JPH06157026A - Inorganic builder - Google Patents
Inorganic builderInfo
- Publication number
- JPH06157026A JPH06157026A JP32841692A JP32841692A JPH06157026A JP H06157026 A JPH06157026 A JP H06157026A JP 32841692 A JP32841692 A JP 32841692A JP 32841692 A JP32841692 A JP 32841692A JP H06157026 A JPH06157026 A JP H06157026A
- Authority
- JP
- Japan
- Prior art keywords
- inorganic builder
- cation exchange
- cation
- exchange capacity
- present
- 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
Links
Landscapes
- Cosmetics (AREA)
- Detergent Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は無機ビルダーに関する。
さらに詳しくは、洗剤に用いられる水軟水化剤、アルカ
リ調整剤として有用な無機ビルダーおよびその水和物に
関する。FIELD OF THE INVENTION The present invention relates to an inorganic builder.
More specifically, it relates to a water softening agent used in detergents, an inorganic builder useful as an alkali modifier, and a hydrate thereof.
【０００２】[0002]
【従来の技術・発明が解決しようとする課題】珪酸ナト
リウムはゼオライト以上のイオン交換能を有している
が、水に完全溶解するため、イオン交換速度が小さくそ
の利用が限られていた。それを解決する手段として、珪
酸ナトリウムを加熱脱水、焼成して、粉末化する方法が
特開昭６０−２３９３２０号公報に、また同様の手法で
珪酸ナトリウムの珪素の一部をアルミニウムあるいはホ
ウ素で同型置換する方法が特開平３−９３６４９号公
報、特開平４−１６００１３号公報に開示されている
が、いずれも耐水性が不十分で、イオン交換能も低く、
イオン交換速度も小さい。また、水熱合成により得られ
る結晶性の珪酸カルシウムアルカリ水和物が特公昭６１
−５９２４５号公報に開示されているが、耐水性は充分
であるもののイオン交換能は低く、実質的に洗剤用ビル
ダーとして適さない。さらに、粒子形状が粗大の長繊維
状あるいは雲母状であるため水への分散性が悪く、実質
的なイオン交換能はさらに低下する。またＤＤ−２７９
２３４Ａ１公報には水熱合成により得られる結晶性のマ
グネシウム含有シリケートが開示されているが、イオン
交換能が極端に低く、実用上洗剤用ビルダーとしては適
用できないという問題が指摘されている。特に、洗剤用
の水軟化剤として利用する場合、限られた時間内にイオ
ン交換する必要があり、初期のカチオン交換速度の大な
るものが要求される。つまり、Ｃａ，Ｍｇイオン等を５
分以内、好ましくは３分以内に充分捕捉する必要があ
る。2. Description of the Related Art Sodium silicate has an ion exchange capacity higher than that of zeolite, but since it is completely dissolved in water, its ion exchange rate is small and its use is limited. As a means for solving the problem, a method of heating sodium silicate to dehydration and firing and pulverizing it is disclosed in JP-A-60-239320, and in the same manner, a part of silicon of sodium silicate is formed in the same shape with aluminum or boron. A method of substituting is disclosed in JP-A-3-93649 and JP-A-4-160013, but both have insufficient water resistance and low ion exchange capacity,
The ion exchange rate is also low. In addition, crystalline calcium silicate alkali hydrate obtained by hydrothermal synthesis is disclosed in JP-B-61.
Although disclosed in JP-A-59245, although it has sufficient water resistance, it has a low ion exchange capacity and is substantially unsuitable as a builder for detergents. Furthermore, since the particle shape is a coarse long fiber shape or a mica shape, the dispersibility in water is poor, and the substantial ion exchange capacity further decreases. Also DD-279
Although 234A1 discloses a crystalline magnesium-containing silicate obtained by hydrothermal synthesis, it has been pointed out that it has an extremely low ion exchange capacity and cannot be practically used as a detergent builder. In particular, when used as a water softener for detergents, it is necessary to perform ion exchange within a limited time, and a high initial cation exchange rate is required. In other words, Ca, Mg ions, etc.
It is necessary to sufficiently capture within minutes, preferably within 3 minutes.
【０００３】従って、本発明の目的は、耐水性に優れか
つ高いイオン交換能と速い初期カチオン交換速度を有す
る新規な無機ビルダーおよびその水和物を提供すること
にある。Therefore, it is an object of the present invention to provide a novel inorganic builder and its hydrate which are excellent in water resistance and have a high ion exchange capacity and a high initial cation exchange rate.
