WO1997038080A1 - High-density granular detergent composition - Google Patents

Abstract

A high-density granular detergent composition having excellent detergency for oily dirt, comprising: (a) 3 to 50 % by weight of an alkylolamide surfactant represented by general formula (1), wherein R1 is a C8-C20 alkyl or alkenyl, R2 is H or a C1-C3 alkyl or alkenyl, and n is a number of 2 to 6, (b) 5 to 60 % by weight of an aluminosilicate, and (c) 5 to 60 % by weight of an alkaline agent, and having a bulk density of 0.5 to 1.2 g/ml.

Description

 Description High density granular detergent composition Background of the invention

Field of the invention

 The present invention relates to a detergent composition for clothing, and more particularly to a detergent composition having excellent oily soil detergency even at low temperatures.

Description of related technology

 Detergents for clothing are surfactants that solubilize stains, dissolve and disperse them from the fiber into the washing liquid, alkaline agents that promote the decomposition and solubilization (emulsification) of stains, and polymer compounds that disperse stains. However, it is basically composed of a sequestering agent for removing calcium, magnesium, and the like, which lower the ability of the surfactant, from the washing liquid. Of these components, surfactants have the primary function of removing soil from the fibers, as described above. Surfactants used in detergents are broadly classified into those based on anionic properties and those based on nonionic properties. Surfactants used for those having anionic properties include alkylbenzene sulfonates having 10 to 16 carbon atoms, sulfates of higher alcohols having 10 to 18 carbon atoms, α-refined sulfonates, α- Surfactants such as sulfo higher fatty acid ester salts and alkane sulfonates (SAS), which are mainly used for nonionics, include polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenols. For example, a rutel. Examples of these are, for example, Japanese Patent Publication No. 64-10039, Japanese Patent Publication No. 4-431119, Japanese Patent Publication No. 5-66440, Japanese Patent Publication No. Hei 4-339898, Japanese Patent Publication No. 5-5100, Japanese Patent Publication No. And JP-A-6-10000.

Generally, dirt attached to clothing, especially oily dirt derived from human secretions or food The higher the washing temperature, the higher the melting or swelling, and the easier it is to remove with detergent. Therefore, when performing washing, using warm water is advantageous from the viewpoint of the cleaning effect, but energy is required to obtain warm water, and from a global perspective, the environmental impact of energy consumption is reduced. Influentially concerned. Therefore, studies are being conducted in the direction of washing without raising the washing temperature, but washing at a low temperature is particularly disadvantageous for washing oily soil. In addition, detergents are also less soluble, which generally reduces overall cleaning power. In view of the above-mentioned environmental problems, washing is preferably performed at a low water temperature. However, a detergent composition exhibiting good detergency especially for oily soil under such low temperature conditions has not yet been found.

 Disclosure of the invention

Summary of the Invention

 The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, it was found that zeolite, which is an inorganic builder and uses an ethylene oxide-added type fatty acid amide derivative, ie, an alkylolamide type surfactant, or The present inventors have found that a high-density granular detergent excellent in detergency can be obtained by using an alkaline agent such as a crystalline silicate in a specific ratio, and have completed the present invention. Furthermore, as a result of examining the relationship between the detergency at low temperature and the number of moles of alkylene oxide surfactant alkylene oxide added, surprisingly, the 2-mol addition product has excellent oil-based soil detergency. The present inventors have found that the use of a composition having a high ratio of this component makes it possible to obtain a desired detergent composition, thereby completing the present invention.

 That is, the present invention provides: (a) 3 to 50% by weight of an alkylamide-type surfactant represented by the following general formula (I):

RlCON—¾Η4. ) _η Η R ₂ (Wherein, is an alkyl or alkenyl group having 8 to 20 carbon atoms, R ₂ is H or an alkyl or alkenyl group having 1 to 3 carbon atoms, and n is a number of 2 to 6.)

 (b) 5-60% by weight of aluminosilicate

 (c) Al liquor 5-60% by weight

A high-density granular detergent composition having a bulk density of 0.5 to 1.2 g / ml.

To provide.

 The amount of the component (a) is preferably 15 to 50 weight *%.

 Brief description of the screen

 FIG. 1 is a graph showing the ethylene oxide added mole number distribution (% by weight) of various alkylolamide-type surfactants prepared in Reference Examples.

Detailed description of the invention

 Alkyl amide surfactants of the component (a) represented by the general formula (I) are used for shampoos and liquid detergents and have been well known as surfactants for a long time. Patent applications and research reports have been made. For example, alcohol amide improves foam stability when used in combination with anionic surfactants such as sulfates of higher alcohols and ester sulfates of ethoxylates of higher alcohols, and acts as foam thickeners. There has been used for a long time in shampoos. This is described in Amer. Perfumer, 81. o. 3, 38 (1986), Defergent Age, _5, 27 (1968). However, it has been reported that when an alkylolamide-type surfactant is used as the main component of the surfactant in a high-density granular detergent composition, a more excellent detergency for clothes can be obtained. Not known at all.

Further, in the present invention, R _{2 in} the formula of the alkylamide-type surfactant represented by the general formula (I) is hydrogen, and RL is a linear or branched alkyl group having 7 to 19 carbon atoms. Is an alkenyl group, and the average addition mole number n is greater than 1 and the proportion of the addition mole number 2 compound is 50% by weight or more, preferably 60% by weight or more, most preferably It has been found that when the content is 70% by weight or more, the detergency at low temperatures is particularly excellent.

 Regarding the method for producing the component (a) used in the present invention, the fatty acid lower alkyl ester or fat and oil and alkanolamines are used as they are, or in the presence of an alkali catalyst such as sodium methylate or a metal catalyst. Incubate for 24 hours. Specific reaction conditions include, for example, a reaction temperature of 60 to 200, preferably 70 to 120 ° C, a pressure of 1 to 760, and preferably 30 to 100 Hg. The alkylamide-type interface represented by the general formula (I) is obtained by adding an alkylene oxide to the obtained amide alcohol as it is or by further adding an alkali catalyst or a metal catalyst to the amide alcohol. An activator is obtained.

