JPH0532733A - Production of varnish for paint - Google Patents
Production of varnish for paintInfo
- Publication number
- JPH0532733A JPH0532733A JP21443091A JP21443091A JPH0532733A JP H0532733 A JPH0532733 A JP H0532733A JP 21443091 A JP21443091 A JP 21443091A JP 21443091 A JP21443091 A JP 21443091A JP H0532733 A JPH0532733 A JP H0532733A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- polymerization initiator
- varnish
- solvent
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐水性、耐溶剤性に優
れた塗膜が得られる塗料用ワニスの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a varnish for paints, which gives a coating film having excellent water resistance and solvent resistance.
【０００２】[0002]
【従来の技術】従来から、塗料用ワニスの製造方法とし
て、特定の重合開始剤を使用する方法が知られている。
例えば、特開昭６３−１６８４１５号公報では、重合開
始剤として、ｔ−アミルヒドロペルオキシドあるいはｔ
−オクチルぺルオキシドの誘導体等を用いることによ
り、狭い分子量分布で高濃度の固形分を含み、かつ比較
的低粘度の塗料用ワニスを製造する方法を開示してい
る。2. Description of the Related Art Conventionally, a method of using a specific polymerization initiator has been known as a method for producing a varnish for paint.
For example, in JP-A-63-168415, t-amyl hydroperoxide or t- is used as a polymerization initiator.
Disclosed is a method for producing a coating varnish having a narrow molecular weight distribution, a high concentration of solids, and a relatively low viscosity by using a derivative of octyl peroxide.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、一般に
塗料用ワニスには種々の性能が要求され、特に耐水性、
耐溶剤性に優れた塗膜が得られる塗料用ワニスの出現が
要望されていた。However, various performances are generally required for coating varnishes, particularly water resistance,
There has been a demand for the appearance of a varnish for paints, which can provide a coating film having excellent solvent resistance.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記従来
法の問題点を長期にわたって研究した結果、特定の重合
開始剤を用いることによって、それらの問題点をすべて
解決した塗料用ワニスが得られることを見いだし、本発
明を完成するに至った。すなわち、本発明は、アクリル
酸ヒドロキシアルキルまたはメタクリル酸ヒドロキシア
ルキルの１種以上とアクリル酸エステルまたはメタクリ
ル酸エステルの１種以上とを重合開始剤を用いて溶媒中
において重合させるにあたり、重合開始剤として一般式DISCLOSURE OF THE INVENTION As a result of long-term studies on the problems of the above-mentioned conventional methods, the inventors of the present invention have found that a varnish for paints that solves all of these problems by using a specific polymerization initiator The inventors have found that they can be obtained and have completed the present invention. That is, in the present invention, when one or more kinds of hydroxyalkyl acrylate or hydroxyalkyl methacrylate and one or more kinds of acrylic acid ester or methacrylic acid ester are polymerized in a solvent using a polymerization initiator, General formula
【化２】 （式中、Ｒ1は炭素数１〜２のアルキル基、Ｒ2は炭素数
１〜５のアルキル基を表わす）で示される１種以上の有
機過酸化物を用いることを特徴とする塗料用ワニスの製
造方法に関する。[Chemical 2] ( 1 ) In the formula, one or more organic peroxides represented by R 1 represents an alkyl group having 1 to 2 carbon atoms and R 2 represents an alkyl group having 1 to 5 carbon atoms. The present invention relates to a method for manufacturing a varnish.
