JPH01132697A - Detergent composition - Google Patents

Abstract

PURPOSE: To obtain a detergent compsn. not harder than toilet soap and suitable for use as a material applied to spots and stains on textile goods prior to laundering by incorporating a peroxygen bleach and a specified hygroscopic salt.

CONSTITUTION: The detergent compsn. is not harder than toilet soap and contains a peroxygen bleach and a hydratable hygroscopic salt stable at a temp. of ≥30°C. The hygroscopic salt is preferably trisodium orthophosphate or tetrasodium pyrophosphate. The detergent compsn. usually contains 1-20 wt.% peroxygen bleach, 2-15 wt.% hygroscopic salt and 5-70 wt.% surfactant (based on the entire compsn). The peroxygen bleach can be advantageously selected in accordance with the compsn. in which it is used but a monopersulfate is generally suitable. This material may be used in the form of a triple salt contg. KHSO₅, KHSO₄ and K₂SO₄ in a molar ratio of about 2:1:1.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to detergent compositions for shaped articles used as pre-treatment products, ie substances applied to stains and soils on textiles prior to normal laundering.

Pretreatment products used for such purposes include, for example, U
S 3953353, US 4295845, EP-^
It is already known from prior patent specifications such as -157653 and UK 1578289.

Powdered detergent compositions used in conventional laundry typically include bleaching agents. In such products, the reactive bleaching agent is present as a separate particle from the other components of the composition. It is unlikely that any commercially available solid pretreatment products have ever been contaminated with bleach. This is because the phenomenon of unstable bleaching substances coming into close contact with other substances appears much more conspicuously than in the case of powdered products, so it is essentially difficult to mix bleaching agents into the above-mentioned pretreatment products.

Generally speaking, the present invention incorporates a bleaching agent into a shaped solid pretreatment product.

One of the objectives of the preferred embodiment of the present invention is to incorporate bleach into a shaped solid pretreatment product that is a practical product that can be stored for a sufficiently long time in temperate and tropical climates.

It is another object of the preferred embodiments of the present invention to provide other desirable attributes of the pre-treatment product, such as its effectiveness against stains, its ability to be easily transferred to the treated textile;
and the incorporation of a bleaching agent into the pre-treatment product which has the property of being easily removed from the textile product during washing over a wide temperature range, e.g. 15 DEG -90 DEG C., after pre-treatment.

One of the objects of the present invention is to provide a solid shaped article detergent composition suitable for application to selected parts of textile products prior to laundering. The composition is substantially less hard than soap, and hardness is an important factor as it contains peroxygen bleach. In order to transfer a sufficient amount of the composition to the fibers by manual application, the composition of the present invention should not be too hard.

This hardness is, for example, from Sommer in Berlin, West Germany.
The measurement is carried out by a penetrometer such as the PNRIO penetrometer from J. and Runge. It has been found that suitable products are substantially no harder than toilet soaps, and may even be softer. The non-soap detergent wash bars are significantly harder than the products of this invention.

The detergent compositions of the present invention may contain various combinations of ingredients, but typically contain both surfactant and non-surfactant substances in addition to the peroxygen bleach.

In order to increase the active retention time of the bleach in the stored product, the free water content should be very low.

It is desirable to prepare the pre-composition so that it is preferably less than 0.5% by weight of the composition.

Desirably, the composition also includes a hygroscopic salt having a hydrate that is stable at temperatures above 30°C. Such salts absorb moisture that enters the composition and trap this moisture as the salt's hydrates. As a result, degradation of the bleach that occurs when moisture and other components of the composition are present is reduced or delayed.

Preferred hygroscopic salts are phosphates, especially tris-orthophosphate.
and tetras-lium pyrophosphate.

Other usable hygroscopic salts include sodium tripolyphosphate, dihydrogen phosphate, sodium metaborate, sodium carbonate, sodium dihydrogen orthophosphate.

The various ingredients mentioned above are typically used in amounts within the ranges set forth below.

Peroxygen bleach = 1-20% by weight Hygroscopic salt: 2-15% by weight Surfactant: 5-70% Weight These weight percentages are based on the entire composition.

The peroxygen bleach may advantageously be selected depending on the composition in which it is used. It turns out that different bleaching agents can be used depending on different compositions.

Monopersulfates are generally suitable. This substance is K
11S05, K11SO, and 2SO, approximately 2:1:
It can be used in the form of a triple 5alt containing a molar ratio of 1.

Depending on the composition it may be appropriate to use perborates and percarbonates.