【０００４】[0004]
【課題を解決するための手段】本発明者らは前記課題を
解決するために鋭意研究を重ねた結果、特定の組成から
なる新規な無機ビルダーおよびその水和物を見出し、本
発明を完成するに至った。即ち、本発明の要旨は、
（１）一般式、ＳｉＯ2 ・ａＢ2 Ｏ3 ・ｂＮａ2 Ｏ・ｃ
Ｋ2 Ｏ・ｄＣａＯ・ｅＭｇＯ（但し、ａ＝０．０１〜
１．０、ｂ＋ｃ＝０．５〜２．０、ｃ／ｂ＝０．００５
〜８．０、ｄ＋ｅ＝０．０１〜１．０、ｅ／ｄ＝０．１
〜１０）で表される組成からなる無機ビルダー、（２）
初期カチオン交換速度が７０ＣａＣＯ3 ｍｇ／ｇ・ｍｉ
ｎ以上であり、カチオン交換容量が２００〜６００Ｃａ
ＣＯ3 ｍｇ／ｇである前記（１）記載の無機ビルダー、
並びに、（３）前記（１）または（２）記載の無機ビル
ダーの水和物に関する。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found a novel inorganic builder having a specific composition and its hydrate, and completed the present invention. Came to. That is, the gist of the present invention is
(1) General formula, SiO 2 · aB 2 O 3 · bNa 2 O · c
K 2 O · dCaO · eMgO (However, a = 0.01~
1.0, b + c = 0.5 to 2.0, c / b = 0.005
~ 8.0, d + e = 0.01-1.0, e / d = 0.1
Inorganic builder having composition represented by (10) to (10), (2)
Initial cation exchange rate is 70 CaCO 3 mg / g · mi
n or more and a cation exchange capacity of 200 to 600 Ca
The inorganic builder according to (1) above, which has CO 3 mg / g,
And (3) a hydrate of the inorganic builder according to (1) or (2) above.
【０００５】本発明の無機ビルダーは、組成が一般式、
ＳｉＯ2 ・ａＢ2 Ｏ3 ・ｂＮａ2 Ｏ・ｃＫ2 Ｏ・ｄＣａ
Ｏ・ｅＭｇＯで表わされるものである。ここで、ａは通
常０．０１〜１．０であり、好ましくは０．０２〜０．
５である。即ち、カチオン交換容量を高めるにはａが
０．０１以上であるのが好ましく、カチオン交換速度を
高めるには１．０以下にするのが好ましい。ｂ＋ｃは通
常０．５〜２．０であり、好ましくは０．５〜１．０で
ある。即ち、カチオン交換容量を高めるにはｂ＋ｃが
０．５以上であるのが好ましく、カチオン交換速度を高
めるには２．０以下にするのが好ましい。ｃ／ｂは通常
０．００５〜８．０であり、好ましくは０．０１〜６．
０である。即ち、カチオン交換速度を高めるにはｃ／ｂ
が０．００５以上であるのが好ましく、耐吸湿性を良好
にする観点から８．０以下にするのが好ましい。ｄ＋ｅ
は通常０．０１〜１．０であり、好ましくは０．０１〜
０．６４である。即ち、カチオン交換速度を高めるには
ｄ＋ｅが０．０１以上であることが好ましく、カチオン
交換容量を高めるには１．０以下にするのが好ましい。
ｅ／ｄはカチオン交換容量を高める観点から通常０．１
〜１０であり、好ましくは０．１〜５．０である。ま
た、本発明の無機ビルダーにおいては、水和物であって
もよく、この場合の水和量はＨ2 Ｏのモル量換算として
通常０〜２０モル％である。The composition of the inorganic builder of the present invention is represented by the general formula:
SiO 2 · aB 2 O 3 · bNa 2 O · cK 2 O · dCa
It is represented by O.eMgO. Here, a is usually 0.01 to 1.0, preferably 0.02 to 0.
It is 5. That is, a is preferably 0.01 or more to increase the cation exchange capacity, and is preferably 1.0 or less to increase the cation exchange rate. b + c is usually 0.5 to 2.0, preferably 0.5 to 1.0. That is, b + c is preferably 0.5 or more to increase the cation exchange capacity, and is preferably 2.0 or less to increase the cation exchange rate. c / b is usually 0.005 to 8.0, preferably 0.01 to 6.
It is 0. That is, to increase the cation exchange rate, c / b
Is preferably 0.005 or more, and is preferably 8.0 or less from the viewpoint of improving the moisture absorption resistance. d + e
Is usually 0.01 to 1.0, preferably 0.01 to 1.0
It is 0.64. That is, d + e is preferably 0.01 or more for increasing the cation exchange rate, and is preferably 1.0 or less for increasing the cation exchange capacity.
e / d is usually 0.1 from the viewpoint of increasing the cation exchange capacity.
