JPH0478493A - Scale inhibitor - Google Patents

Scale inhibitor

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Publication number
JPH0478493A
JPH0478493A JP19187590A JP19187590A JPH0478493A JP H0478493 A JPH0478493 A JP H0478493A JP 19187590 A JP19187590 A JP 19187590A JP 19187590 A JP19187590 A JP 19187590A JP H0478493 A JPH0478493 A JP H0478493A
Authority
JP
Japan
Prior art keywords
scale
bisphenol
type
formula
scale inhibitor
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.)
Granted
Application number
JP19187590A
Other languages
Japanese (ja)
Other versions
JP2974379B2 (en
Inventor
Naoki Nagahashi
長橋 直樹
Toshiharu Wake
敏治 和気
Toshimichi Shimizu
清水 敏通
Taketaka Matsuzaki
松崎 威毅
Tokihiro Nihongi
二本木 時洋
Yoshio Tanaka
祥雄 田中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Organo Corp
Toho Chemical Industry Co Ltd
Original Assignee
Organo Corp
Toho Chemical Industry Co Ltd
Japan Organo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Organo Corp, Toho Chemical Industry Co Ltd, Japan Organo Co Ltd filed Critical Organo Corp
Priority to JP2191875A priority Critical patent/JP2974379B2/en
Publication of JPH0478493A publication Critical patent/JPH0478493A/en
Application granted granted Critical
Publication of JP2974379B2 publication Critical patent/JP2974379B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PURPOSE:To obtain a scale inhibitor having a significant effect especially to silica-based scale by incorporating a specified compd. having a bisphenol type epoxy compd. as the skeleton and an alkylene oxide chain. CONSTITUTION:This scale inhibitor contains a compd. having a bisphenol type epoxy compd. as the skeleton and an alkylene oxide chain and represented by formula I (where R1 is a group represented by formula II, R2 is a group represented by formula III or IV, X shows formula V (bisphenol A type), formula VI (bisphenol S type) or formula VII (bisphenol AF type), n is an integer of 0-12, each of m1 and m2 is an arbitrary integer of >=1 but 2<=m1+m2<=1,000 and each of l1-l7 is an arbitrary integer of >=1 but 50<=l1+l2+l3+l4+l5+l6+ l7<=1,000-). This scale inhibitor has superior power especially to silica-based scale as well as to Ca-based scale and Mg-based scale.

Description

【発明の詳細な説明】 〈産業上の利用分野〉 本発明は水系のスケール防止剤に関する。[Detailed description of the invention] <Industrial application field> The present invention relates to a water-based scale inhibitor.

〈従来の技術〉 近年、水資源の有効利用の観点より工場などで使用水量
の低減を目的とした冷却水などの循環利用が進んでいる
。これに従い水の高濃縮化が進行し、その結果、このよ
うな水系ではカルシウム、マグネシウム、シリカなどの
いわゆるスケール成分の濃縮が起こり熱交換器などの伝
熱面へのスケール付着のトラブルが発生する。スケール
が付着すると熱交換率の低下をきたすだけでなく管の閉
塞、腐食などの障害が発生し最悪の場合は運転の中断に
つながる。このようなスケール障害は冷却水系に限らす
ボイラ水系、地熱発電水系でも発生する。特にシリカ系
スケールは硬質で熱伝導率が低く問題が大きい。
<Conventional Technology> In recent years, from the perspective of effective use of water resources, recycling of cooling water and the like has been progressing in factories and the like in order to reduce the amount of water used. Accordingly, water becomes highly concentrated, and as a result, in such water systems, so-called scale components such as calcium, magnesium, and silica are concentrated, causing problems such as scale adhesion to heat transfer surfaces such as heat exchangers. . When scale builds up, it not only reduces the heat exchange rate but also causes problems such as tube blockage and corrosion, which in the worst case can lead to interruption of operation. Such scale failures occur not only in cooling water systems, but also in boiler water systems and geothermal power generation water systems. In particular, silica scale is hard and has low thermal conductivity, which is a big problem.

