JP2003119663A - Method for washing and detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for washing capable of effectively preventing the generation of a bad smell even in the case of drying under a normal temperature and a high humidity by taking a long time such as the case of drying washed clothes in a room, and a detergent composition for the same. SOLUTION: This method for washing capable of suppressing the generation of the bad smell is provided by making <=10 ppb total of low molecular fatty acids, aldehydes and ketones and <=1 ppb total of sulfur-containing organic compound and nitrogen-containing organic compounds generated from the fibers after washing by prescribed evaluation methods, and the detergent composition for the same is also provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laundry method and a detergent composition, and more particularly, to deteriorate and remove stains that metabolize bacteria to cause a bad odor, so that laundry clothes can be dried, for example. In particular, the present invention relates to a washing method and a detergent composition capable of preventing the generation of a bad odor even when dried for a long time at room temperature and high humidity.

[0002]

2. Description of the Related Art Conventionally, it has been known that a detergent composition is provided with an antibacterial effect and a bactericidal effect by blending an antibacterial component (antibacterial agent, bleaching agent and bleach activator). Also,
It has also been proposed to suppress a bad odor derived from bacteria (for example, the odor of freshly dried laundry) by antibacterial and bactericidal effects. For example, in Japanese Patent Laid-Open No. 9-194899, bacteria are decomposed to sebum stains. It has been proposed to suppress the offensive odor generated by a nonionic activator, an oil absorbing carrier and an antibacterial agent.

However, in the case of the above-mentioned proposal, although the growth of bacteria can be suppressed by antibacterial action and bactericidal action, it is not possible to remove dead bacteria and their bacterial components and stains which are nutrient sources of bacteria. Even if the fibers are washed with a known detergent having good detergency and the stains are sufficiently removed when observed with the naked eye, a bad odor often occurs. Under such circumstances, there has been a demand for a technique capable of sufficiently suppressing a bad odor, even when drying in a room where a bad odor is particularly likely to occur.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and even when laundry clothes are dried for a long period of time under room temperature and high humidity such as room drying and room drying. An object of the present invention is to provide a laundry method and a detergent composition that can effectively prevent the generation of a bad odor.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the stains causing the offensive odor are mainly sebum stains and / or protein stains,
It has been found that it is possible to prevent the generation of offensive odor by removing the stain by washing such that the specific offensive odor component generated from the fibers after washing in a predetermined evaluation method is less than a specific amount. It came to eggplant.

That is, the present invention is the laundry method and detergent composition of the following (1) to (4). (1) In the following evaluation method, the total amount of low molecular weight fatty acids, aldehydes and ketones generated from fibers is 10 p.
When laundering fibers having a total amount of sulfur-containing organic compounds and nitrogen-containing organic compounds of more than 1 ppb exceeding 1 ppb in excess of 1 pb in an aqueous liquid using a detergent composition, in the evaluation method, after washing, 10 ppb of low molecular weight fatty acids, aldehydes and ketones generated from textiles
Hereinafter, the method for washing fibers is characterized in that the low-molecular sulfur-containing organic compound and the nitrogen-containing organic compound are washed so that the total amount thereof is 1 ppb or less, thereby suppressing the generation of malodor when the fibers are dried. . (Evaluation Method) 1 g of fibers before washing or 1 g of fibers dried indoor after washing are put in a 25 mL vial and left at 40 ° C. for 30 minutes, and the components of the headspace are measured by GC-MS and GC-AED. . (2) In the following evaluation method, the total amount of low molecular weight fatty acids, aldehydes and ketones generated from fibers is 10 p.
When laundering fibers having a total amount of sulfur-containing organic compounds and nitrogen-containing organic compounds of more than 1 ppb exceeding 1 ppb in excess of 1 pb in an aqueous liquid using a detergent composition, in the evaluation method, after washing, 10pps of low molecular weight fatty acids, aldehydes and ketones generated from textiles
b or less, the fibers were washed so that the total amount of the low-molecular-weight sulfur-containing organic compound and the nitrogen-containing organic compound was 1 ppb or less, and the production of malodor from the fibers was suppressed when the fibers were dried. A detergent composition comprising: (Evaluation method) 1 g of fibers before washing or dried indoors after washing are put in a 25 mL vial and left at 40 ° C for 30 minutes, and the components of the headspace are measured by GC-MS and GC-AED. . (3) In the above (1), the detergent composition contains an anionic surfactant, a nonionic surfactant, and an enzyme having a lytic activity value of 80% or more and a casein decomposition specific activity of 90% or more. Or the detergent composition according to (2) above. (4) The detergent composition contains a bleaching agent and a protease, and further contains 4% by mass or more of any of anionic surfactants selected from linear alkylbenzene sulfonates, olefin sulfonates, and alkyl sulfates, and 5 soaps. The washing method according to (1) above or the detergent composition according to (2) above, which is contained in an amount of more than mass%.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The present invention, in the following evaluation method, the total amount of low molecular weight fatty acids, aldehydes and ketones generated from fibers exceeds 10 ppb, and / or the total amount of low molecular weight sulfur-containing organic compounds and nitrogen-containing organic compounds. 1
When laundering fibers exceeding ppb in an aqueous liquid using a detergent composition, in the evaluation method, a total of 10 ppb or less of low molecular weight fatty acids, aldehydes and ketones generated from the laundered fibers, Preferably, 7 ppb or less, low molecular weight sulfur-containing organic compounds and nitrogen-containing organic compounds are washed to a total of 1 ppb or less, preferably 0.7 ppb or less, so that the generation of malodor during the drying of the above fibers is prevented. A method for laundering textiles and a detergent composition for inhibiting. (Evaluation method) Fibers before washing or 1 g of fibers dried indoors are put in a 25 mL vial bottle and allowed to stand at 40 ° C for 30 minutes, and the components of the headspace are GC-MS and GC.
-Measured by AED.

