JPH0317199A - Detergent compounds - Google Patents

Abstract

PURPOSE: To provide a detergent compsn. obtained by the compression molding of a detergent powder containing sodium perborate, a specific inorg. peracid salt bleaching agent responsive component, a washing action compd. and a builder and preventing the corrosion of the metal component of a washing machine and having high washing effect.

CONSTITUTION: This detergent compsn. is constituted by the compression molding of a power detergent containing sodium perborate (A), one or more kind of an inorg. peracid salt bleaching agent responsive component (B) selected from among N-diacylated amine and/or N,N'-polyacrylated bleaching agent activator (i), enzyme (ii) and a fluorescent agent (iii), a washing action compd. (C) and a washing force builder (D) and composed of a tablet wherein the components A, B are mutually isolated.

COPYRIGHT: (C)1991,JPO

Description

[Detailed description of the invention] The present invention separates an inorganic persalt bleach (sodium perborate) from a bleach-sensitive ingredient (bleach-sensitive ingredient). s
The present invention relates to a novel tablet-shaped laundry detergent composition containing together without egregation).

Modern high-performance powder detergents for use in automatic washing machines usually contain a bleaching agent consisting of an inorganic persalt and some bleach-sensitive ingredients, especially bleach activators, enzymes and fluorescent ingredients. Contains a whitening agent.

Detergent compositions in tablet form are known to those skilled in the art, as described below, and some products are already commercially available. Tablets have several advantages over powdered products. In other words, it is easy to handle because there is no need to measure it, it is easy to feed the right amount to laundry, the ingredients are less likely to irritate sensitive skin because they do not form powder, and they are compact, which saves storage space. It also becomes.

However, in compacted tablets, the fractions are more closely clustered than in powder, which tends to increase adverse interactions and instability. Heretofore, it has been considered impossible to produce high quality tablets containing bleach and bleach-sensitive ingredients together without some kind of isolation or separation.

For example, U.S. Patent No. 3 953 350 (Kao), Japanese Patent Application No. 60 015 5008 (Lion)
, Japanese Patent Application No. 60 135 4978 (Lion) and Japanese Patent Application No. 60 135 4988 (
Lion) discloses a tablet-shaped detergent that contains a persalt bleach but does not contain bleach-sensitive ingredients. In Spain, detergent tablets containing enzymes but no bleach are available on the market. British Patent No. 900 204 (Un
ilever) discloses a laminated tablet detergent containing sodium perborate and certain bleach activators, such as sodium acetoxybenzenesulfonate and phthalic anhydride, and in a comparative example, these ingredients were It is stated that the tablets contained together are unstable unless isolated in a separate layer. Surprisingly, in the present invention, the bleach activator is an N-diacylated amine or an N,N'-polyacylated amine,
In particular, it has been found that the above-mentioned isolation is not necessary for tetraacetylethylenediamine (TAED).
Also, other bleach-sensitive ingredients, in particular enzymes and fluorescent agents, can be included as well without the need for isolation, which greatly simplifies the manufacture of the tablets.

Full Iy-formulate of the present invention
d) Tablet-shaped detergents compress (compact) powder.
It can be easily manufactured by

The present invention comprises (a) sodium perborate, (b) (bl) N~diacylated amine and N,N.
one or more inorganic persalt bleach-sensing ingredients and ingredients selected from the group consisting of: a polyacylated amine bleach activator, (b2) an enzyme, and (b3) a fluorescent agent; and (c) one or more detergent compounds. , a tablet obtained by compressing a powder detergent containing one or more detergency builders and other optional detergent ingredients, wherein the ingredients (a) and (b) are not isolated from each other. do.

The present invention also provides a method for manufacturing a tablet detergent. The manufacturing method includes the following steps: (i) (a) sodium perborate; (b) (bl) N-diacylated amine and N,N
, N'-polyacylated amine bleach activators, (b2) enzymes, and (b3) fluorescent agents, and (c) one or more cleaning agents. (ii) compressing said powder so that components (a) and (b) are isolated from each other; Not form a tablet.

