JPH0822979B2 - Resin composition for coating exterior materials - Google Patents
Resin composition for coating exterior materialsInfo
- Publication number
- JPH0822979B2 JPH0822979B2 JP62203467A JP20346787A JPH0822979B2 JP H0822979 B2 JPH0822979 B2 JP H0822979B2 JP 62203467 A JP62203467 A JP 62203467A JP 20346787 A JP20346787 A JP 20346787A JP H0822979 B2 JPH0822979 B2 JP H0822979B2
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はアクリル系コーテイング用樹脂組成物に関
し、更に詳しくは、耐透水性に優れた、無機フィラーを
含有する外装材コーティング用樹脂組成物に関する。TECHNICAL FIELD The present invention relates to an acrylic coating resin composition, and more specifically to a resin composition for coating an exterior material, which is excellent in water resistance and contains an inorganic filler. .
従来コーテイング用樹脂組成物としてエポキシ樹脂系
組成物、ポリウレタン樹脂系組成物、不飽和ポリエステ
ル樹脂系組成物、アクリル系組成物をはじめとして数多
くのものが開発されているが、近年外装材用途等の耐候
性が要求される分野においてアクリル系組成物に関する
開発が多々実施されている。Conventionally, many resin compositions for coating have been developed, including epoxy resin compositions, polyurethane resin compositions, unsaturated polyester resin compositions, and acrylic compositions. A lot of developments have been carried out on acrylic compositions in fields where weather resistance is required.
これらアクリル系組成物は建築物や構築物の床面、壁
面等ひ塗装されているが、通常、塗料の隠蔽性，収縮性
等の点からタルク，炭酸カルシウム等の無機フイラーを
配合して用いられる。These acrylic compositions are painted on the floors and walls of buildings and structures, but they are usually used by blending an inorganic filler such as talc or calcium carbonate in view of the hiding property and shrinkage of the paint. .
しかしながら、上記無機フイラーが配合されたアクリ
ル系コーテイング組成物は、透水性が大きいため耐久性
が劣り、特に外装用途においては透水性の優れたアクリ
ル系コーテイング組成物の出現が強く望まれている現状
にある。However, the acrylic coating composition containing the above-mentioned inorganic filler is poor in durability due to its large water permeability, and the appearance of an acrylic coating composition having excellent water permeability is strongly desired especially for exterior applications. It is in.
本発明の目的とするところは、耐候性、塗工作業性、
硬化性に優れ、かつ耐透水性に優れた外装材コーティン
グ用アクリル系樹脂組成物を提供することにある。The object of the present invention is weather resistance, coating workability,
It is intended to provide an acrylic resin composition for coating an exterior material, which has excellent curability and water resistance.
本発明の要旨とするところは、下記樹脂組成物（Ｉ）
100重量部に平均粒径20〜150μのマイカ20〜100重量部
が添加されている外装材コーティング用樹脂組成物にあ
る。The gist of the present invention lies in the following resin composition (I)
A resin composition for coating an exterior material, wherein 100 to 100 parts by weight of 20 to 100 parts by weight of mica having an average particle size of 20 to 150 μm are added.
樹脂組成物（Ｉ） 本発明に用いられる（メタ）アクリル酸アルキルエス
テル（Ａ）は、樹脂組成物（Ｉ）中に50〜80重量％、好
ましくは60〜75重量％含有される。添加量が50重量％未
満では、塗工作業性の点で、又、80重量％を越えると硬
化性の点で好ましくない。Resin composition (I) The (meth) acrylic acid alkyl ester (A) used in the present invention is contained in the resin composition (I) in an amount of 50 to 80% by weight, preferably 60 to 75% by weight. If the addition amount is less than 50% by weight, it is not preferable in terms of coating workability, and if it exceeds 80% by weight, it is not preferable in terms of curability.