However, the ethylene O key side greater than addition molar number of 1, and with the proportion of the pressurized moles 2 compounds 50 wt% or more, preferably 60 wt% or more, most preferred properly 70 wt ⁰ 6 or more of When it is desired to produce ethylene oxide, it is difficult to add ethylene oxide by a usual method. Therefore, it is preferable to use a specific production method described below.

 Reference example>

Specifically, the distribution of the number of added moles will be exemplified. The sample was prepared according to the following procedure. 16.5 mol of L-phosphate monoethanolamide (LEA) and 0.5 to 5 mol% of K0H as a catalyst with respect to LEA were charged into a 7-liter autoclave, and the temperature was raised to 90. Ethylene oxide 33.1 mol was introduced while maintaining the internal pressure at 3.5 kgZcm ² G or less, and reacted at 87 to 97 to obtain an alkylolamide-type surfactant. According to the above conditions, various EO addition moles were synthesized by changing the reaction temperature and the amount of the catalyst. Table 1 shows the analytical values of the synthesized samples A to D, and Fig. 1 shows the distribution of the number of moles of ethylene oxide added. The average number of moles n added to sample A is 1.7. ^ About 40% of the unreacted material remains. 2 moles account for around 42%, and the rest are high-tech chillenoxide side-added products such as 3, 4, 5, 6 moles. The average number of moles added for sample Β is 3, but 2 Approximately 30% of the products are 3%, 3% are about 35%, and 4% are about 15%. In this production method, even if the synthesis is carried out with a target of 2 moles, only about 42% of the 2 moles can be obtained, so post-treatment such as distillation is necessary to increase the content of the 2 moles.

 table 1

Next, when R 'is hydrogen, an example of a production method for selectively synthesizing only a 2 mol product will be described. The fatty acid or lower alkyl ester of fatty acid or fatty acid, preferably a lower ester of fatty acid and diglycolamine are reacted for 2 to 24 hours as they are or in the presence of an alkaline catalyst such as sodium methylate or a metal catalyst. Specific reaction conditions include, for example, a reaction temperature of 60 to 200, preferably 70 to 120 ° C, a pressure of 1 to 760 mmHg, and preferably 30 to 100 mmHg. The molar ratio of diglycolamine to fatty acid or fatty acid lower alkyl ester or fat or oil is preferably in the range of 1: 1 to 1: 5. More preferably, the ratio is 1: 1.01-1: 3. Obtained by this manufacturing method The compound obtained may be blended with the product obtained by the above-mentioned production method to increase the content of 2 mol product. The alkylolamide-type surfactant of the present invention is incorporated in the composition in an amount of 3 to 50% by weight, preferably 5 to 40% by weight.

 Next, the aluminosilicate as the component (b) will be described.

 Both amorphous and crystalline aluminosilicates can be used.

The amorphous aluminosilicate, silicon as Si0 _2, 30 wt% or more, preferably well those containing more than 40 wt%, and if used as the pH of the 5% dispersion of 9 'or Deterioration of detergent solubility after high humidity storage is further improved.

 Examples of the amorphous aluminosilicate used in the present invention include those represented by the following general formula (i), which are highly oil-absorbing and have a high ion exchange capacity.

_{a (2 0) - AI 2O3} - b (Si0 2) - c (H 2 0) (i)

 (In the formula, M is an alkali metal atom, a, b, and c represent the number of moles of each component. Generally, 0.7 ≤a ≤2.0, 0.8 ≤b, 4, and c are arbitrary It is a positive number. ]

 In particular, the following general formula (ii)

_{Na 2 0. A1 2 0 3} · b (Si0 2) · c (H 2 0) (ii)

 [Where b represents a number of 1.8 to 3.2 and c represents a number of 1 to 6. ]

Is preferably represented by

A brief description of the method for producing the amorphous aluminosilicate is given below. First, Si0 ₂ and M ₂ 0 (M denotes an alkali metal) and the molar ratio of _{Si0 2 U 2 0 = 1. 0~4} . 0 of, IHO and the molar ratio of 20 H ₂ 0 / M ₂ 0 = the alkali metal silicate solution is 12 to 200, the molar ratio of M ₂ 0 and A1 ₂ 0 ₃ is _{M 2 0ZA1 2 0 3 = 1.} 0~2. 0, H 2 0 and M ₂ 0 Is added under strong stirring at a temperature of 15 to 60, preferably 30 to 50, with a molar ratio of H ₂ 0 / 2O = 6.0 to 500. Further, an aqueous solution of an alkali metal silicate may be added to the aqueous solution of an alkali metal silicate.

The resulting white precipitate slurry is then subjected to 70-100, preferably at a temperature of 90-100 ° C. It can be advantageously obtained by performing a heat treatment at a temperature of at least 10 minutes and at most 10 hours, preferably at most 5 hours, followed by filtration, washing and drying. According to this method, an amorphous aluminosilicate having an ion exchange capacity of 100 CaC0 ₃ mgZ g or more and an oil absorption capacity SOOralZlOO g or more can be easily obtained.

 The pH of the 5% dispersion of the amorphous aluminosilicate is measured according to JIS K6220. That is, weigh out about 5 g of the sample in a hard Erlenmeyer flask, add 100 ml of water without carbonic acid, stopper and shake for 5 minutes. The pH is measured by the glass electrode method (7.2.3 of JIS Z 8802) using the solution after shaking as a test solution.

 By selecting an amorphous aluminosilicate having a pH of 9.0 or more in the 5% dispersion, it is possible to obtain a high-density detergent composition whose solubility does not deteriorate when stored under high humidity conditions.