The tablet-like detergent of the present invention mainly contains an inorganic persalt bleach (sodium perborate) and at least one bleaching agent, such as an acylated amine bleach activator. ,
Contains enzymes, fluorescent agents, surfactants, detergency builders, and optionally other common ingredients. Below is a more detailed description of these various components. One of the main features of the invention is that sodium perborate (a>
and one or more bleach-sensitive ingredients (b) are not isolated from each other in the tablet. That is, the components are not separated from each other in specific areas of the tablet, such as separating layers or inserts, but are mixed randomly. That is not to say that these ingredients may be in any form normally used in powdered detergents, such as granule form for bleach activators, granule-arume for enzymes, etc.
s or coated marumes, and some protection, coating or dilution means may also be used to obtain these forms.

However, in the tablet of the present invention, in addition to these common methods for powdered detergents, <a) sodium perborate and {b}
No means are used to keep the one or more bleach-sensitive components separate.

In one preferred embodiment of the invention, the tablets of the invention are substantially homogeneous. That is, it is manufactured by compressing a single homogeneous blended powder.

However, tablets containing one or more layers, inserts or other means for isolating components other than components (a) and (b) are also within the scope of the invention.
Components (a) and (b) are randomly mixed and distributed in at least one area of the tablet. Boron a The inorganic persalt bleach used in the tablet detergent of the present invention is sodium perborate. The material may have a monohydrate, a tetrahydrate, a mixture of the two, a partially dehydrated tetrahydrate, or any other stable commercially available form. Sodium perborate-hydrate may have a high surface area form or a low surface area form.

The content of sodium perborate is preferably 1 to 30% by weight, more preferably 5 to 20% by weight.

``I17, b The tablet of the present invention contains as one of the main ingredients (bl),
It contains at least one bleach-sensitive component selected from the group (b2) and (b3). One or more bleach-sensitive ingredients selected from one or more of the above groups may be used in any combination.

The activator for activating the inorganic peracid is an organic compound having one or more reactive acyl residues that induces the peracid form. The presence of a peracid provides a greater effect than the use of an inorganic persalt alone at low wash temperatures, e.g. 20 DEG to 60 DEG C.

The bleach activator used in the tablets of the invention {J-todisylated amines or N,N''-bolyacylated amines.
These materials are disclosed in British Patent No. 855 355 and British Patent No. 907 356 (IJnilever). In the case of polyamines, at least one nitrogen atom must have two acyl groups. A preferred bleach activator for use in the tablets of the present invention is tetraacetylethylenediamine (T^εD). The weight ratio of inorganic persalt (sodium perborate) to bleach activator in the tablets of the present invention may vary from about 30:1 to about 1:1, preferably from 15:1 to 2:1. do.

TAED is advantageously used in the form of granules on an organic carrier. The content of TAED itself in the tablets of the present invention is preferably 1-15% by weight, more preferably 2-10% by weight.

The tablet detergent of the present invention may optionally contain various detersive enzymes well known to those skilled in the art for their ability to break down and promote the removal of various soils and stains. It is possible. Suitable enzymes include various proteases, cellulases, lipases, amylases, and mixtures of these enzymes formulated to remove various soils and stains from fabrics. The present invention particularly uses proteolytic enzymes (proteases).

Preferred proteases are solid catalytically active protein substances that degrade proteinaceous smudges, usually present as fiber smudges, in a hydrolytic reaction.

This material can be of any origin, such as plant, animal, bacterial or yeast.

Proteases of various quality and origin are commercially available and exhibit activity in the pH range of 4 to 12, and these proteases can be used in the tablet-like detergent of the present invention. Specific examples of suitable one-bite teases include B. subt i
l is and B. subtilisins obtained from certain strains of P. licheniformis, such as Gist-Brocades N., Delft, The Netherlands. Subtilisine Maxatase™, commercially available from V.V., and Nova Indust, Copenhagen, Denmark.
It is commercially available from ri^/S! Aalase (trademark) is mentioned. Particularly suitable for use in the present invention are Bacillus, which exhibits maximum activity in the p++8-12 range.
It is a protease derived from the P. illus strain. This is, for example, the registered trademark Esp from NovoIndustri^/S.
Erase and Savinase are commercially available. The manufacture of these and similar enzymes is covered by British Patent No. 124
3 785. Other commercially available proteases include κazusase(TM) (commercially available from Showa Denko, Japan), Opti+sase(TM) (commercially available from Miles Kali-Chemie, Hannover, West Germany), and Superase(TM) (commercially available from Pfi, USA).
Commercially available from ZER Inc. Detergent enzymes are usually used in the form of granules or maruses, optionally with a protective coating, in amounts of about 0. l
% to about 3.0% by weight.