The low molecular weight fatty acids, aldehydes and ketones have a molecular weight of 200 or less, preferably 16
Fatty acids of 0 or less, aldehydes and ketones.
Specifically, a fatty acid having 3 to 10 carbon atoms and 4 to 10 carbon atoms
And aliphatic aldehydes, aromatic genus having 5 to 10 carbon atoms, furan ring aldehydes, and ketones having 4 to 13 carbon atoms.

The low molecular weight sulfur-containing organic compounds and nitrogen-containing organic compounds are sulfur-containing organic compounds and nitrogen-containing compounds having a molecular weight of 150 or less, preferably 130 or less. Examples of the sulfur-containing organic compound include disulfides and trisulfides having 2 to 4 carbon atoms, and 1 to 1 carbon atoms.
3 thiol, specifically dimethyl disulfide,
Examples thereof include dimethyl trisulfide. Examples of the nitrogen-containing organic compound include amines having 3 to 8 carbon atoms, imines, pyridine, and pyrazine, and specific examples thereof include methylpyridine, dimethylpyridine, and dimethylpyrazine.

The amounts of the above-mentioned fatty acids, aldehydes, ketones, sulfur-containing organic compounds and nitrogen-containing compounds generated from the fibers are measured by the above-mentioned method, which will be described in more detail below. (A) Method for measuring the total amount of low-molecular-weight fatty acids, aldehydes, and ketones Fibers before washing or indoor dried fiber 1 g 25 m
Place it in a L vial and leave it at 40 ° C for 30 minutes, then use the SPME method (PDMS / DVB65μ
m) for solid phase adsorption, and GC-MS (column: HP-I)
NNOWAX, length 25 m × diameter 0.2 mm × stationary phase film thickness 0.2 μm, temperature increase: 35 ° C., hold for 5 minutes, then increase temperature at a rate of 10 ° C./minute, and when 250 ° C. is reached, 5 minutes Hold, carrier gas: helium) at the inlet of 250 ℃,
It is thermally desorbed for 5 minutes and measured by GC-MS. The peak detected at a retention time of 4 minutes to 25 minutes was quantified by decanal conversion and calculated as the concentration for 25 mL. The PDMS is polydimethylsiloxane, and the DVB is divinylbenzene porous polymer.

(B) Method for measuring the amount of low-molecular-weight sulfur-containing organic compound AED was used as a detector, and the peak was converted to dimethyldisulfide, and the concentration was calculated in the same manner as above. (C) Method for measuring amount of low-molecular-weight nitrogen-containing organic compound AED was used as a detector and the peak was converted into methylpyridine, and the same procedure as above was performed to calculate the concentration.

