラフト化
エポキシ樹脂(C)を得た。その後、エピコート101
0(前出エポキシ樹脂)25重量部をフラスコ内に添加
し溶解後、合成例1で得たアクリル系樹脂(E)溶液4
5重量部、ジメチルエタノールアミン35重量部及び脱
イオン水23.5重量部の混合液を添加し、80〜85
℃で1時間撹拌し反応させ複合樹脂(F)を得た。この
樹脂の固形分酸価は49であった。その後、脱イオン水
950重量部を1時間30分かけて徐々に滴下し、白色
の水分散体を得た。これを固形分が35%になるように
減圧下で過剰の溶剤を留去した。このときの粘度は95
0cps (B型粘度計6rpm )であった。これを実施例1
と同様の方法で塗膜を作成、塗膜物性試験を行った。試
験結果を表3に示す。Example 15. In a flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet, 155 parts by weight of butyl cellosolve, 390 parts by weight of n-butanol and Phenothote YP-50 (A) (phenoxy resin described above) 3
50 parts by weight were charged and heated. After the temperature was raised to 130 ° C and completely dissolved, the temperature was lowered to 100 ° C.
The monomer mixed solution (B) consisting of 1 part by weight and 7.6 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, a mixed solution of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 1.3 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the temperature was kept for 2 hours for grafting with carboxylic acid. An epoxy resin (C) was obtained. After that, Epicote 101
25 parts by weight of 0 (epoxy resin described above) was added to the flask and dissolved, and then the acrylic resin (E) solution 4 obtained in Synthesis Example 1
A mixed liquid of 5 parts by weight, 35 parts by weight of dimethylethanolamine and 23.5 parts by weight of deionized water was added to 80-85.
The mixture was stirred at 0 ° C. for 1 hour and reacted to obtain a composite resin (F). The solid content acid value of this resin was 49. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is 95
It was 0 cps (B-type viscometer 6 rpm). This is Example 1
A coating film was prepared by the same method as described above, and the physical properties of the coating film were tested. The test results are shown in Table 3.
【0055】比較例1.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
150重量部、n−ブタノール375重量部、フェノト
ートYP−50(A)(前出フェノキシ樹脂)135重
量部及びエピコート1010(A)(前出エポキシ樹
脂)203重量部を仕込み、130℃まで昇温し完全に
溶解後、100℃に降温し、これにスチレン25.5重
量部、アクリル酸エチル24.1重量部、メタクリル酸
34.9重量部及びベンゾイルパーオキシド6.5重量
部からなる単量体混合溶液(B)を3時間かけてフラス
コに徐々に滴下した。同温度に30分保温した後、ブチ
ルセロソルブ7.9重量部、n−ブタノール36.1重
量部及びベンゾイルパーオキシド1.1重量部からなる
混合液を20分間で滴下、更に2時間保温し、カルボン
酸変性グラフト化エポキシ樹脂(C)を得た。これにジ
メチルアミノエタノール23.5重量部及び脱イオン水
950重量部の混合液を1時間30分かけて徐々に滴下
し、白色の水分散体を得た。これを固形分が35%にな
るように減圧下で過剰の溶剤を留去した。このときの粘
度は600cps (B型粘度計6rpm )であった。これを
実施例1と同様の方法で塗膜を作成、塗膜物性試験を行
った。試験結果を表3に示す。Comparative Example 1. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 150 parts by weight of butyl cellosolve, 375 parts by weight of n-butanol, 135 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and Epicoat 1010 (A) (epoxy resin described above). ) 203 parts by weight were charged, the temperature was raised to 130 ° C. and completely dissolved, and then the temperature was lowered to 100 ° C., to which 25.5 parts by weight of styrene, 24.1 parts by weight of ethyl acrylate, 34.9 parts by weight of methacrylic acid and A monomer mixed solution (B) consisting of 6.5 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, a mixed solution consisting of 7.9 parts by weight of butyl cellosolve, 36.1 parts by weight of n-butanol and 1.1 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the mixture was heated for an additional 2 hours, and then heated for 2 hours. An acid-modified grafted epoxy resin (C) was obtained. A mixed solution of 23.5 parts by weight of dimethylaminoethanol and 950 parts by weight of deionized water was gradually added dropwise thereto over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time was 600 cps (B-type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. The test results are shown in Table 3.