In the tablet detergent of the present invention, any fluorescent agent (optical brightener) suitable for use in powdered detergents may be used. The most commonly used fluorescent agents belong to the classes of diaminostilbene-sulfonic acid derivatives, diarylvirazoline derivatives and bisphenyl-distyryl derivatives. Fluorescent agents of the diaminostilbene-sulfonic acid derivative type include, for example, 4,4″-bis-(2-diethanolamino-4-anilino S-}riazin-6-ylamino).
Stilbene-2: 2'-disulfonic acid disodium, 4
．． 4'-bis(2-morpholino-4-anilino sl
-Ryazin-6-ylamino)stilbene-2:2'-
Disulfonic acid disodium, 4.4°-bis-(2.
4-dianilino-S-triazin-6-ylamino)stilbene-2=2゜disodium disulfonate, 4.
4-bisuku2-anilino4-<tomethyl-N-2-
hydroxyethylamino)-S-triazin-6-ylamino)stilbene-2,2'-disulfonic acid disodium, 4.4''-bis-(4-phenyl-2,1.3
-}liazol-2-yl)stilbene 2,2'-disulfonic acid disodium, 4,4゜-bis(2anilino4-(1-methyl-2-hydroxyethylamino)-S
monotriazin-6-ylamino)stilbene-2,2'
-disodium disulfonate and 2-(stilbyl-4)
``゛-Naphtho l''. 2゜:4,5)-1.2.3-
There is triazole-2゜゜sodium sulfonate. A preferred fluorescent agent is available from CibaGei, Basel, Switzerland.
Tinopal™, commercially available from Gy AG
DNS and Tinopal CBS. Tinop
al DMS is 4.4゜-bis(2-morpholino 4-
Anilino S-}riazin-6-ylamino)stilbenedisulfonic acid disodium = Tinopal
CBS is disodium 2,2'-bis(phenylustyryl)disulfonate.

Other fluorescent agents suitable for use in the present invention include: 1.
Examples include 3-diallylbirazoline and 7-alkylaminocoumarin. The preferred content of the fluorescent agent is 0.02-0.8% by weight, more preferably 0.03-0.5% by weight. Bi1191
The total amount of cleaning active substances (surfactants) in the tablet-like detergent of the present invention is suitably 2 to 50% by weight, preferably 5% by weight.
~40% by weight.

The tablet detergents of the present invention may contain one or more soap or non-soap anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, or any suitable combination thereof. Many compounds are commercially available, and for example Schwartz+Perry and B.
erch. ”Surface-＾active＾He
nts and Detergents”, Vol.I
It is also detailed in literature such as and {I. Preferred detersive compounds that may be used are soaps, synthetic non-soap anionic surfactants and nonionic surfactants.

Synthetic anionic surfactants are well known to those skilled in the art. Specific examples include: alkylbenzene sulfonates, especially sodium linear alkylbenzene sulfonates with alkyl chain lengths of C, to CI5; primary and secondary alkyl sulfates, especially sodium primary alcohol sulfates with CI2 to CIS; olefin sulfonates; alkanesulfonates. ;
Dialkyl sulfosuccinates; as well as fatty acid ester sulfonates are mentioned.

Suitable nonionic cleansing compounds which can be used include, in particular, compounds having hydrophobic groups and reactive hydrogen atoms, such as aliphatic alcohols, acids, amides or alkylphenols, il! Mention may be made of the products obtained by reacting ititized alkylenes, especially ethylene oxide alone or with ethylene oxide and propylene oxide. Certain nonionic detersive compounds have an alkyl moiety and (c
i~C22) Phenol monoxide ethylene condensates, linear or branched aliphatic C,~C2. Included are condensation products of primary or secondary alcohols and ethylene oxide, and products formed by condensation of ethylene oxide with reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds include long chain tertiary amines, tertiary phosphine oxides and dialkyl sulfoxides. Particularly preferred are primary and secondary alcohol ethoxylates, especially CI2-cps primary and secondary alcohols ethoxylated with an average of 5 to 20 moles of ethylene oxide per mole of alcohol.

It would be desirable to include at least one type of fatty acid soap. Sodium soaps derived from natural fatty acids, such as those derived from coconut oil, tallow, sunflower or hydrogenated rapeseed oil, are preferred as soaps of this type. Detergent formulations suitable for use in automatic washing machines typically include anionic or nonionic surfactants, or combinations thereof in any proportion. Soaps may also be included if desired in amounts of 0 to 40% by weight of the composition. In general, this type of kumikaimono can be made into tablet form using the method of the invention without any problems. The tablet-shaped detergent of the present invention contains one or more types of detergency builders. The amount thereof is suitably 5 to 80% by weight, more preferably 20 to 80% by weight.

