JPH09202613A - Noncrystalline aluminosilicate and its production - Google Patents
Noncrystalline aluminosilicate and its productionInfo
- Publication number
- JPH09202613A JPH09202613A JP865296A JP865296A JPH09202613A JP H09202613 A JPH09202613 A JP H09202613A JP 865296 A JP865296 A JP 865296A JP 865296 A JP865296 A JP 865296A JP H09202613 A JPH09202613 A JP H09202613A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- aqueous solution
- amount
- amorphous aluminosilicate
- sio
- 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.)
- Pending
Links
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910000323 aluminium silicate Inorganic materials 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 21
- -1 alkali metal aluminate Chemical class 0.000 claims abstract description 16
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 229910001424 calcium ion Inorganic materials 0.000 claims description 20
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 17
- 150000008064 anhydrides Chemical class 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000003599 detergent Substances 0.000 abstract description 26
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract 2
- 238000013019 agitation Methods 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 17
- 235000019198 oils Nutrition 0.000 description 17
- 239000011734 sodium Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000011575 calcium Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 239000002516 radical scavenger Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 101100003996 Mus musculus Atrn gene Proteins 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Detergent Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、特に衣料用洗剤、
食器用洗剤、洗顔洗身用洗剤または工業洗剤へ配合する
洗剤用ビルダーとして好適な、アルカリ土類金属イオン
捕捉剤として使用できる非晶質アルミノシリケートおよ
びその製造方法に関する。TECHNICAL FIELD The present invention relates to a laundry detergent,
The present invention relates to an amorphous aluminosilicate that can be used as an alkaline earth metal ion scavenger and is suitable as a builder for detergents to be added to a dishwashing detergent, a face-washing detergent or an industrial detergent, and a method for producing the same.
【０００２】[0002]
【従来の技術】現在、洗剤用ビルダーとして用いるＮａ
Ａ型ゼオライトはアルカリ土類金属イオン捕捉能が大き
いことから、アニオン系界面活性剤との混合スラリーを
スプレードライする方法で粒状の洗剤に配合されてい
る。2. Description of the Related Art Na currently used as a builder for detergents
Since the A-type zeolite has a large ability to trap alkaline earth metal ions, it is incorporated into a granular detergent by a method of spray-drying a mixed slurry with an anionic surfactant.
【０００３】しかしＮａＡ型ゼオライトの吸油量は４０
ｇ／１００ｇ程度のため、ノニオン系界面活性剤と混練
し洗剤に配合する場合には、ホワイトカーボンのよう
な、吸油量は大きいがアルカリ土類金属イオン捕捉量を
持たない材料を添加しなければ粒状洗剤にならなかっ
た。このため洗剤のコンパクト化が難しいという欠点が
あった。However, the oil absorption of NaA type zeolite is 40
Since it is about g / 100 g, when kneading with a nonionic surfactant and blending it into a detergent, a material such as white carbon that has a large oil absorption but does not have an alkaline earth metal ion trapping amount must be added. Did not become granular detergent. Therefore, it is difficult to make the detergent compact.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、アルカリ土
類金属イオン捕捉能と吸油能に優れ、洗剤用ビルダーと
して好適な、アルカリ土類金属イオン捕捉剤として使用
できる非晶質アルミノシリケートおよびその製造方法を
提供する。DISCLOSURE OF THE INVENTION The present invention relates to an amorphous aluminosilicate which is excellent in alkaline earth metal ion scavenging ability and oil absorption ability and is suitable as a builder for detergents and which can be used as an alkaline earth metal ion scavenger. A manufacturing method is provided.
【０００５】[0005]
【課題を解決するための手段】本発明は、Ａｌ2 Ｏ3 １
モルに対し、Ｒ2 Ｏ（Ｒはアルカリ金属）を０．０１〜
２．０モル、ＳｉＯ2 を１．０〜４．０モル含有する非
晶質アルミノシリケートであって、下記Ａ法によるＣａ
イオン捕捉量が１００ｍｇＣａＯ／ｇ以上、下記Ｂ法に
よるＣａイオン捕捉量が９０ｍｇＣａＯ／ｇ以上、吸油
量が８０〜３００ｇ／１００ｇ、比表面積が１０〜５０
ｍ2 ／ｇである非晶質アルミノシリケートを提供する。The present invention is directed to Al 2 O 3 1
R 2 O (R is an alkali metal) is 0.01 to mol.
An amorphous aluminosilicate containing 2.0 moles and 1.0 to 4.0 moles of SiO 2 , which is Ca according to the following Method A.
Ion trapping amount is 100 mgCaO / g or more, Ca ion trapping amount by the following B method is 90 mgCaO / g or more, oil absorption amount is 80 to 300 g / 100 g, and specific surface area is 10 to 50.
