JPS59194000A - Bleaching detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a cleansing composition with excellent storage stability. More particularly, a bleach cleaning RIJ composition comprising sodium percarbonate coated on the surface with a post agent containing a borate and a magnesium compound 9IJ is preferred.

Soda percarbonate is known as a whitening agent or oxidizing agent.
Sodium perborate is a typical acid-based whitening agent.
Generally, it is manufactured by reacting hydrogen peroxide with soda carbonate.Soda percarbonate has a general formula of 2%.Compared to chlorine-based bleaching agents, sodium percarbonate has a slightly lower whitening rate at room temperature, synthetic fibers, It has the advantage that it does not yellow even when applied to animal fibers, resin-treated fibers, or fluorescent brightener-treated fibers, and does not damage the fabric.
Historically, it has been used particularly as a bleaching agent for household and commercial purposes because a sufficient bleaching effect can be obtained by applying temperature or by using a sieving accelerator in combination.

The reason why dust ash, general detergent, and household whitening agent 64 are attracting attention is that their decomposition products are non-polluting and can be put to practical use in any way without any problems.

However, soda percarbonate is similar to sodium perborate (relative to sodium perborate).
It has a major drawback of having rather poor storage stability and losing effective oxygen more quickly than 1 during storage. Soda percarbonate has a strong affinity for water, so even the slightest amount of moisture causes its surface to adsorb moisture, causing decomposition and the formation of iron,
When ions such as copper, manganese, and cobalt are present, decomposition is further accelerated, and its stability is inferior to that of sodium perborate. When sodium percarbonate is stored alone in an airtight container, its storage stability is no different from that of sodium perborate, but if it is mixed with detergent or left unopened, sodium percarbonate is highly hygroscopic. , its storage stability is poor.

Furthermore, there is concern that sodium tripolyphosphate (SRPP), which has been conventionally used as a builder in detergents, may cause trophication and cause environmental pollution, especially in closed water bodies. For this reason, the demand for low-phosphorus (・)-free detergents is increasing.
Synthetic zeolites (fluminosilicates) are becoming widespread as an alternative to 'rpp.

However, the sodium percarbonate in this zeolite-containing detergent is extremely unstable, and the sodium percarbonate in the zeolite-containing phosphorus-free detergent rapidly loses effective oxygen and decomposes due to the catalytic decomposition action of the zeolite. To go.

For this reason, there has been a strong desire to develop a technology that can reduce the phosphorus content in detergents or increase the amount of phosphorus in detergents, and improve the storage stability of the sodium percarbonate compound.

Conventionally, methods for stabilizing soda percarbonate have been proposed, including halafine and sodium percarbonate with a molecular weight of 10.
Is there a way to use polyethylene glycol of 00 to 8000? It is not effective for long-term stabilization because of its hygroscopic properties.

Another method is to add a small amount (both two types of stabilizers) selected from phosphoric acids, ethylenedi7minetetraacetate silicate, and nitrilotriacetate to an aqueous hydrogen peroxide solution when producing sodium percarbonate. Although these stabilizers are effective at temperature, they have no practical stabilizing effect on moisture or detergent mixtures.

There is also a method of uniformly coating sodium percarbonate with sodium birophosphate, but this method also has a low decomposition rate against heat, but has a moisture content of 7. It is not sufficient in terms of stabilizing effect when blended into detergents and detergents.

The object of the present invention is to provide a whitening detergent containing sodium percarbonate that is stabilized even when incorporated into detergents, especially low-sulfur or phosphorus-free detergents, until practical use.

The Ministry of the Invention and others conducted intensive research with this objective in mind, and as a result,
The above object is achieved by coating both the borate such as sodium percarbonate, which is incorporated in the white detergent, and a magnesium compound such as fAtM magnesium, silicomagnesium, magnesium chloride, and magnesium oxide with a coating agent. The inventors discovered this and completed the present invention.

First, in the bleaching detergent according to the present invention, the sodium percarbonate compounded is coated and stabilized with a coating agent containing a borate and a magnesium compound.

The borate is preferably a sodium salt of boric acid, more preferably metaborate, and the magnesium compound is preferably one or more of magnesium chloride, magnesium oxide, magnesium sulfate, magnesium silicate, and the like. In addition, this coating material contains metal ion sequestering agents,
For example, ethylenecyaminetetraacetate, nitrilotriacetate, etc. can be included.

