JPS5883012A - 1-acetoxy-1,3-butadiene (co)polymer - Google Patents
1-acetoxy-1,3-butadiene (co)polymerInfo
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- JPS5883012A JPS5883012A JP18070481A JP18070481A JPS5883012A JP S5883012 A JPS5883012 A JP S5883012A JP 18070481 A JP18070481 A JP 18070481A JP 18070481 A JP18070481 A JP 18070481A JP S5883012 A JPS5883012 A JP S5883012A
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- butadiene
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Abstract
Description
【発明の詳細な説明】
本発明は、溶媒不溶分を含有する１−アセトキシ−１，
３−ブタジェン（以下５−ＡＢＤと記す）の重合体ま先
は共重合体（以下（共）重合体と記す）Ｋ関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 1-acetoxy-1,
The polymer of 3-butadiene (hereinafter referred to as 5-ABD) is related to copolymer (hereinafter referred to as (co)polymer) K.
１−ムＢＤの（共）重合体は、極性基を有する共役ジエ
ン０（共）重合体であり新しい高分子材料として各種の
展開が考えられるが、１−ＡＢＤの（共）重合体を接着
剤、塗料などとして使用することを考慮すると、他材料
との接着強度をあげることが必要である。The (co)polymer of 1-ABD is a conjugated diene 0 (co)polymer with a polar group, and various developments can be considered as a new polymer material. When considering use as agents, paints, etc., it is necessary to increase the adhesive strength with other materials.
本発明者らは、エマルジ曹ン状態で使用する接着剤、塗
料などとして適した重合体を製造するべく鋭意検討を進
めた結果、１−ＡＢＤの（共）重合体において、溶媒不
溶分を１０重量嘔を越える量含有し、溶媒可溶分の数平
均分子量が＆０００以上のものが接着剤、塗料として用
いたとき極めて大きな接着性と耐油性とを有し、かつ成
膜性もよいことを見いだし、かかる知見に基づいて本発
明を達成した。The present inventors have carried out intensive studies to produce a polymer suitable for adhesives, paints, etc. used in the emulsion state, and as a result, in a (co)polymer of 1-ABD, the solvent insoluble matter was reduced to 10%. It has been found that substances containing more than 100% of the weight and having a number average molecular weight of 000 or more for the solvent-soluble portion have extremely high adhesion and oil resistance when used as adhesives and paints, and also have good film-forming properties. The present invention has been achieved based on this finding.
すなわち本発明線、１０重量％を越える量、好ましくは
３０〜９９重量−の溶媒不溶分を含有し、溶媒可溶分の
数平均分子量がｓ、ｏｏｏ以上である１−ＡＢＤの（共
）重合体を提供するものである。That is, the (co)weight of 1-ABD containing more than 10% by weight, preferably 30 to 99% by weight of solvent-insoluble components and having a number average molecular weight of s, ooo or more of the solvent-soluble components. It provides integration.
次に本発明の詳細な説明する。Next, the present invention will be explained in detail.
本発明の１−ＡＢＤの（共）重合体の製造に用いられる
モノマーである１−ＡＢＤはパラジウムなどの貴金属触
媒の存在下でブタジェンをアセトが
キシ化して得る−、クロトンアルデヒドを無水酢酸およ
びアルカリ金属の酢酸塩の存在下で加熱することによっ
て製造することができる。これらの方法によって得られ
た１−ＡＢＤはシス体とトランス体との混合物であるが
、本発明の洪）重合体の七ツマ−とじてはシス体ま九は
トランス体単独でもこれらの混合物であってもよい。1-ABD, which is a monomer used in the production of the 1-ABD (co)polymer of the present invention, is obtained by oxygenating butadiene with aceto in the presence of a noble metal catalyst such as palladium, and crotonaldehyde with acetic anhydride and an alkali. It can be produced by heating in the presence of a metal acetate. 1-ABD obtained by these methods is a mixture of the cis form and the trans form, but in the case of the polymer of the present invention, the cis form and the trans form alone can be a mixture of these forms. There may be.
また重合に不都合とならない程度の不純物を含んでいて
も何ら差し支えない。Further, there is no problem even if the polymer contains impurities to the extent that they do not cause any inconvenience to the polymerization.
