JPS6011503A - Water-dispersed resin composition - Google Patents
Water-dispersed resin compositionInfo
- Publication number
- JPS6011503A JPS6011503A JP11998183A JP11998183A JPS6011503A JP S6011503 A JPS6011503 A JP S6011503A JP 11998183 A JP11998183 A JP 11998183A JP 11998183 A JP11998183 A JP 11998183A JP S6011503 A JPS6011503 A JP S6011503A
- Authority
- JP
- Japan
- Prior art keywords
- water
- polymerizable
- resistance
- emulsion
- dibasic acid
- 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.)
- Pending
Links
Abstract
Description
【発明の詳細な説明】
本発明は水分散型樹脂組成物に係り、さらに詳しくは耐
水性、耐沸騰水性、耐アルカリ性が格段に改善され、耐
ブロッキング性、密着性、耐溶剤性等に優れた皮膜を形
成する水分散型樹脂組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-dispersed resin composition, and more specifically, it has significantly improved water resistance, boiling water resistance, alkali resistance, and excellent blocking resistance, adhesion, solvent resistance, etc. The present invention relates to a water-dispersed resin composition that forms a film.
耐水性等に優れた皮膜を形成しうる樹脂組成物を得るた
め、コロイダルシリカと界面活性剤を併用し、界面活性
剤を減らして乳化重合手法により樹脂エマルションを得
ることは公知である。就中特公昭５６−９５２４には重
合性全有機上ツマー１００重量部に対し、１〜１０重量
部の重合性二塩基酸、０．５〜５重吊部の少なくとも１
個のＮ−置換メヂロール基を含有するアクリル酸アミド
誘導体もしくはメタクリル酸アミド誘導体、８５〜９８
．５重量部のスヂレンおよびスヂレン誘導体、炭素数１
〜８の直鎖または側鎖を有するアルコールのアクリル酸
エステルもしくはメタクリル酸エステル、またはアクリ
ロニトリルの１種または２種以上からなる混合物を、０
．１〜１重量部のアルコール硫酸エステル塩類、または
アルキルアリルスルホン酸塩類、および固形分で０．２
〜５重量部のコロイダルシルカの存在下で懸濁重合して
得られる水分散型樹脂組成物が開示され、このものは耐
水性、耐沸騰水性、合成樹脂および金属への密着性、耐
薬品性、耐溶剤性、耐ブロッキング性に優れたものとし
て注目されている。In order to obtain a resin composition capable of forming a film with excellent water resistance, etc., it is known to use colloidal silica and a surfactant in combination, reduce the amount of the surfactant, and obtain a resin emulsion by emulsion polymerization. In particular, in Japanese Patent Publication No. 56-9524, 1 to 10 parts by weight of a polymerizable dibasic acid and at least 1 part of a polymerizable dibasic acid of 0.5 to 5 times per 100 parts by weight of a polymerizable total organic compound.
Acrylic acid amide derivatives or methacrylic acid amide derivatives containing N-substituted medylol groups, 85-98
．． 5 parts by weight of styrene and styrene derivatives, 1 carbon number
A mixture consisting of one or more types of acrylic ester or methacrylic ester of an alcohol having a linear or side chain of ~8, or acrylonitrile,
．． 1 to 1 part by weight of alcohol sulfate ester salts or alkylaryl sulfonates, and 0.2 parts by weight of solids.
A water-dispersed resin composition obtained by suspension polymerization in the presence of ~5 parts by weight of colloidal silica is disclosed, and this composition has excellent water resistance, boiling water resistance, adhesion to synthetic resins and metals, and chemical resistance. It is attracting attention for its excellent solvent resistance and blocking resistance.
同特許ではコロイダルシリカの併用で界面活性剤の使用
量をごく少量におさえることの外に、全七ツマ−に対し
特定割合の重合性二塩基酸および特定桁の少なくとも１
コのＮ−置換メチロール基を有する（メタ）アクリル酸
アミド誘導体を使用することにより特に耐水性の良好な
、しかも安定な系のエマルションを得ている点に特徴を
有している。In addition to suppressing the amount of surfactant used in combination with colloidal silica to a very small amount, the patent also describes the use of a specific proportion of polymerizable dibasic acid and at least one
The present invention is characterized in that by using a (meth)acrylic acid amide derivative having an N-substituted methylol group, a stable emulsion with particularly good water resistance can be obtained.