Provide an amorphous aluminosilicate that is m 2 / g.
【０００６】Ａ法：ＣａＯに換算した濃度（以下単にＣ
ａＯ濃度という）が３００重量ｐｐｍのＣａ塩溶液１０
００ｍｌ中に無水物換算で１ｇの非晶質アルミノシリケ
ートを添加して測定される、ＣａＯに換算したＣａイオ
ンの捕捉量（単位：ｍｇＣａＯ／ｇ）。Method A: concentration converted to CaO (hereinafter simply referred to as C
Ca salt solution having an aO concentration of 300 ppm by weight 10
The amount of captured Ca ions converted to CaO (unit: mgCaO / g), which was measured by adding 1 g of an amorphous aluminosilicate in terms of anhydride to 00 ml.
【０００７】Ｂ法：ＣａＯ濃度が３０重量ｐｐｍのＣａ
塩溶液１０００ｍｌ中に無水物換算で０．１ｇの非晶質
アルミノシリケートを添加して測定される、ＣａＯに換
算したＣａイオンの捕捉量（単位：ｍｇＣａＯ／ｇ）。Method B: Ca having a CaO concentration of 30 ppm by weight
The amount of captured Ca ions converted to CaO (unit: mgCaO / g), which was measured by adding 0.1 g of an amorphous aluminosilicate in terms of anhydride to 1000 ml of a salt solution.
【０００８】また、本発明は、ケイ酸アルカリ金属塩水
溶液とアルミン酸アルカリ金属塩水溶液を、ＳｉＯ2 分
とＡｌ2 Ｏ3 分とＲ2 Ｏ（Ｒはアルカリ金属）分とがモ
ル比でＳｉＯ2 ：Ａｌ2 Ｏ3 ：Ｒ2 Ｏ＝５〜３０：２〜
１０：６０〜９３となるように混合し、撹拌しながら４
０℃以下に保持し、析出した沈澱を分離する非晶質アル
ミノシリケートの製造方法を提供する。Further, according to the present invention, an aqueous solution of alkali metal silicate and an aqueous solution of alkali metal aluminate are mixed in a SiO 2 content, an Al 2 O 3 content and a R 2 O content (R is an alkali metal) in a molar ratio. 2: Al 2 O 3: R 2 O = 5~30: 2~
Mix at 10:60 to 93 and mix with stirring 4
Provided is a method for producing an amorphous aluminosilicate, which is maintained at 0 ° C or lower and the precipitated precipitate is separated.
【０００９】[0009]
【発明の実施の形態】本発明の非晶質アルミノシリケー
トは、Ａｌ2 Ｏ3 １モルに対し、Ｒ2 Ｏを０．０１〜
２．０モル、好ましくは０．０１６〜１．２５モル、Ｓ
ｉＯ2 を１．０〜４．０モル、好ましくは１．６〜２．
５モル含有する非晶質の物質である。ＲはＮａまたはＫ
が好ましく、特にＮａが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The amorphous aluminosilicate of the present invention contains 0.01 to 2 moles of R 2 O per 1 mole of Al 2 O 3.
2.0 mol, preferably 0.016-1.25 mol, S
iO 2 1.0 to 4.0 moles, preferably 1.6 to 2.
It is an amorphous substance containing 5 mol. R is Na or K
Is preferred, and Na is particularly preferred.
【００１０】本発明では、アルカリ土類金属イオン捕捉
能を上記Ａ法およびＢ法によるＣａイオン捕捉量で規定
する。本発明の非晶質アルミノシリケートは、Ａ法によ
るＣａイオン捕捉量が１００ｍｇＣａＯ／ｇ以上であ
り、かつ、Ｂ法によるＣａイオン捕捉量が９０ｍｇＣａ
Ｏ／ｇ以上である。特に、Ｂ法のような低いＣａＯ濃度
である場合にも高いアルカリ土類金属捕捉能を有する。
アルカリ土類金属イオン捕捉能は、３０重量ｐｐｍとい
う低いＣａＯ濃度で上記の性能があれば洗剤用ビルダー
として充分機能する。本発明の非晶質アルミノシリケー
トは含水物でもよく、その場合上記のＣａイオン捕捉量
の測定では、添加重量は無水物換算で測定する。In the present invention, the alkaline earth metal ion trapping ability is defined by the amount of Ca ion trapped by the above methods A and B. The amorphous aluminosilicate of the present invention has a Ca ion trapping amount by Method A of 100 mgCaO / g or more and a Ca ion trapping amount by Method B of 90 mgCa.
It is O / g or more. In particular, it has a high alkaline earth metal trapping ability even when the CaO concentration is low as in the method B.