 Also, when the alkalinity of the detergent is very high or the storage conditions are very severe, the amorphous aluminosilicate that satisfies the condition that the amount of dissolution in a 2% fe0B aqueous solution is less than 0.5 is more severe. You should select

That is, 10 g of an amorphous aluminosilicate is dispersed in 100 ml of a 2% aqueous NaOH solution, and the mixture is stirred for 16 hours at 25 ° C. under constant temperature conditions. Then, the SiO ₂ in the filtrate is colorimetrically determined. pl56, 1976), the amount of which is less than 0.5 g as an amorphous aluminosilicate.

 In addition, crystalline aluminosilicate is generally called zeolite, and has the following formula

_{a '(M 2 0) ·} A1 2 0 3 · b' (S1O2) · w (H 2 0) (iii)

 [In the formula, M is an alkali metal atom, a ', b', and w represent the molar ratio of each component. In general, 0.7 ≤ a '≤ 1.5 0.5 ≤ ≤' <6 sw is arbitrary Is a positive number. ]

In particular, the following general formula (iv)

a ₂ 0-AhOa-n (Si0 ₂ )-w (H ₂ 0) (iv) [Here, n represents a number of 1.8 to 3.0, and w represents a number of 1 to 6. ]

Is preferably represented by As the crystalline aluminosilicate (zeolite), a synthetic zeolite having an average primary particle size of 0.1 to 10 m typified by A-type, X-type and P-type zeolite is preferably used. Zeolite may be blended as zeolite aggregated dry particles obtained by drying powder and Z or zeolite slurry.

 In the present invention, the aluminosilicate is incorporated in the composition in an amount of 5 to 60% by weight, preferably 8 to 30% by weight. By incorporating the aluminosilicate in this range, good detergency is exhibited.

 The component (c) is described below.

 As the alkali agent used in the present invention, inorganic alkali metal salts and polyphosphates are preferably used. Specifically, the following (D to (2) can be used. (1) Inorganic alkali metal salts

Sodium carbonate, potassium carbonate, sodium silicate _{[(Na 2 0) m (Si0} 2) n, where, m is 1 to 5, n is 1-3. ], Sodium bicarbonate, potassium bicarbonate, sodium sulfite, sulfurous acid lime, sodium sesquicarbonate, sesquicarbonate, crystalline silicate and the like.

 Among these alkali metal salts, a crystalline silicate is particularly preferable.

The crystalline silicate used in the present invention has a maximum pH of 0.1% dispersion of 11 or more at a temperature of 25, and a 0.1% dispersion of 0.1% HC 1 It requires 5 m1 or more to lower the pH to 10 using an aqueous solution, and it is excellent not only in the degree of force but also in the buffer capacity of the force. In particular alkali metal厲塩is favored by kana of these crystalline silicates in the present invention, inter alia, Si0 ₂ Roh M ₂ 0 of the alkali metal silicate (wherein, M represents an alkali metal.) Is from 0.5 to 2 .6 is preferably used. Conventionally known crystalline silicates have SiOsZMsO strength of 1.9 to 4.0, but those with a ratio exceeding 2.6 are not suitable for the formulation of high-density detergents that are the object of the present invention. Powerful.

 The preferred crystalline silicate used in the present invention has the following composition.

① x (M ₂ 0)-y (Si 0 ₂ )-z (Me _m 0n)-w (H ₂ 0) (II)

 (In the formula, M represents an element of group la of the periodic table, and Me represents one or two of the elements of group Ila, element lib, element Ilia, element IVa or element VII of the periodic table. The above combinations are shown as y / x = 0.5 to 2.6, z / x = 0.01 to 0.9, w = O to 20, and n / m = 0.5 to 2.0. ]

_{② M 2 0 · X '(} Si0 2) · y' (H 2 0) (III)

 [In the formula, M represents an alkali metal, and x ′ = 1.5 to 2.6 and y ′ = O O20. ]. First, the crystalline silicate represented by the above general formula (II) will be described.

In the general formula (Π), M is selected from the group la elements of the periodic table, and examples of the group la elements include Na and K. These may be used alone or, for example, a mixture of Na ₂₀ and K ₂₀ to constitute the tt ₂₀ component.

Me is selected from Ila group element, lib group element, Ilia group element, IVa group element or VIII group element of the periodic table, and examples thereof include Mg, Ca, Zn, Y, Ti, Zr, and Fe. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. These may be used alone or as a mixture of two or more kinds. For example, Mg0, Ca0 and the like may be mixed to form the MeJ) _n component.

In the general formula (II), yZx is 0.5 to 2.6, preferably 1.5 to 2.2. When the y / x force is less than '0.5, the water resistance is insufficient, and the masking property, the solubility, and the powder properties of the detergent composition are significantly adversely affected. On the other hand, when yZx exceeds 2.6, the alkalinity becomes low and becomes insufficient as an alkali agent, and the ion exchange ability also becomes low, making it insufficient as an ion exchanger. In the general formula (II), C and zZx are 0.01 to 0.9, preferably 0.02 to 0.9, particularly preferably 0.05 to 0.9. ~ 0.9. When z / x is less than 0.01, the water resistance is insufficient, and when z / x exceeds 0.9, the ion exchange capacity is lowered and the ion exchange capacity is insufficient. X, y, and z are not particularly limited as long as they are in the relationship indicated by the yZx ratio and the ζΖχ ratio. Incidentally, the x (M ₂ 0), for example, _{χ '(Na 2 0) ·} χ''(Κ 2 0) if the - is like, X is a χ' + χ ''. Such a relationship is the same for z when the z (Me _m 0 _n ) component is composed of two or more components. NZm indicates the number of oxygen ions coordinated to the element, and is substantially selected from the values of 0.5, 1.0, 1.5, and 2.Q.