従来、この様なスケールを防止する薬剤としてはりん化
合物、ポリアクリル酸、ポリマレイン酸あるいはそれら
の水溶性塩が使用されているが単独ではシリカ系スケー
ルに対しては殆ど効果を発揮しない。また、シリカ系ス
ケールの防止剤として第4級アンモニウム化合物(特開
昭57−110398号公報)、ポリアクリルアミド(
特開昭61−107997号公報)、グリオキサール(
特開昭61−293597号公報)、ポリアルキレンオ
キサイド系化合物(特公昭62−43758号公報、特
開昭59−29357号公報)などが提案されているが
その効果は十分でない。
Conventionally, phosphorus compounds, polyacrylic acid, polymaleic acid, or water-soluble salts thereof have been used as agents to prevent such scale, but these alone have little effect on silica scale. In addition, quaternary ammonium compounds (Japanese Unexamined Patent Publication No. 110398/1982), polyacrylamide (
JP-A No. 61-107997), glyoxal (
Although JP-A-61-293597) and polyalkylene oxide compounds (JP-A-62-43758, JP-A-59-29357) have been proposed, their effects are not sufficient.

〈発明が解決しようとする問題点〉 本発明はこれら従来技術の有する問題点を解決するもの
で、従来のものよりも優れたスケール防止効果を有し、
特にシリカ系スケールに対して優れた効果を発揮するス
ケール防止剤を折倒することを目的とする。
<Problems to be solved by the invention> The present invention solves the problems of the conventional techniques, and has a scale prevention effect superior to that of the conventional techniques.
The purpose is to develop a scale inhibitor that is particularly effective against silica scale.

く問題点を解決するための手段〉 上記目的を達成するためになされた本発明よりなるスケ
ール防止剤はビスフェノール型エポキシ化合物を骨格と
し、アルキレンオキサイド鎖を有する一般式(I) H−(Ri)* 1−(Ri)a z−(Rz)s+−
Means for Solving the Problems> The scale inhibitor according to the present invention, which has been made to achieve the above object, has a bisphenol type epoxy compound as a backbone and has an alkylene oxide chain and has a general formula (I) H-(Ri). *1-(Ri)az-(Rz)s+-
.

0J−0−CHt−CH−CHx−(1)0−(Rt)
a s−)! 0−(Ri)a a−(Rz)at−(Ri)j?−H
(式中、R7は−CH2−CHz−0−で表される基、
R2は CHエ          CH。
0J-0-CHt-CH-CHx-(1)0-(Rt)
a s-)! 0-(Ri)a a-(Rz)at-(Ri)j? -H
(In the formula, R7 is a group represented by -CH2-CHz-0-,
R2 is CHe CH.

−CH□−CH−0−または−CH−CH,−0で表さ
れる基、Xは  H5 Q−C−■(ビスフェノールA型)またはCH。
A group represented by -CH□-CH-0- or -CH-CH,-0, X is H5Q-C-■ (bisphenol A type) or CH.

CF3 ■−C−■(ビスフェノールAF型)を示し、CF。CF3 ■-C-■ (bisphenol AF type), CF.

nはO〜12の整数、ml、、 In zはそれぞれ2
≦m1+mz≦1.000の範囲にある1以上の任意の
整数、!、〜l、はそれぞれ50≦1.+1.+p3+
14+Ig、+16+It≦1,000の範囲にある1
以上の任意の整数である) で表される化合物を含有することを特徴とするものであ
る。
n is an integer from O to 12, ml, and Inz are each 2
Any integer greater than or equal to 1 in the range ≦m1+mz≦1.000,! , ~l, are each 50≦1. +1. +p3+
1 in the range of 14+Ig, +16+It≦1,000
It is characterized by containing a compound represented by (any integer above).

上記化合物は単独でも従来にない優れたスケール防止効
果を発揮するが、当該化合物とアクリル酸系重合体およ
び共重合体、マレイン酸系重合体および共重合体、並び
にスルホン酸系重合体および共重合体からなる群から選
ばれる少なくとも一つを含有するスケール防止剤を併用
するとさらに優れた効果が得られる。
The above compound alone exhibits unprecedented scale prevention effects, but it can also be used in conjunction with acrylic acid polymers and copolymers, maleic acid polymers and copolymers, and sulfonic acid polymers and copolymers. Even better effects can be obtained when a scale inhibitor containing at least one selected from the group consisting of:

