JPH0819370B2 - Coating film formation method - Google Patents
Coating film formation methodInfo
- Publication number
- JPH0819370B2 JPH0819370B2 JP5129768A JP12976893A JPH0819370B2 JP H0819370 B2 JPH0819370 B2 JP H0819370B2 JP 5129768 A JP5129768 A JP 5129768A JP 12976893 A JP12976893 A JP 12976893A JP H0819370 B2 JPH0819370 B2 JP H0819370B2
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- Prior art keywords
- weight
- coating
- coating film
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- emulsion
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明は塗膜形成方法に係り、さ
らに詳しくは有機溶剤を含む特定のアクリル樹脂エマル
ションを樹脂ビヒクルとして含むエマルション塗料によ
り素材に密着した塗膜形成方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a coating film, and more particularly to a method for forming a coating film which adheres to a material with an emulsion coating containing a specific acrylic resin emulsion containing an organic solvent as a resin vehicle.
【０００２】[0002]
【従来の技術】建築用素材、例えばモルタル、コンクリ
−ト、スレ−ト等の塗装に於ては、通常下地調整および
素材と上塗双方に対する密着性改善の目的でシ−ラ−や
プライマ−が適用され、次に防水目的の塗料、さらに塗
膜粘着性を消滅させ、耐汚染性を良好ならしめるための
トップコ−トが順次適用されている。しかしながらこの
ような方法では多数の塗料が必要であり、工数、工程が
繁雑となる。そこで必要な塗膜層を可及的に少なくし、
経済的な防水処理を可能ならしめるための提案が多数な
されている。それらの内注目すべき技術の一つに、特開
昭５２−１３６２２９号記載の発明がある。同発明で
は、α，β−モノエチレン性不飽和カルボン酸０．１〜
１０重量％、炭素数２〜１０個のアルキルアクリレ−ト
２０〜９９．５重量％、その他の共重合可能なビニルモ
ノマ−７０重量％以下からなるモノマ−混合物１００重
量部に対し、沸点が１００℃以上の有機溶剤及び／又は
可塑剤３〜５０重量部を混合したものを乳化重合して得
られた合成樹脂エマルション１００重量部に対し、無機
充填剤１０〜１５０重量部、短繊維１〜５０重量部を加
えた粘度が５００ｃｐｓ以上である塗膜防水用組成物を
適用し、トップコ−トがなくても塗膜表面の粘着性がな
く、強伸度バランスがとれ、防水性、美装仕上効果を発
揮する防水層を与えようとするものである。素材に対す
るプライマ−層のことについては何ら言及しておらず、
実施例でも上記組成物をスレ−ト板にスプレ−塗装して
塗膜評価を行なっているにすぎない。しかしながら同特
許には合成樹脂エマルションを用いる先行技術として、
素材に合成樹脂の溶液又はエマルションを塗布してプラ
イマ−層を形成し、その上に合成樹脂エマルションに基
づく防水用塗料組成物を塗装し、さらにその皮膜の表面
粘着性をなくす必要から、Ｔｇの高いトップコ−トを塗
布して仕上げる技術があったこと、このトップコ−ト層
の形成を必要とする従来の防水施行法の欠点を改良する
ために発明がなされたこと等トップコ−トの有無のみに
力点をおいており、プライマ−に関しては明確な言及を
さけている。しかしながら実際の防水施行ではかかるプ
ライマ−層は必要で、事実同特許に示された塗膜の伸度
３００〜４００％、強度２５〜３８ｋｇ／ｃｍ2程度の
ものでは素材に対する密着性が充分なものではなく、そ
の改善目的にはプライマ−層が必須であることを本発明
者らは見出している。2. Description of the Related Art In coating building materials such as mortar, concrete, and slate, a sealer or primer is usually used for the purpose of adjusting the groundwork and improving the adhesion to both the material and the topcoat. Then, a coating material for waterproofing, and then a topcoat for eliminating tackiness of the coating film and improving stain resistance are sequentially applied. However, such a method requires a large number of paints, resulting in complicated man-hours and steps. Therefore, reduce the necessary coating layer as much as possible,
Many proposals have been made to make economical waterproofing possible. Among them, one of the technologies to be noticed is the invention described in JP-A-52-136229. In the present invention, α, β-monoethylenically unsaturated carboxylic acid 0.1 to
The boiling point is 100 parts by weight with respect to 100 parts by weight of a monomer mixture consisting of 10% by weight, an alkyl acrylate having 2 to 10 carbon atoms, 20 to 99.5% by weight, and 70% by weight or less of another copolymerizable vinyl monomer. 10 to 150 parts by weight of inorganic filler and 1 to 50 short fibers per 100 parts by weight of a synthetic resin emulsion obtained by emulsion polymerization of a mixture of 3 to 50 parts by weight of an organic solvent having a temperature of not less than 0 ° C and / or a plasticizer. Applying a coating film waterproofing composition with a viscosity of 500 cps or more including parts by weight, the surface of the coating film does not have tackiness even without a topcoat, and the strength and elongation balance can be balanced, waterproofness, and decorative finish It is intended to provide a waterproof layer that is effective. No mention of the primer layer for the material,
In the examples, the above composition is merely spray-coated on a plate to evaluate the coating film. However, in the patent, as a prior art using a synthetic resin emulsion,
A synthetic resin solution or emulsion is applied to the material to form a primer layer, and a waterproof coating composition based on the synthetic resin emulsion is applied on the material to further eliminate the surface tackiness of the film. There was a technique to apply and finish a high top coat, and an invention was made to improve the drawbacks of the conventional waterproof enforcement method that requires the formation of this top coat layer. The emphasis is on, and the explicit reference to the primer is avoided. However, such a primer layer is necessary for actual waterproofing. In fact, if the coating film has an elongation of 300 to 400% and a strength of 25 to 38 kg / cm 2 shown in the same patent, sufficient adhesion to the material is obtained. However, the present inventors have found that the primer layer is essential for the improvement purpose.