 The preparation method of the crystalline silicate represented by the general formula (II) can be referred to JP-A-7-89712.

 Next, the crystalline silicate represented by the above general formula (III) will be described.

 This crystalline silicate has the general formula (III)

20 · χ '(Si0 ₂ ) -y' (H ₂ 0) (III)

0 のものが好ましく、 陽イオン交換能が 100〜400 CaCOa mg/gのものが使用でき 、 本発明におけるィォン捕捉能を有する物質の一つである。 [In the formula, M represents an alkali metal, and χ ′ = 1.5 to 2.6 y ′ = 0 to 20. X ', y' force in general formula (III)

A substance having a cation exchange capacity of 100 to 400 CaCOa mg / g can be used, and is one of the substances having an ion capturing ability in the present invention.

The production method of the crystalline silicate represented by the general formula (III) is described in Japanese Patent Application Laid-Open No. Sho 60-227895. Generally, amorphous glassy sodium silicate is prepared in the range of 200 to 1000. It is obtained by firing to make it crystalline. Details of the synthesis method are described in, for example, Phys, Chem. Glasses, 7, 127-138 (1966), and Z. ristallogr., 129. 396-404 (1969). The crystalline silicate represented by the general formula (III) is available, for example, in powder or granular form under the trade name “Na-SKS-6” — Na ₂ Si _{20 from} Hoechst. it can.

The crystalline silicate represented by the above general formulas (II) and (II) has an ion exchange capacity of And at least 100 mg of CaCO ₃ mgZg, preferably 200 to 600 mg of CaCO ₃ mg / g, and is one of the substances having an ion-capturing ability in the present invention, and the average particle diameter is 0.1 to 100. Preferably, it is 1 to 60 m. When the average particle size exceeds 100 / m, the rate of onset of ion exchange tends to decrease, leading to a decrease in detergency. Also, 0. hygroscopic and absorption C0 ₂ resistance is increased by increasing the specific surface area is less than 1 DI, it tends to deteriorate the quality becomes significant. Here, the average particle size is the median size of the particle size distribution. The crystalline silicate having such an average particle size and a particle size distribution can be prepared by pulverizing using a pulverizer such as a vibration mill, a hammer mill, a ball mill, a roller mill and the like.

 In the present invention, the crystalline silicate represented by the general formula (II) and the crystalline silicate represented by the general formula (III) can be used alone or in combination of two or more.

(2) Polyphosphate

 Polyphosphates such as orthophosphate, metaphosphate, pyrophosphate, tripolyphosphate, and hexametaphosphate can be used. As salts, H, Na and K are common.

 The alkaline agent such as an alkali metal salt or polyphosphate is contained in the composition in an amount of 5 to 60% by weight, preferably 10 to 40% by weight.

 The alkali silicate contained in the composition preferably contains a crystalline silicate in an amount of preferably 10 to 100% by weight, more preferably 50 to 80% by weight.

 In the present invention, it is preferable to mix the following components in addition to the above essential components.

 Vanionic surfactant>

Alkyl amide-type surfactants represented by the general formula (I) exhibit excellent oil-based dirt-cleaning power. 47

It is preferable to use a surfactant in combination. Examples of the anionic surfactant include sulfates of linear or branched primary or secondary alcohols having 10 to 18 carbon atoms, sulfates of alcohol ethoxylates having 8 to 20 carbon atoms, and alkyls. One or two selected from alkyl benzene sulfonates having 8 to 16 carbon atoms, alkane sulfonates (SAS), haloolefin sulfonates, a-sulfofatty acid salts and α-sulfofatty acid alkyl ester salts That is all. Is a salt of these Anion surfactants, Na, K, NH ₄ is suitable. The anionic surfactant is incorporated in the composition in an amount of 5 to 45% by weight, preferably 10 to 40% by weight. The molar ratio of alkyl amide surfactant nonionic surfactant is desirably at least 10Z90 or more, preferably 20Z80 or more.

<Nonion surfactant>

 One or more selected from polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, polyoxetylene polyoxypropylene block polymers, and alkanoyl N-methyldalcamine A mixture of two or more. Among these, a polyoxyethylene alkyl ether having an HLB value of 10.5 to 15.0 is particularly preferred. The nonionic surfactant is preferably incorporated in the composition in an amount of 1 to 15% by weight.

 In the present invention, other surfactants other than the anionic surfactant and the nonionic surfactant can be used in combination. In the present invention, the total amount of all surfactants such as the alkylolamide-type surfactant, anionic surfactant, and nonionic surfactant of the present invention in the composition is preferably 10 to 60% by weight, more preferably Is from 20 to 40% by weight.

 Ku polycarboxylate>

A copolymer or a compound represented by the following formula (IV) having a molecular weight of several hundreds to 100,000 and (V) Polycarboxylates such as homopolymers represented by the formula

(In the formula, Z is 1 to 8 maleic acid or a monomer copolymerizable with maleic acid (anhydride) such as maleic acid, methacrylic acid, methacrylic acid, itaconic acid, or methallylsulfonic acid, and maleic acid or maleic acid (anhydride) salts of the copolymer salt, m has a value such that the molecular weight of the copolymer exhibits several hundred to 100,000. M is N'a, K, is NH _3.)

 "One P-Ko

(In the formula, P is a monomer capable of being homopolymerized, and examples thereof include acrylic acid, methacrylic acid, and maleic acid. M ′ is a value such that the molecular weight of the homopolymer indicates several hundred to 100,000. Homopolymer salts are N'a, K, NH4, etc.)

 The compounding amount of the copolymer (IV) or the homopolymer of the formula (V) is 1 to 8 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the detergent composition. Among these polycarboxylates, salts of acrylic acid-maleic acid copolymer and salts of polyacrylic acid (Na, K, respectively) are particularly excellent. The molecular weight is preferably from 1,000 to 80,000.