When the bleaching agent is a monopersulfate salt, it is preferred to incorporate an alkaline substance into the composition so that the p119 is greater than Km when the composition is applied to wet fibers. In the case of percarbonates and perborates, the above-mentioned contamination treatment is not necessary since they are themselves alkaline. The alkaline substance may be an orthophosphate or pyrophosphate added together with the hygroscopic salt, or it may be another alkaline substance such as sodium carbonate.

Inorganic peroxy bleaches may be used with organic peroxy acid precursors. This is particularly desirable when the inorganic peroxy bleach is a perborate or percarbonate.

Mixtures of organic peroxy acid precursors and inorganic peroxy salts exhibit bleaching action at low temperatures. Peroxyacid precursors are well known to those skilled in the art and are described, for example, in British Patent No. 836,9.
88, 855, 735 and 970°356, U.S. Patent No. 1.246.339, 3,332,8
No. 82 and No. 4,128,494, Canadian Patent No. 84
No. 4,481, and ^, 11. described in Detergent Age. G11bert's series of papers, namely 19
June 1967 pp, 18-20. July 1967 pp
, 30-33, and August 1967 pp. 26.27.
and 67. Preferred peroxyacid precursors are tetraacetylethylene diamine (TACU), tetraacetyl glycoluryl (TACU), glucose pentaacetate (GP^), xylosetetraacetate (XTΔ) and acyloxybenzenes sulfate.

When using a peroxy acid precursor, the weight ratio of inorganic peroxy salt to peroxy acid precursor is 8:1 to 1:1;
Preferably the ratio is 4:1 to 1:5:1.

The amount of bleach is suitably expressed in terms of available oxygen, ie the amount of oxygen that can theoretically be liberated upon application.

The amount of bleach included in the compositions of the present invention is typically about 0□1
This amount corresponds to ~3.5% (fffffi% of the total composition) of available oxygen. The effective oxygen amount is preferably 0.2 to 2% by weight.

A variety of surfactants may be used in the compositions of the invention, including soaps. Nonionic surfactants are important in some compositions. Non-ionic and synthetic surfactants are well-known compounds and are known in the art, for example, 5chu+
artz, Perry, Vol, II, 1958°”D
eterHects and 5 surface-act
ive Agents”.

Any nonionic surfactants used are preferably selected from condensation products of alkylene oxides with fatty alcohols, alkylphenols, fatty acids and fatty acid amides. Particular preference is given to fatty alcohol ethoxylate agents with a 11LB value of 6 to 18, especially 9 to 13, such as CI3 to CIS alcohols condensed with 7 mol of ethylene oxide per mole of alcohol.

The compositions of the present invention may include a variety of optional ingredients.

One of the optional ingredients is an organic solvent, particularly a charcoal (arsenic) solvent having an average carbon T number of 8 to 16 to facilitate the removal of oil stains. Chūdan%
can be used in amounts of

The pre-treatment detergent composition of the present invention further comprises conventional minor ingredients,
For example, lipolytic enzymes, proteolytic enzymes, amylolytic enzymes, monocarboxylic acid salts, bleach stabilizers such as phosphate bleach stabilizers, optical brighteners, fragrances and dyes may also be included.

The composition of the invention may be in the form of a mixture that can be processed and shaped by extrusion. The compositions of the invention may also be in a form that can be melted and poured into a mold to form the desired shape. Preferred compositions in each category are explained below.

One preferred category of compositions is non-flowable solids. : Yes, and can be treated as such. However, compositions of this type may be formed by extrusion.

These preferred compositions include: 10 to 45 weight percent nonionic surfactant; 1 to 20 weight percent peroxygen bleach; and 10 weight percent or more filler. - organic fillers in the form of soaps, waxes and/or other soft organic solids: 0 to 70% by weight (% by weight relative to the total composition); - clays 0 to 50% by weight (% by weight relative to the total composition); - One or more substances selected from 20 to 40% by weight (weight% of the entire composition) of particulate inorganic fillers other than clay.

However, any substantial amount other than clay (e.g., the entire composition
Book 5 Ichikawa? The above inorganic fillers are used in conjunction with the same or more of the organic solids mentioned above.

The composition maintains a non-flowing solid form upon heating to at least about 50°C, preferably to at least about 70°C.

Sommer and Rude PNR equipped with Rin needle
Using lo, total of 50g! 1! When measured by applying the amount for 10 seconds, it was found that suitable products in this category were not significantly harder than toilet soaps, but were sometimes softer. Penetration is 1.5 mm or more, 4
+n+n can be reached. ;Reni! -t t,, the penetration degree of toilet soap is 1.3-1.7+nm, and the penetration degree of washing bar of non-soap detergent is about 0.5 mm.