（メタ）アクリル酸アルキルエステルの具体例として
は、例えば、（メタ）アクリル酸メチル、（メタ）アク
リル酸エチル、（メタ）アクリル酸ｎ−ブチル、（メ
タ）アクリル酸ｉ−ブチル、（メタ）アクリル酸ｔ−ブ
チル、（メタ）アクリル酸２−エチルヘキシル、（メ
タ）アクリル酸ラウリル等が挙げられ、単独又は混合物
で用いられ、特に塗膜物性、耐候性等の点からメタクリ
ル酸メチルとアクリル酸２−エチルヘキシルの混合物を
用いるのが好ましい。Specific examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and (meth). Examples thereof include t-butyl acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate, which may be used alone or in a mixture. Particularly, from the viewpoints of coating film physical properties, weather resistance, etc., methyl methacrylate and acrylic acid. Preference is given to using a mixture of 2-ethylhexyl.
又、本発明においては、目的に応じて（メタ）アクリ
ル酸アルキルエステル以外のビニル単量体、例えばスチ
レン、α−メチルスチレン等の芳香族ビニル単量体、ア
クリロニトリル、メタクリロニトリル等のシアン化ビニ
ル単量体等を添加することもできる。Further, in the present invention, vinyl monomers other than (meth) acrylic acid alkyl ester, for example, aromatic vinyl monomers such as styrene and α-methylstyrene, acrylonitrile, methacrylonitrile and the like cyanide are used according to the purpose. Vinyl monomers and the like can also be added.
本発明に用いられるアクリル系（共）重合体（Ｂ）は
樹脂組成物（Ｉ）中に10〜25重量％、好ましくは15〜25
重量％含有されている。The acrylic (co) polymer (B) used in the present invention is 10 to 25% by weight, preferably 15 to 25% by weight in the resin composition (I).
It is contained by weight%.
アクリル系（共）重合体（Ｂ）の添加量が10重量％未
満では硬化性の点で好ましくなく、又、25重量％を越え
ると塗工作業性の点で好ましくない。If the amount of the acrylic (co) polymer (B) added is less than 10% by weight, it is not preferable in terms of curability, and if it exceeds 25% by weight, it is not preferable in terms of coating workability.
又、アクリル系（共）重合体（Ｂ）は、塗工作業性、
塗膜物性等の点から平均分子量１万〜20万であることが
好ましい。In addition, the acrylic (co) polymer (B) has a coating workability,
The average molecular weight is preferably 10,000 to 200,000 from the viewpoint of coating film physical properties and the like.
該（共）重合体を構成する単量体としては、前記（メ
タ）アクリル酸アルキルエステルと同様のものを主成分
とするものであり、目的に応じてスチレン、α−メチル
スチレン、アクリロニトリル、メタクリロニトリル等の
他のビニル単量体を添加したものでもよい。尚、該
（共）重合体は通常のラジカル重合法により得ることが
でき、特に限定されるものではない。The monomer constituting the (co) polymer has the same main component as the above-mentioned (meth) acrylic acid alkyl ester, and depending on the purpose, styrene, α-methylstyrene, acrylonitrile, methacrylic acid, etc. It may be one to which another vinyl monomer such as ronitrile is added. The (co) polymer can be obtained by an ordinary radical polymerization method and is not particularly limited.
本発明においては、可塑剤（Ｃ）が外装材コーティン
グ用樹脂組成物の柔軟性を向上させる目的で樹脂組成物
（Ｉ）中に10〜25重量％添加される。添加量が10重量％
未満では、柔軟性向上の効果が低く、添加量が25重量％
を越えると、外装材コーティング用樹脂組成物を硬化し
て得られる塗膜の汚染性が高くなり、好ましくない。In the present invention, the plasticizer (C) is added to the resin composition (I) in an amount of 10 to 25% by weight for the purpose of improving the flexibility of the resin composition for coating the exterior material. 10% by weight
If it is less than 25%, the effect of improving flexibility is low, and the addition amount is 25% by weight.
If it exceeds, the stain resistance of the coating film obtained by curing the resin composition for coating the exterior material increases, which is not preferable.