 Further, the following components can be blended as components other than the above.

Examples of the bleaching agent include sodium percarbonate, sodium perborate (preferably monohydrate) and sodium hydrogen peroxide adduct, and particularly preferred is sodium percarbonate. Since sodium percarbonate is easily decomposed by moisture or aluminoate, it is preferable to use a known technique, that is, a material coated with a boron compound, an alkali agent and / or a hydrophobic compound. Examples of the bleaching activator include tetraacetylethylenediamine, acetatequinbenzenesulfonate, JP-A-59-22999, JP-A-63-258447, and JP-A-6-316700. The organic peracid precursor described above, or a metal catalyst in which a transition metal is stabilized with a sequestering agent, and the like.

 Enzymes (enzymes that essentially perform the enzymatic action during the washing process) can be classified according to the reactivity of the enzymes as follows: hydrolases, oxidoreductases, lyases, transferases, and isomerases. Any of the above can be applied to the present invention. Particularly preferred are proteases, esterases, lipases, nucleases, cellulases, amylases and vectorases.

 Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promerin, carboxypeptidases A and B, aminopeptidase, aspargyl peptidase A and B, commercially available products such as Sabinaze, Alcalaze (Novo Industry Co., Ltd.), API21 (Showa Denko KK), Maxacal (Gistprocades Co., Ltd.), and the proteases described in JP-A-5-43892. There is K-14 or K-16. Specific examples of esterases include gastric lipase, buncreatic lipase, plant lipases, phospholipases, cholinesterases, and phospholipases.

 As a specific example of the lipase, a commercially available lipase such as ribolase (Novo Industries Co., Ltd.) can be used. As cellulase, commercially available cellulase (Novo Industry Co., Ltd.) and the cellulase described in claim 4 of JP-A-63-264699 can be used. As amylase, commercially available termamyl (Novo Industry Co., Ltd.) Etc. can be used.

Enzymes are separately granulated as stable particles and dry-dried into detergent fabric (particles). As the enzyme stabilizer, reducing agents (sodium sulfite, sodium hydrogen sulfite), calcium salts, magnesium salts, polyols, boron compounds and the like can be used. The reducing agent stabilizes the enzyme by removing oxidizing chlorine in tap water. Sulfite also has an effect as an antioxidant and has a function of suppressing discoloration of the detergent due to oxidation.

 Various bluing agents can also be added as needed. Examples of the bluing agent include substances described in JP-B-49-8005, JP-B-49-26286 or JP-B-53-45808.

 Examples of the caking inhibitor include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, finely divided silica, clay, magnesium oxide and the like. Note that a porous material such as finely divided silica can be used as a carrier for the nonionic surfactant. Clay (smectite-like clay) is also effective as a softening agent.

 Antioxidants include tert-butylhydroxytoluene, 4,4'-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2'-butylidenebis- (6-tert-butyl-14-methylphenol) And monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1′-bis (4-hydroxyphenyl) cyclohexane and the like.

 As fluorescent dyes, 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazo One or two or more of 4,4′-bis (triazo-1-yl-2-yl) stilbene derivatives and bis (triazinylamino) stilbene disulfonic acid derivatives are added to the composition in an amount of 0 to 1%. % By weight.

As the fragrance, a fragrance conventionally used in detergents, for example, a fragrance described in JP-A-63-101496 can be used. As the defoaming agent, a conventionally known technique can be used. For example, a silicone Z silica-based one may be mentioned, and an antifoaming composition produced by the method described in JP-A-3-101496 may be used. As another antifoaming agent, stone is effective when used in combination with a sulfonate-type or sulfate-type surfactant.

 As other components, citrate, ethylenediaminetetraacetate, and other known organic sequestering agents and color transfer inhibitors such as vinylpyrrolidone-based polymers can be blended.

 The cleaning composition of the present invention may be in any form such as liquid, powder, or lump, and the production method is not particularly limited, and a conventionally known method can be used. A preferred form of the composition of the present invention is a high-density powdered detergent composition. To increase the bulk density, for example, a method of spraying non-ionic surfactants onto spray-dried particles to increase the density or a method of increasing the density while directly absorbing non-ions into the powder component containing the oil-absorbing carrier are used. Examples thereof include JP-A-61-69897, JP-A-61-69899, JP-A-61-69900, JP-A-2-222498, JP-A-2-222499 and JP-A The methods described in JP-A-3-33199, JP-A-5-86400 and JP-A-5-209200 can be referred to. When a crystalline aluminosilicate is blended as the aluminosilicate, a small amount thereof may be added during granulation or immediately before the completion of granulation, in order to use it as a surface modifier for the granulated material. When a crystalline silicate is blended, it is preferable to add the crystalline silicate at the time of increasing the bulk density or to add the crystalline silicate by dry blending. When an alkali metal carbonate is blended, it may be added to the slurry, during granulation or in a dry blend.

 The alkylolamide-type surfactant represented by the general formula (I) may be added before or after the spray-drying step.

When the cleaning composition of the present invention is used as a high-density granular cleaning composition, the average particle size is 200 to 1000 m, particularly 200 to 600 m, in order to obtain preferable powder properties. Is desirable. Further, when the cleaning composition of the present invention is a high-density composition, the bulk density is

It is about 0.5 to 1.2 g / ci ³ , preferably about 0.6 to 1.0 g / cm ³ .

 The detergent composition of the present invention is used at a concentration suitable for each washing depending on washing methods such as washing machine washing and pickling washing, as well as the amount of clothes and water, the degree of dirt, and the use of machines. be able to. For example, in the case of washing in a washing machine, a washing concentration of 0.03 to 3% by weight can be used.

 ADVANTAGE OF THE INVENTION According to this invention, even if it wash | cleans on low temperature conditions, the detergent composition which shows a favorable oil-based soil wash can be obtained.