An essential component of this category of compositions is a nonionic surfactant. The amount of nonionic surfactant is 4% of the total composition.
Must not exceed 5% by weight. Preferably 10-30
Mix in an amount of %.

-i, the non-ionic surfactant acts as a binder for the composition to provide detergent properties. Preferably, the binder of the composition of the present invention is a liquid, and therefore the nonionic surfactant is preferably a liquid at room temperature, or one that becomes liquid at 30° C. or below.

Since soap is a mixture of liquid and crystalline solid phases, the presence of soap contributes to the liquid phase of the acid. Thus, when a soap is present, the amount of nonionic surfactant can be less than that required to obtain a cohesive extrudable one-piece composition when no soap is used. Adjustment of the amount of nonionic surfactant to obtain a satisfactory composition is less important when soaps, waxes or other organic solids are present than when these solids are absent. . Organic solvents, especially hydrocarbon solvents, can be incorporated to facilitate the removal of oil stains. This contributes to the liquid phase. However, in that case, it is desirable to package the product in a way that prevents evaporation of the solvent.

As mentioned above, it is preferable to use a liquid nonionic surfactant. However, the use of nonionic surfactants that melt and become liquid at processing temperatures of 25°C to 50°C, especially when used in tropical climates, for example, is not possible. , a suitable composition can be obtained.

When the composition contains an organic solvent, it is also possible to use a solid nonionic surfactant, and the nonionic surfactant and organic solvent together constitute the Ia liquid phase. do.

It is desirable to include a nonionic surfactant because it has a high detergency against oil stains. Compositions of the invention may also include other surfactants, such as cationic or anionic surfactants.

It may be advantageous to incorporate nonionic-anionic surfactant combinations containing high foaming anionic surfactants, such as sodium alkylbenzene sulfates (%) to improve the foam profile obtained with nonionic surfactants. . Preferably, the amount of anionic surfactant does not exceed 10% by weight of the composition.

Nonionic surfactants are usually incorporated in higher amounts than other synthetic surfactants. The total amount of synthetic surfactants is 4 in the composition.
It should not exceed 0% by weight, preferably 30% by weight or less.

The bleaching agents used in these extrusion compositions are preferably inorganic peroxy bleaches, especially perborates, percarbonates or monopersulfates. Surprisingly, it has been found that these bleaches exhibit greater stability in this type of composition than the organic peracid diperoxide dodecanoic acid (DPD8).

The filler component of the composition functions as a carrier for the bleach and surfactant. The total amount of fillers is 40~
70% by weight is preferred. As is clear from the weight range above, the filler may be clay, soap, wax, other organic solid or any mixture thereof, or another inorganic filler may be combined with the organic filler and optionally the clay. It may be a combination.

Surprisingly, the use of inorganic materials (other than clay), which are commonly used as fillers, renders the compositions insufficiently cohesive to be extrudable; is not sufficiently transferred to textile products subjected to Irf treatment. However, these problems can be overcome by using an equal or greater amount of organic filler along with the inorganic filler. The clay may be kaolin clay and can be used without or with organic fillers, but is preferred since the amount of non-ionic surfactant is less important with organic fillers. has an organic filler present.

Inorganic materials other than clay that can be used as fillers include talc, calcite and sodium sulfate.

If soap is used, this soap may be one type of substance that is primarily classified as a soap. Usually CI2
-Alkali metal salts of C20 fatty acids.

′? Seven times use thorium salt. This soap is especially
It may be based on a soapy mixed acid such as tallow/coconut oil 80/20.

When soap is used in any substantial amount, it is highly desirable that the water content of the soap be less than 5% by weight of the soap.

If any organic solid or wax other than soap or wax is used in any substantial amount, it is highly desirable that the material have a melting point above 50°C. Desirably, the organic solid, other than soap or wax, is a waxy material that is capable of plastic flow under processing conditions. Examples of suitable waxes and other organic solids include paraffin wax, castor oil, glycerol monostearate, and fatty alcohols.

Kn oxides of this kind, the optional ingredients mentioned above, such as solvents,
May include enzymes, bleach stabilizers, etc.

These extrusion compositions are made by mixing the components together into a homogeneous mixture, extruding this mixture through a goo into rods, and cutting the rods into short lengths to form sticks, which is the preferred shaped article. .

Although such sticks are a preferred form of shaped article,
The compositions of the invention can also be formed into other shapes. The sticks may be packaged for storage and sale, or fitted into screw-on or push-on boulders.