【０００３】他方、アクリル樹脂の有機溶剤溶液を界面
活性剤を用いて水中で乳化して得られるエマルションを
塗料として使用することも知られており、例えば特開昭
５３−２４３８６号には芳香族ビニル系単量体１５〜６
０重量％、長鎖アクリル酸エステル系単量体２５〜５０
重量％、アルコキシアルキル（メタ）アクリルアミド３
〜３０重量％、および不飽和カルボン酸系単量体０〜１
２重量％を有機溶剤中で共重合させて得られるＴｇ−６
℃〜３０℃の共重合体溶液を、該共重合体重量に基づい
て０．２５〜３重量％の界面活性剤を用い水中で乳化
し、ｐＨを６．５〜１０に調整して得られる疎水性共重
合体からなる水性塗料組成物が示されている。しかしな
がらかかる乳化エマルションの重合体はＴｇ値が低く、
また実際に作られている重合体溶液は不揮発分濃度が約
７０％程度と高く、従って数平均分子量も比較的低いア
クリルオリゴマ−である。同特許明細書はこの水性塗料
が食品、ビ−ルおよび飲料用金属製容器のライニング剤
として従来のエポキシ樹脂、塩化ビニル−酢酸ビニル共
重合体の溶剤型塗料と同様の満足しうる性能を有してい
ると述べているが、建築用素材に対し適用できるか否か
については何の示唆も与えていない。On the other hand, it is also known to use an emulsion obtained by emulsifying a solution of an acrylic resin in an organic solvent in water with a surfactant as a coating material. For example, JP-A-53-24386 discloses aromatic compounds. Vinyl monomer 15-6
0% by weight, long-chain acrylate-based monomer 25 to 50
% By weight, alkoxyalkyl (meth) acrylamide 3
-30% by weight, and unsaturated carboxylic acid type monomer 0-1
Tg-6 obtained by copolymerizing 2% by weight in an organic solvent
C. to 30.degree. C. A copolymer solution is obtained by emulsifying in water with 0.25 to 3% by weight of a surfactant based on the weight of the copolymer and adjusting the pH to 6.5 to 10. An aqueous coating composition consisting of a hydrophobic copolymer is shown. However, the polymer of such an emulsion emulsion has a low Tg value,
The polymer solution actually produced is an acrylic oligomer having a high non-volatile concentration of about 70% and a relatively low number average molecular weight. This patent specification shows that this water-based paint has the same satisfactory performance as a solvent-based paint of a conventional epoxy resin or vinyl chloride-vinyl acetate copolymer as a lining agent for metal containers for food, beer and beverages. However, it does not give any suggestion as to whether it can be applied to building materials.
【０００４】本発明者らは事実、上記水性塗料が建築用
素材に対しては全く不満足なものであることを知見して
いる。このように従来提案されてきた有機溶剤を含むエ
マルション塗料はいづれも素材密着性が悪く、プライマ
−層を必須とするし、性能的にまた美装仕上げの点から
もトップコ−トは不可欠とされていた。The present inventors have in fact found that the above-mentioned water-based paint is completely unsatisfactory with respect to building materials. As described above, any of the conventionally proposed emulsion paints containing an organic solvent has poor material adhesion, requires a primer layer, and is required to have a top coat in terms of performance and beauty finish. Was there.
【０００５】[0005]
【発明が解決しようとする課題】そこで、トップコ−ト
のみならず、シ−ラ−やプライマ−層をも必要とするこ
となく、建築用素材に対して密着性の良好な塗膜を形成
することができるならば工数、工程の簡易化と相俟って
経済的に極めて有利であり、また特につや感のある塗膜
形成が美装目的からも望まれており、かかる要望に応え
ることが本発明目的である。Therefore, not only a top coat, but also a sealer and a primer layer are not required, and a coating film having good adhesion to a building material is formed. If it is possible, it is economically extremely advantageous in combination with the number of steps and the simplification of the process. In addition, it is desired to form a coating film with a glossy feeling from the viewpoint of beauty, and it is possible to meet such a request. It is an object of the present invention.
【０００６】[0006]
【課題を解決するための手段】本発明に従えば、上記目
的は、（イ）（ａ）α，β−エチレン性不飽和カルボン
酸及び／又は炭素数２〜８のアルキルアクリレート、
（ｂ）メチルメタクリレート、及び、（ｃ）他の共重合
可能なビニルモノマーを（ａ）／（ｂ）／（ｃ）が１〜
１４／０〜４１／４５〜９９（重量比）の比率の重合性
単量体１００重量部を８０〜１２５重量部の有機溶剤中
で、重合させて得られる、Ｓｐ８．８〜１１、Ｔｇ３０
〜１００℃、数平均分子量２０，０００〜１００，００
０の重合体溶液１００重量部と、（ロ）界面活性剤１〜
４重量部と、（ハ）脱イオン水２０〜５０重量部を乳化
したアクリル系樹脂エマルションを樹脂ビヒクルとして
含むエマルション塗料を無機質素材に直接塗布・乾燥す
ることによって達成される。According to the present invention, the above objects are (a) (a) α, β-ethylenically unsaturated carboxylic acid and / or alkyl acrylate having 2 to 8 carbon atoms,
(B) methylmethacrylate and (c) other copolymerizable vinyl monomer, wherein (a) / (b) / (c) is 1 to
Sp 8.8-11, Tg30 obtained by polymerizing 100 parts by weight of the polymerizable monomer having a ratio of 14 / 0-41 / 45-99 (weight ratio) in 80-125 parts by weight of an organic solvent.
To 100 ° C., number average molecular weight of 20,000 to 100,000
100 parts by weight of the polymer solution of 0, and (b) the surfactant 1 to
This can be achieved by directly coating and drying on an inorganic material an emulsion paint containing 4 parts by weight and (c) an acrylic resin emulsion obtained by emulsifying 20 to 50 parts by weight of deionized water as a resin vehicle.
【０００７】本発明で用いられる合成樹脂エマルション
は、（イ）（ａ）α，β−エチレン性不飽和カルボン酸
及び／又は炭素数２〜８のアルキルアクリレ−ト、
（ｂ）メチルメタアクリレ−ト、及び（ｃ）他の共重合
可能なビニルモノマ−を（ａ）／（ｂ）／（ｃ）が１〜
１４／０〜４１／４５〜９９（重量比）の比率の重合性
単量体１００重量部を８０〜１２５重量部の有機溶剤中
で、重合させて得られる、Ｓｐが８．８〜１１、Ｔｇが
３０〜１００℃、数平均分子量が２０，０００〜１０
０，０００の重合体の溶液１００重量部を（ロ）界面活
性剤１〜４重量部と（ハ）脱イオン水２０〜５０重量部
を用い撹拌混合して乳化させて製造され、塗膜伸び率が
２００％以下、抗張力が４０ｋｇ／ｃｍ2以上の塗膜を
与えうる特徴をもつ。The synthetic resin emulsion used in the present invention comprises (a) (a) an α, β-ethylenically unsaturated carboxylic acid and / or an alkyl acrylate having 2 to 8 carbon atoms,
(B) methyl methacrylate, and (c) other copolymerizable vinyl monomer, wherein (a) / (b) / (c) is 1 to
Sp of 8.8 to 11, which is obtained by polymerizing 100 parts by weight of the polymerizable monomer having a ratio of 14/0 to 41/45 to 99 (weight ratio) in 80 to 125 parts by weight of an organic solvent, Tg is 30 to 100 ° C., number average molecular weight is 20,000 to 10
It is produced by stirring and mixing 100 parts by weight of a solution of 20,000 polymer with (b) 1 to 4 parts by weight of a surfactant and (c) 20 to 50 parts by weight of deionized water to emulsify the coating film. It has a characteristic that a coating film having a rate of 200% or less and a tensile strength of 40 kg / cm 2 or more can be provided.