In the present invention, the total amount of low molecular weight fatty acids, aldehydes, and ketones generated from the washed fibers is 10 ppb or less, and the total amount of low molecular weight sulfur-containing organic compounds and nitrogen-containing organic compounds is 1 ppb or less. For such washing, particularly suitable washing methods and detergent compositions include the following (3) or the above (4).

(3) The detergent composition is an anionic surfactant,
The washing method according to (1) above, which comprises a nonionic surfactant and an enzyme having a bacteriolytic activity value of 80% or more and a casein decomposition specific activity of 90% or more, or the above (2). Detergent composition.

The above (3) is due to the synergistic effect of the anionic surfactant and the nonionic surfactant and the specific enzyme. The above (4) is the combination of the bleaching agent, the protease, the specific anionic surfactant and the soap. It is an invention based on effects. The above (3) will be described in detail below. In the above (3), the bacteriolytic activity value and the casein decomposition specific activity are determined by the following methods.

(D) Lysis activity value In a sample solution prepared by using ion-exchanged water to 1 ppm of enzyme (as enzyme protein) and 150 ppm of sodium α-sulfofatty acid (C16) methyl ester, Escherichia coli as a test bacterium was tested. ATCC8
739 was added so that the turbidity was about 1.0 at the OD600 value, and the turbidity was measured immediately after that (0 minute) and after holding at 37 ° C for 30 minutes, and the lytic activity value was calculated by the following formula. . Lytic activity value (%) = (0 minute turbidity-30 minutes turbidity) / 0 minute turbidity x 100

(E) Milk casein (manufactured by Merck) having a specific activity of decomposing casein of 0.6% by mass, and 10
0.3 pp of enzyme was added to the reaction solution containing mM sodium borate.
m (as enzyme protein) and 0ppm sodium α-sulfofatty acid (C16) methyl ester as activator
Alternatively, the sample solution prepared so as to have a concentration of 300 ppm is 40 ° C.
After the reaction was carried out for 1 hour, 3.2 mL of a reaction completed liquid (containing 0.11 M trichloroacetic acid, 0.22 M sodium acetate and 0.33 M acetic acid) was added, and the mixture was allowed to stand at 35 ° C. for 10 minutes, and then filtered (Advantech, No. 131 filter paper), the absorbance of the filtrate is measured at 275 nm to determine the relative activity value of the enzyme, and the casein decomposition specific activity is calculated by the following formula. Casein decomposition specific activity (%) = (activity value with active agent ÷ activity value without active agent) x 100

The enzyme used in the present invention (3) has an activity-inhibiting effect on bacteria that adhere to fibers and the like and cause an offensive odor, and also has a soil-decomposing effect, such as skin-resident bacteria. Bacteria such as Staphylococcus epidermidis and Escherichia coli are presumed to be the above-mentioned causative bacteria. This enzyme has both a bactericidal activity inhibiting action and a soil decomposing action, and when the following bacteriolytic activity value and casein decomposition specific activity are determined as indicators of these actions, the bacteriolytic activity value is 80% or more, preferably It is desirable to use an enzyme having an enzyme activity of 85% or more and a casein decomposition specific activity of 90% or more.

Examples of the enzyme having the above-mentioned properties include proteases derived from an alkalophilic strain of the genus BACILLUS, and these can be used alone or in combination of two or more. These enzymes are commercially available as enzyme granules, and examples of such enzyme granules include “Sabinase 12T”, “Cannase 24TK”, “Everase 8T” (both manufactured by Novozymes), “Plafect 4000E”.
(Manufactured by Genencore) and the like are commercially available.

The blending amount of the above-mentioned enzyme in the present invention is not particularly limited and may be appropriately selected depending on the kind thereof, but usually 0.001 to 0 as enzyme protein relative to the total amount of the composition. 0.3%, preferably 0.003 to 0.2%, more preferably 0.005 to
It is preferable to add 0.1%. In addition, the above-mentioned commercially available enzyme granules are usually added in an amount of 0.3 to 10%, preferably 0.5 to 7%, and more preferably 1 to 5% with respect to the entire composition, It is suitable.
If the amount of the enzyme is too small, it may be difficult to obtain the desired malodor suppressing effect of the present invention, and if the amount is too large, the effect cannot be enhanced by further blending.
It may be uneconomical.