Particularly preferred are alkali metal phosphates, alkali metal aluminosilicates, and combinations thereof. Preferred alkali metal phosphates are sodium orthophosphate, sodium pyrophosphate and sodium tripolyphosphate. Sodium tripolyphosphate is particularly preferred.
This substance is usually of composition? It can be included in amounts up to 0% by weight.

The alkali metal (preferably sodium) aluminosilicate may typically be used in an amount up to 60% by weight of the composition and has the general formula 0.8-1.5Na20. ^120,. 0.8~6Si
It can be crystalline or non-crystalline, or a mixture of these. The aluminosilicate must contain some bound water and have a calcium ion exchange capacity of at least 50 B CaO/H. Preferred sodium aluminosilicate contains (in the above formula) from 1.5 to 3.5 SiO units. Both non-quality and crystalline materials can be easily prepared by the reaction of sodium silicate and sodium aluminate, as widely described in the literature. Suitable crystalline sodium aluminosilicate ion exchange detergency builders are described, for example, in British Patent No. 1429143 (P
Roctor & Gamble).

Preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X and mixtures thereof. Particularly preferred is zeolite 4^.

The tablet detergents of the invention may also contain other builders if necessary or desired. Suitable organic or inorganic water-soluble or water-insoluble builders will be readily apparent to those skilled in the art. Inorganic builders include alkali metals (usually
Nitrilotriacetate, citrate and canoleboxymethyloxysuccinate can be used as organic builders.

Other particularly preferred builders are polycarboxylate polymers, especially those containing acrylate (methacrylate) and/or maleate units.These polymers also have further effects, such as reducing soil redeposition. These polymers are 0.5-10% by weight
It is appropriate to use the amount of I to 6, more preferably I to 6.
Used in % by weight. These polymers may have acid form or completely or partially neutralized salt form. Preferred polymers are homobolymers and cobolymers of acrylic acid. Particularly advantageous are polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; acrylic/maleic copolymers, such as Sokalan® CP5 from BASF, which is particularly preferred.

Other ingredients that may optionally be used in the tablet detergents of the present invention include soil redeposition inhibitors such as sodium carboxymethylcellulose, polyvinylpyrrolidone and cellulose ethers such as methylcellulose and Ethylhydroxyethylcellulose; stabilizers, such as ethylenediaminetetramethylenephosphonate and diethylenetriaminepentamethylenephosphonate; textile softeners; foam control agents or, if appropriate, foam enhancers; heavy metal ion sequestrants, such as EDT^; fragrances: colorants; and inorganic salts such as sodium sulfate and magnesium sulfate.

Sodium sulfate may be used as a filler, if desired, in amounts up to 40% by weight of the composition. However, sodium sulfate may be contained in an amount less than 10% by weight of the composite, or may not be contained at all.

The tablet detergents of the invention, especially in the case of tablets intended primarily for use in front-loading drum automatic washing machines, advantageously contain an antifoaming agent. Suitable antifoaming agents are typically described in, for example, European Patent Application No. 266 863
It is in the form of granules as described in No. ^ (Unilever). Such granular antifoam agents are typically prepared by combining a mixture of silicone oil, petroleum jelly, hydrophobic silica, and an alkyl phosphate as an antifoam activator into a carbonate-based porous absorbent water-soluble inorganic carrier material. Consists of things that have been absorbed. The content of granular antifoam agent may be up to 5% by weight of the composition.

The tablet-like detergent of the present invention comprises an alkali metal silicate,
Especially sodium orthosilicate, sodium metasilicate,
Alternatively, it may be desirable to also preferably include a suitable amount of a neutral or alkaline silicate. When using alkali metal silicates of this kind in amounts of e.g. 0.1 to 10% by weight,
It can be advantageous in preventing corrosion of metal parts of washing machines,
Furthermore, the cleaning effect can be improved.・'Bullet' The detergent composition of the present invention is produced in the form of a tablet by compressing the powder. As mentioned above, in one of the preferred embodiments of the invention, the tablets of the invention are substantially homogeneous, i.e., without the addition of inserts, separating layers containing separating components, coatings, etc., a single substantially It is formed by compressing homogeneous powder into. Therefore, manufacturing is extremely simplified. However, for example, the starting powder may include inserts or other localized areas that will later remain in the tablet, or two or more powders may be compressed to form separate layers in the final tablet. Such cases are also included within the scope of the present invention. The only condition is
The goal is to ensure that components (a) and (b) are not isolated from each other.