【0056】比較例2.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
90重量部、n−ブタノール225重量部、フェノトー
トYP−50(A)(前出フェノキシ樹脂)200重量
部及びエピコート1010(A)(前出エポキシ樹脂)
150重量部を仕込み、130℃まで昇温し完全に溶解
後、100℃に降温し、これにスチレン30.2重量
部、アクリル酸エチル28.5重量部、メタクリル酸4
1.3重量部及びベンゾイルパーオキシド7.6重量部
からなる単量体混合溶液(B)を3時間かけてフラスコ
に徐々に滴下した。同温度に30分保温した後、ブチル
セロソルブ9重量部、n−ブタノール42重量部及びベ
ンゾイルパーオキシド1.3重量部からなる混合液を2
0分間で滴下、更に2時間保温し、アクリルグラフト化
エポキシ樹脂(C)を得た。その後、合成例1で得たア
クリル系樹脂(E)溶液45.5重量部、ジメチルエタ
ノールアミン35重量部及び脱イオン水40重量部の混
合液を添加し、80〜85℃で1時間撹拌し反応させ複
合樹脂(F)を得た。この樹脂の固形分酸価は40であ
った。その後、脱イオン水950重量部を1時間30分
かけて徐々に滴下し、白色の水分散体を得た。これを固
形分が35%になるように減圧下で過剰の溶剤を留去し
た。このときの粘度は1100cps (B型粘度計6rpm
)であった。これを実施例1と同様の方法で塗膜を作
成、塗膜物性試験を行った。水性樹脂組成物の安定性と
塗膜物性試験結果を表3に示す。Comparative Example 2. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, 200 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and Epicoat 1010 (A) (epoxy resin described above). )
150 parts by weight were charged, the temperature was raised to 130 ° C. and completely dissolved, and then the temperature was lowered to 100 ° C.
A monomer mixed solution (B) consisting of 1.3 parts by weight and 7.6 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After keeping the same temperature for 30 minutes, 2 parts by weight of a mixed solution of 9 parts by weight of butyl cellosolve, 42 parts by weight of n-butanol and 1.3 parts by weight of benzoyl peroxide was added.
The mixture was added dropwise over 0 minutes and kept warm for 2 hours to obtain an acrylic grafted epoxy resin (C). Then, a mixed solution of 45.5 parts by weight of the acrylic resin (E) solution obtained in Synthesis Example 1, 35 parts by weight of dimethylethanolamine and 40 parts by weight of deionized water was added, and the mixture was stirred at 80 to 85 ° C. for 1 hour. The reaction was carried out to obtain a composite resin (F). The acid value of the solid content of this resin was 40. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is 1100 cps (B type viscometer 6 rpm
)Met. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the stability of the aqueous resin composition and the results of the coating film physical property test.
【0057】比較例3.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
150重量部、n−ブタノール375重量部、フェノト
ートYP−50(A)(前出フェノキシ樹脂)203重
量部及びエピコート1010(A)(前出エポキシ樹
脂)135重量部を仕込み、130℃まで昇温し完全に
溶解後、100℃に降温し、これにスチレン16.6重
量部、アクリル酸エチル15.7重量部、メタクリル酸
22.7重量部及びベンゾイルパーオキシド4.2重量
部からなる単量体混合溶液(B)を3時間かけてフラス
コに徐々に滴下した。同温度に30分保温した後、ブチ
ルセロソルブ5重量部、n−ブタノール23重量部及び
ベンゾイルパーオキシド0.7重量部からなる混合液を
20分間で滴下、更に2時間保温し、アクリルグラフト
化エポキシ樹脂(C)を得た。その後、合成例1で得た
アクリル系樹脂(E)溶液128重量部、ジメチルエタ
ノールアミン36重量部及び脱イオン水40重量部の混
合液を添加し、80〜85℃で1時間撹拌し反応させ複
合樹脂(F)を得た。この樹脂の固形分酸価は32であ
った。その後、脱イオン水950重量部を1時間30分
かけて徐々に滴下したが、安定な水分散体を得ることは
できなかった。Comparative Example 3. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 150 parts by weight of butyl cellosolve, 375 parts by weight of n-butanol, 203 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and Epicoat 1010 (A) (epoxy resin described above). ) 135 parts by weight were charged, the temperature was raised to 130 ° C. and completely dissolved, and then the temperature was lowered to 100 ° C., to which 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and A monomer mixed solution (B) consisting of 4.2 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After being kept at the same temperature for 30 minutes, a mixed solution of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the temperature was kept for 2 hours, and the acrylic grafted epoxy resin was added. (C) was obtained. Then, a mixed solution of 128 parts by weight of the acrylic resin (E) solution obtained in Synthesis Example 1, 36 parts by weight of dimethylethanolamine and 40 parts by weight of deionized water was added, and the mixture was stirred at 80 to 85 ° C. for 1 hour to react. A composite resin (F) was obtained. The acid value of the solid content of this resin was 32. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes, but a stable aqueous dispersion could not be obtained.