本発明者らは水分散型樹脂組成物で耐水性の特に優れた
塗膜を与えうる樹脂組成物を得べく研究を続けるうち、
少なくとも１種の共役性不飽和結合を有する重合性七ツ
マ−と重合性二塩基酸とからなるモノマーを、アニオン
系界面活性剤とコロイダルシリカの存在下に乳化重合さ
せ、界面活性剤と、重合性二塩基酸の全モノマーに対す
る割合を極めて少量におさえることにより、耐水性、耐
沸ｌｌｋ水性、耐アルカリ性が格段に改善され、しかも
優れた耐ブロッキング性、密着性、耐溶剤性を有する塗
膜を！ゴえうる樹脂組成物が得られることを見出し本発
明を完成するに至った。The present inventors continued their research to obtain a water-dispersed resin composition capable of providing a coating film with particularly excellent water resistance.
A monomer consisting of a polymerizable heptamer having at least one type of conjugated unsaturated bond and a polymerizable dibasic acid is emulsion polymerized in the presence of an anionic surfactant and colloidal silica, and the surfactant and polymerization By keeping the ratio of dibasic acid to the total monomers to an extremely small amount, the water resistance, boiling water resistance, and alkali resistance are significantly improved, and the coating film has excellent blocking resistance, adhesion, and solvent resistance. of! The present invention was completed by discovering that a resin composition that can be peeled off can be obtained.
即ち本発明は重合性二塩基酸を０．１重量％〜１．０未
満重量％の割合で含む少なくとも１種の共役ｆ１不飽和
結合を有する重合性モノマーを、全モノマーに対し０．
１〜１＠偵％のアニオン系界面活性剤と固形分で・０．
１〜４重市％のコロイダルシリカの存在下に乳化重合さ
けて得られる水分散型樹脂組成物を掟供するものである
。。That is, the present invention uses a polymerizable monomer having at least one type of conjugated f1 unsaturated bond containing a polymerizable dibasic acid in a proportion of 0.1% to less than 1.0% by weight based on the total monomers.
1 to 1% of anionic surfactant and solid content of 0.
A water-dispersed resin composition obtained by emulsion polymerization in the presence of 1 to 4% colloidal silica is prepared. .
本発明において使用される重合性二塩基酸は、イタコン
酸、フマル酸、マレイン酸等であり、その他の水性媒体
中で重合せしめられるべき七ツマ−の主体は少なくとも
１種の共役性不飽和結合を有する重合性モノマーである
。これら共（骨性不飽和結合を右する重合性モノマーは
下記のごときグループに大別される。The polymerizable dibasic acids used in the present invention are itaconic acid, fumaric acid, maleic acid, etc., and the main component of the heptadamine to be polymerized in other aqueous media is at least one conjugated unsaturated bond. It is a polymerizable monomer having the following. These polymerizable monomers that form bony unsaturated bonds are roughly divided into the following groups.
１）カルボキシル基含有単量体：
例えばアクリル酸、メタクリル酸等、
２）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−１〜、ヒドロキ
シプロピルアクリレート、２−ヒドロキシエチルアクリ
レート、ヒドロキシプロピルアクリレート、ヒドロキシ
エチルアクリレート、ヒドロキシブチルヌククリ１ノー
ト、アリルアルコ−３−
ル、メタアリルアルコール等、
３）含窒素アルキルアクリレートもしくはメタクリレ−
１〜
例えばジメチルアミノエチルアクリレ−１−、ジメチル
アミノエチルアクリレート等
４）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
５）手合性ニトリル
例えばアクリロニトリル、メタクリレートリル等
６）アルキルアクリレートもしくはメタクリレート
例えばメチルアクリレート、メチルメタクリレ−１〜、
エチルアクリレート、エチルメタクリレート、叶ブチル
アクリレート、ｎ−ブチルメタクリレート、２−エチル
へキシルアクリレート等７）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
４−
８）ビニル化合物
例えば酢酸ビニル、プロピオン酸ビニル等９）ジエン化
合物
例えばブタジェン、イソプレン等
これらは中独あるいは任意の組合わせで用いられる。1) Carboxyl group-containing monomers: e.g. acrylic acid, methacrylic acid, etc. 2) Hydroxyl group-containing monomers: e.g. 2-hydroxyethyl acrylate-1, hydroxypropyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate , hydroxyethyl acrylate, hydroxybutyl nucleol, allyl alcohol, methalyl alcohol, etc., 3) Nitrogen-containing alkyl acrylate or methacrylate
1 - For example, dimethylaminoethyl acrylate-1-, dimethylaminoethyl acrylate, etc. 4) Polymerizable amides, such as acrylamide, methacrylic acid amide, etc. 5) Hand-processable nitriles, such as acrylonitrile, methacrylateril, etc. 6) Alkyl acrylates or methacrylates, such as methyl Acrylate, methyl methacrylate-1~,
Ethyl acrylate, ethyl methacrylate, butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, etc.7) Polymerizable aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, etc.4-8) Vinyl Compounds such as vinyl acetate, vinyl propionate, etc. 9) Diene compounds such as butadiene, isoprene, etc. These may be used in China or Germany or in any combination.