また１−人ＢＤと共重合可能なモノマーとしては、共役
ジエン、エチレン性不飽和化合物などを挙がることがで
きる。共役ジエンとしては特に限定されるものではガい
が、重合性から炭素数４〜６の共役ジエンが好ましく、
その中でもブタジェン、イソプレン、ピペリレン、クロ
ロプレンが特に好ましい。エチレン性不飽和化合物とし
ては、炭素数２〜５０オレフインが好ましく重合性から
みてエチレンが４ＩＫＮｔｔ、い。Examples of monomers copolymerizable with the 1-person BD include conjugated dienes and ethylenically unsaturated compounds. The conjugated diene is not particularly limited, but conjugated dienes having 4 to 6 carbon atoms are preferred from the viewpoint of polymerizability.
Among them, butadiene, isoprene, piperylene, and chloroprene are particularly preferred. As the ethylenically unsaturated compound, olefins having 2 to 50 carbon atoms are preferred, and from the viewpoint of polymerizability, ethylene is preferred.
またアクリル酸、メタクリル酸およびこれらのエステｋ
Ｉｉが広義のエチレン性不飽和化合物に含まれるが、％
にアクリル酸およびメタクリル酸の炭素数１〜１２のア
ルキルエステル、すなわちメチルエステルからラウリル
エステルまでが好ましく、その中でもメチル、エチル、
プロピル、ｎ−ブチル、５ｅｅ−ブチル、ｔ−ブチル、
２−エチルヘキシルおよびヒドロキシエチルエステルが
、重合性からみて特に好ましい。その他のエチレン性不
飽和化合物として重合性の点で好ましいものとしては、
スチレン、酢酸ビニル、アクリロニトリル、メタアクリ
ロニトリル、アリルアセテート、メタアリルアセテート
、アクリルアミド、メタクリルアミドが挙げられる。Also, acrylic acid, methacrylic acid, and these esters
Ii is included in ethylenically unsaturated compounds in a broad sense, but %
C1-C12 alkyl esters of acrylic acid and methacrylic acid, that is, from methyl esters to lauryl esters, among which methyl, ethyl,
Propyl, n-butyl, 5ee-butyl, t-butyl,
2-ethylhexyl and hydroxyethyl ester are particularly preferred from the viewpoint of polymerizability. Other preferable ethylenically unsaturated compounds in terms of polymerizability include:
Examples include styrene, vinyl acetate, acrylonitrile, methacrylonitrile, allyl acetate, methalylacetate, acrylamide, and methacrylamide.
これらの共重合モノマーは、１種のみを１−ＡＢＤと共
重合させても良いが、２種以上を組みあわせて共重合さ
せることもできる。これらの共重合モノマーと１−ＡＢ
Ｄとの好ましい共重合組成は１−ＡＢＤの（共）重合体
の接着性などの特徴を生かすために１−ＡＢＤが１０〜
９９．９重量−の範囲であるが、それぞれのモノマーの
特徴を生かすためには共重合させる七ツマ−それぞれが
１重量Ｉｓ〜９０重量−の範囲にするのが好ましく、さ
らに５重量−〜８０重量％が共重合させるモノマーの特
徴がさらに明らかになる点で好ましく、２０重量９１〜
７０重量−が一層好ましい。Only one type of these copolymerizable monomers may be copolymerized with 1-ABD, but two or more types can also be copolymerized in combination. These copolymerized monomers and 1-AB
A preferred copolymerization composition with D is such that 1-ABD is 10 to 10 to take advantage of the adhesive properties of the (co)polymer of 1-ABD.
However, in order to take advantage of the characteristics of each monomer, it is preferable that each of the seven monomers to be copolymerized be in the range of 1 weight Is to 90 weight, and more preferably 5 weight Is to 80 weight. It is preferable that the characteristics of the monomer to be copolymerized become clearer when the weight percentage is 20 weight 91~
70 weight - is more preferable.
ま九、１−人ＢＤの（共）重合体の溶媒可溶分の数平均
分子量が＆００Ｇ以上、好ましくは２２，０００以上で
極めて優れ良接着性と耐油性を示す。9. When the number average molecular weight of the solvent-soluble portion of the (co)polymer of 1-man BD is &00G or more, preferably 22,000 or more, it exhibits excellent adhesion and oil resistance.