The alkaline earth metal ion scavenging ability functions sufficiently as a detergent builder if the CaO concentration as low as 30 ppm by weight has the above performance. The amorphous aluminosilicate of the present invention may be a hydrate, and in that case, in the measurement of the amount of Ca ion trapped, the added weight is measured as an anhydride.
【００１１】本発明の非晶質アルミノシリケートは吸油
量が８０〜３００ｇ／１００ｇであり、ノニオン系界面
活性剤と混練する場合にホワイトカーボンなどを添加し
なくてよい。８０ｇ／１００ｇ未満では吸油量が少ない
ため洗剤のコンパクト化が難しいので不適当である。吸
油量は３００ｇ／１００ｇあれば洗剤用ビルダーとして
は充分である。The amorphous aluminosilicate of the present invention has an oil absorption of 80 to 300 g / 100 g, and it is not necessary to add white carbon or the like when kneading with the nonionic surfactant. If it is less than 80 g / 100 g, the oil absorption is small and it is difficult to make the detergent compact. An oil absorption of 300 g / 100 g is sufficient as a builder for detergents.
【００１２】本発明の非晶質アルミノシリケ−トは比表
面積が１０〜５０ｍ2 ／ｇである。１０ｍ2 ／ｇ未満で
は吸油量が低下するので不適当である。５０ｍ2 ／ｇ超
では吸油量は充分であるがアルカリ土類金属イオン捕捉
能が低く、特にＢ法によるＣａイオン捕捉量が不足する
ので不適当である。The amorphous aluminosilicate of the present invention has a specific surface area of 10 to 50 m 2 / g. If it is less than 10 m 2 / g, the oil absorption amount will be reduced, which is not suitable. If it exceeds 50 m 2 / g, the oil absorption is sufficient, but the alkaline earth metal ion-capturing ability is low, and especially the Ca ion-capturing amount by the B method is insufficient, which is not suitable.
【００１３】本発明の非晶質アルミノシリケートは、ケ
イ酸アルカリ金属塩水溶液とアルミン酸アルカリ金属塩
水溶液とを混合し、反応させることによって製造するの
が好ましい。ケイ酸アルカリ金属塩としては、ケイ酸ナ
トリウム、またはケイ酸カリウムなどが使用できる。ア
ルミン酸アルカリ金属塩としては、アルミン酸ナトリウ
ム、アルミン酸カリウムなどが使用できる。The amorphous aluminosilicate of the present invention is preferably produced by mixing and reacting an aqueous solution of alkali metal silicate and an aqueous solution of alkali metal aluminate. As the alkali metal silicate, sodium silicate, potassium silicate or the like can be used. As the alkali metal aluminate, sodium aluminate, potassium aluminate and the like can be used.
【００１４】ケイ酸アルカリ金属塩水溶液またはアルミ
ン酸アルカリ金属塩水溶液には、必要に応じて水酸化ア
ルカリ金属塩水溶液を混合してもよい。また、ケイ酸ア
ルカリ金属塩水溶液とアルミン酸アルカリ金属塩水溶液
の混合の際に水酸化アルカリ金属塩水溶液を混合しても
よい。水酸化アルカリ金属塩水溶液としては水酸化ナト
リウムなどが使用できる。If desired, the aqueous solution of alkali metal silicate or the aqueous solution of alkali metal aluminate may be mixed with an aqueous solution of alkali metal hydroxide. Further, when the alkali metal silicate salt aqueous solution and the alkali metal aluminate salt aqueous solution are mixed, the alkali metal hydroxide aqueous solution may be mixed. Sodium hydroxide or the like can be used as the alkali metal hydroxide aqueous solution.
【００１５】ケイ酸アルカリ金属塩水溶液とアルミン酸
アルカリ金属塩水溶液の混合の方法は特に限定されな
い。一方のアルカリ金属塩水溶液を満たした容器中に他
方のアルカリ金属塩水溶液を添加してもよく、両アルカ
リ金属塩水溶液を同時に反応容器中に添加してもよい。
添加に際しては、それぞれのアルカリ金属塩水溶液が充
分混合できるように撹拌しながら行うことが好ましい。The method for mixing the aqueous solution of alkali metal silicate and the aqueous solution of alkali metal aluminate is not particularly limited. One alkali metal salt aqueous solution may be added to the container filled with one alkali metal salt aqueous solution, or both alkali metal salt aqueous solutions may be simultaneously added to the reaction container.
The addition is preferably carried out with stirring so that the respective alkali metal salt aqueous solutions can be sufficiently mixed.