【0058】比較例4.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
90重量部、n−ブタノール225重量部及びPKHH
(A)(前出フェノキシ樹脂)203重量部を仕込み、
130℃まで昇温し完全に溶解後、100℃に降温し、
合成例3で得たアクリル系樹脂(E)96重量部及びジ
メチルエタノールアミン22重量部と脱イオン水40重
量部の混合液を添加した。その後、80〜85℃で3時
間撹拌し反応させた。その後、脱イオン水950重量部
を1時間30分かけて徐々に滴下したが、安定な水分散
体を得ることはできなかった。Comparative Example 4. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol and PKHH
(A) 203 parts by weight of the above-mentioned phenoxy resin were charged,
After heating up to 130 ℃ and completely dissolving, cool down to 100 ℃,
A mixed solution of 96 parts by weight of the acrylic resin (E) obtained in Synthesis Example 3, 22 parts by weight of dimethylethanolamine and 40 parts by weight of deionized water was added. Then, the mixture was stirred at 80 to 85 ° C. for 3 hours for reaction. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes, but a stable aqueous dispersion could not be obtained.
【0059】比較例5.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
90重量部、n−ブタノール225重量部、フェノトー
トYP−50(A)(前出フェノキシ樹脂)203重量
部及びエピコート1010(A)(前出エポキシ樹脂)
135重量部を仕込み、130℃まで昇温し完全に溶解
後、100℃に降温し、合成例1で得たアクリル系樹脂
(E)128重量部及びジメチルエタノールアミン21
重量部と脱イオン水40重量部の混合液を添加した。そ
の後、80〜85℃で3時間撹拌し反応させ複合樹脂
(F)を得た。この樹脂の酸価は23であった。その
後、脱イオン水950重量部を1時間30分かけて徐々
に滴下したが、安定な水分散体を得ることはできなかっ
た。Comparative Example 5. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, 203 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and Epicoat 1010 (A) (epoxy resin described above). )
135 parts by weight were charged, the temperature was raised to 130 ° C. and completely dissolved, and then the temperature was lowered to 100 ° C., 128 parts by weight of the acrylic resin (E) obtained in Synthesis Example 1 and dimethylethanolamine 21.
A mixture of parts by weight and 40 parts by weight of deionized water was added. Then, it stirred at 80-85 degreeC for 3 hours, and was made to react, and the composite resin (F) was obtained. The acid value of this resin was 23. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes, but a stable aqueous dispersion could not be obtained.
【0060】比較例6.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
90重量部、n−ブタノール225重量部、フェノトー
トYP−50(A)(前出フェノキシ樹脂)203重量
部及びエピコート1010(A)(前出エポキシ樹脂)
135重量部を仕込み、130℃まで昇温し完全に溶解
後、100℃に降温し、合成例1で得たアクリル系樹脂
(E)128重量部及びジメチルエタノールアミン21
重量部と脱イオン水40重量部の混合液を添加した。そ
の後、80〜85℃で1時間撹拌し反応させた。その
後、これにスチレン16.6重量部、アクリル酸エチル
15.7重量部、メタクリル酸22.7重量部及びベン
ゾイルパーオキシド4.2重量部からなる単量体混合溶
液(B)を3時間かけてフラスコに徐々に滴下した。同
温度に30分保温した後、ブチルセロソルブ5重量部、
n−ブタノール23重量部及びベンゾイルパーオキシド
0.7重量部からなる混合液を20分間で滴下、更に2
時間保温した。これに脱イオン水950重量部を1時間
30分かけて徐々に滴下したが、安定な水分散体を得る
ことはできなかった。Comparative Example 6. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, 203 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and Epicoat 1010 (A) (epoxy resin described above). )
135 parts by weight were charged, the temperature was raised to 130 ° C. and completely dissolved, and then the temperature was lowered to 100 ° C., 128 parts by weight of the acrylic resin (E) obtained in Synthesis Example 1 and dimethylethanolamine 21.