【０００８】アクリル樹脂のガラス転移温度（Ｔｇ）は
構成モノマ−のα，β−エチレン性不飽和単量体の種類
および量を変えることにより制御可能であるが、通常Ｔ
ｇは低いほど低温時の伸びが良く、Ｔｇが高くなると硬
くなり、また造膜最低温度（ＭＦＴ）も高くなるため造
膜不良をおこし均一な膜にならず、通常の塗料には３０
℃よりかなり低いＴｇ値のアクリル樹脂が用いられてい
る。The glass transition temperature (Tg) of the acrylic resin can be controlled by changing the type and amount of the α, β-ethylenically unsaturated monomer of the constituent monomer, but usually T
The lower the g, the better the elongation at low temperature, and the higher the Tg, the harder the film becomes, and the higher the minimum film forming temperature (MFT) becomes.
Acrylic resins with Tg values well below ° C are used.
【０００９】本発明者らは素材密着性につき検討した結
果、抗張力と伸び率が重要であり、抗張力が低いと塗膜
の凝集破壊をおこしてもろい塗膜になるし、伸び率が高
すぎると素材面からはがれ易くなること、また樹脂のＴ
ｇおよび数平均分子量も重要な役割をはたし、Ｔｇが３
０℃未満では塗膜が軟かく凝集力が低いため付着力が低
下するし、数平均分子量が２０，０００より小さくても
凝集力が低くなり付着力の低下をきたし、さらには耐候
性、耐水性等塗膜性能上も好ましくないことを知った。
さらにＴｇが３０〜１００℃といった樹脂は通常伸びが
低く、硬すぎるし、ＭＦＴが高すぎて造膜不可と考えら
れているが、有機溶剤を含有することにより造膜性を付
与し、且つ素材への浸透効果もあり均一な膜になしうる
ことを知り、それら知見に基づき本発明が完成されたも
のである。As a result of examining the adhesiveness of materials, the inventors of the present invention have found that the tensile strength and elongation rate are important. If the tensile strength is low, a cohesive failure will occur in the coating film, resulting in a brittle coating film, and if the elongation ratio is too high. It is easy to peel off from the material side, and the resin T
g and number average molecular weight also play an important role, and Tg is 3
If the temperature is lower than 0 ° C, the coating film is soft and the cohesive force is low, so that the adhesive force is reduced, and even if the number average molecular weight is less than 20,000, the cohesive force is low and the adhesive force is lowered, and further, the weather resistance and the water resistance are high. It was found that the coating properties such as properties are not preferable.
Further, it is considered that a resin having Tg of 30 to 100 ° C. usually has low elongation and is too hard, and MFT is too high to form a film. However, by containing an organic solvent, a film forming property is imparted, and a material is used. The present invention has been completed based on the knowledge that a uniform film can be formed due to the effect of penetrating into the skin.
【００１０】即ち、本発明の合成樹脂エマルションの樹
脂はＴｇが３０°〜１００℃の範囲内で、数平均分子量
は２０，０００以上のものである。より好ましい範囲と
してはＴｇ５０°〜８０℃で数平均分子量は約３０，０
００以上である。このように高いＴｇ値にかかわらず、
溶剤が造膜助剤効果をもつため造膜性が良く、素材への
浸透効果もあり、耐汚染性、付着性、初期耐水性に優れ
た塗膜を与えることができる。また重合度が高いため、
膜が強く、膜凝集力に優れていて素材密着性、耐水性、
耐候性が良好である。さらに、かかる樹脂エマルション
は、塗膜伸び率が２００％以下、好ましくは１００％以
下、抗張力が４０ｋｇ／ｃｍ2以上、好ましくは５０ｋ
ｇ／ｃｍ2以上の塗膜を与えることができる特徴をも
つ。このような特徴はＴｇが高く、且つ高分子量の樹脂
を溶剤含有の形で作ることにより達成せられ、素材密着
性と共に建築用素材に対し、極めて良好な強伸度のバラ
ンスを与えるものである。That is, the resin of the synthetic resin emulsion of the present invention has a Tg in the range of 30 ° to 100 ° C and a number average molecular weight of 20,000 or more. A more preferable range is Tg of 50 ° to 80 ° C. and a number average molecular weight of about 30,
It is 00 or more. Despite this high Tg value,
Since the solvent has a film-forming aid effect, it has a good film-forming property and also has an effect of penetrating into the material, and it is possible to provide a coating film excellent in stain resistance, adhesion and initial water resistance. Also, since the degree of polymerization is high,
Strong film, excellent film cohesion, material adhesion, water resistance,
Good weather resistance. Furthermore, such a resin emulsion has a coating film elongation of 200% or less, preferably 100% or less, and a tensile strength of 40 kg / cm 2 or more, preferably 50 k.
It has a feature that it can give a coating film of g / cm 2 or more. These characteristics are achieved by making a high-molecular-weight resin having a high Tg in a solvent-containing form, and give a very good balance of strength and elongation to building materials as well as material adhesion. .
【００１１】本発明において使用する合成樹脂エマルシ
ョンを構成するモノマ−として成分（ａ）は、α，β−
エチレン性不飽和カルボン酸及び／又は炭素数２〜８の
アルキルアクリレ−トである。α，β−エチレン性不飽
和カルボン酸の例としては、アクリル酸、メタアクリル
酸、クロトン酸、イタコン酸、マレイン酸、無水マレイ
ン酸、フマル酸等を用いることができる。炭素数２〜８
のアルキルアクリレ−トの例としては、エチルアクリレ
−ト、プロピルアクリレ−ト、ブチルアクリレ−ト、エ
チルヘキシルアクリレ−ト等を用いることができる。成
分（ｂ）はメチルメタアクリレ−トである。Component (a) as a monomer constituting the synthetic resin emulsion used in the present invention is α, β-
It is an ethylenically unsaturated carboxylic acid and / or an alkyl acrylate having 2 to 8 carbon atoms. Examples of the α, β-ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid and the like. Carbon number 2-8
Examples of the alkyl acrylate include ethyl acrylate, propyl acrylate, butyl acrylate, ethylhexyl acrylate and the like. Ingredient (b) is methylmethacrylate.