【０００５】本発明に使用されるアクリル酸ヒドロキシ
アルキルとしては、例えば２−ヒドロキシエチルアクリ
レート、２−ヒドロキシプロピルアクリレート等が挙げ
られ、メタクリル酸ヒドロキシアルキルとしては、例え
ば２−ヒドロキシエチルメタクリレート、２−ヒドロキ
シプロピルメタクリレート等が挙げられる。また、アク
リル酸エステルとしては、例えばメチルアクリレート、
エチルアクリレート、ｎ−ブチルアクリレート、イソブ
チルアクリレート、オクチルアクリレート、ラウリルア
クリレート等が挙げられ、メタクリル酸エステルとして
は、例えばメチルメタクリレート、エチルメタクリレー
ト、ｎ−ブチルメタクリレート、イソブチルメタクリレ
ート、オクチルメタクリレート、ラウリルメタクリレー
ト等が挙げられる。さらに、上記のモノマーと共重合可
能であって、通常、塗料用ワニスの製造に用いられるモ
ノマーを上記のモノマーと組み合わせて使用することも
できる。そのようなモノマーとしては、例えばアクリル
酸、メタクリル酸、スチレン、α−メチルスチレン、酢
酸ビニル、アクリロニトリル、ポリエチレングリコール
モノアクリレート、ポリエチレングリコールモノメタク
リレート等が挙げられる。Examples of hydroxyalkyl acrylates used in the present invention include 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate, and examples of hydroxyalkyl methacrylates include 2-hydroxyethyl methacrylate and 2-hydroxy. Examples include propyl methacrylate. Examples of acrylic acid esters include methyl acrylate,
Examples thereof include ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, and lauryl acrylate. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, octyl methacrylate, and lauryl methacrylate. Be done. Further, a monomer which is copolymerizable with the above-mentioned monomer and which is usually used for producing a coating varnish can be used in combination with the above-mentioned monomer. Examples of such a monomer include acrylic acid, methacrylic acid, styrene, α-methylstyrene, vinyl acetate, acrylonitrile, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate and the like.
【０００６】これらのモノマー（以下一括して重合用モ
ノマーという）は、製品の塗料用ワニスに対する要求性
能に応じて適宜組み合わせて使用され、そのうち、アク
リル酸ヒドロキシアルキルまたはメタクリル酸ヒドロキ
シアルキルの割合は、重合用モノマー全量の５〜３０重
量％が用いられる。５重量％未満では、製品の塗料用ワ
ニスの塗膜の密着性が低下し、３０重量％を超えると、
塗膜の物性が低下する。[0006] These monomers (hereinafter collectively referred to as "polymerization monomers") are used in an appropriate combination depending on the required performance of the coating varnish of the product, of which the proportion of hydroxyalkyl acrylate or hydroxyalkyl methacrylate is 5 to 30% by weight of the total amount of the monomers for polymerization is used. If it is less than 5% by weight, the adhesiveness of the coating film of the coating varnish of the product will be reduced, and if it exceeds 30% by weight,
The physical properties of the coating film deteriorate.
【０００７】さらに、製品の塗料用ワニスに対する重合
用モノマーの使用量は、４０〜７０重量％が用いられ
る。４０重量％未満では、製品の塗料用ワニス中の溶媒
の使用量が多くなり経済的に不利である。また、７０重
量％を超えると、重合物の粘度が高くなりすぎるため好
ましくない。Further, the amount of the polymerization monomer used in the product coating varnish is 40 to 70% by weight. If it is less than 40% by weight, the amount of the solvent used in the varnish for paint of the product is large, which is economically disadvantageous. On the other hand, if it exceeds 70% by weight, the viscosity of the polymer becomes too high, which is not preferable.
【０００８】本発明に用いられる重合開始剤としての有
機過酸化物としては、具体的には、ｔ−ヘキシルペルオ
キシ−２−エチルヘキサノエート、ｔ−ヘキシルペルオ
キシイソブチレート等が挙げられる。Specific examples of the organic peroxide used as a polymerization initiator in the present invention include t-hexylperoxy-2-ethylhexanoate and t-hexylperoxyisobutyrate.
【０００９】重合開始剤の使用量は、重合用モノマーに
対し、１〜７重量％が用いられる。１重量％未満では、
重合が完結せず、７重量％を超えると、重合開始剤の分
解物が製品の塗料用ワニスの塗膜の物性を低下させるた
め好ましくない。The amount of the polymerization initiator used is 1 to 7% by weight based on the polymerization monomer. Below 1% by weight,
If the polymerization is not completed and exceeds 7% by weight, the decomposition product of the polymerization initiator deteriorates the physical properties of the coating film of the coating varnish of the product, which is not preferable.
【００１０】本発明における溶媒としては、例えばトル
エン、キシレン等の芳香族炭化水素類；メチルエチルケ
トン、メチルイソブチルケトン等のケトン類；酢酸ブチ
ル等の酢酸エステル類；ｎ−ブチルアルコール等のアル
コール類あるいはそれらの混合物が用いられる。Examples of the solvent in the present invention include aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; acetic acid esters such as butyl acetate; alcohols such as n-butyl alcohol and the like. Is used.