本発明の（共）重合体は、例えば１−ＡＢＤ単独あるい
はこれと共重合モノマーを界面活性剤、ラジカル重合開
始剤、連鎖移動剤などを用い乳化もしくは懸濁重合する
ことによりて得られる。The (co)polymer of the present invention can be obtained, for example, by emulsification or suspension polymerization of 1-ABD alone or a monomer copolymerized therewith using a surfactant, a radical polymerization initiator, a chain transfer agent, or the like.
界面活性剤としては、アニオン性、カチオン性およＷま
たはノニオン性゛界面活性剤を使用することができる。As the surfactant, anionic, cationic, W or nonionic surfactants can be used.
アニオン性界面活性剤としては、例えば高級アルコール
の硫−エステル、アルキルベンゼンスルフォン１１塩、
ｍａ族スルフォン酸塩ｓ ｆｙタレンスル７ォン酸ホル
−ｒリン縮金物などが挙げられる。カチオン性界面活性
剤としては、第４級アンモニウム塩またはアルキルアミ
ン塩などが挙げられる。またノニオン性界面活便剤とし
ては、ポリエチレングリコールのアルキルエステル型、
アルキルエーテル型、アルキルフェニルエーテル型など
が挙げられる。Examples of anionic surfactants include sulfur esters of higher alcohols, alkylbenzenesulfone 11 salts,
Examples include ma group sulfonate salts, talenesulfonate phor-rphosphorus metal complexes, and the like. Examples of the cationic surfactant include quaternary ammonium salts and alkylamine salts. In addition, nonionic surfactants include polyethylene glycol alkyl ester type,
Examples include alkyl ether type and alkylphenyl ether type.
ｔ＆保膜コロイドとしてのポリビニルアルコールなどの
使用も可能である。It is also possible to use polyvinyl alcohol and the like as a t&retentive colloid.
ラジカル重合開始剤としては、過硫酸す）９ウム、過硫
酸カリウム、過硫酸アンモニウムなどの水溶性ラジカル
重合開始剤、過酸化ベンゾイル、アゾビスイソブチロニ
トリルなどの油溶性ラジカル重合開始剤を挙げることが
でき、る。Examples of the radical polymerization initiator include water-soluble radical polymerization initiators such as persulfate, potassium persulfate, and ammonium persulfate, and oil-soluble radical polymerization initiators such as benzoyl peroxide and azobisisobutyronitrile. I can do it.
またレドックス系ラジカル重合開始剤を用いることもで
きる。Further, a redox radical polymerization initiator can also be used.
連鎖移動剤としては、ターシャリ−ドデシルメルカプタ
ン、四塩化炭素などを挙げることができ、必ｌ！に応じ
加えられる。さらにキレート剤、無機塩なども用いるこ
とができる。Examples of chain transfer agents include tertiary dodecyl mercaptan and carbon tetrachloride, which are essential! Added accordingly. Furthermore, chelating agents, inorganic salts, etc. can also be used.
重合を高温、特に５０〜１００℃において行うと、重合
率が低い状態から生成（共）重合体の溶媒不溶化が進行
し、１−ＡＢＤの（共）重合体中に溶媒に不溶な部分が
存在することとなる。この１−ＡＢＤ（共）重合体の溶
媒不溶化は、重合温度が高いほど、かつラジカル重合開
始剤濃度が高いほどおこシ品く、５０〜１００℃で重合
すると任意の溶媒不溶分を含有する１−ＡＢＤの（共）
重含体を製造することができる。また溶媒不溶分の少な
い１−ＡＢＤの（共）重合体は、レドックス系ラジカル
重合開始剤の存在下、通常−１０〜２０℃で乳化もしく
は懸濁重合′する仁とによシ得ることができるが、たと
えば反応率が７０１１Ｇをこえ九段階で長時間重合を維
持し１重合率を上昇させることによシ、任意の溶媒不溶
分を含有する１−ＡＢＤの（共）重合体を製造すること
もできる。When polymerization is carried out at high temperatures, particularly at 50 to 100°C, the resulting (co)polymer becomes insolubilized in solvents even at a low polymerization rate, resulting in the presence of solvent-insoluble portions in the (co)polymer of 1-ABD. I will do it. The higher the polymerization temperature and the higher the concentration of the radical polymerization initiator, the higher the solvent insolubility of the 1-ABD (co)polymer. -ABD (co)
Heavy content bodies can be produced. In addition, a (co)polymer of 1-ABD with a low solvent-insoluble content can be obtained by emulsion or suspension polymerization in the presence of a redox radical polymerization initiator, usually at -10 to 20°C. However, it is possible to produce a (co)polymer of 1-ABD containing any solvent-insoluble matter by, for example, increasing the 1 polymerization rate by maintaining polymerization for a long time at a reaction rate exceeding 7011G and in 9 stages. You can also do it.