The ratio of coating agent to soda percarbonate to be blended is 0.1~
60% by weight is preferred, the proportion of borate in the coating is preferably from 10 to 95% by weight, and the proportion of magnesium compound is preferably from 5 to 70% by weight. It is generally preferred that the amount of magnesium compound is equal to or less than the amount of borate.

Magnesium compounds are substances widely used as peroxide stabilizers. Regarding soda percarbonate,
It is known that it is used as a stabilizer for the mother liquor during reaction crystallization, or that it is simply mixed with sodium percarbonate for stabilization. However, in these methods, the phosphorus-free Sufficient effect cannot be obtained in detergent (・
. Furthermore, Japanese Patent Publication No. 47-52519 discloses that magnesium sulfate, magnesium oxide, and magnesium chloride are blended as stabilizers for sodium percarbonate, and this blend is granulated using polyethylene glycol as a binder. As written there 1. ! : Granulating soda percarbonate with a binder is an effective means for stabilizing sodium percarbonate in a zeolite-containing phosphorus-free detergent.

In other words, the stabilizing effect of the magnesium compound and the stabilizing effect of sugar beet granulation act synergistically, resulting in a mulch that can be expected to have excellent storage stability even in phosphorus-free detergents containing zeolite. However, organic bonds such as those found in the polyethylene glycol of Japanese Patent Publication No. 47-32519, +
+:1 When used with peroxides such as soda percarbonate, there is a serious risk of VC business such as ignition during the manufacturing process.

It is also known to use Garlic 1 as a peroxide-coated granulating agent to be added to a bleaching detergent.

For example, British Patent No. 1,575,792 discloses boric acid (orthoboric acid, mekuboric acid, tetraboric acid) as a peroxide resistant agent.

Also, in Japanese Patent Publication No. 49-6760, peroxide water (with purple)
In addition to regular products, storage stability is improved.
ing. However, these known publications do not recommend that the coating of peroxide with borate as described by the present author should be carried out at 1°C.
Not disclosed at all.

The present inventor has previously discovered that coating with borate is highly spreadable,
The coating efficiency of sodium percarbonate is extremely poor, and the storage stability of powdered or granular percarbonate soda whose surface is coated with borate when combined with textile detergent Kat is due to boric acid. I found it to be much better than that.

(See Japanese Patent Application No. 57-99826.) However, as a result of further research, the present inventors have found that when a magnesium compound is used together with a borate, the above-mentioned effect (the ability of the borate to absorb and the stabilizing ability of the magnesium compound) By obtaining a coated soda percarbonate with even better storage stability due to the synergistic effect and incorporating it into this powdered cleaning agent, a significantly superior coexistence stability of >1
We have created a book with a unique character @Akibaibaku Cleaning Agent. According to the present invention, it is possible to avoid the dangers in the manufacturing process when using the above-mentioned organic binders due to the use of borates.

The borate and magnesium compounds used in the coating of sodium percarbonate according to the present invention include the following:

On the contrary, the borates include sodium tetraborate decahydrate (borax Na 0.2B203., 10H20,1, sodium tetraborate pentahydrate (N & 0.2B205.5H20),
Sodium tetraborate tetrahydrate (N & 20.2B203., 4H
20), (anhydrous) tetraborous soda (Na2O, 2B2
03), Sodium octaborate tetrahydrate (Na2O, 4B2
03.4H20), sodium pentaborate pentahydrate (Na2
O, 5B203°10H20), sodium perborate tetrahydrate (Na5o, -4H20), sodium perborate monohydrate (
NaBOs41H20) metaborate tetrahydrate (Na
BO2,4H20), metaborate dihydrate (Na
BO2,2f(20) etc., and among these, particularly preferred are sodium metaborate dihydrate and sodium meborate tetrahydrate.

Examples of magnesium compounds include anhydrous or hydrated salts of magnesium sulfate, magnesium chloride, magnesium oxide, magnesium hydroxide, magnesium silicate, magnesium nitrate, magnesium phosphate, magnesium carbonate, etc.
Alternatively, magnesium salts of various organic acids can also be used;
Among these, particularly preferred are magnesium sulfate, magnesium chloride, magnesium oxide, magnesium silicate, water, or water phase salts.

In the coating agent of sodium percarbonate used in the present invention, borates and magnesium compounds as described above are used in combination with 4.
! It is possible to contain organic or inorganic compounds. Examples include inorganic compounds such as soda carbonate and Glauber's salt, organic polymer compounds such as polyethylene glycol, polyvinylpyrrolidone, and hydroxyglobil cellulose;
A sequestering agent such as Minnishi acetate may also be included. The amount of the sequestering agent contained is preferably 0.01 to 3% by weight based on the sodium percarbonate.