【００１１】本発明の重合方法としては、上記の重合用
モノマー、重合開始剤および溶媒を混合し、重合温度１
００〜１４０℃で２〜１０時間重合させればよい。重合
温度が１００℃未満では、重合速度が遅く、得られた重
合物の平均分子量が大きくなり、１４０℃を超えると、
重合速度の調節が困難となり、いずれも好ましくない。
また、重合時間が２時間未満であると、重合熱の制御が
困難で、逆に１０時間を超えても特に利点はなく、経済
的に不利である。さらに、この重合反応の後期におい
て、重合物中に未反応モノマーが残存するのを防ぐた
め、一般に用いられる重合開始剤を追加してもよい。As the polymerization method of the present invention, the above-mentioned polymerization monomer, polymerization initiator and solvent are mixed and the polymerization temperature 1
Polymerization may be performed at 00 to 140 ° C. for 2 to 10 hours. When the polymerization temperature is less than 100 ° C, the polymerization rate is slow, and the average molecular weight of the obtained polymer is large, and when it exceeds 140 ° C,
It is difficult to control the polymerization rate, which is not preferable.
Further, if the polymerization time is less than 2 hours, it is difficult to control the heat of polymerization, and conversely, if it exceeds 10 hours, there is no particular advantage and it is economically disadvantageous. Further, in the latter stage of this polymerization reaction, a polymerization initiator generally used may be added in order to prevent the unreacted monomer from remaining in the polymer.
【００１２】この際、重合用モノマー、重合開始剤およ
び溶媒の具体的な混合方法としては、 （１）重合用モノマー、重合開始剤および溶媒の混合物
を、空の重合槽に連続的または間欠的に添加しながら攪
拌混合する方法 （２）重合用モノマーと重合開始剤との混合物を、溶媒
を入れた重合槽に連続的または間欠的に添加しながら攪
拌混合する方法 （３）重合用モノマー、重合開始剤および溶媒を、それ
ぞれ単独で同時に並行して重合槽に添加しながら攪拌混
合する方法 のいずれの方法でもよい。なお、これらの方法におい
て、予め、用いられる溶媒の中に重合用モノマーの一部
が、また逆に重合用モノマーの中に溶媒の一部が、それ
ぞれ混合されていても何ら差支えない。これらの場合
の、それぞれの混合割合は、重合装置，重合条件などに
応じて適宜定められる。At this time, as a specific method for mixing the polymerization monomer, the polymerization initiator and the solvent, (1) the mixture of the polymerization monomer, the polymerization initiator and the solvent is continuously or intermittently placed in an empty polymerization tank. (2) A method of stirring and mixing a mixture of a polymerization monomer and a polymerization initiator while continuously or intermittently adding the mixture to a polymerization tank containing a solvent (3) A monomer for polymerization, Any method may be used, in which the polymerization initiator and the solvent are independently added simultaneously and in parallel to the polymerization tank while stirring and mixing. In these methods, it does not matter even if a part of the polymerization monomer is mixed in the solvent used in advance, or conversely, a part of the solvent is mixed in the polymerization monomer. In these cases, the respective mixing ratios are appropriately determined depending on the polymerization equipment, the polymerization conditions and the like.
【００１３】[0013]
【発明の効果】本発明の塗料用ワニスの製造方法は、特
定の重合開始剤を用いることによって、耐溶剤性および
耐水性に優れた塗膜を得ることができる塗料用ワニスの
製造を可能にしたものであって、それにより、従来の塗
料用ワニスに対する要求をすべて満たし得るものであ
る。The method for producing a coating varnish of the present invention enables the production of a coating varnish capable of obtaining a coating film excellent in solvent resistance and water resistance by using a specific polymerization initiator. By doing so, it is possible to meet all the requirements for conventional coating varnishes.