【００１６】具体的には、Ｒ2 Ｏ／ＳｉＯ2 モル比が
０．２５〜４．０のケイ酸アルカリ金属塩水溶液と、Ｒ
2 Ｏ／Ａｌ2 Ｏ3 モル比が１．０〜３．０のアルミン酸
アルカリ金属塩水溶液を混合するのが好ましい。Specifically, an aqueous solution of an alkali metal silicate having a R 2 O / SiO 2 molar ratio of 0.25 to 4.0 and R
It is preferable to mix an aqueous solution of an alkali metal aluminate having a 2 O / Al 2 O 3 molar ratio of 1.0 to 3.0.
【００１７】混合組成は、ケイ酸アルカリ金属塩水溶液
とアルミン酸アルカリ金属塩水溶液を、ＳｉＯ2 分とＡ
ｌ2 Ｏ3 分とＲ2 Ｏ分とがモル比でＳｉＯ2 ：Ａｌ2 Ｏ
3 ：Ｒ2 Ｏ＝５〜３０：２〜１０：６０〜９３となるよ
うにする。The mixed composition is such that an aqueous solution of alkali metal silicate and an aqueous solution of alkali metal aluminate are mixed with SiO 2 content and A
The molar ratio of l 2 O 3 and R 2 O is SiO 2 : Al 2 O.
3: R 2 O = 5~30: 2~10: made to be 60 to 93.
【００１８】ＳｉＯ2 が上記範囲の下限未満またはＡｌ
2 Ｏ3 が上記範囲の下限未満またはＲ2 Ｏが上記範囲の
上限超では、得られる非晶質アルミノシリケ−トは比表
面積が１０ｍ2 ／ｇ未満および吸油量が８０ｇ／１００
ｇ未満となり好ましくない。SiO 2 is less than the lower limit of the above range or Al
When 2 O 3 is less than the lower limit of the above range or R 2 O is more than the upper limit of the above range, the obtained amorphous aluminosilicate has a specific surface area of less than 10 m 2 / g and an oil absorption of 80 g / 100.
It is less than g, which is not preferable.
【００１９】ＳｉＯ2 が上記範囲の上限超またはＡｌ2
Ｏ3 が上記範囲の上限超またはＲ2Ｏが上記範囲の下限
未満では、得られる非晶質アルミノシリケ−トは比表面
積が５０ｍ2 ／ｇ超および吸油量が８０〜３００ｇ／１
００ｇとなるが、Ｂ法によるＣａイオン捕捉量が９０ｍ
ｇＣａＯ／ｇ未満となるので好ましくない。SiO 2 exceeds the upper limit of the above range or Al 2
When O 3 exceeds the upper limit of the above range or R 2 O is less than the lower limit of the above range, the obtained amorphous aluminosilicate has a specific surface area of more than 50 m 2 / g and an oil absorption of 80 to 300 g / 1.
The amount of Ca ions captured by method B is 90m
Since it is less than gCaO / g, it is not preferable.
【００２０】混合終了後さらに撹拌を続けて行うと反応
しアルミノシリケートが析出する。ケイ酸アルカリ金属
塩水溶液とアルミン酸アルカリ金属塩水溶液との混合溶
液の温度は４０℃以下とされ、特に２５〜４０℃が好ま
しい。混合溶液の温度が４０℃より高いと、反応で生成
するアルミノシリケートが結晶化してＢＥＴ比表面積が
１０ｍ2 ／ｇ未満の粒子径の大きなものとなり、Ａ法、
Ｂ法によるＣａイオン捕捉量はそれぞれ１００ｍｇＣａ
Ｏ／ｇ以上となるが、吸油量は８０ｇ／１００ｇ未満と
なる。When stirring is further continued after the completion of mixing, a reaction occurs and aluminosilicate is precipitated. The temperature of the mixed solution of the aqueous solution of alkali metal silicate and the aqueous solution of alkali metal aluminate is set to 40 ° C or lower, and particularly preferably 25 to 40 ° C. When the temperature of the mixed solution is higher than 40 ° C., the aluminosilicate produced by the reaction is crystallized to have a large BET specific surface area of less than 10 m 2 / g and a large particle diameter.
The amount of Ca ions captured by method B is 100 mg Ca each
Although it is O / g or more, the oil absorption amount is less than 80 g / 100 g.
【００２１】スラリー状で得られた非晶質アルミノシリ
ケートは、ろ過および水洗によって母液を除去する。純
水中に再び懸濁してスラリー状としたり、または乾燥し
て粉末状としたりできる。そしてスラリー状または粉末
状で他の洗浄成分と混合して使用する。The amorphous aluminosilicate obtained as a slurry is filtered and washed with water to remove the mother liquor. It can be suspended again in pure water to form a slurry, or dried to form a powder. Then, it is used in the form of slurry or powder mixed with other cleaning components.