【００１２】成分（ｃ）は、成分（ａ）及び（ｂ）と共
重合可能なビニルモノマ−であり、下記の単量体の単独
もしくは、複数組み合せて用いることができる。 １）ヒドロキシル基含有単量体 例えば２−ヒドロキシエチルアクリレ−ト、ヒドロキシ
プロピルアクリレ−ト、２−ヒドロキシプロピルメタク
リレ−ト、ヒドロキシプロピルメタクリレ−ト、ヒドロ
キシブチルアクリレ−ト、ヒドロキシブチルメタクリレ
−ト、アリルアルコ−ル、メタアリルアルコ−ル等 ２）重合性アミド 例えばアクリル酸アミド、メタクリル酸アミド等 ３）重合性ニトリル 例えばアクリロニトリル、メタクリロニトリル等 ４）炭素数２以上のアルキルメタアクリレ−ト 例えばエチルメタアクリレ−ト、ｎ−ブチルメタアクリ
レ−ト、２−エチルヘキシルアメタクリレ−ト等 ５）重合性芳香族化合物 例えばスチレン、α−メチルスチレン、ビニルトルエ
ン、ｔ−ブチルスチレン等 ６）α−オレフィン 例えばエチレン、プロピレン等 ７）ビニル化合物 例えば酢酸ビニル、プロピオン酸ビニル等 ８）ジエン化合物 例えばブタジエン、イソプレン等 これらは、所望Ｔｇ値をうるため適宜選択される。The component (c) is a vinyl monomer copolymerizable with the components (a) and (b), and the following monomers can be used alone or in combination. 1) Hydroxyl group-containing monomer For example, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl. Methacrylate, allyl alcohol, methallyl alcohol, etc. 2) Polymerizable amide, such as acrylic acid amide, methacrylic acid amide, etc. 3) Polymerizable nitrile, such as acrylonitrile, methacrylonitrile, etc. 4) Alkyl meta having 2 or more carbon atoms Acrylate such as ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, etc. 5) Polymerizable aromatic compound such as styrene, α-methylstyrene, vinyltoluene, t- Butyl styrene, etc. 6) α-olefins such as ethylene, Propylene, etc. 7) vinyl compounds such as vinyl acetate, vinyl propionate, etc. 8) diene compounds such as butadiene, isoprene they are appropriately selected to sell the desired Tg value.
【００１３】本発明の（ａ）、（ｂ）及び（ｃ）の比率
は重量比で１〜１４／０〜４１／４５〜９９でなければ
ならず、成分（ａ）が１未満ではエマルションの安定性
が低下する。１４を越えると、耐水性、耐候性が低下す
る。（ｂ）が４１を越えると、付着性、耐水性が低下す
る。（ｃ）が４５未満では、耐水性が低下する。９９を
越えるとエマルションの安定性が低下する。The ratio of (a), (b) and (c) of the present invention must be 1 to 14/0 to 41/45 to 99 by weight ratio, and if the component (a) is less than 1, the emulsion is not. Stability decreases. If it exceeds 14, water resistance and weather resistance are deteriorated. If (b) exceeds 41, the adhesiveness and water resistance will deteriorate. When (c) is less than 45, the water resistance is reduced. If it exceeds 99, the stability of the emulsion decreases.
【００１４】又合成樹脂溶液が水中で乳化せしめるエマ
ルション法により作られるので、アクリル樹脂の溶解性
パラメ−タ−（Ｓｐ）値は８．８〜１１の範囲に限定さ
れ、これ以上では溶解性が大となりすぎて、所望のエマ
ルションが得られない。従って前述のモノマ−はまた所
望のＳｐ値を与えるよう適宜選択され、単独もしくは任
意の組合せで用いられる。尚、樹脂の溶解性パラメ−タ
−（δｓｐ）はＫ．Ｗ．ＳＵＨ，Ｊ．Ｍ．ＣＯＲＢＥＴ
Ｔ：Journal of Applied Polymer Science 12,2359('6
8)に示されている式１より算出することができる。な
お、式１においてｍｌは低ＳＰ溶剤を；ｍｈは高ＳＰ溶
剤を；δは溶解度パラメ−タ−を；Ｖは濁点における分
子容を示す。Further, since the synthetic resin solution is prepared by an emulsion method in which it is emulsified in water, the solubility parameter (Sp) value of the acrylic resin is limited to the range of 8.8 to 11, and the solubility is further exceeded. It becomes too large to obtain the desired emulsion. Therefore, the above-mentioned monomers are also appropriately selected so as to give a desired Sp value and used alone or in any combination. The solubility parameter (δsp) of the resin is K.K. W. SUH, J. M. CORBET
T: Journal of Applied Polymer Science 12,2359 ('6
It can be calculated from Equation 1 shown in 8). In the formula 1, ml is a low SP solvent; mh is a high SP solvent; δ is a solubility parameter; V is a molecular volume at the cloud point.
【００１５】[0015]
【数１】 [Equation 1]
【００１６】また有機溶剤としては、アクリル樹脂の溶
剤となり得るものであれば良く、トルエン、キシレン等
の芳香族炭化水素、ミネラルスピリット等の脂肪族炭化
水素、ケトン、アルコ−ル、エステル等、さらに溶剤便
覧（槙書店発行）で示されている沸点３００℃付近又は
それ以上の可塑剤及び軟化剤も溶剤として使用せられ
る。本発明では前述のエチレン性不飽和単量体が有機溶
剤中で重合開始剤を用いる通常の方法で重合せしめられ
るが、単量体と有機溶剤の重量比は前者１００に対し、
後者８０〜１２５の範囲に選定せられる。これは重合体
の分子量を調整するもので後者が８０未満では均一な重
合体溶液が得られず、また１２５をこえると均一な重合
体溶液は得られるが、分子量が低くなり、密着性をそこ
なうものである。The organic solvent may be any solvent that can serve as a solvent for acrylic resins, such as aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as mineral spirits, ketones, alcohols and esters. A plasticizer and a softening agent having a boiling point of around 300 ° C. or higher, which is shown in a solvent manual (published by Maki Shoten), can also be used as a solvent. In the present invention, the above-mentioned ethylenically unsaturated monomer is polymerized by a usual method using a polymerization initiator in an organic solvent, but the weight ratio of the monomer to the organic solvent is 100, with respect to the former 100.
The latter is selected in the range of 80 to 125. This is to adjust the molecular weight of the polymer. If the latter is less than 80, a uniform polymer solution cannot be obtained, and if it exceeds 125, a uniform polymer solution can be obtained, but the molecular weight becomes low and the adhesion is impaired. It is a thing.
【００１７】本発明に於ては、このようにして得られた
Ｓｐ８．８〜１１、Ｔｇ３０〜１００℃、数平均分子量
２０，０００〜１００，０００の重合体の溶液が次に界
面活性剤および脱イオン水を用いて後乳化手法で乳化せ
しめられ、エマルションが作られる。界面活性剤として
は、通常の型のものであるが、特にポリオキシエチレン
ノニルフェニルエ−テル、ポリオキシエチレンオクチル
フェニルエ−テル、ポリオキシエチレンラウリルエ−テ
ル、ポリオキシエチレンオレイルエ−テル、ポリオキシ
エチレントリデシルエ−テル、ポリオキシエチレンアル
キルエ−テル、ポリオキシエチレンセチルエ−テル、ポ
リオキシエチレンステアリルエ−テル等のアルキルエ−
テル型の非イオン活性剤；ポリオキシエチレンラウレ−
ト、ポリオキシエチレンオレエ−ト、ポリオキシエチレ
ンステアレ−ト等のアルキルエステル型非イオン活性
剤；ソルビタンラウレ−ト、ポリオキシエチレンソルビ
タンオレエ−ト等のソルビタン誘導体の非イオン界面活
性剤；ドデシルベンゼンスルフォン酸ナトリウム、ポリ
オキシエチレンアルキルフェニルエ−テル硫酸ナトリウ
ム等の陰イオン界面活性剤等が任意の組合せで好ましく
用いられる。In the present invention, a solution of the thus obtained polymer having Sp 8.8 to 11, Tg of 30 to 100 ° C. and a number average molecular weight of 20,000 to 100,000 is then added with a surfactant and The emulsion is emulsified by a post-emulsification technique using deionized water. The surfactant is of a usual type, but in particular, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, Alkyl ethers such as polyoxyethylene tridecyl ether, polyoxyethylene alkyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, etc.