10 to 10, preferably 0.1 to 5.0. In addition, the inorganic builder of the present invention may be a hydrate, and the hydration amount in this case is usually 0 to 20 mol% in terms of molar amount of H 2 O.
【０００６】本発明の無機ビルダーは、一般式に示され
るようにＳｉＯ2 、Ｂ2 Ｏ3 、Ｎａ2 Ｏ、Ｋ2 Ｏ、Ｃａ
Ｏ、ＭｇＯの各成分よりなっている。従って、本発明の
無機ビルダーを製造するには、その原料として各成分が
必要になるが、本発明においては特に限定されることな
く公知の化合物が適宜用いられる。例えばＳｉＯ2 以外
の各成分としては、各々の当該元素の単独あるいは複合
の酸化物、水酸化物、塩類、当該元素含有鉱物が用いら
れる。具体的には、Ｎａ2 Ｏ成分、Ｋ2 Ｏ成分の原料と
しては、ＮａＯＨ，ＫＯＨ，Ｎａ2 ＣＯ3 ，Ｋ2 Ｃ
Ｏ3 ，Ｎａ2 ＳＯ4等が、ＣａＯ成分の原料としては、
ＣａＣＯ3 ，Ｃａ（ＯＨ）2 ，ドロマイト，ホウ酸カル
シウム等が、ＭｇＯ成分の原料としては、ＭｇＣＯ3 ，
Ｍｇ（ＯＨ）2 ，ドロマイト，ホウ酸マグネシウム等
が、Ｂ2 Ｏ3 成分の原料としては、ホウ酸カリウム、ホ
ウ酸ナトリウム等が挙げられる。ＳｉＯ2 成分としては
ケイ石，ケイ砂，カオリン，タルク，溶融シリカ，ケイ
酸ソーダ等が用いられる。The inorganic builder of the present invention comprises SiO 2 , B 2 O 3 , Na 2 O, K 2 O and Ca as represented by the general formula.
It is composed of O and MgO. Therefore, in order to produce the inorganic builder of the present invention, each component is required as a raw material thereof, but known compounds are appropriately used in the present invention without any particular limitation. For example, as each component other than SiO 2 , single or complex oxides, hydroxides, salts of the relevant element, and the element-containing mineral are used. Specifically, the raw materials for the Na 2 O component and the K 2 O component are NaOH, KOH, Na 2 CO 3 , and K 2 C.
O 3 , Na 2 SO 4, etc. are the raw materials for the CaO component.
CaCO 3, Ca (OH) 2 , dolomite, calcium borate, and examples of the raw material of MgO component, MgCO 3,
Mg (OH) 2 , dolomite, magnesium borate and the like, and examples of the raw material of the B 2 O 3 component include potassium borate, sodium borate and the like. As the SiO 2 component, silica stone, silica sand, kaolin, talc, fused silica, sodium silicate and the like are used.
【０００７】本発明においては、これらの原料成分を目
的とする無機ビルダーの１：ａ：ｂ：ｃ：ｄ：ｅとなる
ように所定の量比で混合し、通常３００〜１５００℃、
好ましくは５００〜１０００℃、さらに好ましくは６０
０〜９００℃の範囲で焼成して結晶化させる方法、また
原料成分を溶融させガラス化し、さらに加水した後ある
いは水ガラス化した後、焼成する方法が例示される。こ
の場合、加熱温度が３００℃未満では結晶化が不充分で
耐水性に劣り、１５００℃を超えると粗大粒子化しイオ
ン交換能が低下する。加熱時間は通常０．１〜２４時間
である。このような焼成は通常、電気炉、ガス炉等の加
熱炉で行うことができる。また、焼成後、必要に応じて
粉砕し所定の粒度に調製される。粉砕機としては例えば
ボールミル、ローラーミル等を用いてなされる。粉砕粒
度は特に限定されないが、分散性の観点から０．１〜５
０μｍの範囲が好ましい。また、本発明の無機ビルダー
の水和物を調製するには、公知の方法により容易に行う
ことができ、特に制限されるものではない。例えば、前
記のようにして得られた無機ビルダーの無水物をイオン
交換水に懸濁して水和させ、乾燥せしめて粉末化する方
法が挙げられる。In the present invention, these raw material components are mixed in a predetermined amount ratio of the desired inorganic builder so as to be 1: a: b: c: d: e, and usually 300 to 1500 ° C.,
Preferably 500 to 1000 ° C., more preferably 60.