The anionic surfactant and nonionic surfactant used in the present invention (3) are not particularly limited in kind as long as they can be blended in the detergent composition. Examples of such anionic surfactants include linear alkylbenzene sulfonates, α-olefin sulfonates, sulfo fatty acid lower alkyl ester salts, alkyl sulfates, soaps and the like.

Among these, straight chain alkylbenzene sulfonates having 8 to 18 carbon atoms and α-containing 10 to 20 carbon atoms.
An olefin sulfonate, a sulfo fatty acid lower alkyl (C1 to C3) ester salt having 13 to 19 carbon atoms, a long-chain alkyl sulfate having 10 to 20 carbon atoms, and the like can be preferably used. As these salts, alkali metal salts such as sodium salts and potassium salts, amine salts, ammonium salts and the like can be used. As the soap, for example, an alkali salt such as a sodium salt of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms or the like can be preferably used.

Examples of nonionic surfactants include polyoxyalkylene alkyl ethers and fatty acid polyoxyalkylene alkyl ethers. These can be used alone or in combination of two or more. Among these, when the polyoxyalkylene alkyl ether is represented by, for example, R-O- (AO) m-H, R represents a linear or branched alkyl group or alkenyl group having 12 to 15 carbon atoms, and AO represents One or two such as an oxyethylene group (EO) and an oxypropylene group (PO) having preferably 1 to 4 carbon atoms, and more preferably 2 or 3 carbon atoms.
It shows one or more oxyalkylene groups, and the average number of moles of addition of AO is m (when two or more oxyalkylene groups are contained,
A polyoxyalkylene alkyl ether having a total average added mole number) of 3 to 30 is preferably used. As the fatty acid polyoxyalkylene alkyl ether, when represented by R1-COO- (AO) m-R2, R1 is a linear or branched C7-21, preferably 11-17 alkyl or alkenyl group, R2 Represents a linear or branched alkyl group having 1 to 4 carbon atoms, preferably 1 and AO is preferably an oxyethylene group (EO) or oxypropylene group (PO) having 1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms. ), Etc., showing one or more kinds of oxyalkylene groups, and the average number of addition moles of AO is m (in the case of containing two or more kinds of oxyalkylene groups, the total number of addition moles).
Is preferably 3 to 30, more preferably EO and m is 5 to
A fatty acid polyoxyalkylene alkyl ether having 30 or the like is preferably used.

The amount of the anionic surfactant blended in the detergent composition of the present invention is not particularly limited,
It can be appropriately selected depending on its type, etc., but is usually preferably 5 to 90% (mass%, the same applies hereinafter), and is preferably 5 to 50% in the case of detergents such as powder, granules, tablets, briquettes and sheets. More preferably 10-4
0%, preferably 10 to 50 for liquid detergents
%, More preferably 20 to 40%.

The content of the nonionic surfactant is usually 2 to 50%, and preferably 2 to 30%, more preferably 3 to 20% in the case of detergents such as powder, granules and tablets. , In the case of liquid detergent, preferably 3 to
It is 40%, more preferably 5 to 30%.

Next, the above (4) will be described in detail.
In the above (4), the detergent composition contains a bleaching agent and a protease, and further contains 4% by mass or more of an anionic surfactant selected from linear alkylbenzene sulfonate, olefin sulfonate, and alkyl sulfate. The laundry method according to (1) or the detergent composition according to (2), which contains soap in an amount of more than 5% by mass.

The bleaching agent used in the above (4) is preferably an oxygen-based bleaching agent, for example, a peroxide such as percarbonate or perborate, specifically, percarbonate. Examples thereof include sodium and sodium perborate. Particularly, percarbonate and perborate coated with boric acid, borate, silicate and a mixture thereof are preferable. As the bleaching agent, it is preferable to use a bleaching activator together with the peroxide.