A mixture of parts by weight and 40 parts by weight of deionized water was added. Then, the mixture was stirred at 80 to 85 ° C. for 1 hour for reaction. Thereafter, a monomer mixed solution (B) consisting of 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide was added thereto over 3 hours. Slowly dropped into the flask. After incubating at the same temperature for 30 minutes, 5 parts by weight of butyl cellosolve,
A mixed solution of 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and further 2
I kept it warm for an hour. Although 950 parts by weight of deionized water was gradually added dropwise thereto over 1 hour and 30 minutes, a stable aqueous dispersion could not be obtained.
【0061】比較例7.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
90重量部、n−ブタノール225重量部及びフェノト
ートYP−50(A)(前出フェノキシ樹脂)203重
量部を仕込み、加熱した。130℃まで昇温し完全に溶
解後、100℃に降温し、これにスチレン16.6重量
部、アクリル酸エチル15.7重量部、メタクリル酸2
2.7重量部及びベンゾイルパーオキシド4.2重量部
からなる単量体混合溶液(B)を3時間かけてフラスコ
に徐々に滴下した。同温度に30分保温した後、ブチル
セロソルブ5重量部、n−ブタノール23重量部及びベ
ンゾイルパーオキシド0.7重量部からなる混合液を2
0分間で滴下、更に2時間保温し、カルボン酸変性グラ
フト化エポキシ樹脂(C)を得た。その後、フェノトー
トYP−50(D)(前出フェノキシ樹脂)135重量
部をフラスコ内に添加し溶解後、合成例1で得たアクリ
ル系樹脂溶液(E)128重量部、ジメチルエタノール
アミン21重量部及び脱イオン水40重量部の混合液を
添加した。その後、80〜85℃で1時間撹拌し反応さ
せた。その後、脱イオン水950重量部を1時間30分
かけて徐々に滴下したが、安定な水分散体を得ることは
できなかった。Comparative Example 7. Stirrer, reflux condenser, thermometer,
A flask equipped with an inert gas inlet was charged with 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol and 203 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate and 2 parts of methacrylic acid were added.
A monomer mixed solution (B) consisting of 2.7 parts by weight and 4.2 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After being kept at the same temperature for 30 minutes, 2 parts by weight of a mixed solution of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added.
The mixture was added dropwise over 0 minutes and kept warm for 2 hours to obtain a carboxylic acid-modified grafted epoxy resin (C). Then, 135 parts by weight of Phenototo YP-50 (D) (phenoxy resin described above) was added to the flask and dissolved, and then 128 parts by weight of the acrylic resin solution (E) obtained in Synthesis Example 1 and 21 parts by weight of dimethylethanolamine. And 40 parts by weight of deionized water was added. Then, the mixture was stirred at 80 to 85 ° C. for 1 hour for reaction. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes, but a stable aqueous dispersion could not be obtained.
【0062】比較例8.撹拌機、還流冷却器、温度計、
不活性ガス注入口を備えたフラスコにブチルセロソルブ
90重量部、n−ブタノール225重量部及びフェノト
ートYP−50(A)(前出フェノキシ樹脂)203重
量部を仕込み、加熱した。130℃まで昇温し完全に溶
解後、100℃に降温し、これにスチレン16.6重量
部、アクリル酸エチル15.7重量部、メタクリル酸2
2.7重量部及びベンゾイルパーオキシド1.9重量部
からなる単量体混合溶液(B)を3時間かけてフラスコ
に徐々に滴下した。同温度に30分保温した後、ブチル
セロソルブ5重量部、n−ブタノール23重量部及びベ
ンゾイルパーオキシド0.7重量部からなる混合液を2
0分間で滴下、更に2時間保温した。その後、エピコー
ト1010(D)(前出エポキシ樹脂)135重量部を
フラスコ内に添加し、溶解後、合成例1で得たアクリル
系樹脂溶液(E)128重量部、ジメチルエタノールア
ミン21重量部及び脱イオン水40重量部の混合液を添
加した。その後、80〜85℃で1時間撹拌し反応させ
複合樹脂(F)を得た。この樹脂の固形分酸価は21で
あった。その後、脱イオン水950重量部を1時間30
分かけて徐々に滴下したが、安定な水分散体を得ること
はできなかった。Comparative Example 8. Stirrer, reflux condenser, thermometer,
A flask equipped with an inert gas inlet was charged with 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol and 203 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate and 2 parts of methacrylic acid were added.