従来、例えば特公昭５６−９５２４号等では重合性二塩
基酸は全モノマーに対し１重量％以上使用せねば重合進
行性の点で問題があるものと考えられていた。しかしな
がら本発明者らは全モノマーに対し重合性二塩基酸の割
合を１重量％以下にＩノでも反応は容易に進行し、かえ
って皮膜の官能基数を減少させる結果、耐水性、耐アル
カリ性等が格段に改善されることを見出した。また重合
性二塩基酸の割合が少なくなると系の安定性がそこなわ
れると考えられていたが、本発明者らは従来法の下限す
なわち全モノマーに対し１重量％以下でも安定なエマル
ションが得られることを見出した。かくして本発明にお
いては重合性二塩基酸が全モノマーに対し０．１ｉ１１
％〜１．０未満重量％の割合で用いられ、特定量の界面
活性剤おＪ：びコロイダルシリカの存在下に重合性モノ
マーを乳化重合することにより安定なエマルションでし
かも耐水性、耐アルカリ性の格段に改善された樹脂組成
物が得られるのである。重合性二塩基酸が全七ツマ−の
０．１重間％に満たぬ場合には本発明目的が達成せられ
ず、他方１重量％以上では従来技術程度の耐水性、耐ア
ルカリ性しか得られない。Conventionally, for example, in Japanese Patent Publication No. 56-9524, it has been thought that polymerizable dibasic acids must be used in an amount of 1% by weight or more based on the total monomers or there will be problems in terms of polymerization progress. However, the present inventors found that even if the ratio of polymerizable dibasic acid to the total monomer was 1% by weight or less, the reaction would proceed easily, and as a result, the number of functional groups in the film would be reduced, resulting in poor water resistance, alkali resistance, etc. I found that it was significantly improved. In addition, it was thought that the stability of the system would be compromised if the proportion of polymerizable dibasic acid decreased, but the present inventors were able to obtain a stable emulsion even at the lower limit of the conventional method, that is, 1% by weight or less based on the total monomers. I found out that it can be done. Thus, in the present invention, the amount of polymerizable dibasic acid is 0.1i11 with respect to all monomers.
% to less than 1.0% by weight, and by emulsion polymerizing a polymerizable monomer in the presence of a specific amount of surfactant and colloidal silica, a stable emulsion with water resistance and alkali resistance can be obtained. A significantly improved resin composition can be obtained. If the content of the polymerizable dibasic acid is less than 0.1% by weight of the total seven polymers, the object of the present invention cannot be achieved, while if it is more than 1% by weight, only the water resistance and alkali resistance comparable to the conventional technology can be obtained. do not have.