本髪明の１−ＡＢＤの（共）重合体は、溶媒不溶分を含
有し、溶媒可溶分の数平均分子量が高いために、１−Ａ
ＢＤの（共）重合体そのものの有するガラス、木材、紙
などへの接着強度が極めて高められ、かつ耐油性を有す
るものであシ、エマルジ冒ン状態で使用する接着剤、塗
料などとして好適な（共）重合体である。The (co)polymer of 1-ABD according to the present invention contains a solvent-insoluble component and a high number average molecular weight of a solvent-soluble component.
The BD (co)polymer itself has extremely high adhesion strength to glass, wood, paper, etc., and is oil resistant, making it suitable as an adhesive, paint, etc. to be used in an emulsion state. It is a (co)polymer.
なお本明細書で記述する溶媒不溶分は、１−ＡＢＤの（
共）重含体の組成において、１−ＡＢＤと極性基を含む
モノマ一単位の総量が７０重量−以上の場合はアセトン
を溶媒とし、７０重量−未満の場合はトルエンを溶媒と
し、このようにして決めた溶媒１０００重量部に１−Ａ
ＢＤの（共）重合体１重量部を導入し、３０”Ｃ，２４
時間浸せき、かくはんしたのち、２００メツシユの金あ
みでろ過した時の金あみ上に残留した（共）重合体量を
測定して求めたものである。また溶媒可溶分の数平均分
子量は、上記溶媒不溶分をろ別した後の１−ＡＢＤの（
共）重合体を適当な溶媒、たとえばアセトン、テトラヒ
ドロフランなどに溶解して、ＧＰＣによシボリスチレン
を標準サンプルとして測定したものである。Note that the solvent-insoluble portion described in this specification is 1-ABD (
Co) In the composition of the polymer, if the total amount of one monomer unit containing 1-ABD and a polar group is 70 weight or more, use acetone as a solvent, and if it is less than 70 weight, use toluene as a solvent. 1-A to 1000 parts by weight of the solvent determined by
Introducing 1 part by weight of BD (co)polymer, 30"C, 24
After soaking and stirring for a period of time, the sample was filtered through a 200-mesh gold wire, and the amount of (co)polymer remaining on the gold wire was measured. In addition, the number average molecular weight of the solvent-soluble component is the (
The co)polymer was dissolved in an appropriate solvent such as acetone or tetrahydrofuran, and measured by GPC using siboristyrene as a standard sample.
以下実施例によシ１本発明を一層具体的に説明する。The present invention will be explained in more detail below by way of examples.
〔実施例１〕
容量ｓ ｏ ｏ ｃｃのガラス製耐圧ビンに窒素下、１
−ＡＢＤｔｌＯＯＮ、）’７’シルベンゼンスルフォン
酸ナトリウム６Ｉｉ、水２００ Ｎ、エチレンジアミン
四酢酸ナトリウム０．１Ｎ、硫酸第１鉄０．１．１Ｆ。[Example 1] In a glass pressure bottle with a capacity of s o o cc, under nitrogen, 1
-ABDtlOON,) '7' Sodium sylbenzenesulfonate 6Ii, water 200N, sodium ethylenediaminetetraacetate 0.1N, ferrous sulfate 0.1.1F.