The coating step using the coating agent containing the borate of sodium percarbonate and the magnesium compound used in the present invention can be carried out by a conventional method that has been conventionally performed at ℃. For example, a method may be used in which a coating solution or powder is uniformly mixed and adsorbed onto wet or dry sodium percarbonate powder or granules, and then dried. The applied soda percarbonate has an average particle size of 100 to 2000 μm, preferably 250 to 10 μm.
It is preferable to use a powder of 00 μm.

Soda percarbonate prepared as described above is also very effective when incorporated into ordinary powder cleaning agents (spray-dried products), especially low-sulfur or non-phosphorus detergents containing zeolite. It showed no storage stability. The festival cleaning composition of the present invention can be prepared by blending 1 to 40% of the sodium percarbonate thus obtained into a powdered cleaning agent.

Additionally, the concentrated sodium percarbonate used in the present invention has very improved storage stability and is therefore less likely to be used in other detergent formulations that may be present in the detergent, such as fluorescent dyes, detergents, etc. It is not possible to minimize the impact on enzymes, activators, etc. that act during the process. Therefore, according to the present invention, detergent formulations containing enzymes, fluorescent dyes, daily activators, etc., which are susceptible to the decomposition of sodium percarbonate, and detergent systems in which sodium percarbonate is used in combination can also be used to improve the effectiveness of each formulation. It is possible to resolve all stability issues. In other words, according to the present invention, a phosphorus-free antidetergent is provided which is formulated with sodium percarbonate, an enzyme, a fluorescent dye, and the white color in combination with a occupancy agent, etc., and which has excellent storage stability. be done.

The bleaching detergent compositions of the present invention may optionally contain water bathing soaps and anionic, nonionic or amphoteric surfactants, specific or inorganic builders or metal compounds, which are well known in the art. However, these Jl and others are limited to #, and formulations according to the purpose KJ5 may be made.

Well-known ingredients such as surfactants and builder ingredients are disclosed in Japanese Patent Application No. 57-99 filed by the present applicant, for example.
Those exemplified in the specification of No. 826 may be used as appropriate.

Next, the Kinoi EA will be explained using examples, but the present invention is not limited to these examples.

Example 1 Sodium percarbonate was placed in a stirring mixer at 25 O.
While stirring at rpm.
A 25% water bath solution of NaBo2 4H2 5I (heat cured) and magnesium acid A
,,) 11 f) A 25% water bath solution was poured into the solution, stirred for 1°, and then dried with hot air to obtain acid percarbonate.

For comparison, sodium percarbonate coated using only metaboric acid powder (NaBO2-
To 4H20Y19), sodium percarbonate coated with boron M (boric acid 3.41 per 100g of soda percarbonate!
), sodium percarbonate coated with boric acid and anhydrous magnesium sulfate (boron [2
,4&.

MgSO41 & ), soda percarbonate coated only with anhydrous magnesium sulfate (MgSO41 & ),
gSO45,4,9) was also produced. 1. During washing with phosphorus-free powder of the following composition,
0% by weight was uniformly mixed to obtain a whitening detergent.

Phosphorus-free whitening detergent composition Weight% Sodium dodecylbenzenesulfonate 20.0 Synthetic zeolite (Type 4A) 2 0
．． 0 Sodium silicate (JIS No. 2)
1 0.0 carbonate
5.0 fluorescent dye
0.5 Carboxymethyl cellulose salt 1.0 Enzyme (alcalase) 0.6 Sodium percarbonate 10
．． 0 moisture
5.0 sulfuric acid
Remaining total: 100 As the soda percarbonate blended in the above composition, a coating using metaborate powder and MgSO4 according to the present invention as described above was used, and for comparison, a coating using only metaborate powder and a coating by thinning. material, coating with boric acid and MgSO4, coating with MgSO4 alone and coating r, t
A storage stability test was conducted on a total of 6 samples using less than 1 liter of sodium percarbonate, and the results are shown in Table 1.

〔Test method〕

10F of each of the above chain cleaning compositions was placed in a 50α volume plastic container with a lid, and the containers were left to stand for 14 days at 40°C, 80% R)i, and then the effective acid cumulative residual rate was determined by the following formula.

In addition, 0.1N permanganate titration method was used to determine the effective acid accumulation.