【００１４】[0014]
【実施例および比較例】以下、実施例および比較例によ
り本発明を具体的に説明する。なお、これらの例におい
て、重合開始剤としての有機過酸化物および重合用モノ
マーの略号は以下のとおりである。 ＡｍＯ：ｔ−アミルペルオキシ−２−エチルヘキサノエ
ート（純度９７％） ＨｘＯ：ｔ−ヘキシルペルオキシ−２−エチルヘキサノ
エート（純度９８％） ＨｘＩＢ：ｔ−ヘキシルペルオキシイソブチレート（純
度９７％） ＯｃＯ：ｔ−オクチルぺルオキシ−２−エチルヘキサノ
エート（純度９５％） ＢｕＺ：ｔ−ブチルぺルオキシベンゾエート（商品名：
パーブチルＺ、日本油脂（株）製、純度９９％） ＭＭＡ：メチルメタクリレート ＢＭＡ：ｎ−ブチルメタクリレート ＬＭＡ：ラウリルメタクリレート ＨＥＭＡ：２−ヒドロキシエチルメタクリレート ＡＡ：アクリル酸EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. In these examples, the abbreviations of the organic peroxide as a polymerization initiator and the monomer for polymerization are as follows. AmO: t-amylperoxy-2-ethylhexanoate (purity 97%) HxO: t-hexylperoxy-2-ethylhexanoate (purity 98%) HxIB: t-hexylperoxyisobutyrate (purity 97%) OcO: t-octylperoxy-2-ethylhexanoate (purity 95%) BuZ: t-butylperoxybenzoate (trade name:
Perbutyl Z, manufactured by NOF CORPORATION, purity 99%) MMA: methyl methacrylate BMA: n-butyl methacrylate LMA: lauryl methacrylate HEMA: 2-hydroxyethyl methacrylate AA: acrylic acid
【００１５】実施例１ 滴下漏斗、攪拌機、ガス導入管、還流冷却器を有する１
０００ｍｌ四つ口フラスコ内を窒素ガスで置換したの
ち、キシレン３００ｇを入れ、滴下漏斗から、重合用モ
ノマーとしての、ＢＭＡ／ＬＭＡ／ＨＥＭＡ／ＡＡ（４
０／４０／１８／２（重量比））の混合物４５０ｇと重
合開始剤としてのＨｘＯ１６ｇとの混合物を１３０℃で
５時間かけて均一速度で滴下した。その後、未反応モノ
マーを除くためＢｕＺ４．５ｇを添加し、１３０℃で２
時間反応をつづけて粘性溶液７７１ｇを得た。この粘性
溶液について、まずガスクロマトグラフィーにより未反
応モノマー量を測定して重合転化率を求め、ついでＢ型
粘度計で粘度を測定した。さらに、粘性溶液１００ｇ
に、キシレン５０ｇ、ｎ−ブタノール１０ｇ、メラミン
硬化剤（商品名：サイメル３７０、三井東圧化学（株）
製）１０ｇを混合し、７０×１５０ｍｍの鋼板にスプレ
ー塗布したのち、１５０℃で３０分間乾燥して塗膜を形
成させ試験片とした。この試験片をトルエンに浸漬し、
室温で１週間放置したのち１００℃で１時間乾燥したも
のについて、浸漬前後の塗膜の重量を比較し、塗膜溶出
量を求めた。次に、以下の方法により浸漬前後の塗膜の
鮮映性を比較評価した。すなわち、直径５〜１０ｍｍの
１０段階の大きさの「○印」を印刷したセロファンテー
プを蛍光灯に貼り、それを試験片の塗膜に映してどの段
階の大きさまで判別できるかを評価した（評価基準とし
ては、小さい○印が判別できるほど鮮映性が高いとし、
測定値として大きい値となるようにした）。それらの結
果を表１に示す。Example 1 1 having a dropping funnel, a stirrer, a gas introduction pipe, and a reflux condenser
After purging the inside of the 000 ml four-necked flask with nitrogen gas, 300 g of xylene was put in, and BMA / LMA / HEMA / AA (4
A mixture of 450 g of a mixture of 0/40/18/2 (weight ratio) and 16 g of HxO as a polymerization initiator was added dropwise at 130 ° C. over 5 hours at a uniform rate. After that, 4.5 g of BuZ was added to remove unreacted monomer, and the mixture was added at 130 ° C for 2 hours.
The reaction was continued over time to obtain 771 g of a viscous solution. With respect to this viscous solution, the amount of unreacted monomer was first measured by gas chromatography to obtain the polymerization conversion rate, and then the viscosity was measured with a B-type viscometer. Furthermore, 100 g of viscous solution
In addition, xylene 50 g, n-butanol 10 g, melamine curing agent (trade name: Cymel 370, Mitsui Toatsu Chemicals, Inc.)