本発明で使用せられる乳化剤は一般にアニオン系界面活
性剤として知られるもので例えばラウリルスルボン酸す
］〜リウム等のアルコールｖＡ酸エステル、ドデシルベ
ンゼンスルホン酸ナトリウム等のアルキルアリールスル
ホン酸塩、等の任意のものでありうる。界面活性剤量は
全七ツマ−に対し０゜１〜１．０重量％の範囲内である
。界面活性剤があまりにも生部でありすぎると分散液が
不安定になるし、また１重量％をこえると生成樹脂の耐
水性その他に影響を及ぼし好ましくない。本発明におい
ては上記範囲内のアニオン界面活性剤が少量のコロイダ
ルシリカと組合わせて用いられ極めて安定化されたエマ
ルションが得られる。コロイダルシリカは負に帯電した
無定形シリカが水中に分散してコローｒド状をなしてい
るもので例えば各種グレードのスノーテックスにッサン
化学製品）、カタロイド（触媒化成工業製品）、ルドッ
クス（デコボン社製品）等が市販されており、それらが
好都合に使用せられる。しかしながらｐｌ−１が１０を
こえると重合反応が進行しにくくなる傾向がみられるの
でｐＨ１０以下のものを選択づることが好ましい。コロ
イダルシリカは固形分換算で、全モノマーに対し０．１
〜４手量％の範囲内で使用ぜられる。というのは０．１
％未満ではブツが発生し乳化剤との相乗効果が発揮され
ず、また４％をこえると皮膜外観がイこなわれる傾向が
認められるからである。The emulsifier used in the present invention is generally known as an anionic surfactant, such as alcohol vA acid esters such as lauryl sulfonate, alkylaryl sulfonates such as sodium dodecylbenzenesulfonate, etc. It can be anything. The amount of surfactant is within the range of 0.1 to 1.0% by weight based on the total weight of the surfactant. If the surfactant is present too much, the dispersion will become unstable, and if it exceeds 1% by weight, it will affect the water resistance and other properties of the resulting resin, which is not preferable. In the present invention, an anionic surfactant within the above range is used in combination with a small amount of colloidal silica to obtain an extremely stabilized emulsion. Colloidal silica is negatively charged amorphous silica dispersed in water to form a colloidal shape.For example, various grades of Snowtex, Nissan Chemical Products), Cataloid (Catalyst Chemical Industry Products), Ludox (Decobon Co., Ltd.) products) etc. are commercially available and are conveniently used. However, if pl-1 exceeds 10, the polymerization reaction tends to be difficult to proceed, so it is preferable to select one with a pH of 10 or less. Colloidal silica is 0.1% of all monomers in terms of solid content.
It is used within the range of ~4%. That is 0.1
If it is less than 4%, lumps will occur and the synergistic effect with the emulsifier will not be exhibited, and if it exceeds 4%, the appearance of the film tends to be poor.
本発明においては上述の如く選定された特定割合の重合
性二塩基酸を含む共役性不飽和結合を有する重合性七ツ
マ−が、特定■のアニオン界面活性剤ならびにコロイダ
ルシリカの存在下に、乳化重合手法で重合せしめられ水
分散型樹脂組成物が７−
作られる。乳化重合は常法に従い実施せられるが、すで
に述べた如く重合性二基Ｍ酸の割合が少ない場合、例え
ば全モノマーに対し０．１〜０．５型間％程度である場
合には、重合反応での比較的後段にこの二塩基酸を添加
し、エマルション粒子の表面付近に該酸成分を集中する
ことが系の安定性を保つうえで特に好ましい。In the present invention, a polymerizable heptamine having a conjugated unsaturated bond containing a specific proportion of a polymerizable dibasic acid selected as described above is emulsified in the presence of a specific anionic surfactant and colloidal silica. A water-dispersed resin composition is produced by polymerization using a polymerization method. Emulsion polymerization is carried out according to a conventional method, but as mentioned above, when the proportion of the polymerizable dibasic M acid is small, for example, about 0.1 to 0.5% by type with respect to the total monomers, the polymerization is difficult. In order to maintain the stability of the system, it is particularly preferable to add this dibasic acid at a relatively late stage in the reaction and to concentrate the acid component near the surface of the emulsion particles.
かくして得られる本発明にかかる樹脂組成物は塗膜化し
た際に耐水性、耐沸騰水性、耐アルカリ性で特段に優れ
、しかも耐ブロッキング性、密着性、耐溶剤性にも優れ
た塗膜を与えうるので、金属、紙、木材、プラスチック
等各種基材に対する塗料用として極めて有用である。When the resin composition of the present invention thus obtained is formed into a coating film, it provides a coating film that is particularly excellent in water resistance, boiling water resistance, and alkali resistance, and also has excellent blocking resistance, adhesion, and solvent resistance. Therefore, it is extremely useful as a coating for various substrates such as metal, paper, wood, and plastic.
以下実施例により本発明を説明する。特にことわりなき
限り部とあるは重量部である。The present invention will be explained below with reference to Examples. Unless otherwise specified, parts are by weight.
実施例１
攪拌機、冷却管、温度制御装置をそなえた１リツトルの
反応容器をあらかじめ窒素ガスで飽和させ、その容器に
ドデシルベンゼンスルホン酸ナトリウム０．７部、脱イ
オン水３５０部、スチレン９ １、。Example 1 A 1-liter reaction vessel equipped with a stirrer, a cooling tube, and a temperature control device was saturated with nitrogen gas in advance, and 0.7 parts of sodium dodecylbenzenesulfonate, 350 parts of deionized water, styrene 91, .