ナトリウムホルムアルデヒドスルホキシレート０、ＩＩ
、パラメンタンヒドロペルオキシｔ”ｔｅｌを仕込み、
１５℃で４００時間反応せた。その後Ｎ、Ｎ−ジエチル
ヒドロキシルアミン１．０１を入れ−て重合を停止させ
た。これにょシ凝固物のないエマルジ冒ンが得られ、重
合率は９９．９１！であった。このエマルジ璽ン１００
Ｉを１１のメタノール中に滴下し重合体を析出させ、メ
タノールで充分洗浄したのち乾燥した。この重合体ｉｐ
を１０００Ｊｌｌのアセトンにいれ、３０℃、２４時間
、！グネテックスターラーで攪拌し、２００メツシ＆の
金網でろ過した。重合体のアセトン可溶分は、６五７−
であ如、不溶分は３４．３重量−でありた。このアセト
ン可溶分の数平均分子量は２０龜・ＳＯであった。Sodium formaldehyde sulfoxylate 0, II
, paramenthane hydroperoxy t"tel was prepared,
The reaction was carried out at 15°C for 400 hours. Thereafter, 1.01 l of N,N-diethylhydroxylamine was added to terminate the polymerization. This resulted in an emulsion free of coagulum, and the polymerization rate was 99.91! Met. This emulsion seal 100
I was added dropwise to methanol in Step 11 to precipitate a polymer, which was thoroughly washed with methanol and then dried. This polymer ip
Put it in 1000 Jll of acetone, 30℃, 24 hours! The mixture was stirred with a Gnetex stirrer and filtered through a 200 mesh wire mesh. The acetone soluble content of the polymer is 657-
As a result, the insoluble content was 34.3 weight. The number average molecular weight of this acetone soluble portion was 20 mm SO.
〔比較例１〕
実施例Ｉにおいて、パラメンタンヒドロペルオキシドを
１．ＯＮとし１０℃で１５時間重合させた以外は実施例
１と同様に重合した。このもののアセトン不溶分は０．
２重量−であ）、可溶ノ分は９＆８−で、アセトン可溶
分の数平均分子量は２３０，０００ であった。[Comparative Example 1] In Example I, paramenthane hydroperoxide was added to 1. Polymerization was carried out in the same manner as in Example 1 except that the polymerization was turned on and polymerized at 10° C. for 15 hours. The acetone insoluble content of this product is 0.
2 weight), the soluble fraction was 9 & 8, and the number average molecular weight of the acetone soluble fraction was 230,000.
〔実施例２〕 容量５００ ｃｃのガラス製耐圧ビンに窒素下。[Example 2] Under nitrogen in a glass pressure bottle with a capacity of 500 cc.
１−ＡＢＤを１００Ｌドデシルベンゼンスルフオン酸ナ
トリウム６１１％水２０ＯＮ、ターシャリ−ドデシルメ
ルカプタン０．１Ｎ、硫酸水素ナトリウム（Ｌ２ｊ’、
過硫酸カリウム０．２ＪｉＦを仕込み６０℃で９時間反
応させた。その後Ｎ、Ｎ−ジエチルヒドロキシルアミン
０．５Ｎを入れて反応を停止させた。重合率９７．７−
であシ、実施例１と同様にしてアセトン不溶分およびア
セトン可溶分の数平均分子量を調べたところ、それぞれ
８五３重量−および１３０，０００であった。1-ABD was added to 100 L of sodium dodecylbenzenesulfonate 611% water, 20 ON of water, tertiary dodecyl mercaptan 0.1 N, sodium hydrogen sulfate (L2j',
0.2 JiF of potassium persulfate was added and reacted at 60°C for 9 hours. Thereafter, 0.5N of N,N-diethylhydroxylamine was added to stop the reaction. Polymerization rate 97.7-
The number average molecular weights of the acetone-insoluble and acetone-soluble components were examined in the same manner as in Example 1, and found to be 853 and 130,000, respectively.
〔実施例３〕
実施例２において、過硫酸カリウムの代わシにアゾビス
イソブチロニトリルを１．０ν用い、７５℃で９時間重
合させた以外は実施例２と同様に重合した。重合率９６
％で、この重合体のアセトン不溶分およびアセトン可溶
分の数平均分子量は、それぞれ８８．７重量％および１
３２，０００であった。[Example 3] Polymerization was carried out in the same manner as in Example 2, except that 1.0v of azobisisobutyronitrile was used instead of potassium persulfate, and the polymerization was carried out at 75°C for 9 hours. Polymerization rate 96
%, the number average molecular weights of the acetone-insoluble and acetone-soluble portions of this polymer are 88.7% by weight and 1% by weight, respectively.
It was 32,000.