Examples thereof include a method of calcination by firing in the range of 0 to 900 ° C., and a method of melting and vitrifying the raw material components, further hydrolyzing or water vitrifying, and then firing. In this case, if the heating temperature is lower than 300 ° C., crystallization is insufficient and the water resistance is poor, and if it exceeds 1500 ° C., coarse particles are formed and the ion exchange capacity is lowered. The heating time is usually 0.1 to 24 hours. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace. Further, after firing, the powder is crushed as necessary to have a predetermined particle size. As the crusher, for example, a ball mill, a roller mill or the like is used. The pulverized particle size is not particularly limited, but from the viewpoint of dispersibility, it is 0.1 to 5
The range of 0 μm is preferable. Further, the hydrate of the inorganic builder of the present invention can be easily prepared by a known method and is not particularly limited. For example, there may be mentioned a method in which the anhydrous inorganic builder obtained as described above is suspended in ion-exchanged water to be hydrated, dried and powdered.
【０００８】このようにして得られた本発明の無機ビル
ダーまたはその水和物は、初期カチオン交換速度が通常
７０ＣａＣＯ3 ｍｇ／ｇ・ｍｉｎ以上であり、好ましく
は１００ＣａＣＯ3 ｍｇ／ｇ・ｍｉｎ以上を有するもの
である。また、本発明の無機ビルダーまたはその水和物
は、カチオン交換容量が通常２００〜６００ＣａＣＯ3
ｍｇ／ｇであることが好ましく、更に好ましくは２５０
〜６００ＣａＣＯ3 ｍｇ／ｇである。The thus-obtained inorganic builder of the present invention or its hydrate has an initial cation exchange rate of usually 70 CaCO 3 mg / g · min or more, preferably 100 CaCO 3 mg / g · min or more. I have. The cation exchange capacity of the inorganic builder or hydrate thereof of the present invention is usually 200 to 600 CaCO 3.
It is preferably mg / g, more preferably 250
˜600 CaCO 3 mg / g.
【０００９】本発明の無機ビルダーは、衣料、食器、金
属、歯、身体等の洗浄剤構成物として幅広く用いられ、
従来のものに較べ優れたＣａ，Ｍｇ等のカチオン捕捉能
及びアルカリ度調整能さらに緩衝効果を発現する。その
結果、本発明の無機ビルダーを配合した洗浄剤は、優れ
た洗浄性能を有する。本発明において使用される洗浄剤
としては、特に限定されるものではないが、衣料用洗
剤、柔軟剤、食器用洗剤、歯ミガキ、身体用洗浄剤、金
属用洗浄剤等に本発明の無機ビルダーを配合して用いら
れる。その配合量は特に限定されないが、通常０．１〜
９０％、好ましくは０．５〜８０％、さらに好ましくは
１〜７５％である。０．１％未満であると充分な洗浄性
能を発現せず、９０％を超えると分散性が不良となる。
なかでも衣料用洗浄剤としての本発明の無機ビルダーの
配合量は、通常０．５〜７０％、好ましくは１〜６０
％、さらに好ましくは２〜５５％である。また、本発明
の無機ビルダーは２種以上を併用してもよく、ゼオライ
ト、クエン酸ソーダ、炭酸ソーダ、トリポリリン酸ソー
ダ、メタリン酸ソーダ等の他のビルダーと組合せて使用
することもできる。The inorganic builder of the present invention is widely used as a detergent composition for clothing, tableware, metal, teeth, body, etc.,
It excels in cation trapping ability of Ca, Mg, etc. and alkalinity adjusting ability as well as buffering effect superior to conventional ones. As a result, the detergent containing the inorganic builder of the present invention has excellent cleaning performance. The cleaning agent used in the present invention is not particularly limited, but it is an inorganic builder of the present invention such as a detergent for clothes, a softening agent, a detergent for tableware, a toothpaste, a personal detergent, a detergent for metals, etc. It is used by mixing. The blending amount is not particularly limited, but is usually 0.1 to
90%, preferably 0.5-80%, more preferably 1-75%. If it is less than 0.1%, sufficient cleaning performance will not be exhibited, and if it exceeds 90%, dispersibility will be poor.
Above all, the content of the inorganic builder of the present invention as a detergent for clothes is usually 0.5 to 70%, preferably 1 to 60%.
%, And more preferably 2 to 55%. The inorganic builders of the present invention may be used in combination of two or more, and may be used in combination with other builders such as zeolite, sodium citrate, sodium carbonate, sodium tripolyphosphate, sodium metaphosphate.