【００２２】本発明の非晶質アルミノシリケートは、ア
ルカリ土類金属イオン捕捉剤、特に、衣料用洗剤、食器
用洗剤、洗顔洗身用洗剤または工業洗剤へ配合する洗剤
用ビルダーとして好適である。The amorphous aluminosilicate of the present invention is suitable as a detergent builder incorporated into an alkaline earth metal ion scavenger, in particular, a detergent for clothes, a detergent for dishes, a detergent for face-washing or an industrial detergent.
【００２３】[0023]
【実施例】以下、実施例（例１）および比較例（例２〜
４）により本発明をさらに詳しく説明するが、本発明は
これらにより限定されない。なお、例１〜４における測
定値は次に示す方法により測定した。EXAMPLES Hereinafter, Examples (Example 1) and Comparative Examples (Examples 2 to 2)
The present invention will be described in more detail with reference to 4), but the present invention is not limited thereto. The measured values in Examples 1 to 4 were measured by the following method.
【００２４】［Ａ法によるＣａイオン捕捉量］無水物換
算で試料１．０ｇを秤取し、塩化カルシウム溶液（Ｃａ
Ｏ濃度は３００重量ｐｐｍ）１０００ｍｌ中に加え、さ
らに１Ｎの水酸化ナトリウム溶液を加えてｐＨを１０.
０〜１０. ５に調整した後、２５℃で１０分間撹拌し
た。１０分後、５種Ｃ番（ＪＩＳ Ｐ３８０１に規定さ
れる、以下同じ）のろ紙を用いてろ過した。そのろ液２
０ｍｌを取って、ＥＤＴＡ滴定によりろ液中のＣａ量を
測定し、その値より試料の無水物１ｇあたりのＣａイオ
ン捕捉量を求めた。[Amount of Ca ions captured by Method A] 1.0 g of a sample was weighed in terms of anhydride, and a calcium chloride solution (Ca
(O concentration is 300 ppm by weight), and the pH is adjusted to 10.
After adjusting to 0 to 10.5, the mixture was stirred at 25 ° C for 10 minutes. After 10 minutes, the mixture was filtered using a filter paper of Type 5 C (specified in JIS P3801, hereinafter the same). The filtrate 2
0 ml was taken, the amount of Ca in the filtrate was measured by EDTA titration, and the amount of Ca ion trapped per 1 g of anhydrous sample was determined from the value.
【００２５】［Ｂ法によるＣａイオン捕捉量］無水物換
算で試料０. １０ｇを秤取し、塩化カルシウム溶液（Ｃ
ａＯ濃度は３０ｐｐｍ）１０００ｍｌ中に加え、さらに
１Ｎの水酸化ナトリウム溶液を加えてｐＨを１０. ０〜
１０. ５に調整した後、２５℃で１０分間撹拌した。１
０分後、５種Ｃ番のろ紙を用いてろ過ＳＩた。そのろ液
１０ｍｌを取って、純水で１０倍に希釈した後、原子吸
光分析によってろ液中のＣａ濃度を測定し、その値より
試料の無水物１ｇあたりのＣａイオン捕捉量を求めた。[Amount of Ca ions captured by Method B] 0.10 g of a sample, calculated as an anhydride, was weighed to obtain a calcium chloride solution (C
(aO concentration is 30 ppm) and added to 1000 ml, and 1N sodium hydroxide solution is added to adjust the pH to 10.0.
After adjusting to 10.5, the mixture was stirred at 25 ° C for 10 minutes. 1
After 0 minutes, filtration SI was performed using a filter paper of type 5 C. After taking 10 ml of the filtrate and diluting it 10 times with pure water, the concentration of Ca in the filtrate was measured by atomic absorption spectrometry, and the amount of Ca ion trapped per 1 g of the anhydride of the sample was determined from the value.
【００２６】［吸油量］ビーカーに乾燥試料粉末２５ｇ
を秤取し、よく混ぜながらアマニ油を１ｇずつ加えた。
光沢のある滑らかなペースト状になったところで重量を
測定し、試料１００ｇあたりの吸油量を求めた。[Oil absorption] 25 g of dried sample powder in a beaker
Was weighed, and 1 g of linseed oil was added to each with thorough mixing.
When the paste became glossy and smooth, the weight was measured to determine the oil absorption amount per 100 g of the sample.