〔実施例４〕
実施例１〜３および比較例１で得たエマルジ璽ンを真空
下、固形分４５重量−に濃縮し、これらのエマルジ璽ン
をガラス板に１００Ｎ／ｊの割合で塗布し、ガラス板ど
うしをはりあわせ、５０℃で真空下、８時間乾燥したの
ち、テンシロ／で圧縮せん断を測定した結果、次の通シ
であっ九。[Example 4] The emulsions obtained in Examples 1 to 3 and Comparative Example 1 were concentrated under vacuum to a solid content of 45% by weight, and these emulsions were applied to a glass plate at a rate of 100 N/j. After gluing the glass plates together and drying them under vacuum at 50°C for 8 hours, the compressive shear was measured using Tensilo/.
〔実施例５〜８および比較例２〕
１−ムＢＤ７０ｊＦｍスチレン３０ｊｌとし、パラメン
タンヒト四ペルオキシドをラジカ゛ル重合開始剤とし、
重合時間を下記のようｋして重合した以外は実施例１と
同様にして重合し、共重合体のアセトン不溶分およびア
セトン可溶分の数平均分子量を測定した。結果を以下に
示す。[Examples 5 to 8 and Comparative Example 2] 1-membrane BD70jFm styrene 30jl, p-menthane tetraperoxide as a radical polymerization initiator,
Polymerization was carried out in the same manner as in Example 1 except that the polymerization time was changed as shown below, and the number average molecular weights of the acetone-insoluble and acetone-soluble parts of the copolymer were measured. The results are shown below.
〔実施例９〕
スチレンの代わシにブタジェンを用い、実施例５と同様
に重合した。この共重合体のアセトン不溶分は４９％で
あり、アセトン可溶分の数平均分子量は３１０，０００
であった。[Example 9] Polymerization was carried out in the same manner as in Example 5, using butadiene instead of styrene. The acetone-insoluble content of this copolymer was 49%, and the number average molecular weight of the acetone-soluble content was 310,000.
Met.
〔実施例１０〕゛
実施例４と同様にして実施例５〜９および比較例２で得
た共重合体を用いガラス板を接着し、圧縮せん断応力を
測定した。結果を以下に示す。[Example 10] Glass plates were adhered using the copolymers obtained in Examples 5 to 9 and Comparative Example 2 in the same manner as in Example 4, and the compressive shear stress was measured. The results are shown below.
特許出願人 日本合成ゴム株式会社Patent applicant: Japan Synthetic Rubber Co., Ltd.
Claims (1)
分の数平均分子量がｓ、ｏｏｏ以上であるｌ−アセトキ
シ−１，３−ブタジェンの重合体または共重合体A polymer or copolymer of l-acetoxy-1,3-butadiene containing a solvent-insoluble component in an amount exceeding 10% by weight and a solvent-soluble component having a number average molecular weight of s, ooo or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18070481A JPS5883012A (en) | 1981-11-11 | 1981-11-11 | 1-acetoxy-1,3-butadiene (co)polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18070481A JPS5883012A (en) | 1981-11-11 | 1981-11-11 | 1-acetoxy-1,3-butadiene (co)polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5883012A true JPS5883012A (en) | 1983-05-18 |
| JPH0222763B2 JPH0222763B2 (en) | 1990-05-21 |
Family
ID=16087851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18070481A Granted JPS5883012A (en) | 1981-11-11 | 1981-11-11 | 1-acetoxy-1,3-butadiene (co)polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5883012A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0444866U (en) * | 1990-08-09 | 1992-04-16 | ||
| JPH0614819U (en) * | 1992-07-15 | 1994-02-25 | タカラスタンダード株式会社 | Unit with built-in heating and hot air generation functions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5694408A (en) * | 1979-12-27 | 1981-07-30 | Kawasaki Steel Corp | Level control method of ore storage tank |
| JPS56128784A (en) * | 1980-02-14 | 1981-10-08 | Roussel Uclaf | Triazoloquinazolinone derivative |
-
1981
- 1981-11-11 JP JP18070481A patent/JPS5883012A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5694408A (en) * | 1979-12-27 | 1981-07-30 | Kawasaki Steel Corp | Level control method of ore storage tank |
| JPS56128784A (en) * | 1980-02-14 | 1981-10-08 | Roussel Uclaf | Triazoloquinazolinone derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0222763B2 (en) | 1990-05-21 |
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