Example

 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1

 (1) Preparation of high-density granular detergent composition

 Sample No. 1 in Table 2 was prepared by the following method.

 1.0 kg of zeolite, 0.5 kg of AM, AS-1 2. Okg, 1.25 kg of sodium carbonate, 0.1 kg of PEG, 0.3 kg of FA, sodium sulfate and fluorescent dye (4,4'-bis (2-sulphate) used for balance A slurry having a water content of 50% by weight is prepared from 0.05 kg of phosphyryl-biphenyl salt), and the resulting powder is spray-dried. Then, 1.0 kg of zeolite, 1.5 kg of alkylolamide type surfactant (A-1) and 1.0 kg of silicate (II) were added and granulated. 30 kg before the end of granulation, 0.5 kg of zeolite was further added. The resulting particles and 0.1 kg of the enzyme were dry-mixed with a V blender to obtain a high-density granular detergent composition (average particle size: 521 m, bulk density: 786 g / U turtle).

Other detergent compositions having the sample numbers described in Table 2 were also prepared according to the above-mentioned scheme to prepare high-density granular detergent compositions having respective mixing ratios. <Detergency test>

 (Preparation of artificially stained cloth)

An artificially stained cloth having the following composition was attached to the cloth to prepare an artificially stained cloth. The artificial contaminated liquid was attached to the cloth using a gravure roll coater. The process of making the artificially contaminated cloth by attaching the artificially contaminated liquid to the cloth was performed with a gravure roll cell capacity of 58 cm ³ / m ² , an application speed of l. OmZmin, a drying speed of 100, and a drying time of 1 minute. The cloth used was a cotton gold cloth 2003 (manufactured by Tanito Shoten).

 (Composition of artificial contaminated liquid)

 Lauric acid 0.44% by weight

 Myristic acid 3.09% by weight

 Pentadecanoic acid 2.31% by weight

 0 Lumitic acid 6.18% by weight

 Heptadecanoic acid 0.44% by weight

 Stearic acid 1.57% by weight

 Oleic acid 7.75% by weight

 Trioleic acid 13.06% by weight

 ,. N-Hexadecyl lumitate 2.18% by weight

 6. 53% by weight

 Egg white lecithin liquid crystal 1.94% by weight

 Kanuma Red Clay 8. 11% by weight

 Carbon black 0.01% by weight

 Tap water / lance.

 (Cleaning conditions and evaluation method)

Five liters of the lOcm x lOcra artificially contaminated cloth prepared above were placed in one liter of the aqueous detergent solution for evaluation, and washed with a targometer at 100 rpm. The washing conditions are as follows, Cleaning conditions

 Washing time 10 minutes

 Detergent concentration Q.067%

 Water hardness 2 ° DH

 Water temperature 10 ° C

 Rinse in tap water for 5 minutes

 The detergency was measured by measuring the reflectance at 550nm of the original cloth before and after the cleaning and the contaminated cloth before and after the cleaning with a self-recording colorimeter (manufactured by Shimadzu Corporation). Was shown as detergency.

 Reflectance after cleaning-Reflectance before cleaning

 Cleaning rate (%) = xlOO

Original cloth reflectance-reflectance before cleaning

Table 2

(注）

(note)

 A—1: In formula (I), R CnH23, R2: H, 2 mole ratio of added product 100% by weight

• A-2: In formula (I), R CitH23, R2: Ratio of H, 2 mol added product 80% by weight

• A- 3: In the formula _{(I), RC tl H 23} , R 2: H, 2 mol adduct product ratio 60 wt%

• A-4: In formula (I), R CnH23, R ₂ : Ratio of H, 2 mol added product 55% by weight

• A—5: In formula (I), R 0: ^ 23 ^ 2: ratio of H, 2 mole addition product 42% by weight n of A5 (average addition mole number) = 1.7

 * However, A-2, 3, and 4 were prepared by appropriately mixing A-1 and A-5.

 AS-1: Alkyl sulfate sodium salt (coconut fatty acid composition)

LAS - 1: linear alkyl (C _{1 ()} -C ₁₃₎ benzenesulfonate Natoriumu salt Zeoraito (crystalline aluminosilicate): Composition _{Μ 2 0 · A1 2 0 3} · 2Si0 2 · 2H 2 0,

Average particle size 2 m, ion exchange capacity 290 CaCO ₃ mg / g, M is Na, K silicate (II): Composition Μ ₂₀ · 1.8Si02 ₂ · 0.02Μ'Ο (where Μ: Na, K, K /Na=0.03>

M '= Ca, Mg, g / Ca = 0.01) ^ Ion exchange capacity 290 CaCOs mg / g, Average particle size 30 / zm [Crystalline silicate represented by general formula (II)] Silicate (III): Composition Μ ₂ 0 · 2Si0 _2, ion exchange capacity of 224 CaC0 ₃ mg / g,

 Average particle size 30 μm [Crystalline silicate represented by the general formula (111)] AE-1: Nonionic surfactant, polyoxyethylene dodecyl ether

 (HLB = 15)

 FA: Sodium palmitate

 AM: Na salt of acrylic acid / maleic acid (7/3 molar ratio) copolymer,

 Average molecular weight 70,000

 PA: sodium polyacrylate, average molecular weight 8000

 Common components: PEG (polyethylene glycol with an average molecular weight of 7,000) 1%,

Enzyme CAPI-21H (manufactured by Showa Denko KK), Rebollaze 100T (Novo Nordisk), Celzym 0.1T (Novo Nordisk), Tamima Mill 60T (Novo Nordisk)

2: 1 _: 1: 1) 1%,

 0.5% of fluorescent dye,

 Glauber's salt, which was adjusted to 100% with Glauber's salt.