When mixing the components, it is preferred that either the wax or the solid nonionic surfactant be melted before being added, or dissolved in the liquid nonionic surfactant and added with the surfactant. It is preferable to add bleach last.

In use, the composition is rubbed onto stains and soils on fabrics that have been premoistened with water, and the fabrics are then subjected to a conventional laundering process. Best results are obtained if the composition is left in the machine for a period of time, such as 5 minutes, to allow the composition to act on stains and soils prior to normal laundry processing.

Another category of compositions is solid at room temperature but melts when heated, so they can be cast in molds. The following two types of compositions for injection molding are preferred.

Compositions of this type melt in the temperature range of 40°C, preferably 50°C to 90°C, and contain 50 to 70% by weight of nonionic surfactants. , 1 to 20% by weight of peroxygen bleach, and 10 to 80% by weight of one or more organic compounds.

The chemical compound or mixture thereof melts and becomes fluid at a temperature of 40''C or higher.

Standard 9° cone S o +n +n e r a n
A suitable product of the above type is found to be somewhat softer than one soap, as measured by applying a total of 50 g of weight for 60 seconds using a R10 needle. found. The penetration of toilet soap is 1-211 m under similar conditions, and the wash bar of non-soap detergent is about 0.5 mm.

The actual amount of nonionic surfactant is not critical. The surfactant may be incorporated in an amount ranging from 5 to 70 or 75% by weight of the total composition. Preferably, it is 10 to 50% by weight, more preferably 20 to 40% by weight.

It is also possible to use non-ionic surfactants 3 which are either liquid or solid at room temperature, for example 20°C.

If a solid nonionic surfactant is used, it is desirable that the surfactant melt or dissolve in the composition at the processing temperature. When using a nonionic surfactant, it is desirable that the surfactant melts at a temperature of 50°C or lower.

It is desirable to incorporate a nonionic surfactant because it has high cleaning properties against oil stains. The compositions of the invention may also include other seed surfactants, such as cationic or anionic surfactants.

In addition to the nonionic surfactant, up to 30% (wt% of the total composition) of a high foaming anionic surfactant, provided that the foam profile is not higher than that obtained with the nonionic surfactant; For example, alkylbenzene sulfate
It may be advantageous to use nonionic-anionic surfactant combinations containing lithium. In this case, it is thought that it is better to keep the amount of anionic surfactant at 0% or less of the Gjl compound acid.

Nonionic surfactants are usually present in greater amounts than other synthetic surfactants. The total amount of synthetic surfactants is 5% of the composition.
It is preferable that the amount is 0 or less, more preferably 10 to 40% by weight.

Bleaching agents used in compositions of this type are preferably perborates, percarbonates or monopersulfates.

Yes (diperoxide dodecanoic acid (DI'D) which is a bleaching agent)
^) is not particularly stable in this type of composition;
ff: Decreases performance. Therefore, it is preferable not to use this substance.

The third essential component of this type of composition is an organic compound or mixture thereof that melts at temperatures above 40' CC and serves as a carrier for the components of the pond. This compound or mixture is preferably present in an amount of 10 to 30% by weight of the composition.

As this organic compound, similar/Z compounds can be used,
The main requirement is that it must have a suitable melting point. Examples of organic waxes that can be used include paraffin wax, waxes such as castor oil, polyalkylene glycol esters, fatty alcohols, and fatty acids.

The alcohol or acid may have 12 to 20 carbon atoms.

Fatty alcohols have the advantage of being cheaper than polyalkylene glycol esters and can be used in lower amounts than waxes. Fatty acids are cheaper and more expensive, but they are alkaline when used.
It must be used with a sufficient amount of alkali salt to obtain a1. This is also necessary to improve the performance of stored inorganic peroxygen bleach to Ft5m. The preferred amount of fatty alcohol or fatty acid is 15-40% by weight of the composition.

In one preferred manufacturing method, in the first step, the organic compound or mixture thereof is mixed with one or more synthetic surfactants and heated to about 70-100°C. Peracid bleach is then added while optionally followed by the precursor to obtain a homogeneous mixture.The composition thus obtained is poured into a mold and allowed to solidify into the desired shape by cooling to room temperature. .

The preferred composition of this type is also suitable for temperatures above 40'C,
It preferably melts at a temperature of 45 DEG C. to 90 DEG C. and contains 1 to 20 weight percent peracid bleach, 5 to 40 weight percent soap, and 15 to 70 weight percent polyhydric alcohol.