As the bleach activator, an organic peracid precursor,
Examples include metal ions and metal ion complex catalysts. The organic peracid precursor is composed of a fatty acid and a leaving group, and as the leaving group, there are phenol, imide, sugar and the like, and examples thereof include alkanoyloxybenzenecarboxylic acid / salt having 8 to 18 carbon atoms and 8 carbon atoms. ~ 18 alkanoyloxybenzenesulfonic acid / salt, specifically, C8-12 alkanoyloxybenzoic acid / salt, C8-12 alkanoyloxybenzenesulfonic acid / salt and the like are preferably used. It As the metal ions, iron, copper, cobalt,
Examples of the metal ion complex catalyst include chromium and the like. Examples of the metal ion complex catalyst include manganese, iron, copper, cobalt, molybdenum for the metal portion, amine compounds such as aromatic amine and cyclic amine for the complex portion, Schiff base, porphyrin, condensed imidazole, and the like.

In the case of detergents such as powder, granules and tablets,
The bleach activator is preferably blended as a granulated product together with a binder and a surfactant. The blending amount of the bleaching agent is preferably 1 to 10 for the oxygen-based bleaching agent.
%, More preferably 1 to 5%, bleach activator is preferably 0.1 to 5%, more preferably 0.5 to 3%.

The protease of (4) above is the same as that of (3) above.
In addition to the protease used in 1., a protease that decomposes protein stains can be used. Particularly preferred is the protease used in (3) above.

The amount of the above-mentioned protease added is preferably 0.001 to 0.3%, preferably 0.003 to 0.2%, more preferably 0.003 as enzyme protein.
It is preferable to add 5 to 0.1%. In addition, the above-mentioned commercially available enzyme granules are usually added in an amount of 0.3 to 10%, preferably 0.5 to 7%, and more preferably 1 to 5% with respect to the entire composition, It is suitable. If the amount of the enzyme is too small, it may be difficult to obtain the desired malodor suppressing effect of the present invention. If the amount is too large, the effect cannot be enhanced by further blending, which is uneconomical. May be.

Any of the anionic surfactants selected from the linear alkylbenzene sulfonates, olefin sulfonates, and alkyl sulfates used in the above (4) is 4
% Or more, preferably 5 to 20%, a total of 4 to 30% is suitable, and the soap exceeds 5%, preferably 6 to 15%.
% Is preferable.

The linear alkylbenzene sulfonate, olefin sulfonate, and alkyl sulfate preferably include linear alkylbenzene sulfonate having 8 to 18 carbon atoms, α-olefin sulfonate having 10 to 20 carbon atoms, A sulfofatty acid lower alkyl (C1 to C3) ester salt having 13 to 19 carbon atoms, a long chain alkyl sulfate having 10 to 20 carbon atoms, and the like can be preferably used. As these salts, alkali metal salts such as sodium salts and potassium salts, amine salts, ammonium salts and the like can be used. Further, as the soap, for example, carbon number 12 to 2
2, preferably, sodium salts such as saturated or unsaturated fatty acids having 12 to 18 carbon atoms, alkali metal salts such as potassium salts, amine salts, ammonium salts and the like can be preferably used.

The detergent composition of the present invention may contain, in addition to the above-mentioned essential components, various components which are usually contained in a detergent composition within a range that does not impair the effects of the present invention. Sodium, potassium carbonate, sodium silicate, monoethanolamine, diethanolamine, etc., calcium scavenger (A type zeolite, P type zeolite, acrylic acid maleic acid copolymer, polyacrylic acid / salt, layered silicate, citric acid) Etc.), enzyme granules other than the above (amylase, lipase, cellulase, pectinase, etc.), enzyme stabilizers (sodium sulfite, etc.),
A fluorescent agent, a fragrance, a solvent (polyethylene glycol, alcohol, etc.), a hydrotrope agent and the like can be added in a usual dose within a range that does not impair the effects of the present invention.

Especially when the detergent composition of the present invention is used as a detergent such as powder, granules, tablets, briquettes, sheets, etc., a large amount of the above-mentioned alkaline agent can be blended, and it is effective for removing the substance causing an offensive odor. ,preferable.

[0035]

EFFECTS OF THE INVENTION According to the present invention, even when laundry clothes are dried for a long time at room temperature and high humidity, such as indoor drying, by decomposing and removing stains that cause an offensive odor during washing. It is possible to prevent the generation of bad odor.