【００１０】[0010]
【実施例】以下、実施例、比較例および試験例により本
発明をさらに詳しく説明するが、本発明はこれらの実施
例等によりなんら限定されるものではない。尚、本実施
例及び比較例における測定値は、次に示す方法により測
定した。 （１）初期カチオン交換速度 試料０．１ｇを精秤し、塩化カルシウム溶液（濃度はＣ
ａＣＯ3 として５００ｐｐｍ）２００ｍｌ中に加え、２
５℃で３０秒、６０秒、１２０秒、１８０秒間撹拌した
後、それぞれについて孔サイズ０．２μｍのメンブラン
フィルター（アドバンテック社，ニトロセルロース製）
を用いて濾過を行い、その濾液を１０ｍｌ取って濾液中
のCa量をEDTA滴定によりそれぞれ測定した。その値より
試料のカルシウムイオン交換容量（カチオン交換容量）
を求め、各々の時間でのカチオン交換速度を平均した値
を初期カチオン交換速度とした。 （２）カチオン交換容量 前記の方法において、試料溶液を６０分間撹拌した後、
同様にして濾液中のCa量をEDTA滴定により測定し、試料
のカルシウムイオン交換容量を求めた。EXAMPLES The present invention will be described in more detail with reference to Examples, Comparative Examples and Test Examples, but the present invention is not limited to these Examples. The measured values in the examples and comparative examples were measured by the following method. (1) Initial cation exchange rate 0.1 g of a sample was precisely weighed and a calcium chloride solution (concentration was C
aCO 3 ( 500 ppm) added to 200 ml, 2
After stirring at 5 ° C for 30 seconds, 60 seconds, 120 seconds, and 180 seconds, a membrane filter with a pore size of 0.2 µm (Advantech, nitrocellulose)
Was filtered using 10 ml of the filtrate, and the amount of Ca in the filtrate was measured by EDTA titration. From that value, the calcium ion exchange capacity (cation exchange capacity) of the sample
Was calculated, and the value obtained by averaging the cation exchange rates at each time was defined as the initial cation exchange rate. (2) Cation exchange capacity In the above method, after stirring the sample solution for 60 minutes,
Similarly, the amount of Ca in the filtrate was measured by EDTA titration to determine the calcium ion exchange capacity of the sample.
【００１１】実施例１ １号水ガラス（ＳｉＯ2 ／Ｎａ2 Ｏ＝２．１４，Ｈ2 Ｏ
量４５．０％）１００ｇと水酸化ナトリウム（ＮａＯ
Ｈ）４．１０ｇとホウ酸カリウム（Ｋ2 Ｂ4 Ｏ7・４Ｈ
2 Ｏ）４．７２ｇ、Ｃａ（ＯＨ）2 ３．６４ｇ、Ｍｇ
（ＯＨ）2 １．４３ｇ、Ｈ2 Ｏ５０ｇをホモミキサーを
用いて混合した。混合物をニッケル製坩堝に適量採り、
７００℃の温度で、空気中１時間焼成し、急冷後得られ
た焼成体を粉砕して、本発明の無機ビルダー１を得た。
この粉体の初期カチオン交換速度は８６ＣａＣＯ3 mg/g
・min であり、カチオン交換容量は２９１ＣａＣＯ3 mg
/gであった。また、得られた焼成体の粉末Ｘ線（ＣｕＫ
α）回折パターンは、焼成前の混合物とは異なる回折パ
ターンを示し、新規な結晶構造を示す物質であった。ま
た、３０℃，８０°ＨＤの恒温恒湿槽内に１週間放置
後、ケーキング現象がなく、耐水性は充分であった。Example 1 No. 1 water glass (SiO 2 / Na 2 O = 2.14, H 2 O
45.0%) and sodium hydroxide (NaO
H) 4.10 g of potassium borate (K 2 B 4 O 7 · 4H
2 O) 4.72 g, Ca (OH) 2 3.64 g, Mg
1.43 g of (OH) 2 and 50 g of H 2 O were mixed using a homomixer. Take an appropriate amount of the mixture in a nickel crucible,
After firing in air at a temperature of 700 ° C. for 1 hour and quenching, the obtained fired body was pulverized to obtain an inorganic builder 1 of the present invention.
The initial cation exchange rate of this powder is 86CaCO 3 mg / g
・ Min, cation exchange capacity is 291CaCO 3 mg
It was / g. In addition, powder X-ray (CuK
The α) diffraction pattern showed a diffraction pattern different from that of the mixture before firing, and was a substance having a novel crystal structure. Moreover, after standing in a constant temperature and constant humidity tank at 30 ° C. and 80 ° HD for 1 week, there was no caking phenomenon and the water resistance was sufficient.