本発明の化合物はエポキシオリゴマーとポリエチレンオ
キサイドーボリブロビレンオキサイドブロック共重合体
をカセイアルカリの触媒存在下、温度130ないし17
0℃で反応させ、次いでこの反応物にエチレンオキサイ
ドを同しくアルカリ触媒存在下、温度120ないし18
0℃で反応させて得ることができる。使用するエポキシ
オリゴマーとしてはビスフェノールA型、ビスフェノー
ルS型、ビスフェノールAF型のいずれも使用できるが
なかでもA型が一般的である。ビスフェノールA型はエ
ビコート#828、#10Q1、#1004、#100
7、#1008  (昭和シェル化学製)、エビトート
YD〜128、YD−011、YD−014、YD−0
17、YD〜019(東部化成製)などの商品名で市販
されており、これらのいずれもが利用できるが中でも前
記式(I)におけるnの値がn=0ないし4となるよう
なものが特に好まL7い。また、使用するポリエチレン
オキサイドーボリブロビレンオキサイドブロック共重合
体はブロロニソクし−43、L−63、L−103(旭
電化製)ニューボールPE−63、PE−73、PE−
83(三洋化成製)などの商品名で市販されており、こ
れらのいずれもが利用できる。
The compound of the present invention is prepared by combining an epoxy oligomer and a polyethylene oxide-polybropylene oxide block copolymer in the presence of a caustic catalyst at a temperature of 130 to 17°C.
The reaction was carried out at 0°C, and then ethylene oxide was added to the reaction product in the presence of an alkali catalyst at a temperature of 120 to 18°C.
It can be obtained by reacting at 0°C. As the epoxy oligomer to be used, any of bisphenol A type, bisphenol S type, and bisphenol AF type can be used, but type A is the most common. Bisphenol A type is Ebicoat #828, #10Q1, #1004, #100
7, #1008 (Showa Shell Chemical), Ebitoto YD~128, YD-011, YD-014, YD-0
17, YD~019 (manufactured by Tobu Kasei Co., Ltd.), and any of these can be used, but among them, those in which the value of n in the above formula (I) is n = 0 to 4 are used. I especially like L7. In addition, the polyethylene oxide-polybropylene oxide block copolymers used are Broronisokushi-43, L-63, L-103 (manufactured by Asahi Denka), New Ball PE-63, PE-73, PE-
It is commercially available under trade names such as 83 (manufactured by Sanyo Chemical), and any of these can be used.

また、併用するアクリル酸系重合体および共重合体、マ
レイン酸系重合体および共重合体、スルホン酸系重合体
および共重合体にはポリアクリル酸、ポリマレイン酸、
スチレンスルホン酸(以上単独重合体)、アクリル酸−
アクリルアミド共重合体、メタクリル酸−アクリルアミ
ド共重合体、マレイン酸−イソブチレン共重体、マレイ
ン酸スチレンスルホン酸共重合体およびそれらのナトリ
ウム塩、カリウム塩などのような水溶性塩があり、これ
らの一種または二種以上を併用する。これらの重合体は
公知の方法で容易に重合することができる。なお、これ
らの重合体の分子量は200ないし100000好まし
くは500ないし3ooooのものが適当である。
In addition, acrylic acid polymers and copolymers, maleic acid polymers and copolymers, sulfonic acid polymers and copolymers used in combination include polyacrylic acid, polymaleic acid,
Styrene sulfonic acid (homopolymer), acrylic acid-
There are water-soluble salts such as acrylamide copolymer, methacrylic acid-acrylamide copolymer, maleic acid-isobutylene copolymer, maleic acid styrene sulfonic acid copolymer, and their sodium salts, potassium salts, etc., and one of these or Use two or more types together. These polymers can be easily polymerized by known methods. The molecular weight of these polymers is suitably from 200 to 100,000, preferably from 500 to 3oooo.

上記重合体あるいは共重合体を、前記式(1)の化合物
と併用する場合は、各々を別々に用水中に添加してもよ
いが、各薬剤をあらかじめ所定の割合で混合して一剤と
なしておいた方が、取り扱いおよび添加操作が容易とな
るので便利である。
When the above polymer or copolymer is used in combination with the compound of formula (1), each may be added to the water separately, but each drug may be mixed in advance at a predetermined ratio to form a single agent. It is convenient to do so because handling and addition operations become easier.

各薬剤を混合して一剤とする場合の混合比率は、式(1
)の化合物二重合体およびまたは共重合体−9:1ない
し4:6 (重量比、以下同じ)、好ましくは8:2な
いし5:5が適当である。
The mixing ratio when mixing each drug to form a single drug is calculated using the formula (1
) compound polymers and/or copolymers in a weight ratio of 9:1 to 4:6 (weight ratio, same hereinafter), preferably 8:2 to 5:5.