Ter-type nonionic activator; polyoxyethylene laure
Alkyl ester type nonionic surfactants such as polyoxyethylene oleate and polyoxyethylene stearate; nonionic surface active agents of sorbitan derivatives such as sorbitan laurate and polyoxyethylene sorbitan oleate Agents; anionic surfactants such as sodium dodecylbenzene sulfonate and sodium polyoxyethylene alkylphenyl ether sulfate are preferably used in any combination.
【００１８】重合体溶液、界面活性剤および脱イオン水
の割合は通常の乳化手法により適宜選択されるが、水性
塗料の樹脂ビヒクルとして使用する為、重量比で１０
０：１〜４：２０〜５０の範囲とすることが望ましい。
このようにして得られる乳化エマルションを樹脂ビヒク
ルとして含む塗料組成物は素材密着性が良好であるので
そのままクリヤ−塗料として、あるいはこのものに顔料
および充填剤を配合し、１コ−ト用塗料として使用す
る。The proportions of the polymer solution, the surfactant and the deionized water are appropriately selected according to the usual emulsification method, but since they are used as the resin vehicle of the aqueous paint, the weight ratio is 10%.
It is desirable to set it in the range of 0: 1 to 4:20 to 50.
The coating composition containing the emulsion emulsion thus obtained as a resin vehicle has good material adhesion, so that it can be used as a clear coating as it is, or as a coating for one coat by adding a pigment and a filler to this. use.
【００１９】顔料として例えば二酸化チタンのルチル
型、アナタ−ゼ型、リトポン、酸化鉄、酸化クロ−ムな
どの無機質顔料、その他有機顔料など通常の塗料用顔料
が用いられ、またフィラ−としてはバライタ、マイカ、
炭酸カルシウム、硅砂など通常の塗料用充填剤が好適に
使用せられる。本発明の樹脂は前述の如く、素材密着性
に優れているが、顔料、充填剤を加える場合、それらの
顔料体積濃度（ＰＶＣ）を３５％以下に保つことが密着
性に対し相剰効果を示し、特に好ましいことも見出され
ている。また所望により、酸化ポリエチレン系、アマイ
ド系、三次元架橋を有するアクリル系、シリカ系などの
チクソトロピック付与効果のある任意の増粘材を加える
ことも可能である。Usable pigments are, for example, titanium dioxide rutile type, anatase type, inorganic pigments such as lithopone, iron oxide, chromium oxide, etc., and other conventional pigments for paints such as organic pigments. , Mica,
Ordinary fillers for paints such as calcium carbonate and silica are preferably used. As described above, the resin of the present invention has excellent material adhesion, but when pigments and fillers are added, maintaining the pigment volume concentration (PVC) at 35% or less has a residual effect on adhesion. It has been shown and has also been found to be particularly preferred. Also, if desired, it is possible to add any thickening agent having a thixotropic effect, such as polyethylene oxide, amide, acrylic having three-dimensional cross-linking, or silica.
【００２０】このように無機質充填剤の量にあまり影響
されずに強度が保たれるため、ＰＶＣを３５％以下とい
った低い値に保持でき、艶有塗料となし、且つ所望の塗
膜強度が維持せられる。また、本発明に於いて被塗装物
とは建築用素材、例えばモルタル、コンクリ−ト、スレ
−ト等の無機質素材である。塗料塗装面、例えばセメン
ト系の無機系塗料の塗装面、アクリル樹脂、ウレタン樹
脂等の有機系塗装面にも直接塗装できる。また、本発明
の塗膜形成方法は公知の方法で行うことができる。すな
わち、エアスプレ−塗装、エアレススプレ−塗装、ロ−
ラ−塗装等いずれの方法によっても良い。本発明で直接
塗布とは密着性向上、発泡防止として通常用いるシ−ラ
−及びプライマ−を必要とせず特定エマルション塗料を
被塗素材に直接塗布することである。塗布量は塗料組成
物の固形分、比重にもよるが、均一に厚みを付け防水層
となしうるため、塗料粘度５０〜２５０ｐｓで、およそ
０．５〜１．０ｋｇ／ｍ2が適当である。この際、この
ベ−スコ−ト層のみでも耐水性、耐候性、耐汚染性に優
れ、且つ被塗装物密着性にも優れた強じんな塗膜の形成
が可能であるが、ベ−スコ−ト層の乾燥後、再度上記塗
料組成物を塗装することが出来るので模様状塗膜の形成
も可能である。なお、模様状塗膜は、例えば玉吹き模
様、凹凸模様はタイルガンやリシンガン等の吹付ガンが
好適で、塗布量の目安は塗料組成物の固形分や比重にも
よるが、塗料粘度２００〜４００ｐｓで、およそ０．４
〜０．８ｋｇ／ｍ2が適当である。また、波状模様は多
孔質ロ−ラ−、ウ−ロ−ラ−等が好適で、その際の塗布
量の目安は塗料成分の固形分、比重にもよるが塗料粘度
１００〜２５０ｐｓで、およそ０．４〜０．８ｋｇ／ｍ
2が適当である。以上述べたように、本発明では建築用
素材に対し、シ−ラ−やプライマ−もトップコ−トも必
要とせず、１コ−トにより耐水性、耐候性、耐薬品性等
に優れ、耐汚染性にも優れた強じんな塗膜を与えること
ができ、素材密着性の上でも申し分のない塗膜形成が可
能となる。以下実施例により本発明を説明する。特にこ
とわりなき限り、部および％は重量による。As described above, since the strength is maintained without being largely affected by the amount of the inorganic filler, the PVC can be maintained at a low value of 35% or less, a glossy paint can be formed, and desired coating strength can be maintained. Sent. In the present invention, the article to be coated is an architectural material, for example, an inorganic material such as mortar, concrete, or slate. It can also be directly applied to a paint coating surface, for example, a cement-based inorganic paint coating surface, or an acrylic resin, urethane resin, or other organic coating surface. The coating film forming method of the present invention can be performed by a known method. That is, air spray coating, airless spray coating, roll coating
Any method such as color coating may be used. In the present invention, the direct application means that the specific emulsion paint is directly applied to the material to be coated without the need for a sealer and a primer which are usually used for improving adhesion and preventing foaming. The coating amount depends on the solid content and specific gravity of the coating composition, but since it can form a uniform thickness and form a waterproof layer, a coating viscosity of 50 to 250 ps and about 0.5 to 1.0 kg / m 2 are suitable. . At this time, it is possible to form a strong coating film having excellent water resistance, weather resistance, stain resistance, and adhesion to an object to be coated, even with this base coat layer alone. Since the coating composition can be applied again after the drying of the coating layer, it is possible to form a patterned coating film. The pattern coating film is preferably a spray gun such as a tile gun or a resin gun for the ball-blowing pattern and the uneven pattern. The coating amount depends on the solid content and specific gravity of the coating composition, but the coating viscosity is 200 to 400 ps. And about 0.4
Appropriately 0.8 kg / m 2 . Further, the corrugated pattern is preferably a porous roller, a wool roller, or the like, and the standard of the coating amount at that time depends on the solid content of the coating component and the specific gravity, but the coating viscosity is 100 to 250 ps. 0.4-0.8kg / m
2 is appropriate. As described above, the present invention does not require a sealer, a primer, or a top coat with respect to the building material, and one coat is excellent in water resistance, weather resistance, chemical resistance, etc. A strong coating film with excellent stain resistance can be provided, and it is possible to form a coating film with satisfactory material adhesion. Hereinafter, the present invention will be described with reference to examples. Unless stated otherwise, parts and percentages are by weight.