【００１２】実施例２〜８ ＫＯＨ，ＮａＯＨ，Ｃａ（ＯＨ）2 ，Ｍｇ（ＯＨ）2 ，
Ｋ2 Ｂ4 Ｏ7 ・４Ｈ2Ｏを適宜添加して、表１に示す組
成となるようにした以外は実施例１と同様にして無機ビ
ルダー２〜８を得た。得られた粉体について初期カチオ
ン交換速度、カチオン交換容量を測定し、その結果を表
１に示した。表１が示すように、いずれも初期カチオン
交換速度、カチオン交換容量が共に優れたものであっ
た。また、得られた焼成体の粉末Ｘ線（ＣｕＫα）回折
パターンは、いずれも焼成前の混合物とは異なる回折パ
ターンを示し、新規な結晶構造を示す物質であった。ま
た、いずれの無機ビルダーも３０℃，８０°ＨＤの恒温
恒湿槽内に１週間放置後、ケーキング現象がなく、耐水
性は充分であった。Examples 2-8 KOH, NaOH, Ca (OH) 2 , Mg (OH) 2 ,
K 2 B 4 O 7 · 4H 2 O was added appropriately, to obtain an inorganic builder 2-8 except that as the composition shown in Table 1 in the same manner as in Example 1. The initial cation exchange rate and cation exchange capacity of the obtained powder were measured, and the results are shown in Table 1. As shown in Table 1, the initial cation exchange rate and the cation exchange capacity were both excellent. Further, the powder X-ray (CuKα) diffraction patterns of the obtained fired bodies all showed diffraction patterns different from those of the mixture before firing, and were substances showing a novel crystal structure. Further, all the inorganic builders had no caking phenomenon after being left for 1 week in a constant temperature and constant humidity chamber of 30 ° C. and 80 ° HD, and had sufficient water resistance.
【００１３】[0013]
【表１】 [Table 1]
【００１４】比較例１〜５ 実施例１と同様に表１の組成となるよう混合し、これを
ニッケル製坩堝に適量採り、７００℃の温度で、空気中
１時間焼成した。急冷後、粉砕を行い比較ビルダー１〜
５を得た。３０℃，８０°ＨＤの恒温恒湿槽内に１週間
放置後、ケーキング現象が認められ、耐水性は不充分で
あった。Comparative Examples 1 to 5 Mixing was carried out in the same manner as in Example 1 so that the composition was as shown in Table 1, and an appropriate amount of this mixture was put into a crucible made of nickel and calcined in air at a temperature of 700 ° C. for 1 hour. After rapid cooling, crush and compare builder 1
Got 5. After left for 1 week in a thermo-hygrostat at 30 ° C. and 80 ° HD, a caking phenomenon was observed and the water resistance was insufficient.
【００１５】洗浄剤組成物の調製例 表２に示す組成からなる洗浄剤（配合Ａ、Ｂは本発明の
無機ビルダーを含有する本発明品を、配合Ｃは含有しな
い比較品を示す）を以下の方法により製造した。即ち、
粉末原料（珪酸ソーダ、炭酸ソーダ、芒硝、非晶質シリ
カ、無機ビルダーＡ、Ｂ）を攪拌式転動造粒機（レディ
ゲミキサー）に入れ、ポリオキシエチレンドデシルエー
テルとポリエチレングリコールを添加し、平均粒径３６
８〜４１２μｍの粉末洗浄剤を得た。ここで用いられる
無機ビルダーＡ、Ｂはそれぞれ前記の実施例２、５で得
られた無機ビルダーである。Preparation Example of Detergent Composition A detergent having the composition shown in Table 2 (formulations A and B are the products of the present invention containing the inorganic builder of the present invention, and formulation C is a comparative product not containing the same) is shown below It was manufactured by the method of. That is,
Put powder raw materials (sodium silicate, sodium carbonate, salt cake, amorphous silica, inorganic builders A, B) in a stirring type rolling granulator (Ledige mixer), add polyoxyethylene dodecyl ether and polyethylene glycol, Average particle size 36
A powder detergent of 8-412 μm was obtained. The inorganic builders A and B used here are the inorganic builders obtained in Examples 2 and 5, respectively.
【００１６】[0016]
【表２】 [Table 2]
【００１７】同様にして、表３に示す組成からなる洗浄
剤（配合Ｄ、Ｅは本発明の無機ビルダーを含有する本発
明品を、配合Ｆは比較ビルダーを含有するものである）
を製造した。ここで、無機ビルダー以外の成分の水性ス
ラリーを６０℃で作製し、噴霧乾燥機によって乾燥粉末
とした。これを遠心転動造粒機（ハイスピードミキサ
ー）にいれ、若干の水を添加して造粒し平均粒径３９６
〜４１８μｍの粉末洗浄剤を得た。Similarly, a detergent having the composition shown in Table 3 (Formulations D and E are products of the present invention containing the inorganic builder of the present invention, and Formula F is a composition containing a comparative builder).