【００２７】［例１］市販の３号ケイ酸ナトリウム水溶
液（Ｎａ2 Ｏ：９. ４３重量％、ＳｉＯ2 ：２９. ２４
重量％）３７９. ６ｇをビーカーに取り、撹拌しながら
４８％水酸化ナトリウム水溶液５２０. ４ｇを加えて、
９００ｇのオルトケイ酸ナトリウム水溶液（Ｎａ2 Ｏ／
ＳｉＯ2 モル比２．０）を調製した。Example 1 Commercially available aqueous solution of No. 3 sodium silicate (Na 2 O: 9.43% by weight, SiO 2 : 29.24)
(% By weight) 379.6 g was placed in a beaker, and 520.4 g of 48% aqueous sodium hydroxide solution was added with stirring,
900 g of sodium orthosilicate aqueous solution (Na 2 O /
A SiO 2 molar ratio of 2.0) was prepared.
【００２８】これに純水１１３５. ３ｇを加えてホモミ
キサーで強力に撹拌しながら（７０００ｒｐｍ）、市販
のアルミン酸ナトリウム水溶液（Ｎａ2 Ｏ：１９. ０重
量％、Ａｌ2 Ｏ3 ：２０. ０重量％、Ｎａ2 Ｏ／Ａｌ2
Ｏ3 モル比１．５６）２３５. ３ｇを２０分かけてゆっ
くりと添加した。混合溶液中の各酸化物成分の割合はモ
ル比でＳｉＯ2 ：Ａｌ2 Ｏ3 ：Ｎａ2 Ｏ＝２７．５：
６．８：６５．７であり、ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比
は４．０であった。Pure water (1135.3 g) was added thereto, and the mixture was vigorously stirred with a homomixer (7000 rpm), and a commercially available sodium aluminate aqueous solution (Na 2 O: 19.0 wt%, Al 2 O 3 : 20.0) was used. % By weight, Na 2 O / Al 2
235.3 g of an O 3 molar ratio of 1.56) was slowly added over 20 minutes. The molar ratio of each oxide component in the mixed solution is SiO 2 : Al 2 O 3 : Na 2 O = 27.5:
6.8: a 65.7, SiO 2 / Al 2 O 3 molar ratio was 4.0.
【００２９】添加終了後も３０分間撹拌を続け、反応さ
せ沈殿を析出させた。添加中および添加後の反応液の温
度は多少変化したが２５〜４０℃の範囲内であった。撹
拌終了後、反応物を５種Ｃ番のろ紙でろ過し、純水４３
２２ｇを用いて洗浄した。得られたケーキを乾燥しアル
ミノシリケートの粉末を得た。After the addition was completed, stirring was continued for 30 minutes to cause a reaction and precipitate was deposited. The temperature of the reaction liquid during and after the addition changed somewhat, but was within the range of 25 to 40 ° C. After the stirring was completed, the reaction product was filtered through a filter paper of Class 5 C to obtain pure water 43
Washed with 22 g. The cake obtained was dried to obtain aluminosilicate powder.
【００３０】このアルミノシリケートの重量は、無水物
換算で１２６. ８ｇであった。化学分析したところ、酸
化物モル比でＮａ2 Ｏ：Ａｌ2 Ｏ3 ：ＳｉＯ2 ＝０. ８
８：１. ００：１. ９６であった。またＸ線回折により
非晶質であることを確認した。ＢＥＴ比表面積（単位：
ｍ2 ／ｇ）、Ａ法およびＢ法によるＣａイオン捕捉量
（単位：ｍｇＣａＯ／ｇ）、吸油量（単位：ｇ／１００
ｇ）を測定した結果を表１に示す。The weight of this aluminosilicate was 126.8 g in terms of anhydride. Chemical analysis showed that the oxide molar ratio was Na 2 O: Al 2 O 3 : SiO 2 = 0.8.
It was 8: 1.00: 1.96. Further, it was confirmed by X-ray diffraction that it was amorphous. BET specific surface area (unit:
m 2 / g), Ca ion trapping amount (unit: mgCaO / g) by method A and method B, oil absorption (unit: g / 100)
The results of measuring g) are shown in Table 1.
【００３１】［例２］例１のケイ酸ナトリウム水溶液と
純水とアルミン酸ナトリウム水溶液の混合溶液を、混合
終了後８０℃に保持しながら３時間撹拌を続けた。この
結果ＮａＡ型ゼオライト結晶粉末が得られた。例１と同
様にして測定した物性を表１に示す。Example 2 The mixed solution of the aqueous sodium silicate solution of Example 1, pure water and aqueous sodium aluminate solution was stirred at 80 ° C. for 3 hours after the completion of mixing. As a result, NaA type zeolite crystal powder was obtained. Table 1 shows the physical properties measured in the same manner as in Example 1.