The powder itself may be manufactured by any suitable method, such as mixing, granulation or any combination of these methods, optionally with atomization of the liquid component. For example, solid components may be prepared by dry blending, adding water and/or liquid components, granulating the mixture, and then drying. Alternatively, an aqueous slurry of detergent ingredients may be spray dried to form granules, followed by post-addition of a heat-sensitive agent such as a bleach or an enzyme. Again, the liquid component may be sprayed at any stage of the process.

One preferred method using spray drying includes the steps of: (i) spray drying an aqueous slurry to contain one or more detergent compounds, one or more detergency builders, and a fluorescent agent to be included; (b3) and other desired ingredients; (1) adding sodium perborate (a>
and any triacylation or N,N to be included.
'-polyacylated amine bleach activator (bl) and/or enzyme (b2) and optionally other ingredients if desired to form a homogeneous powder, (iii) compressing said powder. Form a tablet.

The tablet detergent of the present invention can be, and is preferably, formulated to be used as a complete heavy duty detergent composition for textiles. In this way, the consumer does not have to mix and use several different sets of tablets.

One tablet may contain all of the ingredients in sufficient quantities to provide exactly the amount needed for an average load, but preferably the consumer can adjust the amount depending on the size and type of load. Each tablet contains the submuftiple q required for average washing conditions so that the dosage can be varied.
uar+tity). For example, the tablet size may be selected such that two tablets provide enough composition for one average laundry load. If the amount of laundry is particularly large or the laundry is extremely dirty, add 1 more
You can add more than one tablet and only use one tablet if the load is small or the soiling is light.

The present invention will now be described in more detail with reference to non-limiting examples. Parts and percentages used in these examples are by weight. Examples and compositions of the present invention are indicated by numbers, and comparative examples and compositions are indicated by letters.

A phosphorus-free detergent base powder containing a fluorescent agent was prepared using spray drying followed by spraying with 3EO nonionic surfactant with the following formula.

Linear alkylbenzene sulfones CI2-C,, 7EO nonionic surfactants C. ~C,
, 3EO non-ionic surfactant fatty acid soap zeolite 4^ (anhydrous based) acrylic acid/maleic acid Koboli (Sokalan* CP5) sodium genate carboxymethyl cellulose nato fluorescent agent (Tinopa order* DMS and Tinopa sodium carbonate water book trademark; German , Mar 6.0 0.7 Rium 0.8 K * CBS-X) 0.3 12.9 100% remainder Manufactured by BASF AG, Ludwigshafen.

Ciba-Geigy 9.2 4.2 9.2 2.5 36.8 0 Trademark; Ciba-Geigy, Basel, Switzerland
Made by AG. Tablets and powders were made in the following sets.

The enzyme used was the granular protease Savinase (
Trademark)6. OT, sodium perborate, has a large surface area (5.
9m27g) monohydrate, TAED is in granular form (83% by weight)
TAED, 17% by weight inert phosphorus-free carrier).

! L! ILfLt
p-himu-dama Soyu-based powder 85.4 85.
4 enzymes 1.0 1.
0 perborate 10.0 10
．． OTAED* grain 3.6
The 3.6 tablet uses an Instron(TM) constant speed extensometer with a crosshead speed of 10On+
It was formed by compressing the powder at 1.5 kN at m/min. Each tablet weighs 60g and has a diameter of 5
The performance of these tablets and powders of bleach, fluorescent agents and enzymes was tested under harsh conditions (temperature 37℃, relative humidity 70%, A comparison was made between the composition after being stored for one week (unprotected, unpackaged) and the composition after being stored for two weeks. This comparison is performed by measuring the hardness (
This was carried out by washing at an isothermal temperature of 40°C for 15 minutes using 1 liter of 12' hard water (France). The tablets are crushed before washing and are 5g/1! was used at a dose of The powder dose was also 5 g/l.

Table 1 shows the results of the enzyme performance measured using the enzyme-sensitive test cloth (polyester/cotton cloth with casein stain) as the difference in reflectance (ΔR at 460 nm).