Was manufactured. Here, an aqueous slurry of components other than the inorganic builder was prepared at 60 ° C. and made into a dry powder by a spray dryer. Put this in a centrifugal tumbling granulator (high speed mixer), add some water and granulate to obtain an average particle size of 396
A powder cleaner of ˜418 μm was obtained.
【００１８】[0018]
【表３】 [Table 3]
【００１９】試験例 前記の洗浄剤組成物の調製例により得られた配合Ａ〜Ｆ
を用いて、以下の方法によって洗浄テストを行った。 （１）泥汚れ汚染布（人工汚染布）：鹿沼園芸用赤玉土
を１２０℃±５℃で４hr乾燥後粉砕、１５０Mesh(100μ
ｍ）パスのものを１２０℃±５℃で２hr乾燥後、土１５
０g を1000リットルのパークレンに分散し、金巾＃2023
布をこの液に接触、ブラッシングし、分散液の除去、過
剰付着汚れを脱落させる（特開昭55−26473 号公報）。 （２）皮脂／カーボン汚れ汚染布（人工汚染布）： （モデル皮脂／カーボン汚れ組成） カーボンブラック １５％ 綿実油 ６０％ コレステロール ５％ オレイン酸 ５％ パルミチン酸 ５％ 液体パラフィン １０％ 上記組成物１kgを８０リットルのパークレンに溶解分散
し、金巾＃2023布を浸漬して汚れを付着させた後パーク
レンを乾燥除去する。Test Examples Formulations A to F obtained by the above-mentioned preparation examples of the cleaning composition.
A cleaning test was performed using the following method. (1) Dirty dirt-contaminated cloth (artificial-contaminated cloth): Kanuma gardening red tama soil was dried at 120 ° C ± 5 ° C for 4 hours and then crushed and then 150 mesh (100μ)
m) After drying the pass one at 120 ° C ± 5 ° C for 2 hours, soil 15
Disperse 0 g in 1000 liters of perkren, gold width # 2023
A cloth is contacted with this liquid and brushed to remove the dispersion liquid and remove excess adhered dirt (Japanese Patent Laid-Open No. 55-26473). (2) Sebum / carbon dirt contaminated cloth (artificial dirt cloth): (model sebum / carbon dirt composition) carbon black 15% cottonseed oil 60% cholesterol 5% oleic acid 5% palmitic acid 5% liquid paraffin 10% 1 kg of the above composition Dissolve and disperse in 80 liters of Perkren, dip a cloth of gold # 2023 to attach dirt, and then dry and remove Perkren.
【００２０】（３）洗浄条件：評価用洗剤水溶液１リッ
トルに10cm×10cmの綿の泥汚れ汚染布又は皮脂／カーボ
ン汚れ汚染布（人工汚染布）を各５枚入れ、ターゴトメ
ーターにて100rpmで次の洗浄条件で洗浄した。 （洗浄条件） 洗浄時間 10分 洗浄濃度 0.133 ％ 水の硬度 ４° 水 温 20℃ ススギ 水道水にて５分間 （４）洗浄試験の評価方法：洗浄力は汚染前の原布及び
洗浄前後の汚染布の460nm における反射率を自記色彩計
（島津製作所製）を用いて測定し、次式によって洗浄率
（％）を求めた。 洗浄率（％）＝（洗浄後の反射率−洗浄前の反射率）／
（原布の反射率−洗浄前の反射率）×１００ 得られた結果を表４に示すが、本発明の洗浄剤組成物を
用いることにより、優れた洗浄性能が認められた。(3) Washing conditions: 5 liters of 10 cm × 10 cm cotton dirt soiled cloth or sebum / carbon soiled soiled cloth (artificial soiled cloth) are put in 1 liter of an aqueous detergent solution for evaluation, and 100 rpm is applied with a tergo meter. Was washed under the following washing conditions. (Washing conditions) Washing time 10 minutes Washing concentration 0.133% Water hardness 4 ° Water temperature 20 ° C Susugi 5 minutes with tap water (4) Evaluation method of washing test: Detergency is raw cloth before contamination and contamination before and after washing The reflectance of the cloth at 460 nm was measured using a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (%) was calculated by the following formula. Cleaning rate (%) = (reflectance after cleaning-reflectance before cleaning) /
(Reflectance of original fabric-reflectance before washing) x 100 The obtained results are shown in Table 4. By using the detergent composition of the present invention, excellent washing performance was recognized.