10 g) was mixed and spray-coated on a 70 × 150 mm steel plate, and then dried at 150 ° C. for 30 minutes to form a coating film, which was used as a test piece. Immerse this test piece in toluene,
About the thing dried at 100 degreeC for 1 hour after leaving it to stand at room temperature for 1 hour, the weight of the coating film before and after immersion was compared, and the coating film elution amount was calculated | required. Next, the following method was used to compare and evaluate the sharpness of the coating film before and after the immersion. That is, a cellophane tape having a diameter of 5 to 10 mm and a 10-step size of "○" printed thereon was attached to a fluorescent lamp, and it was projected on the coating film of the test piece to evaluate up to which size the size can be determined ( As the evaluation standard, the sharpness is high enough to distinguish small circles,
I made it a large value as a measured value). The results are shown in Table 1.
【００１６】実施例２、比較例１，２ 実施例１において、ＨｘＯ１６ｇの代わりに表１にそれ
ぞれ示す重合開始剤を使用する以外は、実施例１に準じ
て重合を行なった。その結果を表１に示す。Example 2, Comparative Examples 1 and 2 Polymerization was carried out according to Example 1 except that the polymerization initiators shown in Table 1 were used instead of 16 g of HxO. The results are shown in Table 1.
【００１７】実施例３，４、比較例３ 実施例１において、重合用モノマーとしての、ＢＭＡ／
ＬＭＡ／ＨＥＭＡ／ＡＡ（４０／４０／１８／２（重量
比））の代わりに、ＭＭＡ／ＢＭＡ／ＨＥＭＡ／ＡＡ
（４３／４０／１５／２（重量比））を用いる以外は、
実施例１に準じて粘性溶液を得た。ついで、この粘性溶
液１００ｇに、キシレン５０ｇ、ｎ−ブタノール１０ｇ
を混合し、７０×１５０ｍｍの鋼板にスプレー塗布した
のち、１５０℃で３０分間乾燥して塗膜を形成させ試験
片とした。この試験片を沸騰水に浸漬し、５時間放置し
たのち１００℃で１時間乾燥したものについて、浸漬前
後の塗膜の重量を比較し、塗膜溶出量を求め、さらに塗
膜の鮮映性を測定した。それらの結果を表１に示す。Examples 3, 4 and Comparative Example 3 In Example 1, BMA / as the polymerization monomer was used.
Instead of LMA / HEMA / AA (40/40/18/2 (weight ratio)), MMA / BMA / HEMA / AA
Except using (43/40/15/2 (weight ratio))
A viscous solution was obtained according to Example 1. Then, 50 g of xylene and 10 g of n-butanol were added to 100 g of this viscous solution.
Was mixed and spray-coated on a 70 × 150 mm steel plate, and then dried at 150 ° C. for 30 minutes to form a coating film, which was used as a test piece. This test piece was immersed in boiling water, allowed to stand for 5 hours and then dried at 100 ° C. for 1 hour, the weights of the coating film before and after immersion were compared, the amount of coating film elution was determined, and the sharpness of the coating film was further determined. Was measured. The results are shown in Table 1.
【００１８】[0018]
【表１】 この表１の結果から明らかなように、本発明の重合開始
剤を使用した実施例１，２においては、従来の重合開始
剤を使用した比較例１，２と比較して、有機溶剤に浸漬
したときの塗膜溶出量が少なく、さらに浸漬前後の塗膜
の鮮映性の劣化がないことが分かる。一方、同じく本発
明の重合開始剤を使用した実施例３，４においても、従
来の重合開始剤を使用した比較例３と比較して、沸騰水
に浸漬したときの塗膜溶出量が少なく、また浸漬前後の
塗膜の鮮映性の劣化もないことが分かる。以上のことか
ら、本発明の重合開始剤を用いることにより、耐溶剤
性、耐水性に優れた塗膜が得られることが認められる。[Table 1] As is clear from the results of Table 1, in Examples 1 and 2 using the polymerization initiator of the present invention, as compared with Comparative Examples 1 and 2 using the conventional polymerization initiator, immersion in an organic solvent It can be seen that the amount of coating film elution at that time was small and there was no deterioration in the clarity of the coating film before and after immersion. On the other hand, also in Examples 3 and 4 in which the polymerization initiator of the present invention was also used, the elution amount of the coating film when immersed in boiling water was small as compared with Comparative Example 3 in which the conventional polymerization initiator was used. Further, it can be seen that there is no deterioration in the sharpness of the coating film before and after the immersion. From the above, it is recognized that a coating film having excellent solvent resistance and water resistance can be obtained by using the polymerization initiator of the present invention.