また、本発明のスケール防止剤の添加量は、式(I)の
化合物を単独で使用する場合、および式(1)の化合物
に加えて前記重合体およびまたは共重合体を含有するス
ケール防止剤の場合のいずれにおいても水中の濃度で1
ないし500■/l、好ましくは5ないし200■/l
となるような量とするとよい。添加は液状で行っても固
体状で行ってもいずれでもよいが、添加量の正確を期す
ためには液状で添加する方がよい。
Further, the amount of the scale inhibitor of the present invention to be added is determined when the compound of formula (I) is used alone, and when the scale inhibitor contains the above polymer and/or copolymer in addition to the compound of formula (1). In either case, the concentration in water is 1.
from 5 to 500 ■/l, preferably from 5 to 200 ■/l
It is best to set the amount so that It may be added in either liquid or solid form, but in order to ensure accuracy in the amount added, it is better to add in liquid form.

なお、本発明のスケール防止剤は水酸化すトリウム、炭
酸ナトリウムのようなpH調整剤、りん酸化合物、ヘキ
サメタりん酸化合物、ホスホン酸化合物のようなりん酸
またはそれらの塩、亜鉛化合物、モリブデン化合物のよ
うな通常防食側として使用される金属化合物、ベンゾト
リアゾール、トリルトリアゾールのようなアゾール化合
物、塩素系化合物、4級アンモニウム系化合物、有機窒
素硫黄系化合物、アルデヒド系化合物のような殺菌剤な
どと併用したり、配合して使用することは何ら差し支え
ない。
Incidentally, the scale inhibitor of the present invention is a pH adjuster such as storium hydroxide or sodium carbonate, a phosphoric acid compound, a hexametaphosphoric acid compound, a phosphoric acid compound, or a salt thereof such as a phosphonic acid compound, a zinc compound, or a molybdenum compound. metal compounds that are usually used as anti-corrosion agents, azole compounds such as benzotriazole and tolyltriazole, chlorine compounds, quaternary ammonium compounds, organic nitrogen sulfur compounds, and disinfectants such as aldehyde compounds. There is no problem in using them together or in combination.

〈作用〉 ビスフェノール型エポキシ化合物を骨格としアルキレン
オキサイド鎖を有する一般式(1)で表される化合物は
前記した特公昭62−43758号公報、特開昭59−
29357号公報でN案されているようなポリアルキレ
ンオキサイド系化合物と比較すると疎水基と親木基の配
列が大きく異なっており、この特異な構造により水中の
カルシウム系、マグネシウム系析出物だけでなく特にシ
リカ系析出物の表面に物理的に強く吸着して結晶の成長
を抑制することができ、よってスケールの生成を防止す
ると考えられる。
<Function> The compound represented by the general formula (1) having a bisphenol type epoxy compound skeleton and an alkylene oxide chain is disclosed in the aforementioned Japanese Patent Publication No. 62-43758 and Japanese Patent Application Laid-Open No. 1983-1989.
Compared to polyalkylene oxide compounds such as the one proposed in Publication No. 29357, the arrangement of hydrophobic groups and parent groups is significantly different, and this unique structure prevents not only calcium-based and magnesium-based precipitates in water. In particular, it is thought that it can strongly physically adsorb to the surface of silica-based precipitates and suppress crystal growth, thereby preventing scale formation.

また、上記化合物と併用するアクリル酸系重合体および
共重合体、マレイン酸系重合体および共重合体、並びに
スルボン酸系重合体および共重合体は、特にカルシウム
系、マグネシウム系析出物の表面に強く吸着するため両
化合物を併用することによりカルシウム系、マグネシウ
ム系析出物だけでなくカルシウムとシリカ、マグネシウ
ムとシリカの反応析出物の結晶成長を抑制することがで
き、相乗的にさらに優れた効果を発揮すると考えられる
In addition, acrylic acid polymers and copolymers, maleic acid polymers and copolymers, and sulfonic acid polymers and copolymers used in combination with the above compounds are particularly effective against the surface of calcium and magnesium precipitates. Because of their strong adsorption, by using both compounds together, it is possible to suppress the crystal growth of not only calcium-based and magnesium-based precipitates, but also reaction precipitates of calcium and silica, and magnesium and silica, resulting in an even better effect synergistically. It is thought that it will be effective.