1 (tablet) 26.9 28.8
26.9P (powder) 27.0 26.6 26.4 Despite being close to the bleaching agent component, enzymatic decomposition did not proceed faster in the tablet than in the powder. Table 2 shows the results of the fluorescer performance measured using the fluorescein-sensitive test cloth as the difference in reflectance (ΔR at 460 nm) in the presence and absence of UV radiation.

1 (Tablet > 15.7 18.6
15.7P (powder > 15.6
16.2 15.3 Again, no significant difference was observed between the tablet and powder.

Table 3 shows the difference in reflectance (ΔR at 460 nm) of the bleach performance measured using a cotton test cloth with tea stains.
).

Table 3 1 (Tablet) 5.3 4.3
4. OP (powder) 3.8
3.1 3.2 Surprisingly, the results were consistently better for the tablets than for the powders of the same composition.

Spray drying detergent base powder containing phosphoric acid and fluorescent agent with the following composition and subsequent <: 3EO
It was prepared using a nonionic surfactant spray.

Linear alkylbenzene sulfone C. ~Cps 7EO nonionic surfactant C. ~C. ，
3EO Nonionic Surfactant Fatty Acid Soap Sodium Tripolyphosphate κ To 8.3 5.3 3,5 0.7 29.3 Sodium Silicate 7.0 Sodium Canoleboxymethylcellulose 0.4EDT
A.O. 15 fluorescent agents (Tinopal DMS and Tinopal C
BS-X) 0.35 sodium carbonate
5.9 Sodium Tarate, water
100% residual tablets and powder were prepared as in Example 1 with the following formulation. The enzyme, sodium perborate-hydrate and TAED used were the same as in Example 1.

4l Mori ζ (9ii}
Cane & Base Powder 85.4 85.
4 enzymes 1.0 1.0
Perborate 10.0 10.
OTAED granules 3,6 3
．． 6 The bleach, fluorescent agent and enzyme performance of these tablets and powders were compared in the same manner as in Example 1. Enzyme results are shown in Table 4, fluorescent agent results are shown in Table 5, and bleach results are shown in Table 6.

2 (Tablet) 26.6 27, ■ 25.8 q (Powder) 26 8 26.1 25.7 2 (Tablet) 16.1 15.4 15.6Q (Powder) 15.0 15.5 15.3 Again, no significant difference was observed between the tablet and powder.

Shuichi” [1L Ward Kayu 012 2 (Tablet) 6.0 5.4
5. OQ (powder) 5.6
5.2 4.3 Bleach performance decreased with storage as expected, but surprisingly, results were consistently better with tablets than powders. Phosphorus-free base powder of Example 1 and three different types of sodium perborate, namely large surface area (5.9+2/g)
The above comparison was repeated using a monohydrate, a small surface area (3.2 m''/g) monohydrate, and a tetrahydrate.

Tablets and powders were manufactured according to the following guidelines.

Examples 3, 4 and 5 are tablets, Examples R, S and T
is a powder. Tomoichie L and L alternating ebase powder 89.0 89.0 84.
0 enzymes 1. O Co
1.0 perborate: Monohydrate (large surface area) 10.0 monohydrate (small surface area) - 10.0 tetrahydrate
- 15.0 Freshly prepared composition, as in Example 1 for the composition after storage for 2 weeks (at a temperature of 37 °C and 70% relative humidity) and for the composition after storage for 43 l. The performance of bleach and enzymes was compared.The results are shown in Table 7 (bleach) and Table 8 (enzyme).

East-L customary 1± 'lJLL East 43 (tablet) 2.3 0.9R (powder)
1.5' 1.14 tablets) 2.0 0.8S
(Powder) 2.4 0.55
(Tablet) 1.3 1.6T
(Powder > 2.3 0.8 In the presence of perborate monoaqueous phase, bleach performance always decreased after 4 weeks of storage, as expected, but this was not more pronounced for tablets than for powders. Surprisingly, when the perborate was in the form of a small surface fi!? substance, the performance degradation was smaller in the tablet than in the powder.When the perborate was in the form of a tetra-aqueous phase, the tablet showed even better results.

3 (tablet) 29.1 31.8
34. IR (powder) 33.6
34.5 32.84 (tablet) S (powder) 33.4 32.3 33.2 34.3 34.1 34.2 5 (tablet) T (powder) 33.0 32.2 33.8 33. 4 33.1 32.9 X 70 years old TAED (83% by weight phosphorus-free granules used in Example 1)
Examples 3-5 were repeated using a similar series of compositions including: Tablets and powders were manufactured in the following sets. Examples 6, 7 and 8 are tablets, Example U, ■
and W are powders.