【００２１】[0021]
参考例１ ３ｌの４つ口フラスコに温度計、撹拌器、窒素導入管、
滴下ロ−トを備え、キシレン４００ｇを仕込み、８５℃
に内温を保つ。メチルメタアクリレ−ト４０５ｇ、イソ
ブチルメタアクリレ−ト５８３ｇ、メタアクリル酸１２
ｇを均一に混合し、さらにｔ−ブチルパ−オキシ２−エ
チルヘキサノエ−ト７ｇを加えて混合した液を窒素を吹
き込みながら３時間かけて滴下し、８５℃で撹拌しなが
ら重合を行なった。滴下終了後、キシレン８００ｇを３
時間かけて滴下した。その後、さらに８５℃で２時間反
応を行なった。不揮発分４５．４％、数平均分子量４
２，０００、Ｔｇ（計算値）＝７０℃、Ｓｐ値１０．０
の無色透明な共重合体液（Ａ）を得た。Reference Example 1 A thermometer, a stirrer, a nitrogen introduction tube,
Equipped with dropping funnel, charged with 400 g of xylene, 85 ° C
Keep the internal temperature at. Methyl methacrylate 405 g, isobutyl methacrylate 583 g, methacrylic acid 12
g was evenly mixed, 7 g of t-butylperoxy-2-ethylhexanoate was further added, and the mixed solution was added dropwise over 3 hours while blowing nitrogen, and polymerization was carried out at 85 ° C. with stirring. After the dropping is completed, 800 g of xylene is added to 3
It dripped over time. Then, the reaction was further performed at 85 ° C. for 2 hours. Nonvolatile matter 45.4%, number average molecular weight 4
2,000, Tg (calculated value) = 70 ° C., Sp value 10.0
To obtain a colorless and transparent copolymer liquid (A).
【００２２】参考例２〜４，６ 参考例１と同様な方法で行ない、モノマー、有機溶剤の
組成を表１の如く変更して、無色透明な共重合体液
（Ｂ）、（Ｃ）、（Ｄ）、（Ｆ）及び（Ｇ）をそれぞれ
得た。 参考例５ 参考例１と同様な方法で行ない、重合開始剤ｔ−ブチル
パーオキシ２−エチルヘキサノエートの量を調製して、
無色透明な共重合体液（Ｅ）を得た。Reference Examples 2 to 4, 6 The same procedure as in Reference Example 1 was carried out. The composition of the monomer and the organic solvent was changed as shown in Table 1, and the colorless and transparent copolymer liquids (B), (C), ( D) , (F) and (G) were obtained respectively . Reference Example 5 The procedure of Reference Example 1 was repeated to prepare an amount of a polymerization initiator t-butylperoxy 2-ethylhexanoate,
A colorless and transparent copolymer liquid (E) was obtained.
【００２３】[0023]
【表１】 [Table 1]
【００２４】製造例１ 乳化エマルションの調製 乳化エマルション−（１） 共重合体液（Ａ）１０００ｇと非イオン活性剤Ｎｅｗｃ
ｏｌ１７１０（日本乳化剤社製）３０ｇをディスパ−で
撹拌しながらイオン交換水３００ｇを徐々に加えて、エ
マルション化した。さらにアンモニア水を加えてｐＨ＝
８に調製し、乳化エマルション−（１）を得た。不揮発
分３６％、エマルション平均粒径１．０μProduction Example 1 Preparation of Emulsion Emulsion- (1) 1000 g of copolymer liquid (A) and nonionic activator Newc.
While stirring 30 g of ol1710 (manufactured by Nippon Emulsifier Co., Ltd.) with a disperser, 300 g of ion-exchanged water was gradually added to form an emulsion. Ammonia water is added and the pH =
8 to obtain an emulsion emulsion- (1). Nonvolatile content 36%, emulsion average particle size 1.0μ
【００２５】製造例２〜７ 乳化エマルション−（２）〜（７） 乳化エマルション−（１）の調製と同様の方法で行な
い、乳化エマルション−（２）〜（７）を得た。配合
量、不揮発分、エマルション平均粒径は表２に示す。Production Examples 2 to 7 Emulsion emulsion- (2) to ( 7 ) Emulsion emulsion- (2) to ( 7 ) were obtained in the same manner as in the preparation of emulsion emulsion- (1). The compounding amount, the non-volatile content, and the emulsion average particle size are shown in Table 2.
【００２６】分散ペ−ストの調製 ＳＭＡ−１４４０（アルコケミカル社製、スチレン・マ
レイン酸エステル分散剤）１５部、二酸化チタン１００
部、炭酸カルシウム（ルミナス丸尾カルシウム社製）１
００部、水７０部を混合分散して、分散ペ−ストを得
た。Preparation of dispersion paste SMA-1440 (manufactured by Arco Chemical Co., styrene-maleic acid ester dispersant) 15 parts, titanium dioxide 100
Part, calcium carbonate (made by Luminous Maruo Calcium Co.) 1
00 parts and 70 parts of water were mixed and dispersed to obtain a dispersion paste.