Standard 96 cone Som+ner and Runge
Using a PNRlo j1 human scale, weigh a total of 50g (
A suitable product of the type described above was found to be somewhat softer than a single soap, as measured by applying ^ for 60 seconds. Penetration usually exceeds 5 +n +n and 14 +n +
It can even reach n. The penetration level of toilet soap is 1 under similar conditions.
~2+nm, and non-soap detergent wash bars are approximately 0.5
It is nun.

In this type of composition, the soap and polyhydric alcohol components constitute a gel (so-called soap core gel) which exists in a non-flowing solid form and serves as a carrier for the silica bleach and other components.

Although the soap may be any substance that is generally differentiated as a soap, it is preferable to use a saturated soap.
! Delicious. Soaps of this type are usually alkali metal salts of CI2-C20 fatty acids. Normally, 3 types of thorium salt are used. The soap may be specifically 1-lium stearate or sodium palmitate, or may be based on a saturated soap mixture. It is strongly desired that the moisture &I'2 of this soap be less than 5wt2≦.

(Left below) The polyhydric alcohol itself may be solid or liquid. Alcohols that can be used are propane-1,2-diol and other diols, triols and polyols, such as ethylene glycol, diethylene glycol,
These include sorbitol, butanediol and triethanolamine.

The diol may have no more than 6 carbon atoms,
Higher polyols may also have no more than 12 carbon atoms.

The polyhydric alcohol is preferably aliphatic, substantially non-volatile, and has a boiling point above 120°C.

The ratio of soap to polyhydric alcohol is usually 1:1 to 1;9, preferably 1:1.5 to 1:5, more preferably 1
: 2.5 to 1:4.

Preferably, the peroxygen bleach is a monopersulfate. Surprisingly, this bleach has a better combination of stability and effectiveness than other peroxygen bleaches.

Monopersulfate is KHSO5: KHSO4: K2S
A commercially available triple salt containing 01 in a molar ratio of about 2:1:1 (
It can be used in the form of triple 5 alt).

The preferred amount of monopersulfate is 4 to 10% by weight of the total composition as triple salt.

Although percarbonates are stable in the preferred compositions of the invention,
Bleaching effect is poor. The organic peroxy acid precursor tetraacetylethylenediamine (TAE) was used to improve the bleaching effect.
Inclusion of D) reduces the stability of the percarbonate. Perborate salts do not tend to be stable in the preferred compositions of the present invention.

Compositions of this type desirably also contain synthetic (ie, non-soap) surfactants, which can be, for example, anionic, cationic or non-ionic. of the composition,
Preferably, the surfactant is non-ionic to enhance its ability to remove oily soils; the synthetic surfactant can be used alone or in combination with other types of surfactants.

If a higher foaming profile than can be achieved with non-ionic surfactants is desired, it may be advantageous to use a combination of non-ionic and anionic surfactants in the composition. could be. The amount of anionic surfactant will probably not exceed 10% by weight of the composition.

The actual amount of synthetic surfactant is less critical.

The synthetic surfactant may be included in the composition in an amount up to 50% by weight of the total composition, and in some cases somewhat more. Preferably, the synthetic surfactant accounts for 20-50% by weight of the composition.
of which at least a portion is preferably a nonionic surfactant. Preferably, the nonionic surfactant is 10-50%, more preferably 15-40% by weight of the composition.

You can. A preferred method of preparing this type of composition using a solid nonionic surfactant is to first mix the polyhydric alcohol and any nonionic synthetic surfactant;
Heat to a temperature higher than 80°C.

The soap is dissolved in this mixture and the other substances are then added at a somewhat lower temperature and stirred continuously until a homogeneous mixture is obtained. Preferably:
Add bleach last. After preparation, the composition is cast and allowed to solidify into the desired shape by cooling to ambient temperature.

Both castable compositions of the type described above may contain some organic solvent in an amount of 4 to 15 weight percent of the composition.

Also, exclusion of other liquids mentioned above, such as enzymes, may result in solid compositions.

This means that anionic surfactants, especially diC6-CI
2-alkyl sulfosuccinate or direct Mc a~
This can be prevented by the inclusion of C16 alkylbenzene sulfonates.

For example, the hydrocarbon solvent and the anionic surfactant are combined in an amount of 4 to 15% by weight of the composition, but in a weight ratio of 2:1.
~1:2, preferably 1.5+1~1:15.

It may contain in addition to. The four inorganic minerals are 5% by weight of the composition.
It may desirably be included only in small amounts, such as below, or it may be included in relatively large amounts, up to approximately 20% by weight.

When casting the composition at a temperature which is generally between 50 and 70<0>C, it is usually suitable for the liquid to remain in the form of a liquid to maintain the solids in suspension. It is also possible to add thickeners to the mixture, such as, for example, hydroxypropylcellulose derivatives, in order to increase the viscosity.