〈実施例〉 以下に本発明の詳細な説明する。<Example> The present invention will be explained in detail below.

実施例1 伝熱面積0.3−の熱交換器を有し、保有水量0゜8−
の実験用開放循環式冷却装置を使用し、所定の薬品を所
定量維持しながら循環水の濃縮倍数が7倍になるように
下記の条件で運転を行った。
Example 1 A heat exchanger with a heat transfer area of 0.3- and a retained water amount of 0°8-
Using an experimental open circulation type cooling device, operation was carried out under the following conditions so that the concentration ratio of the circulating water was increased to 7 times while maintaining the specified amount of the specified chemicals.

運転条件 熱交換器入口温度 30℃ 熱交換器出口温度 45℃ 流速       1.0m/s 補給氷水質 p H6,8 電気伝導率   180a/cd シリカ     61■s i Oz/ ’カルシウム
   35 N Ca CO:l/ I!マグネシウム
  9.0mgCaC0,/1運転終了後、循環水のシ
リカ濃度およびカルシウム濃度の分析を行った。
Operating conditions Heat exchanger inlet temperature 30℃ Heat exchanger outlet temperature 45℃ Flow rate 1.0m/s Makeup ice water quality pH 6,8 Electrical conductivity 180a/cd Silica 61■s i Oz/ 'Calcium 35N Ca CO:l / I! Magnesium: 9.0 mgCaC0,/1 After the operation was completed, the silica concentration and calcium concentration of the circulating water were analyzed.

使用した薬剖の種類を表m1ll、(2)に、また実験
結果を表2に示す。
The type of pharmacological analysis used is shown in Table ml, (2), and the experimental results are shown in Table 2.

表2 実験結果 表1−(21 使用薬剤 表2に見られるごとく、本発明のスケール防止剤を添加
した循環水の場合は、特にそのシリカ濃度において比較
例の場合より著しく高くなっている。このことは、使用
した熱交換器の伝熱面等へのシリカスケールの析出、付
着が少ないことを意味しており、本発明のスケール防止
剤が優れた効果を発揮することがわかる。
Table 2 Experimental Results Table 1-(21 Chemicals Used As seen in Table 2, the silica concentration in the circulating water to which the scale inhibitor of the present invention was added was significantly higher than in the comparative example. This means that there is little precipitation or adhesion of silica scale on the heat transfer surface of the heat exchanger used, and it can be seen that the scale inhibitor of the present invention exhibits excellent effects.

実施例2 伝熱面積100dのヒーターを有し保有水量100!の
循環装置に、あらかじめ工業用水を濃縮して作成した下
記の水質の水を入れ、その中に所定の薬品を所定量添加
し14日間運転した。
Example 2 It has a heater with a heat transfer area of 100 d and has a water capacity of 100! Water of the following quality, which had been prepared by concentrating industrial water in advance, was placed in a circulation device, and a specified amount of a specified chemical was added thereto, and the system was operated for 14 days.

循環水水質 p H7,8 電気伝導率  1550ハ/− ”’)’:h     l 85aS ioz/lカル
シウム410 ■c a CO:I/ 1マグネシウム
  91 [Ca CO,/ 1運転終了後、ヒーター
に付着したスケールの付着速度を測定した。
Circulating water quality pH 7,8 Electrical conductivity 1550ha/- ``')': h l 85aS ioz/l Calcium 410 ■ca CO:I/ 1Magnesium 91 [Ca CO,/ 1 Adheres to the heater after completion of operation The adhesion rate of scale was measured.

その結果を比較例とともに表3に示す。なお、表3にお
いて前記表1と同じ薬剤記号は同一の薬剤を示している
The results are shown in Table 3 along with comparative examples. Note that in Table 3, the same drug symbols as in Table 1 above indicate the same drugs.

表3より本発明のスケール防止剤が優れた効果を発揮す
ることがわかる。
Table 3 shows that the scale inhibitor of the present invention exhibits excellent effects.