【００２７】[0027]
【表２】 [Table 2]
【００２８】実施例１ 分散ペ−スト２６部、乳化エマルション−（１）１００
部、消泡剤１部、増粘剤２部を混合撹拌して、塗料組成
物を得た。この塗料組成物はＰＶＣ＝１３、粘度３００
Ｐ（ポイズ）であった。塗料組成物を１８０ＰＳ（ポイ
ズ）に調整し、スレ−ト板上に吹付ガンで乾燥膜厚５０
０μになる様に塗装し、塗膜を形成させた。室温で２週
間乾燥後の光沢は６０度グロスで７０、伸び率５％、抗
張力７０ｋｇ／ｃｍ2、アドヒ−ジョンテスタ−で付着
力を測定したところ２０ｋｇ／ｃｍ2であった。またこ
の塗膜のピ−リング付着性評価は、素材から剥離し、密
着性は良好であった。更に塗膜硬度は鉛筆硬度でＨＢで
あった。また、この塗料組成物をベ−スコ−トとし、お
よそ一日乾燥後、この上に２４０ＰＳに調整した塗料組
成物をタイルガンで０．６ｋｇ／ｍ2塗装し、凹凸模様
塗膜を形成させた。これを室温で２週間乾燥後、２０℃
水中に１週間浸漬した後塗膜状態をＡＳＴＭ法で判定し
たところ、塗膜のふくれは全く見られなかった。Example 1 26 parts of dispersion paste, emulsion emulsion- (1) 100
Parts, 1 part antifoaming agent and 2 parts thickener were mixed and stirred to obtain a coating composition. This coating composition has PVC = 13, viscosity 300
It was P (poise). The coating composition was adjusted to 180 PS (poise), and the dry film thickness was 50 with a spray gun on the plate.
Coating was performed so that the thickness became 0 μ, and a coating film was formed. After being dried at room temperature for 2 weeks, the gloss was 70 at 60 degree gloss, the elongation rate was 5%, the tensile strength was 70 kg / cm 2 , and the adhesion was 20 kg / cm 2 as measured by an adhesion tester. Further, the peeling adhesion of this coating film was peeled from the material and the adhesion was good. Further, the coating film hardness was HB in terms of pencil hardness. Further, this coating composition was used as a base coat, and after drying for about one day, the coating composition adjusted to 240 PS was coated thereon with a tile gun at 0.6 kg / m 2 to form an uneven pattern coating film. . Dry this at room temperature for 2 weeks, then at 20 ℃
After immersion in water for 1 week, the state of the coating film was judged by the ASTM method, and no swelling of the coating film was observed.
【００２９】実施例２〜５ 実施例１と同様の方法で塗料組成物を得て塗膜の形成を
行った。配合及び物性評価は表３の結果を得た。Examples 2 to 5 A coating composition was obtained in the same manner as in Example 1 to form a coating film. The results of Table 3 were obtained for the blending and evaluation of physical properties.
【００３０】比較例１〜３ 実施例１と同様の方法で塗料組成物を得て塗膜の形成を
行った。配合及び物性評価は表３の結果を得た。Comparative Examples 1 to 3 A coating composition was obtained in the same manner as in Example 1 to form a coating film. The results of Table 3 were obtained for the blending and evaluation of physical properties.
【００３１】比較例４ 市販の合成樹脂エマルション系複層仕上塗材の一例とし
て、「ダイヤＥタイル主材（恒和化学工業株式会社
製）」を１５０ＰＳ（ポイズ）に調整し、アクリル系シ
−ラ−を入れスレ−ト板に吹付ガンで乾燥膜厚５００μ
になる様に塗装し塗膜を形成させ、実施例１と同様に物
性評価を実施した。また更に、この塗膜上に２１０ＰＳ
に調整した「ダイヤＥタイル主材」をタイルガンで１．
０ｋｇ／ｍ2塗装し、凹凸模様塗膜を形成させた。物性
評価は表３の結果を得た。Comparative Example 4 As an example of a commercially available synthetic resin emulsion-based multi-layer finish coating material, “Diamond E tile main material (manufactured by Kowa Chemical Industry Co., Ltd.)” was adjusted to 150 PS (poise) to prepare an acrylic sheet. Insert the liner and spray on the plate with a spray gun to dry film thickness 500μ
Was coated to form a coating film, and the physical properties were evaluated in the same manner as in Example 1. Furthermore, 210PS on this coating
"Diamond E tile main material" adjusted to 1. with a tile gun.
The coating was applied at 0 kg / m 2 to form an uneven coating film. As for the physical property evaluation, the results shown in Table 3 were obtained.
【００３２】比較例５ 市販の合成樹脂エマルション単層弾性仕上材の一例とし
て、「アレスゴムテックス（関西ペイント株式会社
製）」を１６０ＰＳに調整し、塩ゴム系シ−ラ−を入れ
スレ−ト板に多孔質ロ−ラ−で乾燥膜厚４００μになる
様に塗装し塗膜を形成させ、実施例１と同様に物性評価
を実施した。また更に、この塗膜上に６０ＰＳに調整し
た「アレスゴムタイル」を中毛ウ−ロ−ラ−で０．２５
ｋｇ／ｍ2塗装し、さざ波模様塗膜を形成させた。物性
評価は表３の結果を得た。Comparative Example 5 As an example of a commercially available synthetic resin emulsion single layer elastic finishing material, “Ales Rubber Tex (Kansai Paint Co., Ltd.)” was adjusted to 160 PS and a salt rubber sealer was put in to give a sheet. The plate was coated with a porous roller to a dry film thickness of 400 μm to form a coating film, and the physical properties were evaluated in the same manner as in Example 1. Furthermore, "Ares rubber tile" adjusted to 60 PS on this coating film is 0.25 with a medium wool roller.
It was applied with kg / m 2 to form a rippled coating film. As for the physical property evaluation, the results shown in Table 3 were obtained.
【００３３】塗膜の試験方法は次の方法によって行っ
た。 １．伸び率、抗張力の測定 ＪＩＳ Ａ ６９１０に準拠して塗料を２ｍｍに塗布
し、１４日間室温で乾燥した後、ダンベル状２号形に成
形したものを試験片とした。 ２．付着力の測定 塗料をスレ−ト板にドクタ−ブレ−ドで２ｍｍに塗布
し、室温で２週間乾燥後、アドヒ−ジョンテスタ−で付
着力を測定した。 ３．ピ−リング付着性 塗膜を巾５ｍｍ、長さ１０ｍｍにカッティングしてカッ
タ−で塗膜の剥れ具合を測定し、次のように評価した。 〇…素材から剥離するもの ×…素材と塗膜の界面で剥離するもの ４．鉛筆硬度 塗料をスレ−ト板にドクタ−ブレ−ドで２ｍｍに塗布
し、室温で２週間乾燥後、ＪＩＳ−Ｋ−５４００−８−
４法に準じて測定した。 ５．耐水性 スレ−ト板上にベ−スコ−トを形成し更に模様塗膜を形
成させた試験片を室温で２週間乾燥後、２０℃水中に７
日間浸漬し、取出し後の塗膜状態をＡＳＴＭ法で測定し
た。 ただし、比較例４〜５は、比較例で述べた条件で塗布し
た。The coating film was tested by the following method. 1. Measurement of Elongation Rate and Tensile Strength A coating material was applied to 2 mm in accordance with JIS A 6910, dried at room temperature for 14 days, and then molded into a dumbbell-shaped No. 2 shape to give a test piece. 2. Measurement of Adhesion Force A coating material was applied to a plate by a doctor blade to a thickness of 2 mm, dried at room temperature for 2 weeks, and then the adhesion force was measured with an adhesion tester. 3. Peeling Adhesion The coating film was cut into a width of 5 mm and a length of 10 mm, and the degree of peeling of the coating film was measured with a cutter, and evaluated as follows. ○… Peeling from the material ×… Peeling at the interface between the material and the coating film 4. Pencil hardness A coating of 2 mm was applied on a plate with a doctor blade and dried at room temperature for 2 weeks, and then JIS-K-5400-8-
It measured according to the 4th method. 5. A test piece on which a base coat was formed on a water resistant plate and a pattern coating film was further formed was dried at room temperature for 2 weeks and then placed in water at 20 ° C. for 7 weeks.