８−
２０部、メチルメタクリレ−１・４０部、２エチルへキ
シルアクリレート２５部、イタコン酸２部、アクリロニ
トリル２０部、ルドックスＡＭ７．５部、重亜硫酸ナト
リウム１部を仕込み攪拌しながら５５℃に昇渇し、過硫
酸アンモニウム２部、脱イオン水５０部を仕込み温度を
６０℃にする。この反応容器中に攪拌下、脱イオン水２
００部、スチレン９０部、メチルメタクリレート１６０
部、２工ヂルヘキシルアクリレート１２５部、イタコン
酸１部、アクリロニトリル２０部、ドデシルベンゼンス
ルホン酸ナトリウム０．３部、ルドックスＡＭ５部を添
加して得られたモノマー乳濁液１００分間で滴下する。8- 20 parts of methyl methacrylate, 1.40 parts of 2-ethylhexyl acrylate, 2 parts of itaconic acid, 20 parts of acrylonitrile, 7.5 parts of Ludox AM, and 1 part of sodium bisulfite were charged and heated to 55°C with stirring. After raising the temperature to 60°C, add 2 parts of ammonium persulfate and 50 parts of deionized water. Into this reaction vessel, under stirring, add 2 mL of deionized water.
00 parts, styrene 90 parts, methyl methacrylate 160 parts
A monomer emulsion obtained by adding 125 parts of 2-functional dihexyl acrylate, 1 part of itaconic acid, 20 parts of acrylonitrile, 0.3 parts of sodium dodecylbenzenesulfonate, and 5 parts of Ludox AM was added dropwise over 100 minutes.
滴下終了後１時間攪拌を継続して反応を終了する。後、
２５％アンモニア水でｐｌ−１６〜９の範囲に調節し固
形分４６％のエマルションを得た。After the dropwise addition was completed, stirring was continued for 1 hour to complete the reaction. rear,
The emulsion was adjusted to pl-16 to 9 with 25% ammonia water to obtain an emulsion with a solid content of 46%.
なお、ルドックスＡＭは固形分３０％デュポン製のコロ
イダルシリカである。Note that Ludox AM is colloidal silica manufactured by DuPont and has a solid content of 30%.
実施例２〜８ 実施例１と同様方法で、但し下記処方により夫１０− 々エマルションを得た。Examples 2-8 In the same manner as in Example 1, but with the following prescription: An emulsion was obtained.
（以下余白）
第１表
１１−
なおりタロイド各種は触媒化成工業で下表に示すもので
ある。(The following is a blank space) Table 1 11 - Various types of Naori taloids are manufactured by Catalysts and Chemicals Industries and are shown in the table below.
比較例Ｔ〜■
実施例１と同様方法で、但し下記第２表の処方により夫
々エマルションを得た。Comparative Examples T~■ Emulsions were obtained in the same manner as in Example 1, but according to the formulations shown in Table 2 below.
（以下余白〉
１２−
第２表
実施例および比較例の各エマルションを用い塗膜性能評
価を行なった。(The following is a margin.) 12- The coating film performance was evaluated using each emulsion in the Examples and Comparative Examples in Table 2.
・塗膜作成条件
上記実施例ならびに比較例で得られたエマルシコン３０
部にブチセロと水の１：４混合溶液を７゜５部を添加し
、攪拌後直後７ｃｍブリキ製の円筒器に４ｇサンプリン
グし４０℃で２０時間乾燥する。・Coating film creation conditions Emulsicon 30 obtained in the above examples and comparative examples
7.5 parts of a 1:4 mixed solution of Butycello and water was added to the mixture, and immediately after stirring, 4 g was sampled into a 7 cm tin cylinder and dried at 40°C for 20 hours.
１４−
・試験方法
耐水ｆ［：ブリキ１ｆｆ１等の塗膜上に２０！］の１１
２イオン水を添加し、４０℃で２０時間放置
耐アルカリ性：ブリキ冊の塗膜上に２０ｇの５％Ｎａ
Ｏｌ−１水溶液を添加し、２０℃で２０時間放置耐沸騰
水性：ブリキ冊の塗膜を１００℃の沸騰水に３０分間浸
漬
性能試験後の塗膜状態を目視判定。ブリキ冊の水分をペ
ーパータオルで吸い取り２０℃、湿度７５％の室内で１
５分間放置後、重量を測定し塗膜の膨潤率を算出する。14- ・Test method Water resistance f [: 20! on coating film such as tinplate 1ff1! ] No. 11
2 Add ion water and leave at 40℃ for 20 hours Alkali resistance: 20g of 5% Na on the coating film of the tin book
Added Ol-1 aqueous solution and left at 20°C for 20 hours Boiling water resistance: The coating film on a tin book was immersed in boiling water at 100°C for 30 minutes, and the coating film condition was visually judged after a performance test. Absorb the moisture from the tin book with a paper towel and store it indoors at 20℃ and 75% humidity.