Claims (1)
タクリル酸ヒドロキシアルキルの１種以上とアクリル酸
エステルまたはメタクリル酸エステルの１種以上とを重
合開始剤を用いて溶媒中において重合させるにあたり、
重合開始剤として一般式 【化１】 （式中、Ｒ1は炭素数１〜２のアルキル基、Ｒ2は炭素数
１〜５のアルキル基を表わす）で示される１種以上の有
機過酸化物を用いることを特徴とする塗料用ワニスの製
造方法。Claim: What is claimed is: 1. When polymerizing one or more hydroxyalkyl acrylates or hydroxyalkyl methacrylates and one or more acrylates or methacrylates in a solvent using a polymerization initiator. ,
General formula as a polymerization initiator ( 1 ) In the formula, one or more organic peroxides represented by R 1 represents an alkyl group having 1 to 2 carbon atoms and R 2 represents an alkyl group having 1 to 5 carbon atoms. Method of manufacturing varnish.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21443091A JPH0532733A (en) | 1991-07-31 | 1991-07-31 | Production of varnish for paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21443091A JPH0532733A (en) | 1991-07-31 | 1991-07-31 | Production of varnish for paint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0532733A true JPH0532733A (en) | 1993-02-09 |
Family
ID=16655657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21443091A Pending JPH0532733A (en) | 1991-07-31 | 1991-07-31 | Production of varnish for paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0532733A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4885445A (en) * | 1987-12-09 | 1989-12-05 | Kabushiki Kaisha Toshiba | High-frequency transformer for microwave oven |
| JPH07149836A (en) * | 1993-07-23 | 1995-06-13 | Hoechst Ag | Production of oh-containing copolymer and its use for high-solid coating material |
| GB2456893A (en) * | 2007-12-25 | 2009-08-05 | Nippon Paint Co Ltd | Clear coating composition for multilayered coating film |
| JP2014105255A (en) * | 2012-11-27 | 2014-06-09 | Nof Corp | Organic peroxide-containing polymerizable monomer composition, suspension polymerization composition, and suspension polymer for manufacturing suspension polymerization toner |
| US9669851B2 (en) | 2012-11-21 | 2017-06-06 | General Electric Company | Route examination system and method |
| US9834237B2 (en) | 2012-11-21 | 2017-12-05 | General Electric Company | Route examining system and method |
| US10308265B2 (en) | 2006-03-20 | 2019-06-04 | Ge Global Sourcing Llc | Vehicle control system and method |
-
1991
- 1991-07-31 JP JP21443091A patent/JPH0532733A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4885445A (en) * | 1987-12-09 | 1989-12-05 | Kabushiki Kaisha Toshiba | High-frequency transformer for microwave oven |
| JPH07149836A (en) * | 1993-07-23 | 1995-06-13 | Hoechst Ag | Production of oh-containing copolymer and its use for high-solid coating material |
| US10308265B2 (en) | 2006-03-20 | 2019-06-04 | Ge Global Sourcing Llc | Vehicle control system and method |
| GB2456893A (en) * | 2007-12-25 | 2009-08-05 | Nippon Paint Co Ltd | Clear coating composition for multilayered coating film |
| GB2456893B (en) * | 2007-12-25 | 2010-05-19 | Nippon Paint Co Ltd | Clear coating composition and method for producing multilayered coating film |
| US9669851B2 (en) | 2012-11-21 | 2017-06-06 | General Electric Company | Route examination system and method |
| US9834237B2 (en) | 2012-11-21 | 2017-12-05 | General Electric Company | Route examining system and method |
| JP2014105255A (en) * | 2012-11-27 | 2014-06-09 | Nof Corp | Organic peroxide-containing polymerizable monomer composition, suspension polymerization composition, and suspension polymer for manufacturing suspension polymerization toner |
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