【００３２】［例３］混合溶液の中の各酸化物成分の割
合がモル比でＳｉＯ2 ：Ａｌ2 Ｏ3 ：Ｎａ2Ｏ＝３８．
８：２０．２：４１．０、すなわちＳｉＯ2 ／Ａｌ2 Ｏ
3 モル比１．９になるように、かつ固形分濃度が例１と
同じになるようにケイ酸ナトリウム水溶液とアルミン酸
ナトリウム水溶液を混合し、反応温度を６５℃にする以
外は例１と同様にしてアルミノシリケートの粉末を得
た。Example 3 The ratio of each oxide component in the mixed solution was SiO 2 : Al 2 O 3 : Na 2 O = 38.
8: 20.2: 41.0, that is, SiO 2 / Al 2 O
Same as Example 1 except that the sodium silicate aqueous solution and the sodium aluminate aqueous solution were mixed so that the 3 molar ratio was 1.9 and the solid content concentration was the same as in Example 1, and the reaction temperature was 65 ° C. To obtain an aluminosilicate powder.
【００３３】この粉末を化学分析したところ、酸化物モ
ル比でＮａ2 Ｏ：Ａｌ2 Ｏ3 ：ＳｉＯ2 ＝０. ９８：
１. ００：２. ６０であり、Ｘ線回折により非晶質であ
ることを確認した。例１と同様にして測定した物性を表
１に示す。Chemical analysis of this powder showed that the oxide molar ratio was Na 2 O: Al 2 O 3 : SiO 2 = 0.98:
It was 1.00: 2.60 and confirmed to be amorphous by X-ray diffraction. Table 1 shows the physical properties measured in the same manner as in Example 1.
【００３４】［例４］混合溶液の組成がモル比でＳｉＯ
2 ：Ａｌ2 Ｏ3 ：Ｎａ2 Ｏ＝２５．１：２４．９：５
０．０、すなわちＳｉＯ2 ／Ａｌ2 Ｏ3 モル比１．０に
なるように、かつ固形分濃度が例１と同じになるように
ケイ酸ナトリウム水溶液とアルミン酸ナトリウム水溶液
を混合し、反応温度を５０℃にする以外は例１と同様に
してアルミノシリケートの粉末を得た。[Example 4] The composition of the mixed solution was SiO in molar ratio.
2 : Al 2 O 3 : Na 2 O = 25.1: 24.9: 5
0.0, that is, the SiO 2 / Al 2 O 3 molar ratio was 1.0, and the sodium silicate aqueous solution and the sodium aluminate aqueous solution were mixed so that the solid content concentration was the same as in Example 1, and the reaction temperature Aluminosilicate powder was obtained in the same manner as in Example 1 except that the temperature was changed to 50 ° C.
【００３５】この粉末を化学分析したところ、酸化物モ
ル比でＮａ2 Ｏ：Ａｌ2 Ｏ3 ：ＳｉＯ2 ＝０. ９６：
１. ００：３. １７であり、Ｘ線回折により非晶質であ
ることを確認した。例１と同様にして測定した物性を表
１に示す。Chemical analysis of this powder showed that the oxide molar ratio was Na 2 O: Al 2 O 3 : SiO 2 = 0.96:
It was 1.00: 3.17 and was confirmed to be amorphous by X-ray diffraction. Table 1 shows the physical properties measured in the same manner as in Example 1.
【００３６】[0036]
【表１】 [Table 1]
【００３７】例１の非晶質アルミノシリケートは例２の
ＮａＡ型ゼオライトと比較してＣａイオン捕捉量が同等
で吸油量が大きい。また、例１の非晶質アルミノシリケ
ートは例３および例４の非晶質アルミノシリケートより
Ｃａイオン捕捉量が大きい。The amorphous aluminosilicate of Example 1 has a similar Ca ion trapping amount and a larger oil absorption amount than the NaA type zeolite of Example 2. Further, the amorphous aluminosilicate of Example 1 has a larger Ca ion trapping amount than the amorphous aluminosilicates of Examples 3 and 4.
【００３８】[0038]
【発明の効果】本発明により、現在洗剤用ビルダーとし
て用いられているＮａＡ型ゼオライトと比較してアルカ
リ土類金属イオン捕捉能はほぼ同等でかつ吸油量が大き
く、界面活性剤の含浸性に優れた、衣料用洗剤、食器用
洗剤、洗顔洗身用洗剤または工業洗剤へ配合する洗剤用
ビルダーとして好適な、アルカリ土類金属イオン捕捉剤
として使用できる非晶質アルミノシリケートを容易に製
造できる。EFFECTS OF THE INVENTION According to the present invention, compared with NaA type zeolite currently used as a builder for detergents, the alkaline earth metal ion scavenging ability is almost the same, the oil absorption is large, and the impregnation property of the surfactant is excellent. In addition, it is possible to easily produce an amorphous aluminosilicate that can be used as an alkaline earth metal ion scavenger, which is suitable as a builder for detergents to be added to laundry detergents, dish detergents, face wash detergents or industrial detergents.