After standing for 5 minutes, the weight is measured and the swelling rate of the coating film is calculated.
その後塗膜を６０℃で４時間乾燥し重量を測定して塗膜
の溶解率を算出した。Thereafter, the coating film was dried at 60° C. for 4 hours, the weight was measured, and the dissolution rate of the coating film was calculated.
（以下余白）
・耐ブロッキング性
エマルシコン３０部にブヂセロと水の１：４混合溶液を
１５部添加し攪拌後、＃５０バーコーターにてアーｉ−
紙に塗布し、４０℃×１０分乾燥後３ ｘ ３ ｃｍに
切断し、表面と表面を重ね１０ｋａ及び２０ｋａの加重
をかけ５０℃で２時間放置した後、剥がし、付着状態を
みる。(Left below) ・Add 15 parts of a 1:4 mixed solution of Budicero and water to 30 parts of anti-blocking emulsion, stir, and coat with a #50 bar coater.
It was coated on paper, dried for 10 minutes at 40°C, cut into 3 x 3 cm pieces, stacked on top of each other and left at 50°C for 2 hours under a load of 10 ka and 20 ka, and then peeled off to examine the state of adhesion.
特許出願代理人 弁理士 伊 藤 ！ 雄 １７− １８−patent application agent Patent attorney Ito! Male 17- 18-
Claims (1)
含む少なくとも１種の共役性不飽和結合を有する重合性
モノマーを、全モノマーに対し０゜１〜１重量％のアニ
オン系界面活性剤および固形分で０．１〜４重世％のコ
ロイダルシリカの存在下、乳化重合させて得られる水分
散型樹脂組成物。An anionic monomer containing at least one conjugated unsaturated bond containing a polymerizable dibasic acid in a proportion of 0.1 to 1% by weight based on the total monomers. A water-dispersed resin composition obtained by emulsion polymerization in the presence of a surfactant and colloidal silica having a solid content of 0.1 to 4 times %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11998183A JPS6011503A (en) | 1983-06-30 | 1983-06-30 | Water-dispersed resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11998183A JPS6011503A (en) | 1983-06-30 | 1983-06-30 | Water-dispersed resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6011503A true JPS6011503A (en) | 1985-01-21 |
Family
ID=14774950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11998183A Pending JPS6011503A (en) | 1983-06-30 | 1983-06-30 | Water-dispersed resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6011503A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7037590B2 (en) | 2001-11-06 | 2006-05-02 | Bayer Aktiengesellschaft | Water vapor-permeable coating composite |
| WO2011062173A1 (en) * | 2009-11-18 | 2011-05-26 | 綜研化学株式会社 | Resin particles and process for production thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52102363A (en) * | 1976-02-25 | 1977-08-27 | Toyo Ink Mfg Co Ltd | Cold curable water-based resin composition |
| JPS53992A (en) * | 1976-06-25 | 1978-01-07 | Hitachi Ltd | Digital display system |
-
1983
- 1983-06-30 JP JP11998183A patent/JPS6011503A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52102363A (en) * | 1976-02-25 | 1977-08-27 | Toyo Ink Mfg Co Ltd | Cold curable water-based resin composition |
| JPS53992A (en) * | 1976-06-25 | 1978-01-07 | Hitachi Ltd | Digital display system |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7037590B2 (en) | 2001-11-06 | 2006-05-02 | Bayer Aktiengesellschaft | Water vapor-permeable coating composite |
| WO2011062173A1 (en) * | 2009-11-18 | 2011-05-26 | 綜研化学株式会社 | Resin particles and process for production thereof |
| CN102597012A (en) * | 2009-11-18 | 2012-07-18 | 综研化学株式会社 | Resin particles and process for production thereof |
| US20120238705A1 (en) * | 2009-11-18 | 2012-09-20 | Soken Chemical & Engineering Co., Ltd. | Resin Particles and Process for Producing the Same |
| JPWO2011062173A1 (en) * | 2009-11-18 | 2013-04-04 | 綜研化学株式会社 | Resin particles and method for producing the same |
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