As shown in Table 1, the chain cleaning agent of the present invention containing sodium metaborate and sodium percarbonate using MgSO4 as a coating has a larger effective oxygen residual amount than those of Comparative Examples 1 to 5, which is clear. The acid effect was excellent.

In addition, the hard surface cleaning agent of this example is a phosphorus-free detergent that contains no phosphorus and contains ceolite, but the white-white detergent of the present invention has excellent coating stabilizing effects with metaboric acid powder and MgSO4. Showing good stability.

Example 2 Using the same covering power method as in Example 1, the glaze of the Mg compound used in combination with the metaborate powder was changed and sodium percarbonate was coated. The coating material used is shown below.

■ NaBO2-4H20, 5% + Mg5O4 (anhydrous solid content) 1% ■ NaBO2"4H20, 5% + Mgct
2 (Anhydrous solid content) 1%■ NaBO254H20.5%
+ 2Mg Phosphorus-free chain cleaning agent with similar composition (each containing 10% by weight of sodium percarbonate)
A storage stability test was conducted in the same manner as in Example 1, and the results are shown in Table 2. In the present inventions ■ to ■, which were carried out, extremely high K
h) Indicates storage stability.

Example 6 Using the same coating method as in Example 1, sodium metaborate, magnesium sulfate, and other coating agents were used in combination to coat sodium percarbonate. The coating material used is shown below. Incidentally, the amount of the coating agent used is expressed as a percentage of the amount of sodium percarbonate.

■ NaBO254H20.5% + Mg5O4 (anhydrous solid content) 1% + polyethylene glycol (PEG, min-f
Amount = 6000) 5% ■ NaBO254H20,5% + Mg5o4 (anhydrous solids) 1% decacarbonate, 5% ■ N,! LBO2114H20.5%+Mg5O4(
Anhydrous solid content) 1% decaethylenedi7minetetra vinegar & (EDT
A) 2Nδ salt 0.5% ■ tJaBo2-4H20.5% + Mg5O4 (anhydrous solid content) 1% + EDTA・2 triethanolamine (2
TKA) salt 0.5% ■ NaBO254H20.5% + Mg804 (anhydrous solid content 21% - nitrilotriacetic acid fi (NTA) lain
O, 59 upper layer 5 types of coating soda percarbonate and coating 1
A total of six types of good soda percarbonate were mixed with a phosphorus-free waste mountain cleaning agent having the same composition as in Example 1 (each containing 10% by weight of sodium percarbonate), and a storage stability test was conducted in the same manner as in Example 1. The results are shown in Table 3.

As shown in Table 3 and Table 6, it was revealed that even when using metaborate powder, magnesium sulfate, and other coating agents in combination, very poor storage stability was exhibited.

%, organic polymer compounds such as PEσ and EDTA@NT
Sequestering agents such as A and sodium metaborate and M
It shows a synergistic effect with the combined use of gSO4, improving storage stability.

Example 4 The coated soda percarbonate produced in Example 6 was evaluated for solubility, compressive strength, and disintegration, and the results are shown in Table 4.

[Test method]

Solubility〉 Put tap water 1-e into a beaker (1.13 volumes), add granular percarbonate, add 1.9 Y of IJum, and turn at 200 rpm.
Stirring was performed at a rotational speed of . After the stirring was started, the time required for the solution to reach 1 KW without any change in electrical constant was measured and this time was taken as the dissolution time.

Compressive strength> Fill a certain amount of sample under specified conditions, apply a load using an autograph, and show the load required to compress the sample.

Disintegration property〉 Sample (12 mesh permeable to 80 mesh impermeable to 100
11? : Transfer to a 500ml wide robot container and add a stainless steel ball (3φ) 50. ? '4 Put on the stopper. Shake a! Fix the smile container and adjust the amplitude 4. sm.

It was shaken for 10 minutes at a shaking rate of 660 times/min and expressed as the amount of N permeated through 80 meshes (%). A force with a small numerical value (%) is desirable.

As shown in Table 4, the solubility, compressive strength, and disintegration properties of sodium percarbonate coated by the method of the present invention were almost the same as those of uncoated sodium percarbonate.

Example 5 20 kp of wet sodium percarbonate was placed in a centrifugal diffusion mixer (Lödeige mixer, FKM-150D, T.M. Engineering Co., Ltd.), and while stirring, the coating powder was added, for a total of 10 minutes. Mixed. Thereafter, the coated sodium percarbonate was taken out and dried with hot air.

The following coating materials were used.

■ Sodium metaborate (NaBO2'4H20) 5%
+higso4 (anhydrous solid content) 1% + EDTA/2TE
A.