〈効果〉 以上説明したごとく本発明のスケール防止剤はカルシウ
ム系、マグネシウム系のみならず特にシリカ系スケール
に対して優れた防止力を発揮し25、伝熱面の熱交換率
の低下を防止するだけでなく種々の障害の発生を防止し
産業に与える影響は大きい。
<Effects> As explained above, the scale inhibitor of the present invention exhibits excellent preventive power not only against calcium-based and magnesium-based scales but also particularly against silica-based scales25, and prevents a decrease in the heat exchange coefficient of the heat transfer surface. Not only that, but it also prevents the occurrence of various disorders and has a great impact on industry.

Claims (1)

【特許請求の範囲】 1、ビスフェノール型エポキシ化合物を骨格とし、アル
キレンオキサイド鎖を有する次の一般式( I )で表さ
れる化合物を含有するスケール防止剤。 ▲数式、化学式、表等があります▼( I ) (式中、R_1は−CH_2−CH_2−O−で表され
る基、R_2は ▲数式、化学式、表等があります▼または▲数式、化学
式、表等があります▼ で表される基、Xは ▲数式、化学式、表等があります▼(ビスフェノールA
型)または ▲数式、化学式、表等があります▼(ビスフェノールS
型)または ▲数式、化学式、表等があります▼(ビスフェノールA
F型)を示し、 nは0〜12の整数、m_1、m_2はそれぞれ2≦m
_1+m_2≦1,000の範囲にある1以上の任意の
整数、l_1〜l_7はそれぞれ50≦l_1+l_2
+l_3+l_4+l_5+l_6+l_7≦1,00
0の範囲にある1以上の任意の整数である)2、一般式
( I )で表される化合物と、アクリル酸系重合体およ
び共重合体、マレイン酸系重合体および共重合体、並び
にスルホン酸系重合体および共重合体からなる群から選
ばれる少なくとも一つを含有する特許請求の範囲第1項
記載のスケール防止剤。 3、スケールがシリカ系スケールである特許請求の範囲
第1項または第2項記載のスケール防止剤。
[Scope of Claims] 1. A scale inhibitor containing a compound represented by the following general formula (I) having a bisphenol-type epoxy compound skeleton and an alkylene oxide chain. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 is a group represented by -CH_2-CH_2-O-, R_2 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲Mathematical formulas, chemical formulas, There are tables, etc. ▼ For the group represented by,
Type) or ▲Mathematical formulas, chemical formulas, tables, etc.▼(Bisphenol S
Type) or ▲Mathematical formulas, chemical formulas, tables, etc.▼(Bisphenol A
F type), n is an integer from 0 to 12, m_1 and m_2 are each 2≦m
Any integer greater than or equal to 1 in the range of _1+m_2≦1,000, l_1 to l_7 are each 50≦l_1+l_2
+l_3+l_4+l_5+l_6+l_7≦1,00
(any integer greater than or equal to 1 within the range of 0) 2, a compound represented by the general formula (I), an acrylic acid polymer and copolymer, a maleic acid polymer and copolymer, and a sulfone The scale inhibitor according to claim 1, which contains at least one selected from the group consisting of acid polymers and copolymers. 3. The scale inhibitor according to claim 1 or 2, wherein the scale is a silica scale.
JP2191875A 1990-07-21 1990-07-21 Scale inhibitor Expired - Fee Related JP2974379B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2191875A JP2974379B2 (en) 1990-07-21 1990-07-21 Scale inhibitor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2191875A JP2974379B2 (en) 1990-07-21 1990-07-21 Scale inhibitor

Publications (2)

Publication Number Publication Date
JPH0478493A true JPH0478493A (en) 1992-03-12
JP2974379B2 JP2974379B2 (en) 1999-11-10

Family

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Application Number Title Priority Date Filing Date
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Country Link
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006150180A (en) * 2004-11-26 2006-06-15 Kurita Water Ind Ltd Scale inhibitor and scale inhibition method
US8277004B2 (en) 2004-08-26 2012-10-02 Lg Electronics Inc. Refrigerator and opening/closing apparatus of the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8277004B2 (en) 2004-08-26 2012-10-02 Lg Electronics Inc. Refrigerator and opening/closing apparatus of the same
JP2006150180A (en) * 2004-11-26 2006-06-15 Kurita Water Ind Ltd Scale inhibitor and scale inhibition method
JP4634780B2 (en) * 2004-11-26 2011-02-16 栗田工業株式会社 Scale inhibitor and scale prevention method

Also Published As

Publication number Publication date
JP2974379B2 (en) 1999-11-10

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