Example 2

 A cleaning composition having the composition shown in Table 3 was prepared according to Example 1 described above, and a cleaning power test was performed on sebum dirt and mud dirt. The symbols of the compositions in Table 3 have the same meanings as in Example 1. Sebum stains were evaluated using the same artificially stained cloth as in Example 1, and mud stains were evaluated using a mud stained cloth prepared as described below. The test method of the detergency is the same as in Example 1. However, the temperature of the washing water used was set to 20. Table 3 shows the results.

 (Preparation of mud stained cloth)

Kanuma gardening Akadama soil was dried at 120 ° C ± 5 for 4 hours, crushed, and dried to 150 mesh (120 am pass with 120 ± 5). Then, a cloth # 2023 is brought into contact with this solution, brushed to remove the dispersion, and to remove the excessively adhered dirt (Japanese Patent Laid-Open No. 55-26473).

Table 3

Example 3

 (1) Preparation of high-density granular detergent composition

 Sample No. 10 in Table 4 was prepared by the following method.

Zeolite 1.0 kg, LAS-2 0.5 kg, AM 0.5 kg, soda ash 0.75 kg, PEG 0.1 kg, fluorescent dye (4,4'-bis-bis (2-sulfostyryl) -biphenyl salt) 0.05 kg to water content 50% by weight The slurry is prepared by spray-drying, and the powder obtained is poured into a high speed mixer (portable tumbling granulator, Fukae Kogyo Co., Ltd.), and Zeolite 1.0 kg, alkylolamide (A0-1) Add 3.0 kg, 2.0 kg of silicate (II) and granulate, further add 0.5 kg of zeolite and granulate. Add 0.5 kg of zeolite and 0.5 kg of enzyme to the obtained particles. Was dry-mixed to obtain a high-density granular detergent composition (average particle size). 430 m, bulk density 780 g Z liter).

 With respect to other products of the present invention and comparative products shown in Tables 4 to 7, high-density granular detergent compositions were prepared according to the above-mentioned schemes with the respective mixing ratios.

 The porous silica compound of sample No. 26 was added to the high speed mixer, and zeolite was reduced accordingly.

 In the case of sample Nos. 25, 30, and 47, zeolite was not added before spray drying, but was used in appropriate steps for the subsequent steps.

 In sample No. 47, a porous silica compound was added to a high-speed mixer in the same manner as silicate or A0-1 and granulated, and a predetermined amount of AE-1 heated to 70 was added and granulated. Zeolite was added and granulated, and the remaining zeolite was further added and granulated to obtain a high-density granular detergent composition.

 (2) The obtained high-density granular detergent composition was subjected to a detergency test by the following method. The results are shown in Tables 4-7.

 Cleansing power test>

 (Preparation of artificially stained cloth)

The same artificially contaminated liquid as in Example 1 was attached to the cloth to prepare an artificially contaminated cloth. The artificial contaminant was attached to the cloth using a gravure roll coater. Process for manufacturing the artificially stained cloth artificially contaminated liquid is stick to a fabric, the cell capacitance 58 η ³ Ζπι ² of the gravure roll, the coating fabric speed l. Om / min., Drying rate 100 ° C, drying time 1 minute went. The cloth used was a cotton cloth 2003 (manufactured by Tanito Shoten).

 (Cleaning conditions and evaluation method)

 Five liters of the artificially contaminated cloth of 10 cm × 10 cm prepared above were placed in one liter of the aqueous cleaning agent solution for evaluation, and washed with a targometer at 100 rpm. The cleaning conditions are as follows <• Cleaning conditions

Washing time 10 minutes Detergent concentration 0.067%

 Water hardness 4 ° D H

 Water temperature 20

 Rinse in tap water for 5 minutes

The detergency was measured by measuring the reflectance at 550 mn of the original cloth before and after cleaning with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (%) was calculated by the formula shown in Example 1. The measured average value of the five sheets was shown as detergency.

Table 4

 1

 Sample ¾ ■ 15 16 17 18 1 19 20 21 22 23 a A 0-1 00- U 00.U 00- u J.U 0.υ 00 · U 00-U Composition A 0-2 0 0 0 0 0 0 0 0 0 distribution

 Minute A 0-3 0 0 0 0

0 0 0 0 0 b Zeolite 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0

 Porous silica compound 0 0 0 0 0 0 0 0 0 min

 Sodium carbonate 7 R 7 R 7 (7 c n n ϋ.d 0

 No. 2 sodium silicate U n u 7 ί c

 · Ό n n u

 1 Sodium polyphosphate TP HP TP

 n V nn υ 7 ς 4 nn min silicate (Π) f] o on nnu 1 nn on n on n on n u u u u silicate (III) nuow on n 1 n (ln Π u π n Ryoji interface Activator LAS ς-2

 Π n

 o. U u n

 U U U U U U

 of

 Other Noni Surfactant 0 0 0 0 0 0 0 0 0 origami—AM AM AM AM AM AM AM AM AM

5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Common components 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Total (%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 f / Phase washing ratio (%) 73.2 75.4 75.0 74.8 74.7 75.8 75.5 75.1 75.0

Table 5

Table 6

 1

 Sample number 1 O a A 0-1 30 0 30 0 35 0 oo 25 0 15 0? R fl? Nn n Composition A 0-2 u 'u n u n π u π u

 Min A 0-3 n n u n fl J. N v n n n n

 Zeolite 0 \ J · 0 u oy · u u-u

 Porous silica compound 0 0 0 0 0 0 0 0 0 min

 Sodium carbonate 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 c

 1 No. 2 sodium silicate n V n υ n υ n u 0 n n n y n u Sodium polyphosphate 0 0 0 0 0 0 0 0 0 Silicate (Π) 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 min

 Silicate (III) 0 0 0 0 0 0 0 0 0 Anion meta-activity 剂 FA LAS-LAS-2 So 5.0 0 0 0 0 0 0 5.0 10.0 Nonionic surfactant AE-2 AE-2 AE-2