A monomer mixed solution (B) consisting of 2.7 parts by weight and 1.9 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After being kept at the same temperature for 30 minutes, 2 parts by weight of a mixed solution of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added.
The mixture was added dropwise over 0 minutes and kept warm for 2 hours. Thereafter, 135 parts by weight of Epicoat 1010 (D) (epoxy resin) was added to the flask, and after dissolution, 128 parts by weight of the acrylic resin solution (E) obtained in Synthesis Example 1, 21 parts by weight of dimethylethanolamine, and A mixture of 40 parts by weight of deionized water was added. Then, it stirred at 80-85 degreeC for 1 hour, and was made to react, and the composite resin (F) was obtained. The acid value of the solid content of this resin was 21. Then, 950 parts by weight of deionized water is used for 1 hour 30
Although the solution was gradually added dropwise over a period of time, a stable aqueous dispersion could not be obtained.
【0063】実施例16.17.18.19.20.及
び比較例9.10.単量体混合物(B)を表4に示す組
成にした以外は、実施例1と同様にして、白色の水分散
体を得た。これを固形分が35%になるように減圧下で
過剰の溶剤を留去した。この時の粘度を表4に示す。こ
れを実施例1と同様の方法で塗膜を作成、塗膜物性試験
を行った。水性樹脂組成物の安定性と塗膜物性試験結果
を表4に示す。Example 16.17.18.19.20. And comparative example 9.10. A white aqueous dispersion was obtained in the same manner as in Example 1 except that the monomer mixture (B) had the composition shown in Table 4. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is shown in Table 4. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 4 shows the stability of the aqueous resin composition and the test results of coating film physical properties.
【0064】[0064]
【表4】 [Table 4]
【0065】実施例21.22.23.24.25.2
6.及び比較例11.単量体混合物(B)と共に滴下す
るベンゾイルパーオキシドを表5に示す量にした以外は
実施例1と同様にして、白色の水分散体を得た。これを
固形分が35%になるように減圧下で過剰の溶剤を留去
した。この時の粘度を表5に示す。これを実施例1と同
様の方法で塗膜を作成、塗膜物性試験を行った。水性樹
脂組成物の安定性と塗膜物性試験結果を表5に示す。Example 21.22.23.24.25.2
6. And Comparative Example 11. A white aqueous dispersion was obtained in the same manner as in Example 1 except that the amount of benzoyl peroxide added dropwise together with the monomer mixture (B) was changed to the amount shown in Table 5. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is shown in Table 5. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 5 shows the stability of the aqueous resin composition and the test results of the coating film physical properties.
【0066】[0066]
【表5】 [Table 5]
【0067】実施例27.28.29.30.及び比較
例12.13.アクリル系樹脂(E)を表6に示すアク
リル系樹脂(E)溶液にした以外は実施例1と同様にし
て、白色の水分散体を得た。これを固形分が35%にな
るように減圧下で過剰の溶剤を留去した。この時の粘度
を表6に示す。これを実施例1と同様の方法で塗膜を作
成、塗膜物性試験を行った。水性樹脂組成物の安定性と
塗膜物性試験結果を表6に示す。Example 27.28.29.30. And comparative example 12.13. A white water dispersion was obtained in the same manner as in Example 1 except that the acrylic resin (E) solution shown in Table 6 was used as the acrylic resin (E). The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is shown in Table 6. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 6 shows the stability of the aqueous resin composition and the results of the coating film physical property test.