添加される可塑剤（Ｃ）の具体例としては、例えば、
ジブチルフタレート、ジｎ−オクチルフタレート、ジ２
−エチルヘキシルフタレート、ジｎ−デシルフタレー
ト、ジイソデシルフタレート等のフタル酸エステル類、
ジ２−エチルヘキシルアジペート、オクチルアジペート
等のアジピン酸エステル類、ジ２−エチルヘキシルセバ
ケート、ジブチルセバケート等のセバシン酸エステル
類、ジ２−エチルヘキシルアゼレート等のアゼライン酸
系エステル類等の２塩基性脂肪酸エステル類、塩素化パ
ラフイン等のパラフイン類、ポリプロピレングリコール
等のグリコール類、エポキシ化大豆油、エポキシ化アマ
ニ油等のエポキシ系高分子可塑剤、トリオクチルフオス
フエート、トリフエニルフオスフエート等のリン酸エス
テル類、トリフエニルフオスフアイト等の亜リン酸エス
テル類、アジピン酸と1,3−ブチレングリコールとのエ
ステル化物等のエステル類等が挙げられ、単独又は混合
物で用いられる。Specific examples of the added plasticizer (C) include, for example,
Dibutyl phthalate, di-n-octyl phthalate, di-2
Phthalates such as ethylhexyl phthalate, di-n-decyl phthalate, diisodecyl phthalate,
Adipic acid esters such as di2-ethylhexyl adipate and octyl adipate, sebacic acid esters such as di2-ethylhexyl sebacate and dibutyl sebacate, and dibasic azelaic acid esters such as di2-ethylhexyl azelate. Fatty acid esters, paraffins such as chlorinated paraffins, glycols such as polypropylene glycol, epoxy polymer plasticizers such as epoxidized soybean oil and epoxidized linseed oil, trioctyl phosphate, triphenyl phosphate, etc. Examples thereof include phosphoric acid esters, phosphite esters such as triphenyl phosphite, and esters such as esterification products of adipic acid and 1,3-butylene glycol, which may be used alone or in a mixture.
本発明に用いられる樹脂組成物（Ｉ）には、硬化性及
び硬化物の耐久性，耐溶剤性を改善するために、１分子
中に少なくとも２個の不飽和結合を有する架橋剤、例え
ば、エチレングリコールジ（メタ）アクリレート、1,3
−ブチレンジ（メタ）アクリレート等のアルカンジオー
ルジ（メタ）アクリレート、ジエチレングリコールジ
（メタ）アクリレート、ジプロピレングリコールジ（メ
タ）アクリレート等のポリオキシアルキレングリコール
（メタ）アクリレート、ジアリルフタレート、トリアリ
ルフタレート、トリアリルシアヌレート、トリアリルイ
ソシアヌレート、アリル（メタ）アクリレート等を添加
することができる。The resin composition (I) used in the present invention contains a crosslinking agent having at least two unsaturated bonds in one molecule, for example, in order to improve curability, durability of the cured product, and solvent resistance. Ethylene glycol di (meth) acrylate, 1,3
-Alkanediol di (meth) acrylates such as butylene di (meth) acrylate, polyoxyalkylene glycol (meth) acrylates such as diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, diallyl phthalate, triallyl phthalate, tri Allyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate and the like can be added.
尚、該架橋剤の添加量は塗膜の柔軟性等の点から樹脂
組成物（Ｉ）100重量部に対して0.1〜10重量部程度が好
ましい。The amount of the crosslinking agent added is preferably about 0.1 to 10 parts by weight based on 100 parts by weight of the resin composition (I) from the viewpoint of flexibility of the coating film.
本発明においては、樹脂組成物（Ｉ）100重量部に、
平均粒径20〜150μのマイカが20〜100重量部添加されて
いる。In the present invention, 100 parts by weight of the resin composition (I),
20 to 100 parts by weight of mica having an average particle size of 20 to 150 μ is added.
マイカを樹脂組成物（Ｉ）に添加することにより、本
発明の組成物を塗布したときに生じるタレを防止するこ
とが可能となるだけでなく、驚くべきことに硬化塗膜の
耐透水性，耐水性が大幅に向上する。By adding mica to the resin composition (I), it is possible not only to prevent sagging that occurs when the composition of the present invention is applied, but surprisingly, the water resistance of the cured coating film, Water resistance is greatly improved.