 0 5.0 0 0 0 0 0 5.0 5.0 Ori Gomer AM AM AM AM AM AM AM AM AM

5.0 5.0 1.0 5.0 5.0 5.0 5.0 5.0 5.0 Common components 2.5 2.5 6.5 2.5 2.5 12.5 22.5 2.5 2.5 Total () 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Washing (%) 73.0 73.0 74.2 72.8 69.1 68.5 65.5 68.0 67.4

Table 7

(note)

 • AO-1: Polyoxyethylene (3 mol) dodecyl alkylolamide

 • AO-2: Polyoxyethylene (2 mol) dodecyl alkylamine

 • AO-3: polyoxyethylene (5 mol) dodecyl alkylamine

 • Polysilicide compound: Thixorex 25 (manufactured by Kofran Chemical Co.)

 • TP: Sodium tripolyphosphate

 • HP: Sodium phosphate

 • F A: Palmitic acid sodium salt

 • AE-2: polyoxyethylene (8.0 mol) dodecyl ether (HLB 13.1)

• LAS-2: straight chain alkyl (d ₂ ) benzenesulfonic acid sodium salt

• AS-2: Alkyl (Ct ₂ ) sulfate sodium salt

 (Note) Other than the above, the symbols of the compositions in Example 3 have the same meanings as in Example 1.

Example 4

 (1) Preparation of high-density granular detergent composition

 Sample No. 48 in Table 8 was prepared by the following method.

Zeolite 1.0 kg, LAS-2 0.5 kg, AM 0.5 kg, No. 2 sodium silicate 0.5 kg, soda ash 1.25 kg, PEG 0.1 kg, fluorescent dye (4,4'-bis- (2-sulfostyryl)) A slurry having a water content of 50% by weight was prepared from 0.05 kg and spray-dried, and the resulting powder was put into a high-speed mixer (stirring-rolling granulator, Fukae Kogyo Co., Ltd.), Aqueous solution of monoamide (A0-1) 3. Granulate by adding Okg (as AO-1), 1.0 kg of zeolite, 1.0 kg of silicate (II), and granulate by adding 0.5 kg of zeolite. The remaining particles were dry-mixed with 0.5 kg of zeolite and 0.1 kg of enzyme to obtain a high-density granular detergent composition (average particle size: 450, bulk density: 760 g / liter) (Other samples shown in Table 8) For the detergent compositions with the numbers, the high-density granular detergent compositions were prepared in accordance with the above-mentioned schemes with the respective proportions. It was. In sample No. 54, a porous silica compound high-speed mixer was granulated in the same manner as silicate and the like, a predetermined amount of AE-2 heated to 70 was added, and granulated, and zeolite was added. Then, the remaining zeolite was further added and granulated to obtain a high-density granular detergent composition.

(2) The resulting high-density granular detergent composition was subjected to a detergency test by the following method. _C The results are shown in Table 8. The symbol of the composition in Example 4 has the same meaning as in Example 3.

Detergency test>

 (Preparation of artificially stained cloth)

The same artificially contaminated liquid as in Example 1 was attached to the cloth to prepare an artificially contaminated cloth. The artificial contaminated liquid was attached to the cloth using a gravure roll. The process of applying the artificially contaminated liquid to the cloth to prepare the artificially contaminated cloth is performed with a gravure roll cell capacity of 58 η ³ η ² , a coating speed of 1.Om/niin., A drying speed of 100, and a drying time of 1 minute. Was. The cloth used was a cotton cloth 2003 (manufactured by Tanito Shoten).

 (Cleaning conditions and evaluation method)

 Washing was performed under the same washing conditions as in Example 3.

The detergency was measured by measuring the reflectance at 550 nm of the original cloth before and after cleaning with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (%) was calculated by the formula shown in Example 1. The measured average value of the five sheets was shown as detergency.

Eclectic 8

Claims

The scope of the claims  1. (a) An alkylolamide-type surfactant represented by the following general formula (I): 3 to 50% by weight RlCON —— (C2H4.) _N H R2 (Wherein, is an alkyl or alkenyl group having 8 to 20 carbon atoms, R ₂ is H or an alkyl or alkenyl group having 1 to 3 carbon atoms, and n is a number of 2 to 6.)  (b) 5-60% by weight of aluminosilicate  (c) Alkaline agent 5-60% by weight A high-density granular detergent composition having a bulk density of 0.5 to 1.2 gZml. 2. In the formula of the alkylolamide surfactant represented by the general formula (I), R ₂ is hydrogen, and is a linear or branched alkyl or alkenyl group having 7 to 19 carbon atoms. 2. The high-density granular detergent composition according to claim 1, wherein the average number of moles of addition n is larger than 1, and the ratio of the compound having the number of moles of addition 2 is 50% by weight or more.  3. The composition contains an anionic surfactant in an amount of 5 to 45% by weight, and the total amount of the surfactants including the alkyl amide type surfactant in the composition is 10 to 60% by weight. The cleaning composition according to 1.  4. The cleaning composition according to claim 1, comprising 1 to 40% by weight of a crystalline silicate represented by the following formula (II) and Z or (III). _{x (2 0) · y (} Si0 2) · z (Me m 0n) · w (H 2 0) (II) (In the formula, M represents an element of group la in the periodic table, and Me represents one or a combination of two or more elements selected from group Ila, group lib, group Ilia, group IVa or group VIII. , YZx = 0.5 to 2.6, ζ / χ = 0 to 01, 9, w = 0 to 20, n / m = 0.5 to It is 0. ] Μ ₂₀・ '' (SiO.- y'H ₂ 0 (III)  [In the formula, M represents an alkali metal, and x ′ = 1.5 to 2.6 and y ′ = O to 20. ]