The present invention provides a stick suitable for use in a variety of situations, thereby providing consumers with an extremely convenient product shape. For this purpose, the composition can simply be poured into the stick holder, without the need for any lubricant. Alternatively, the product may be in the form of a stick wrapped with a cover.

In use, the castable composition can be rubbed onto soils and stains on dry or damp fabric. In any case, the fabric is then laundered as normal. It is usually more desirable for the user to use it directly on dry fabrics.

When used on dry fabrics, the composition acts on stains or soils early in the normal laundering process and is removed later in the laundering process. When used on pre-moistened fabrics, best results are obtained if some time is spent, for example about 5 minutes, to give the composition time to act on the stain or stain prior to the normal washing process. can get.

Embodiments of the invention will now be described, by way of example only, with reference to the following examples. In the following examples: The nonionic surfactants used were CI3-CI5 fatty alcohols ethoxylated with an average of 7 EO. The soap used was an 80/20 tallow/coconut oil soap dried to less than 5% water by weight.

Birophosphate and orthophosphate were added as anhydrous salts.

The calcite used was a high surface area calcite sold under the trademark "5ocal".

Monopersulfates include KHSo 5, KIISO, and Ni 2
SO4 was added in the form of a commercially available triple salt containing a molar ratio of approximately 2:1:1.

Dequest 2041 is ethylene diamine tetramethylene phosphonic acid and is a sequestering agent.

TAED stands for the peroxyacid precursor tetraacetylethylenediamine.

(Hereinafter in the margins) Includes Cleaning pre-treated sticks were made with the extrudable preparations listed in Table I. Table 1 shows the amounts of stick components in weight percentages relative to the final stick composition.

Each composition was mixed with a Z-shaped blade mixer at a temperature of 30 to 50 ml.
It was prepared by mixing at 0°C.

Bleach was added at the final stage, after the other ingredients were thoroughly mixed. Do not let the wax in the preparation dissolve by heating before adding it to the mixture along with the surfactant.

The resulting homogeneous mixture was passed through a screw extruder with diameter 3
It was extruded through an orifice with a co+ circular cross section.

Each formulation except Formulation C was extrudable into solid stick form. The extruded sticks were stored at 40° C. to simulate storage in a hot climate. The remaining bleaching activity after a given period of time was tested by titrating the available oxygen and thereby determining the bleach half-life. The determined half-lives are shown in Table I.

Composition B has 0.0% water, as seen from a comparison with Composition A, which contained a small amount of water added alone during the preparation of the composition.
This water in Composition B had a severe negative effect on the stability of the bleach.

Composition J was an alkylbenzene sulfonate, sodium carbonate, and water as the water of carbonate hydration. The composition was prepared using high quality alkylbenzene sulfonates with low water content.

Support 1: The effect of Composition A of Example 1 was evaluated as follows using a newly manufactured stick.

4cm x 4cm on a test cloth piece (dimensions: approx. 7cm x 7cm)
The simple area was marked. After moistening the specimen with a small amount of water,
Place 0°1 g of raw acid on the entire 4cm x 4cm area marked.
did.

After pretreatment, the specimens were allowed to stand for 10 minutes and then washed with 1 g of powdered detergent/tergoLometer.
Washing was performed at 25° C. for 10 minutes using a washing solution containing l.

Control strips (no pretreatment) for turbotometer cleaning
Also added. The test and control specimens were rinsed and the reflectance at 460 nm was compared to that before pretreatment and cleaning.

The results of the pretreatment are shown in Table ■. Composition A clearly demonstrated the benefits of pretreatment for all stains except blood.

Table L "Results due to chaff (all results shown are increases in reflectance at 460n obtained as a result of pre-treatment and turbotometer cleaning) Black tea 14-2 Wine (E
HP^114) 29 8
Banana juice 185 Coffee 3019 Blood (EMP
^116) 7 7 dog J
The effects of compositions F and G on fabrics stained with JL and black tea were evaluated using a procedure similar to Example 2. The 39CII+2 area was moistened with a small amount of water and 0.15-0.2 g of product was applied thereto. After this pretreatment, the test pieces were allowed to stand for 10 minutes, and then washed at 25 DEG C. in a turbotometer with a washing solution containing 2 g/l of powdered detergent. A piece of cloth treated with soap was used as a control. The test pieces and control pieces were immersed in the cleaning solution for 2 minutes and then washed for 10 minutes while stirring as usual. The specimens and controls were rinsed and the reflectance at 460 nm was compared to that before pretreatment and cleaning. The increase in reflectance was as follows: Composition F 17.9 Composition G 27.5 Soap 1.