用いられるマイカの平均粒径は20〜150μが好まし
く、20μ未満であると耐透水性が低下し好ましくない。
又、粒径が大きくなりすぎると、本発明の組成物の塗工
作業性，外観が低下してくるので好ましくない。同様に
添加量も耐透水性、塗工作業性、外観の点で、樹脂組成
物（Ｉ）100重量部に対して20〜100重量部が好ましく、
特に好ましくは25〜60重量部である。The average particle size of the mica used is preferably 20 to 150 μm, and if it is less than 20 μm, the water permeation resistance decreases, which is not preferable.
On the other hand, if the particle size becomes too large, the coating workability and appearance of the composition of the present invention will deteriorate, which is not preferable. Similarly, the addition amount is preferably 20 to 100 parts by weight based on 100 parts by weight of the resin composition (I) in terms of water resistance, coating workability, and appearance.
It is particularly preferably 25 to 60 parts by weight.
本発明の組成物は公知の硬化剤と促進剤とを組み合せ
たレドツクス系触媒を添加することにより容易に硬化さ
せることができる。これらの中で、低温硬化性の点か
ら、硬化剤として有機過酸化物、促進剤として第３級ア
ミンを用いるのが好ましい。有機過酸化物の中では過酸
化ベンゾイルが特に好ましく、第３級アミンとしては特
にN,N′−ジメチルアニリン、N,N′−ジメチルパラトル
イジン、N,N−ジ（ヒドロキシエチル）パラトルイジン
等が好ましい。The composition of the present invention can be easily cured by adding a redox catalyst in which a known curing agent and accelerator are combined. Among these, it is preferable to use an organic peroxide as a curing agent and a tertiary amine as an accelerator from the viewpoint of low temperature curability. Among the organic peroxides, benzoyl peroxide is particularly preferable, and as the tertiary amine, N, N'-dimethylaniline, N, N'-dimethylparatoluidine, N, N-di (hydroxyethyl) paratoluidine, etc. Is preferred.
又、硬化性を向上させる目的で本発明の組成物にパラ
フインワツクス、ポリエチレンワツクス等のワツクス、
ステアリン酸等の高級脂肪酸等を、通常樹脂組成物
（Ｉ）100重量部に対して0.1〜３重量部程度添加するこ
とができる。In addition, waxes such as paraffin wax and polyethylene wax are added to the composition of the present invention for the purpose of improving curability.
Higher fatty acids such as stearic acid can be added in an amount of about 0.1 to 3 parts by weight with respect to 100 parts by weight of the resin composition (I).
更に、耐候性を向上させるために、２−ヒドロキシベ
ンゾフエノール誘導体、ベンゾトリアゾール誘導体、サ
リチル酸エステル等の紫外線吸収剤を通常樹脂組成物
（Ｉ）100重量部に対して0.01〜５重量部添加すること
ができ、又被塗物との密着性を改善させるために、ｔ−
メタクリロキシプロピルトリメトキシシラン、γ−グリ
シドキシプロピルトリメトキシシラン、γ−メルカプト
プロピルトリメトキシシラン等のシランカツプリング剤
を添加してもよい。Further, in order to improve weather resistance, an ultraviolet absorber such as a 2-hydroxybenzophenol derivative, a benzotriazole derivative, a salicylic acid ester, etc. is usually added in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin composition (I). In addition, in order to improve the adhesion to the coated object, t-
A silane coupling agent such as methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane may be added.
本発明においては、目的に応じて本発明の組成物に硬
化性向上剤としてトリブチルフオスフアイト、トリ（２
−エチルヘキシル）フオスフアイト、トリデシルフオス
フアイト、トリフエニルフオスフアイト等のフオスフア
イト類を添加することができる。In the present invention, depending on the purpose, the composition of the present invention may contain tributyl phosphite, tri (2) as a curability improver.
Phosphites such as ethylhexyl) phosphite, tridecyl phosphite, triphenyl phosphite and the like can be added.
又、耐透水性を低下させない程度であれば、本発明の
組成物に硅砂、石英粉、アルミナ粉、ガラスビーズ、陶
磁器粉、ガラス繊維等の繊維状物、アエロジル等の揺変
性付与剤、染料、顔料等の着色剤を添加してもよい。Further, as long as it does not reduce the water permeation resistance, the composition of the present invention contains silica sand, quartz powder, alumina powder, glass beads, ceramic powder, fibrous materials such as glass fibers, thixotropic agents such as Aerosil, and dyes. A colorant such as a pigment may be added.