【0068】[0068]
【表6】 [Table 6]
【0069】実施例31.32.33.34.アクリル
系樹脂(E)を表2に示すアクリル系樹脂(E)溶液に
した以外は実施例1と同様にして、白色の水分散体を得
た。これを固形分が35%になるように減圧下で過剰の
溶剤を留去した。この時の粘度を表7に示す。これを実
施例1と同様の方法で塗膜を作成、塗膜物性試験を行っ
た。水性樹脂組成物の安定性と塗膜物性試験を表7に示
す。Example 31.2.32.33.34. A white aqueous dispersion was obtained in the same manner as in Example 1 except that the acrylic resin (E) solution shown in Table 2 was used as the acrylic resin (E). The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is shown in Table 7. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 7 shows the stability and coating film physical property test of the aqueous resin composition.
【0070】[0070]
【表7】 [Table 7]
【0071】[0071]
【発明の効果】本発明の水性樹脂組成物は、安定性に優
れ、塗膜表面がワキの発生しない平滑で、且つその硬化
塗膜が耐熱水性、加工性、耐蝕性、耐溶剤性、フレーバ
ー性に優れたものである。EFFECT OF THE INVENTION The aqueous resin composition of the present invention is excellent in stability, the surface of the coating film is smooth without cracking, and the cured coating film has hot water resistance, processability, corrosion resistance, solvent resistance, and flavor. It has excellent properties.
Claims (8)
シ樹脂(A)にエチレン性不飽和脂肪族カルボン酸とこ
れと共重合性の不飽和単量体からなる酸価100〜50
0の単量体混合物(B)をグラフト重合させたカルボン
酸変性グラフト化エポキシ樹脂(C)と、芳香族エポキ
シ樹脂(D)との混合物に、酸価100〜500のカル
ボキシル基含有アクリル系樹脂(E)を部分的に結合さ
せた複合樹脂(F)を、水分散又は水溶解させた水性樹
脂組成物。1. An acid value of 100 to 50 comprising an ethylenically unsaturated aliphatic carboxylic acid and an unsaturated monomer copolymerizable therewith in an aromatic epoxy resin and / or phenoxy resin (A).
A carboxyl group-containing acrylic resin having an acid value of 100 to 500 is added to a mixture of a carboxylic acid-modified grafted epoxy resin (C) obtained by graft-polymerizing a monomer mixture (B) of 0 and an aromatic epoxy resin (D). A water-based resin composition in which a composite resin (F) in which (E) is partially bound is dispersed or dissolved in water.
ポキシ樹脂とフェノキシ樹脂の混合物である請求項1の
水性樹脂組成物。2. The aqueous resin composition according to claim 1, wherein the aromatic epoxy resin (D) is a mixture of an aromatic epoxy resin and a phenoxy resin.
(G)をさらに混合した請求項1又は2の水性樹脂脂組
成物。3. The aqueous resin / fat composition according to claim 1, further comprising a phenol resin and / or an amino resin (G).
(G)が、芳香族エポキシ樹脂及び/又はフェノキシ樹
脂(A)、グラフト化エポキシ樹脂(C)、芳香族エポ
キシ樹脂(D)及びアクリル系樹脂(E)から選ばれる
少なくとも一つと予備縮合したものである請求項3の水
性樹脂組成物。4. The phenol resin and / or amino resin (G) is an aromatic epoxy resin and / or a phenoxy resin (A), a grafted epoxy resin (C), an aromatic epoxy resin (D) and an acrylic resin ( The aqueous resin composition according to claim 3, which is pre-condensed with at least one selected from E).
キシ樹脂(A)に、エチレン性不飽和脂肪族カルボン酸
とこれと共重合性の不飽和単量体からなる酸価100〜
500の単量体混合物(B)とをグラフト重合させてカ
ルボン酸変性グラフト化エポキシ樹脂(C)を得、 このカルボン酸変性グラフト化エポキシ樹脂(C)を
芳香族エポキシ樹脂(D)と混合し、 次に、この混合物に酸価100〜500のカルボキシ
ル基含有アクリル系樹脂(E)を反応させて複合樹脂
(F)を得、 この複合樹脂(F)を水分散又は水溶解させることを
特徴とする水性樹脂組成物の製造法。5. An aromatic epoxy resin and / or phenoxy resin (A) having an acid value of 100 to 100, which is composed of an ethylenically unsaturated aliphatic carboxylic acid and an unsaturated monomer copolymerizable therewith.
Graft-polymerize 500 monomer mixture (B) to obtain carboxylic acid-modified grafted epoxy resin (C), and mix this carboxylic acid-modified grafted epoxy resin (C) with aromatic epoxy resin (D). Next, the mixture is reacted with a carboxyl group-containing acrylic resin (E) having an acid value of 100 to 500 to obtain a composite resin (F), and the composite resin (F) is dispersed or dissolved in water. And a method for producing an aqueous resin composition.