Composition K of Example 1 was tested in a similar manner using test fabrics with various stains. After pretreatment, the specimens were left for only 2 minutes, and a cleaning solution containing 1 g/l of powdered detergent was used for the final cleaning. Table shows the increase in reflectance at 460 nm■
Shown below.

Ai-to] Eiben (7) Crab lipstick 39.4
20.9 1" 1 L Cleaning pretreatment sticks were prepared from a castable preparation having the composition listed in Table 1. In Table 1, the amounts of stick ingredients are given as weight percentages with respect to the final stick composition.

In the preparation of each composition, an organic material with a melting point above 40° C. was heated and mixed with a nonionic detergent until the melted organic material yielded an isotropic liquid. The other ingredients were then added and mixed thoroughly to keep the solids in suspension. The mixture was cooled to one temperature above its solidification temperature and then poured into molds.

If the preparation contains a hydrocarbon solvent, the solvent is
It was added at a temperature below 0°C. Bleach was added last, below 70°C.

All compositions could be in the form of solid sticks with sufficient hardness to allow the compositions to be manually rubbed onto fabrics.

Do not store the composition at 40°C to simulate storage in a hot climate. The remaining bleaching activity was determined intermittently by titration of available oxygen. The half-life of bleach was calculated from the results, and the calculation results are shown in Table 3.

The effect of Composition 4A of Example 4 was evaluated according to the procedure of Example 2 using a newly manufactured stick.

The pretreatment results are shown in Table V. Composition 4A clearly demonstrated the benefits of pretreatment for all stains except blood.

Table - ■Two results (all results shown are increases in reflectance at 460 nm obtained as a result of pretreatment and turbotometer cleaning) Black tea 12-2 Wine (EM
P^114) 28 8
Banana juice 165 Coffee 3119 Blood (EMP^
116) 5 7 1
1 [A stick similar to the stick of Composition 4B was prepared containing the organic bleach diperoxide dodecanoic acid (DPD^). Disodium dihydrogen birophosphate was used as the hydratable salt to obtain an acidic composition since DPD^ is unstable under alkaline conditions. The composition contained the following ingredients.

(C1, ~ CI5.7EO) Stearyl alcohol 22.5 Castor oil wax 9 Talc
9.9 Hydrocarbon solvents (mainly isododecane) 12.6 Amount of remaining bleach in Example 4
When tested intermittently as above, the half-life was shorter than 1 day.

Pre-treated sticks were prepared from castable soap core gel preparations having the compositions listed in Table 1. In Table 1, the amounts of stick components are given in weight I percentages with respect to the final stick composition.

In preparing each composition listed in the table, the liquid glycol and non-ionic detergent are heated to above 80'C and -
Numerically, the mixing was carried out at a temperature below 105°C.

Finely powdered dry soap (sodium stearate or sodium balmitate) was added and stirred until dissolved. After cooling to 70-80"C any hydrocarbon solvent was added followed by the addition of the finely divided inorganic solids. Finally the bleach was added at a temperature of 60-70"C.

Once the solid was homogeneously dispersed in the liquid, the dispersion was poured into a mold and allowed to solidify. - numerically between 50 and 70°C;
At the temperature of pouring to form a stick,
The viscosity of the liquid was high enough to keep the solids in suspension.

Proteolytic enzymes are Novo Industry
8/S.

“^1calase 2-5 S” by Denmark
A material sold under the name L'' was used.

All compositions could be formed into solid sticks with sufficient hardness to allow the compositions to be manually rubbed onto fabrics.

Composition 7F showed some phase separation observed as granulation of the liquid on the gel surface. This phenomenon could be avoided in formulations 7D and 7E by the inclusion of anionic surfactants.

The composition was stored at 40°C to simulate storage in a hot climate. The remaining bleaching activity was determined intermittently by titration of available oxygen. The half-life of the bleach was calculated from the obtained results, and the calculated half-life is shown in Table 1. From Table 1, it is clear that the composition containing monopersulfate exhibits excellent bleach stability. It is. Percarbonates also provide good stability, but perborate as well as mixtures of percarbonate and TAED provide poor stability.

Volume 1'' 1L The effectiveness of compositions 7C and 7E of Example 7 was evaluated according to the procedure of Example 2 using freshly manufactured sticks. The effectiveness of Composition Q, which does not contain bleach, was also evaluated. Composition Q contained the following ingredients.