以下、本発明を実施例を用いて説明する。尚、実施例
中、部又は％はそれぞれ重量，重量％を示す。Hereinafter, the present invention will be described using examples. In the examples, parts and% mean weight and% by weight, respectively.
〔実施例１〜4,比較例１〜５〕 表−１に示す各種組成にて各化合物をフラスコ内に添
加し、50℃で２時間加熱溶解して樹脂組成物（Ｉ）溶液
（Ａ）〜（Ｂ）を得た。[Examples 1 to 4 and Comparative Examples 1 to 5] Resin compounds (I) solution (A) were added by adding each compound in a flask with various compositions shown in Table 1 and heating and dissolving at 50 ° C for 2 hours. ~ (B) was obtained.
次いで表−２に示す各種組成にてコーテイング用樹脂
組成物を調整し、これを石綿パーライト板上（７×15×
15cm）にバーコーターを用いて厚み約0.3mmになるよう
に塗布し、20℃で硬化させた。Next, a resin composition for coating was prepared with various compositions shown in Table-2, and this was applied on an asbestos pearlite board (7 × 15 ×
15 cm) with a bar coater to a thickness of about 0.3 mm and cured at 20 ° C.
又、上記各種試料について、樹脂組成物の塗工作業
性、硬化性、タレの状態及び硬化塗膜の透水度、汚染
性、外観を下記方法により評価し、得られた結果を表−
２に示した。Further, with respect to the above various samples, the coating workability of the resin composition, the curability, the state of sagging, the water permeability of the cured coating film, the stain resistance, and the appearance were evaluated by the following methods, and the obtained results are shown in Table-
Shown in 2.
（塗工作業性） ローラーとコテを使用して作業の円滑性，塗膜の仕上
り状態により評価した。(Coating workability) The workability was evaluated by using a roller and a trowel, and the finished state of the coating film was evaluated.
（硬化性） 塗膜表面の指触乾燥度合（タツクフリーの度合）によ
り硬化性を評価した。(Curability) The curability was evaluated by the dryness to the touch of the coating film surface (degree of tack-freeness).
（タレの状態） 各種コーテイング用樹脂組成物100部に対し、タレ止
め剤としてアエロジル＃200を１〜２部添加した配合物
を垂直塗工面に0.3〜0.5mm厚に塗工し、タレの状態を評
価した。(Sagging state) 100 parts of various coating resin compositions were coated with a composition containing 1 to 2 parts of Aerosil # 200 as a sagging preventive agent on a vertically coated surface to a thickness of 0.3 to 0.5 mm, and a sagging state Was evaluated.
（透水度） コーテイング用樹脂組成物を塗布硬化したパーライト
板を20℃の精水中に30日間浸漬し、次式により垂直増加
率を測定し、透水度を評価した。(Water Permeability) The pearlite plate coated with the resin composition for coating and cured was immersed in purified water at 20 ° C. for 30 days, and the vertical increase rate was measured by the following formula to evaluate the water permeability.
W0:精水浸漬前のパーライト板重量（ｇ） W30:精水浸漬30日間後のパーライト板重量（ｇ） （汚染性） 汚染物質（カーボンブラツク／はくとう土／グリセリ
ン＝2/35/63）を塗工面に刷毛で塗布し、30分後に洗浄
試験機で洗浄した後、塗工面の汚染の程度を肉眼で評価
する。 W 0 : Weight of pearlite plate before immersion in purified water (g) W 30 : Weight of pearlite plate after immersion in purified water (g) (g) (Staining property) Pollutants (carbon black / soil / glycerin = 2/35) / 63) is applied to the coated surface with a brush, and after 30 minutes, it is washed with a cleaning tester, and the degree of contamination of the coated surface is evaluated with the naked eye.