[0036]

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

[0037]

Examples 1-4, Comparative Example 1 Table 1 prepared by the following method
Using the detergent composition having the composition shown in (1), the fibers were washed and dried according to the following washing method, and then the odor of the fibers was sniffed, and the effect of suppressing the generation of malodor was evaluated according to the following odor sensory evaluation criteria. In addition, the total amount of low molecular weight fatty acids, aldehydes, and ketones, and the total amount of low molecular weight sulfur-containing organic compounds and nitrogen-containing organic compounds are determined by the following method using a part of the fibers before and after washing. The odor was evaluated according to the following odor component amount evaluation criteria. The results are shown together in Table 1. Fibers before washing (wearing a new 100% cotton T-shirt for about 1 day in normal life)
The total amount of low molecular weight fatty acids, aldehydes, and ketones was about 20 ppb, and the total amount of low molecular weight sulfur-containing organic compounds and nitrogen-containing organic compounds was about 3 ppb.

(1) Method for preparing detergent composition Each of the detergent compositions shown in Table 1 except for the nonionic surfactant, a part of zeolite, enzyme granules, perfume, sodium percarbonate, and bleach activator. An aqueous detergent slurry having a solid content of 40% by mass is prepared by using the components, and this is prepared by using a countercurrent type drying tower.
Spray drying was performed at a temperature of 70 ° C. to obtain a dry powder having a water content of 5% by mass. As the zeolite for the detergent slurry, fine powder type A zeolite (Shilton B, manufactured by Mizusawa Chemical Co., Ltd.) was used. A non-ionic surfactant or P was added to a biaxial continuous kneader (KRC Kneader # 2 type manufactured by Kurimoto) that was kept warm at 40 ° C.
A kneaded product was obtained by adding it together with EG and water for adjusting the water content.
Then, this kneaded product is extruded and cut into 1 to 2 cm square dice, and granules A type zeolite (average particle size 200 μm
m: manufactured by Cosmo Co., Ltd.) and crushed and granulated. Rotation speed of 150 using a crusher (Okada Seiko, speed mill ND-10 type)
A 2 mm aperture screen was used at 0 rpm. A small amount of finely divided A type zeolite (silton B,
Mizusawa Chemical Co., Ltd.), and then the average particle size was adjusted to 550 μm. Further, an enzyme granulated product, a fragrance composition, and Na percarbonate and a bleach activator depending on the composition were mixed to obtain a high bulk density granular detergent composition.

(2) Washing method After wearing 10 new 100% cotton T-shirts for about 1 day in normal life, fully automatic washing machine (NA-F manufactured by Matsushita Electric Industrial Co., Ltd.)
70AP), tap water with a temperature of about 20 ° C. and a hardness of about 3 ° DH was poured, and washing was performed on a standard course. The amount of detergent added was in accordance with the detergent amount display on the washing machine. After dehydration, dry in a room with room temperature of about 25 ° C and humidity of about 70% RH.
It was dried for 8 hours.

(3) Total amount of low-molecular-weight fatty acids, aldehydes, and ketones 25 mL of fibers before washing or 1 g of indoor dried fibers
In a vial and left at 40 ° C. for 30 minutes, and the headspace is SPME method (PDMS / DVB 65 μm)
Adsorbed on solid phase at GC-MS (column: HP-INN
OWAX, length 25 m × diameter 0.2 mm × stationary phase film thickness 0.2 μm, temperature increase 35 ° C., 5 minutes → 10 ° C./min→250
℃, 5 minutes, 25 at the inlet of carrier gas: helium)
Thermal desorption is performed at 0 ° C. for 5 minutes, and measurement is performed by GC-MS.
The peak detected at a retention time of 4 minutes to 25 minutes was quantified by decanal conversion and calculated as the concentration for 25 mL.

(4) The concentration was calculated in the same manner as above except that AED was used as a detector for the amount of low molecular sulfur-containing organic compound and the peak was converted to dimethyldisulfide. (5) The concentration was calculated by performing the same operation as above except that AED was used as a detector for the amount of low-molecular nitrogen-containing organic compounds and the peak was converted with methylpyridine.