14 dogs - 61J 7V 8W based powder 85.4 85.4 80
．． 4 enzymes 1.0 1.0
1.0 perborate: Monohydrate (large surface area) 10.0 monohydrate (small surface area) - 10.0 tetrahydrate
1-15. OTEAD granules
3.6 3.6 Similar to Example 1, the composition as freshly prepared, the composition after storage for 2 weeks (at a temperature of 37°C and 70% relative humidity) and the composition after storage for 4 weeks. The performance of bleach and enzyme was compared for the composite.The results are shown in Table 9 (bleach): No major difference was observed.The results are shown in Table 1.0 (enzyme).

0 4 6 (tablet) U (powder) 7 (tablet) ■ (powder) 8 (tablet) W (powder) 2.7 4.4 3.8 4.0 4.0 4.1 3.3 3.0 3.2 3.5 3.3 3,6 No significant difference was observed between the tablet and powder.

6 (tablet) 33.4 31.7
34. IU (powder) 32,6
33.8 32.47 (Tablet>
33.5 32.5 33.8V (powder)
32.2 32.7 33.5
8 (tablet) 33.3 33.6
33.6-(powder) 33.3
33.9 32.6 No significant difference was observed.

The operations of Examples 3 and 6 were repeated using the phosphate builder-containing base powder of Example 2 in place of the phosphorus-free base powder of Example 1. Tablets and powders were manufactured with the following compositions. Examples 9 and 10 are tablets, and Examples X and Y are powders.

Front tatami mouth raw 9X IO
Y-based powder 89.0 85.
4 Enzyme 1.0 1.0 Perborate (monohydrate, large surface area) to. o io
．． oTEAD Granules 3
．． 6 Similar to Example 1, bleach and We compared the performance of enzymes. The results are shown in Table 11 (bleach) and Table 12 (enzyme).

04 9 (tablet) X (powder) 10 (tablet) Y (powder) 1.7 2.4 5.7 50 1.9 1.1 4,4 4.1 After storage for 4 weeks, tablet is the same The powder composition showed better results.

9 (tablet) 34.1 32.4
32.0X (powder > 32
．． 6 33.5 31.410 (tablet)
34.3 32.4 31.4Y (powder) 32.1 31.3
32.8 No significant difference was observed.

Natsuhitsuji phosphate is used as a bilgu, and a bleaching agent consisting of sodium perborate tetrahydrate is used as a proteolytic enzyme (Savina).
se) and a fluorescent agent with the following composition:
Manufactured using spray drying and post-addition. Star-like alkylbenzene sulfone} 18.0
C. 2~C. s7EO nonionic surfactant 8
．． 0 fatty acid soap 2・O
Sodium tripolyphosphate 300 acrylic acid/maleic acid copolymer (Sokalan CP5)
1.5 alkaline sodium silicate
10.0 Ruboxymethyl cellulose sodium
0.5EDTA
0.25 fluorescent agent: Tinopal DMS O
．． 13Tinopal C8S-X
O. 08 Sodium sulfate
3.6 Sodium perborate tetrahydrate 1
0.0 enzyme (Savinase 6CM)
0.75 Granular antifoaming agent
3.0 fragrance
0.22 moisture, salt l
The bulk density of the remaining powder at OO% was 400-425 g/l. This powder was compressed to about half its volume using a pilot-scale tablet machine, weighing 32 g, and having a diameter of 50 mm.
A tablet with a thickness of 23lIII1 was formed. This tablet showed effective laundry cleaning performance in a washing machine. The appropriate dose was 2 tablets for soft water and 3 tablets for hard water.

Fruit 104u, a powder detergent containing phosphate as a builder and a bleaching agent consisting of sodium perborate tetrahydrate together with TAED granules, proteolytic enzyme <Savinase> and a fluorescent agent, was spray-dried and washed with the following composition. Tablets were prepared using addition and then compressed as in Example 11 to form tablets.