（外観） 肉眼評価 〔発明の効果〕 以上詳述したように、本発明のコーテイング用樹脂組
成物は塗工作業性、硬化性に優れ、塗布硬化塗膜は耐透
水性、耐汚染性、柔軟性、外観が優れていることから、
耐透水性が要求される外装材用コーテイング材として優
れた効果を発揮することができる。(Appearance) Visual evaluation [Effects of the Invention] As described in detail above, the coating resin composition of the present invention has excellent coating workability and curability, and the coating and cured coating film has excellent water permeability, stain resistance, flexibility, and appearance. Because
It is possible to exert an excellent effect as a coating material for exterior materials that requires water resistance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小西 偉夫 愛知県名古屋市東区砂田橋４丁目１番60号 三菱レイヨン株式会社内 (72)発明者 近藤 貞夫 東京都千代田区丸の内１丁目５番１号 三 菱レイヨン・エンジニアリング株式会社内 (56)参考文献 特開 昭57−175（ＪＰ，Ａ) 特開 昭61−129071（ＪＰ，Ａ) 特開 昭57−38870（ＪＰ，Ａ) 特開 昭48−78238（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Takeo Konishi 4-chome, Sunadabashi, Higashi-ku, Aichi Prefecture, Aichi Prefecture, 60-1 Mitsubishi Rayon Co., Ltd. (72) Sadao Kondo, 1-1-5, Marunouchi, Chiyoda-ku, Tokyo Ryo Rayon Engineering Co., Ltd. (56) Reference JP 57-175 (JP, A) JP 61-129071 (JP, A) JP 57-38870 (JP, A) JP 48- 78238 (JP, A)
Claims (1)
径が20〜150μのマイカ20〜100重量部が添加されている
外装材コーティング用樹脂組成物。 樹脂組成物（Ｉ） Ａ）アルキル基の炭素数が１〜12である（メタ）アクリ
ル酸アルキルエステルから選ばれる少なくとも一種50〜
80重量％ Ｂ）アルキル基の炭素数が１〜12である（メタ）アクリ
ル酸アルキルエステルを主成分とするモノマーからなる
アクリル系（共）重合体 10〜25重量％、 Ｃ）可塑剤 10〜25重量％1. A resin composition for coating an exterior material, wherein 100 parts by weight of the following resin composition (I) is added with 20 to 100 parts by weight of mica having an average particle size of 20 to 150 μm. Resin composition (I) A) At least one selected from alkyl (meth) acrylates having 1 to 12 carbon atoms in the alkyl group 50 to
80% by weight B) Acrylic (co) polymer 10 to 25% by weight of a monomer whose main component is a (meth) acrylic acid alkyl ester having an alkyl group with 1 to 12 carbon atoms, C) a plasticizer 10 to 25% by weight
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62203467A JPH0822979B2 (en) | 1987-08-18 | 1987-08-18 | Resin composition for coating exterior materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62203467A JPH0822979B2 (en) | 1987-08-18 | 1987-08-18 | Resin composition for coating exterior materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6448867A JPS6448867A (en) | 1989-02-23 |
| JPH0822979B2 true JPH0822979B2 (en) | 1996-03-06 |
Family
ID=16474614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62203467A Expired - Lifetime JPH0822979B2 (en) | 1987-08-18 | 1987-08-18 | Resin composition for coating exterior materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0822979B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100409160B1 (en) * | 1995-12-29 | 2004-03-18 | 고려화학 주식회사 | Non-metallic surface coating agent composition |
| KR100671405B1 (en) * | 2004-12-15 | 2007-01-19 | 주식회사 에이스 디지텍 | Acryl adhesive composition having superior residual stress relexation, and optical film using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4878238A (en) * | 1972-01-22 | 1973-10-20 | ||
| JPS57175A (en) * | 1980-05-31 | 1982-01-05 | Matsushita Electric Works Ltd | Emulsion paint |
| JPS5738870A (en) * | 1980-08-19 | 1982-03-03 | Kyoko Kawai | Paint having pearly gloss |
| JPS61129071A (en) * | 1984-11-27 | 1986-06-17 | Nippon Paint Co Ltd | Laminated paint film |
-
1987
- 1987-08-18 JP JP62203467A patent/JPH0822979B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6448867A (en) | 1989-02-23 |
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