Claims (2)
ルカリ金属）を０．０１〜２．０モル、ＳｉＯ2 を１．
０〜４．０モル含有する非晶質アルミノシリケートであ
って、下記Ａ法によるＣａイオン捕捉量が１００ｍｇＣ
ａＯ／ｇ以上、下記Ｂ法によるＣａイオン捕捉量が９０
ｍｇＣａＯ／ｇ以上、吸油量が８０〜３００ｇ／１００
ｇ、比表面積が１０〜５０ｍ2 ／ｇである非晶質アルミ
ノシリケート。 Ａ法：ＣａＯに換算した濃度が３００重量ｐｐｍのＣａ
塩溶液１０００ｍｌ中に無水物換算で１ｇの非晶質アル
ミノシリケートを添加して測定される、ＣａＯに換算し
たＣａイオンの捕捉量（単位：ｍｇＣａＯ／ｇ）。 Ｂ法：ＣａＯに換算した濃度が３０重量ｐｐｍのＣａ塩
溶液１０００ｍｌ中に無水物換算で０．１ｇの非晶質ア
ルミノシリケートを添加して測定される、ＣａＯに換算
したＣａイオンの捕捉量（単位：ｍｇＣａＯ／ｇ）。1. To 1 mol of Al 2 O 3 , 0.01 to 2.0 mol of R 2 O (R is an alkali metal) and 1. 2 mol of SiO 2 .
An amorphous aluminosilicate containing 0 to 4.0 mol, wherein the amount of Ca ions captured by the following Method A is 100 mgC
aO / g or more, the amount of Ca ions captured by Method B below is 90
mgCaO / g or more, oil absorption of 80 to 300 g / 100
g, an amorphous aluminosilicate having a specific surface area of 10 to 50 m 2 / g. Method A: Ca whose concentration converted to CaO is 300 weight ppm
The amount of captured Ca ions converted to CaO (unit: mgCaO / g), which was measured by adding 1 g of an amorphous aluminosilicate in terms of anhydride to 1000 ml of a salt solution. Method B: CaO-converted Ca ion trapping amount (measured by adding 0.1 g of an amorphous aluminosilicate in terms of anhydride to 1000 ml of a Ca salt solution having a concentration converted to CaO of 30 ppm by weight ( Unit: mgCaO / g).
アルカリ金属塩水溶液を、ＳｉＯ2分とＡｌ2 Ｏ3 分と
Ｒ2 Ｏ（Ｒはアルカリ金属）分とがモル比でＳｉＯ2 ：
Ａｌ2 Ｏ3 ：Ｒ2 Ｏ＝５〜３０：２〜１０：６０〜９３
となるように混合し、撹拌しながら４０℃以下に保持
し、析出した沈澱を分離する非晶質アルミノシリケート
の製造方法。2. An alkali metal silicate aqueous solution and an alkali metal aluminate aqueous solution, wherein SiO 2 content, Al 2 O 3 content and R 2 O (R is an alkali metal) content are in a molar ratio of SiO 2 :
Al 2 O 3: R 2 O = 5~30: 2~10: 60~93
A method for producing an amorphous aluminosilicate, in which the mixture is mixed so that it is maintained at 40 ° C. or lower with stirring and the precipitated precipitate is separated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP865296A JPH09202613A (en) | 1996-01-22 | 1996-01-22 | Noncrystalline aluminosilicate and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP865296A JPH09202613A (en) | 1996-01-22 | 1996-01-22 | Noncrystalline aluminosilicate and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09202613A true JPH09202613A (en) | 1997-08-05 |
Family
ID=11698875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP865296A Pending JPH09202613A (en) | 1996-01-22 | 1996-01-22 | Noncrystalline aluminosilicate and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09202613A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018054881A (en) * | 2016-09-29 | 2018-04-05 | デンカ株式会社 | Amorphous aluminosilicate-based toner external additive |
| CN112645610A (en) * | 2020-09-12 | 2021-04-13 | 重庆鑫景特种玻璃有限公司 | Boron-free and phosphorus-free high-stability ionic sieve and application thereof |
-
1996
- 1996-01-22 JP JP865296A patent/JPH09202613A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018054881A (en) * | 2016-09-29 | 2018-04-05 | デンカ株式会社 | Amorphous aluminosilicate-based toner external additive |
| CN112645610A (en) * | 2020-09-12 | 2021-04-13 | 重庆鑫景特种玻璃有限公司 | Boron-free and phosphorus-free high-stability ionic sieve and application thereof |
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