Linear alkylbenzene sulfone CI2~Cp57EO Nonionic surfactant Fatty acid soap Sodium tripolyphosphate Acrylic acid/maleic acid copolymer (Sokalan CP5) 亙} 18.0 8.0 2.0 30, O Alkaline sodium silicate Sodium carboxymethylcellulose 1.5 10,0 0.5 EDT8
〇． 25 Fluorescent agent: Tin
opal DMS O. 13T
inopal CBS-X
O. 08 Sodium sulfate
1.3 Sodium perborate tetrahydrate
10. OTAED Granules (83% active ingredient by weight) 2.4 Enzymes (Savinase 6CM)
0.75 Granular antifoaming agent
3.0 Fragrance 0
．． 22 Moisture, Salt 100% Remaining This tablet showed effective laundry cleaning performance when used at a dosage of 2-3 tablets per wash.

Containment 1 A bleaching agent consisting of phosphate as a builder and sodium perborate hydrate as TAED, proteolytic enzyme (S
A powder detergent with higher bleaching power containing avinase) and a fluorescent agent was prepared using spray drying and post-addition with the following composition.

? Alkylbenzene sulfonate C1~Cps 7EO Nonionic surfactant Fatty acid soap Sodium tripolyphosphate Acrylic acid/maleic acid copolymer (Sokalan* CP5) Alkaline sodium silicate Sodium carboxymethyl cellulose EDT^ Fluorescent agent: Tinopal DMS Tinopal CBS-X Salt water peroxide Sodium acid hydrate TAED enzyme (Savinase 6CM) Stars 18, 0 8.0 2.0 30. O 1.5 lO,0 0.5 0.25 0.13 0.08 4,24 8.0 10.0 3.33 0.75 Granular antifoaming agent 3.0 Fragrance 0.22 This powder was used Compressed in the same manner as Example 11, each weight is 26 ~
A tablet of 28 g, diameter 40 mm, and thickness 26 lll+ was formed. The tablets showed effective laundry cleaning performance when used at a dosage of 2-3 tablets per wash. TAED a bleaching agent consisting of sodium perborate and hydrated sodium perborate.
A phosphorus-free powder detergent containing a phosphorus-free powder with a proteolytic enzyme (Say inase) and a fluorescent agent was prepared using spray drying and post-addition in the following combination. This powder is compressed according to the method of the present invention. Suitable for forming tablets. ? 4 15 Linear alkylbenzene sulfonate ts. os.
oC1■~Cps 7EO nonionic surfactant 3.
0 4.5C. ~CIs3EO nonionic surfactant
5.0 4.0 Fatty acid soap zeolite 4A (anhydrous base) Acrylic acid/maleic acid copolymer (Sokalan CP5) Carboxymethyl cellulose sodium fluorescent agent: Tinopal DMS-X Tinopal CBS-X Sodium carbonate sodium perborate-hydrate TAED granules ( 83%) Enzyme (Savinase 6.OT) Granular antifoam fragrance water and trace ingredients 2.0 30, O 37.0 4.0 5 O 0.5 0.5 0.13 0.13 0.08 0 .07 9.0 14.9 10.0 7.5 4.5 4.5 1.0 1.0 3.0 1.5 0.4 0.4 too. o% remaining

Claims (5)

[Claims] (1) selected from (a) sodium perborate; (b) (b1) N-diacylated amine and N,N'-polyacylated amine bleach activator; (b2) enzyme; and (b3) fluorescent agent. (c) one or more detergent compounds, one or more detergency builders, and other optional detergent ingredients; A detergent tablet formed in which components (a) and (b) are not isolated from each other. (2) The detergent tablet according to claim 1, comprising tetraacetylethylenediamine as bleach activator (b1). (3) The detergent tablet according to claim 1 or 2, which is substantially homogeneous. (4) (i) (a) sodium perborate; (b) (b)
1) N-diacylated amine and N,N'-polyacylated amine bleach activator, (b2
) enzymes, and (b3) one or more inorganic persalt bleach-sensitive ingredients selected from fluorescent agents; (c) one or more detergent compounds, one or more detergency builders, and other optional and (ii) compressing said powder to form a tablet in which components (a) and (b) are not isolated from each other. (5) (i) Spray drying the aqueous slurry to add one or more detergent compounds and one or more detergency builders;
forming a base powder containing the fluorescent agent (b3) to be included and other desired ingredients; (ii) adding sodium perborate (a) and any N- diacylated or N,N'-polyacylated amine bleach activator (b1) and/or enzyme (b2) and optionally other ingredients if desired to form a homogeneous powder; (iii) 5. The method of claim 4, including compressing the powder to form a tablet.