Hydrocarbon solvent (mainly indodecane) 20 talc
9.5 Borax 5) 1.0
5 proteolytic enzymes
The results of the 0.5 pretreatment are shown in Table ■. Composition 7
C clearly shows the advantage of pretreatment for all stains except blood, while for blood enzyme-containing compositions 7E and Q showed an absolute advantage.

Table 1: Taro strawberries 22 nt 4
-1 black tea 6 nt
-0,5-2 wine (EMP^114) 2
0 nt 14 8 banana juice
16 nt 9 5 coffee 30 nt 23
19 blood (EMP^116) 5 2
The effectiveness of Composition 7J of Example 7 was evaluated using the method used in Example 3 for Composition K of Example 1 using freshly prepared sticks. The increase in reflectance at 460 nm is
As shown in the following table ■.

Front - Chestnut stain on Seji Kaidokoro plate Composition 7J Soap black strawberry 19.8
9.1 Black tea 10.9
0.8 banana juice 11.6
2.3 Red wine 3
2.3 21.6 Dirty motor oil
12.0 11.10 Beni
24.9 20.9 Another person, Takeshi Funa Yama, a patent attorney representing Yosukitsu V-t.

Claims (16)

[Claims] (1) A detergent composition in the form of a solid shaped article suitable for application to selected areas of textile products prior to laundering, which is substantially less hard than toilet soap and is stable with peroxygen bleach and above 30°C. A detergent composition comprising a hygroscopic salt having a hydrate. (2) The detergent composition according to claim 1, which melts in a fluid state at 40° C. or higher and can be molded by injection. (3) An extrudable composition comprising a filler selected from clays, soaps and non-surface-active organic solids.
The detergent composition described in . (4) Peroxygen bleach 1-20% by weight, hygroscopic salt with hydrates stable above 30°C (considered anhydrous)
2 to 15% by weight, and 5 to 70% by weight of a surfactant, and the free water content is 0.5% by weight or less.
The detergent composition according to any one of the above. (5) A detergent composition in the form of a solid shaped article, comprising at least 5 to 45% by weight of a nonionic surfactant, 1 to 20% by weight of a peroxygen bleach, and a hydrate that is stable at 30°C or higher. A soap containing 2 to 15% by weight of one type of hygroscopic salt and 10% by weight or more of a filler, the filler being -0 to 70% by weight (value based on the entire composition),
organic fillers consisting of waxes and/or other soft organic solids; -0 to 50% by weight (based on the total composition) of clay; -0 to 40% by weight (based on the total composition) of particulate inorganic material other than clay; one or more substances selected from fillers, provided that if any inorganic filler other than clay is present in an amount greater than 5% by weight of the total composition, an equal amount of said organic solid; is used together with the detergent composition, wherein the composition maintains a non-flowing solid form upon heating to at least 50°C. 6. The detergent composition of claim 5, comprising 40 to 70% by weight of filler, a portion of which is clay. (7) A detergent composition in the form of a solid shaped article that melts at a temperature of 40°C or higher, comprising 5 to 70% by weight of nonionic surfactant.
, peroxygen bleach 1-20% by weight, at least one hygroscopic salt having a hydrate stable above 30°C 2-15
% by weight and 10 to 80% by weight of one or more organic compounds or mixtures thereof that melt and become fluid at temperatures above 40°C. (8) The detergent composition according to claim 7, which melts in a temperature range of 50°C to 90°C. (9) The organic compound or mixture thereof is selected from waxes, polyalkylene glycol esters, fatty alcohols having 12 to 20 carbon atoms, and fatty acids having 12 to 20 carbon atoms. detergent composition. (10) The detergent composition according to any one of claims 7, 8, or 9, wherein the amount of nonionic surfactant is 10 to 50% by weight. (11) The detergent composition according to any one of claims 1 to 12, wherein the peroxygen bleach is selected from perborates, percarbonates, and monopersulfates. (12) The detergent composition of claim 11, which also contains an organic peroxy acid precursor. (13) A detergent composition in the form of a solid shaped article that melts at a temperature of 40° C. or higher, comprising 1 to 20% by weight of peroxygen bleach, 5 to 40% by weight of soap, 15 to 70% by weight of polyhydric alcohol,
and hygroscopic salt 2 having a hydrate that is stable at 30°C or higher
A detergent composition comprising ~10% by weight. (14) Claim 1: Melting in a temperature range of 45°C to 90°C
3. The detergent composition according to 3. (15) Claim 13 wherein the peroxygen bleach is a monopersulfate.
The detergent composition described in . (16) The detergent composition according to any one of claims 13 to 15, also comprising 10 to 50% by weight of a non-soap surfactant.