ポキシ樹脂とフェノキシ樹脂の混合物である請求項5の
水性樹脂組成物の製造法。6. The method for producing an aqueous resin composition according to claim 5, wherein the aromatic epoxy resin (D) is a mixture of an aromatic epoxy resin and a phenoxy resin.
(G)を、複合樹脂(F)を水分散又は水溶解させる前
又は後に加える請求項5又は6の水性樹脂組成物の製造
法。7. The method for producing an aqueous resin composition according to claim 5, wherein the phenol resin and / or amino resin (G) is added before or after the composite resin (F) is dispersed or dissolved in water.
(G)が、芳香族エポキシ樹脂及び/又はフェノキシ樹
脂(A)、グラフト化エポキシ樹脂(C)、芳香族エポ
キシ樹脂(D)及びアクリル系樹脂(E)から選ばれる
少なくとも一つと予備縮合したものである請求項7の水
性樹脂組成物の製造法。8. A phenol resin and / or an amino resin (G) is an aromatic epoxy resin and / or a phenoxy resin (A), a grafted epoxy resin (C), an aromatic epoxy resin (D) and an acrylic resin ( The method for producing an aqueous resin composition according to claim 7, which is pre-condensed with at least one selected from E).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6499594A JPH07268064A (en) | 1994-04-01 | 1994-04-01 | Water-base resin composition and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6499594A JPH07268064A (en) | 1994-04-01 | 1994-04-01 | Water-base resin composition and its production |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH07268064A true JPH07268064A (en) | 1995-10-17 |
Family
ID=13274162
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6499594A Pending JPH07268064A (en) | 1994-04-01 | 1994-04-01 | Water-base resin composition and its production |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH07268064A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998006782A1 (en) * | 1995-12-04 | 1998-02-19 | Toyo Ink Manufacturing Co., Ltd. | Aqueous dispersion composition |
US6046256A (en) * | 1996-08-12 | 2000-04-04 | Toyo Ink Manufacturing Co., Ltd. | Aqueous dispersion composition |
WO2001048105A1 (en) * | 1999-12-27 | 2001-07-05 | Kansai Paint Co., Ltd. | Water-based coating composition |
JP2009215474A (en) * | 2008-03-12 | 2009-09-24 | Toyo Ink Mfg Co Ltd | Water-based coating material composition and coated material obtained by using the same |
JP2010126638A (en) * | 2008-11-27 | 2010-06-10 | Showa Highpolymer Co Ltd | Aqueous emulsion composition of thermally crosslinkable polymer, method for producing the same, and fiber treatment agent |
JP2013076095A (en) * | 2013-01-29 | 2013-04-25 | Showa Denko Kk | Production method of aqueous emulsion composition of thermal crosslinking polymer, production method of treated paper, and production method of treated fiber |
-
1994
- 1994-04-01 JP JP6499594A patent/JPH07268064A/en active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998006782A1 (en) * | 1995-12-04 | 1998-02-19 | Toyo Ink Manufacturing Co., Ltd. | Aqueous dispersion composition |
US6046256A (en) * | 1996-08-12 | 2000-04-04 | Toyo Ink Manufacturing Co., Ltd. | Aqueous dispersion composition |
WO2001048105A1 (en) * | 1999-12-27 | 2001-07-05 | Kansai Paint Co., Ltd. | Water-based coating composition |
US6780902B2 (en) | 1999-12-27 | 2004-08-24 | Kansai Paint Co., Ltd. | Water-based coating composition |
JP2009215474A (en) * | 2008-03-12 | 2009-09-24 | Toyo Ink Mfg Co Ltd | Water-based coating material composition and coated material obtained by using the same |
JP2010126638A (en) * | 2008-11-27 | 2010-06-10 | Showa Highpolymer Co Ltd | Aqueous emulsion composition of thermally crosslinkable polymer, method for producing the same, and fiber treatment agent |
JP2013076095A (en) * | 2013-01-29 | 2013-04-25 | Showa Denko Kk | Production method of aqueous emulsion composition of thermal crosslinking polymer, production method of treated paper, and production method of treated fiber |
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