After being immersed for a day, the state of the coating film after being taken out was measured by the ASTM method. However, Comparative Examples 4 to 5 were applied under the conditions described in Comparative Example.
【００３４】[0034]
【表３】 [Table 3]
【００３５】[0035]
【発明の効果】以上の通り本発明により形成される塗膜
はプライマ−もトップコ−トも必要とせず、１種類の塗
料で耐水性、耐候性、耐汚染性に優れ、且つ被塗物への
密着性にも優れ、その結果、塗膜が被塗物の保護と美装
性を保持することが可能となる。また、水で希釈して粘
度を調整することにより、ロ−ラ−塗り、スプレ−塗
り、ハケ塗り等の使用が可能で、下地調整材、建築内外
装仕上げ材となり、１つの塗料で単層仕上げ、複層仕上
げが可能となった。As described above, the coating film formed according to the present invention does not require a primer or a top coat and is excellent in water resistance, weather resistance and stain resistance with one type of coating material, and can be applied to an object to be coated. The adhesiveness is excellent, and as a result, the coating film can protect the article to be coated and maintain the appearance. In addition, it is possible to use roller coating, spray coating, brush coating, etc. by diluting with water to adjust the viscosity, and it becomes a base conditioning material and a building interior / exterior finishing material. Finishing and multi-layer finishing are now possible.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 5/02 ＰＰＵ Continuation of front page (51) Int.Cl. 6 Identification number Office reference number FI technical display area C09D 5/02 PPU
Claims (1)
ルボン酸及び／又は炭素数２〜８のアルキルアクリレー
ト、（ｂ）メチルメタクリレート、及び、（ｃ）他の共
重合可能なビニルモノマーを（ａ）／（ｂ）／（ｃ）が
１〜１４／０〜４１／４５〜９９（重量比）の比率の重
合性単量体１００重量部を８０〜１２５重量部の有機溶
剤中で、重合させて得られる、Ｓｐ８．８〜１１、Ｔｇ
３０〜１００℃、数平均分子量２０，０００〜１００，
０００の重合体溶液１００重量部と、 （ロ）界面活性剤１〜４重量部と、 （ハ）脱イオン水２０〜５０重量部を乳化したアクリル
系樹脂エマルションを樹脂ビヒクルとして含むエマルシ
ョン塗料を無機質素材に直接塗布・乾燥することを特徴
とする塗膜形成方法。1. (a) (a) α, β-ethylenically unsaturated carboxylic acid and / or alkyl acrylate having 2 to 8 carbon atoms, (b) methyl methacrylate, and (c) other copolymerizable 100 parts by weight of the vinyl monomer (a) / (b) / (c) is 1 to 14/0 to 41/45 to 99 (weight ratio) and 80 to 125 parts by weight of an organic solvent. In, obtained by polymerizing, Sp8.8 ~ 11, Tg
30 to 100 ° C., number average molecular weight of 20,000 to 100,
100 parts by weight of a polymer solution of 000, (b) 1 to 4 parts by weight of a surfactant, and (c) 20 to 50 parts by weight of deionized water as an inorganic resin emulsion paint containing an acrylic resin emulsion as a resin vehicle. A coating film forming method characterized by directly coating and drying the material.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61119891A JPH0739556B2 (en) | 1986-05-23 | 1986-05-23 | Emulsion coating composition |
| JP5129768A JPH0819370B2 (en) | 1986-05-23 | 1993-05-31 | Coating film formation method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61119891A JPH0739556B2 (en) | 1986-05-23 | 1986-05-23 | Emulsion coating composition |
| JP5129768A JPH0819370B2 (en) | 1986-05-23 | 1993-05-31 | Coating film formation method |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61119891A Division JPH0739556B2 (en) | 1986-05-23 | 1986-05-23 | Emulsion coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0673328A JPH0673328A (en) | 1994-03-15 |
| JPH0819370B2 true JPH0819370B2 (en) | 1996-02-28 |
Family
ID=26457544
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61119891A Expired - Lifetime JPH0739556B2 (en) | 1986-05-23 | 1986-05-23 | Emulsion coating composition |
| JP5129768A Expired - Fee Related JPH0819370B2 (en) | 1986-05-23 | 1993-05-31 | Coating film formation method |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61119891A Expired - Lifetime JPH0739556B2 (en) | 1986-05-23 | 1986-05-23 | Emulsion coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JPH0739556B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0827410A (en) * | 1994-07-18 | 1996-01-30 | Mitsui Toatsu Chem Inc | Acrylic resin composition for paint |
| DE10011643A1 (en) | 2000-03-10 | 2001-09-13 | Basf Ag | Aqueous high-gloss emulsion paint with a long open time |
| KR20010100297A (en) * | 2000-04-11 | 2001-11-14 | 이계안 | An extrusion-type protective coating film composition containing acryl resin |
| JP5405791B2 (en) * | 2008-04-22 | 2014-02-05 | アイカ工業株式会社 | Water-based coating composition |
| CA2733421C (en) * | 2008-08-08 | 2013-06-11 | Saint-Gobain Performance Plastics Corporation | Thermal spray masking tape |
| US9434137B2 (en) | 2008-08-08 | 2016-09-06 | Saint-Gobain Performance Plastics Corporation | Thermal spray masking tape |
| KR102036737B1 (en) * | 2018-02-20 | 2019-10-28 | (주)시공사우리 | Coating materials and flooring sheet using color sand and acrylic resin |
| CN114093553A (en) * | 2021-11-18 | 2022-02-25 | 江苏聚盈新材料科技有限公司 | Organic carrier for crystalline silicon solar cell front silver paste, preparation method, application and method for evaluating conversion efficiency of cell piece |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51122131A (en) * | 1975-04-18 | 1976-10-26 | Nagoya Yukagaku Kogyo Kk | Surface coating compound for plastics |
| JP2542813B2 (en) * | 1985-12-05 | 1996-10-09 | 大日本インキ化学工業株式会社 | Resin composition for paint |
-
1986
- 1986-05-23 JP JP61119891A patent/JPH0739556B2/en not_active Expired - Lifetime
-
1993
- 1993-05-31 JP JP5129768A patent/JPH0819370B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62277474A (en) | 1987-12-02 |
| JPH0673328A (en) | 1994-03-15 |
| JPH0739556B2 (en) | 1995-05-01 |
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