0.5% ■ Hokusand (Na2B4O7'1OH20) 4.54
%+Mg5O4 (anhydrous solid content) 1%+EDTA・2TE
A, 0.5%■ Boric acid (H3BO,) 2.4%+
Mg5O4 (anhydrous solid content) 1% + EDTA・QTEll
o, 5% (Note: % is weight % based on soda percarbonate) These six types of coated soda percarbonate (two types according to the present invention and comparative example 1)
A storage stability test was conducted by mixing 10% by weight of the following phosphorus-free bleaching detergent composition with a total of four types of sodium percarbonate (seed) and uncoated sodium percarbonate in the same manner as in Examples 1 and 2. (Same as Example 1), the results are shown in Table 5. Incidentally, the residual activity of the enzyme (Alcalase 2.OM) blended at the same time was also measured, and the residual rate of enzyme activity was measured using the following formula and is also shown.

J, B, C for the method of measuring the residual activity of the enzyme.

244(4) 1969. pp. 789-795, Analysis
st■ 1971, pages 159-163.

Dodecylbenzenesulfone e-sorter 20.0 Synthetic zeolite (4A type) 20.0 7-da silicate (JI No. 82) 10.0 Soda carbonate
5.0 fluorescent dye
0.5 strength ruboxymethylcellulose soda m
1.0 enzyme (Alcalase 2.0M)
0.3 Sodium percarbonate (coated)
10.0 water
5.0 Sodium sulfate residue
Total: 100 Table 5: The coverage ratio of the soda percarbonate was adjusted to 3.9% as anhydrous solid content.

As shown in Table 5, the phosphorus-free bleach cleaning agent according to the present invention■
and ■, despite containing zeolite,
The stability of sodium percarbonate was very good, and at the same time, the stability of the enzyme was also excellent.

Example 6 Coated soda percarbonate (N
aBO□-4H20 and Na2B40. -10H20 and MgSO4 coatings and two comparative examples (H
, Bo, / MgSO4 coating and unheated soda percarbonate] were mixed at 10% by weight each into a powder bleaching detergent having the following composition, and a storage stability test was conducted to determine the residual effective oxygen in the sodium percarbonate. rate and alcalase 2
．． The results of the residual rate of enzyme activity at 0M are shown in Table 6. The test method was the same as in Examples 1 and 5.

Bleach cleaning agent composition Weight % Sodium dodecylbenzenesulfonate 20.0 Sodium tripolyphosphate 18.0 Sodium silicate (JIS No. 2) 10.0 Sodium carbonate 5.0 Fluorescent dye
0.5 carboxymethyl cellulose sorter salt 0.
5 enzyme (Alcalase 2.0M) 0.
5 Soda percarbonate 10.0 Water
5.0 Sodium sulfate
Total remaining 100 Table 6 Coverage rate as a fish culture water product is 5.9% This example shows a conventional cleansing composition containing 5TPP, and the composition according to the present invention has excellent storage stability. showed his sexuality. This shows that the bleaching detergent according to the present invention has excellent storage stability regardless of the zeolite content.

8th person (ji1 person Takeru Furuya)

Claims (1)

[Scope of Claims] t. A zero white cleaning composition comprising soda percarbonate whose surface has been damaged by a coating agent containing at least both a borate and a magnesium compound. 2 0.1 to 60 for coating agent or soda percarbonate
%, and borate is 10 to 99.5ff in the coating material.
The bleaching detergent composition according to claim 1, wherein the magnesium compound is 0.5 to 50% by weight in terms of i%. (5) The bleaching detergent composition according to claim 1 or 2, wherein the borate is a sodium salt of boric acid. 4. Magnesium compounds include magnesium sulfate, magnesium chloride, magnesium oxide, and magnesium silicate. The cleaning composition according to claim 1, 2 or 3, which has the above features. 5. Claim 3, wherein the sodium salt of boric acid is sodium meborate. or the target cleaning composition according to claim 4. 6. The target cleaning composition according to any one of claims 1 to 5, wherein the coating agent contains a sequestering agent. Z metal The bleaching detergent composition according to claim 6, wherein the sequestering agent is ethylenediaminetetraacetate or nitrilotriacetate.8. 250-1000μ The cleaning composition according to any one of claims 1 to 7, wherein the amount of the coated percarbonate powder is 1 to 4 in the composition.
The white detergent composition according to any one of claims 1 to 8, which has a content of 0% by weight.