【００２１】[0021]
【表４】 [Table 4]
【００２２】[0022]
【発明の効果】本発明の無機ビルダーは、カチオン交換
能、初期カチオン交換速度及び耐水性に共に優れたもの
であるため、例えば洗剤に用いられる水軟水化剤、アル
カリ調整剤として有用である。INDUSTRIAL APPLICABILITY The inorganic builder of the present invention is excellent in both cation exchange ability, initial cation exchange rate and water resistance, and is therefore useful as a water softening agent and an alkali adjusting agent used in, for example, detergents.
Claims (3)
2 Ｏ・ｃＫ2 Ｏ・ｄＣａＯ・ｅＭｇＯ（但し、ａ＝０．
０１〜１．０、ｂ＋ｃ＝０．５〜２．０、ｃ／ｂ＝０．
００５〜８．０、ｄ＋ｅ＝０．０１〜１．０、ｅ／ｄ＝
０．１〜１０）で表される組成からなる無機ビルダー。1. A general formula, SiO 2 .aB 2 O 3 .bNa
2 O · cK 2 O · dCaO · eMgO (however, a = 0.
01-1.0, b + c = 0.5-2.0, c / b = 0.
005-8.0, d + e = 0.01-1.0, e / d =
An inorganic builder having a composition represented by 0.1 to 10).
ｍｇ／ｇ・ｍｉｎ以上であり、カチオン交換容量が２０
０〜６００ＣａＣＯ3 ｍｇ／ｇである請求項１記載の無
機ビルダー。2. The initial cation exchange rate is 70 CaCO 3.
It is more than mg / g · min, and the cation exchange capacity is 20.
The inorganic builder according to claim 1, which is 0 to 600 CaCO 3 mg / g.
水和物。3. A hydrate of the inorganic builder according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32841692A JP3270156B2 (en) | 1992-11-12 | 1992-11-12 | Inorganic builder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32841692A JP3270156B2 (en) | 1992-11-12 | 1992-11-12 | Inorganic builder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06157026A true JPH06157026A (en) | 1994-06-03 |
| JP3270156B2 JP3270156B2 (en) | 2002-04-02 |
Family
ID=18210021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32841692A Expired - Fee Related JP3270156B2 (en) | 1992-11-12 | 1992-11-12 | Inorganic builder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3270156B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999002643A1 (en) * | 1997-07-09 | 1999-01-21 | Vitro Corporativo, S.A. De C.V. | Unique multifunctional product for detergent formulations |
| WO2000003948A1 (en) * | 1998-07-17 | 2000-01-27 | Kao Corporation | Composite powder |
| JP2017095585A (en) * | 2015-11-24 | 2017-06-01 | 靖志 鎌田 | Powder detergent |
| KR20220085515A (en) * | 2020-12-15 | 2022-06-22 | 엘지전자 주식회사 | Glass composition for eco-friendly laundry detergent and cleaning aid and manufactruing method of glass powder using the same |
| KR20220085517A (en) * | 2020-12-15 | 2022-06-22 | 엘지전자 주식회사 | Glass composition for eco-friendly detergent and manufactruing method of glass powder for eco-friendly detergent using the same |
-
1992
- 1992-11-12 JP JP32841692A patent/JP3270156B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999002643A1 (en) * | 1997-07-09 | 1999-01-21 | Vitro Corporativo, S.A. De C.V. | Unique multifunctional product for detergent formulations |
| WO2000003948A1 (en) * | 1998-07-17 | 2000-01-27 | Kao Corporation | Composite powder |
| JP2017095585A (en) * | 2015-11-24 | 2017-06-01 | 靖志 鎌田 | Powder detergent |
| KR20220085515A (en) * | 2020-12-15 | 2022-06-22 | 엘지전자 주식회사 | Glass composition for eco-friendly laundry detergent and cleaning aid and manufactruing method of glass powder using the same |
| KR20220085517A (en) * | 2020-12-15 | 2022-06-22 | 엘지전자 주식회사 | Glass composition for eco-friendly detergent and manufactruing method of glass powder for eco-friendly detergent using the same |
| WO2022131550A1 (en) * | 2020-12-15 | 2022-06-23 | 엘지전자 주식회사 | Environmentally-friendly glass composition for laundry detergents and washing supplements, and method for manufacturing glass powder thereof |
| WO2022131552A1 (en) * | 2020-12-15 | 2022-06-23 | 엘지전자 주식회사 | Glass composition for eco-friendly detergent and method for preparing glass powder for eco-friendly detergent using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3270156B2 (en) | 2002-04-02 |
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