(6) Odor sensory evaluation criteria ◎: No offensive odor ○: Almost no offensive odor △: Slight odor is felt ×: A foul odor is felt Average of 5 evaluators

(7) Odor component amount evaluation criteria <Low molecular weight fatty acids, aldehydes and ketones:
Indicated below as fatty acids and the like> ◎: Total amount is 5 ppb or less ○: Total amount is more than 5 ppb, 7 ppb or less Δ: Total amount is more than 7 ppb, 10 ppb or less ×: Total amount is more than 10 ppb <Low molecular sulfur content Organic compounds, nitrogen-containing organic compounds: hereinafter referred to as sulfur compounds and the like> ◎: Total amount is 0.5 ppb or less ○: Total amount is more than 0.5 ppb, 0.7 ppb or less Δ: Total amount is more than 0.7 ppb, 1 ppb or less ×: Total amount is more than 1 ppb

(8) Enzyme lytic activity and casein degrading activity Table 2 shows the lytic activity value and casein degrading activity of the enzyme of the present invention contained in the specific enzyme granules used in the examples. The test amount of each of the enzyme granules was adjusted so that the lytic activity value was 100 ppm and the casein decomposition specific activity was 30 ppm.

The components used in the examples and comparative examples are
It is as follows. LAS-Na: straight-chain alkyl (carbon number 10-14) sodium benzenesulfonate (made by Lion) LAS-K: straight-chain alkyl (carbon number 10-14) potassium benzenesulfonate (made by Lion) α-SF-Na: Sodium salt of α-sulfofatty acid methyl ester of C12-18 fatty acid (made by Lion) Soap: C12-18 fatty acid (unsaturation 60%)
Sodium salt (manufactured by Lion) AOS-Na: α having an alkyl group having 14 to 18 carbon atoms
-Sodium olefin sulfonate (manufactured by Lion) AEt1: average 15 mol of ethylene oxide of DIAdol 13 (manufactured by Mitsubishi Chemical) adduct (manufactured by Lion Chemical) AEt2: average of 8 mol of ethylene oxide of straight-chain alcohol (having 12 to 14 carbon atoms) Adduct (Lion Chemical Co., Ltd.) AEs: ethylene oxide average 15 moles of C12-18 fatty acid methyl ester Adduct (Lion Chemical Co., Ltd.) AEP: diadol 13 (Mitsubishi Chemical Corporation) ethylene oxide average 15 moles and propylene oxide average 3 mol adduct (Lion Chemical Co., Ltd.) Zeolite: Type A zeolite (Mizusawa Chemical Co., Ltd. Shilton B and Cosmo Granules) AA / MA copolymer salt: Acrylic acid / maleic acid sodium salt, product Name Sokaran CP7 (manufactured by BASF) Na polyacrylate: Sodium polyacrylate Nippon Pure Chemical) Na Carbonate: Sodium Carbonate (Asahi Glass) Carbonate K: Potassium Carbonate (Asahi Glass) Na Silicate: JIS No. 1 Sodium Silicate (Nippon Kagaku) Na Sulfate: Neutral Anhydrous Glauber (Nippon Kagaku) Chloride Na: sodium chloride (reagent) sodium sulfite Na: sodium sulfite (manufactured by Mitsui Chemicals, Inc., anhydrous sodium sulfite) Fluorescent agent CBS: Chinopearl CBS-X (manufactured by Ciba Specialty Chemicals) Fluorescent agent AMS: Chinopearl AMS-GX ( Ciba Specialty Chemicals Co., Ltd.) Enzyme Granules Lipase: Trade name Lipolase Ultra (Novozymes Co.) Enzyme Granules Amylase: Trade name Termamyl (Novozymes Co.) Enzyme Granules Cellulase: Trade name Cellzyme (Novozymes Co.) Na) Percarbonate: coated sodium percarbonate (Mitsubishi Gas Chemical S CD) Bleach activator OBC: Extruded Ohmics EM-6 type manufactured by Hosokawa Micron Co., Ltd., and 4-decanoyloxybenzoic acid and polyethylene glycol (PEG) # 6000 (manufactured by Lion) which are bleach activators. C14 alpha olefin sulfonate sodium powder product (Liporan P
B-800 (manufactured by Lion) was mixed in a mass ratio of 70/25/5, charged, and kneaded and extruded to obtain a noodle-shaped extruded product having a diameter of 0.8 mmφ. This extruded product (60 ° C.) was introduced from the same direction as the kneaded extruded granulated product was introduced by a Hitzokawa Micron Fitzmill DKA-3 model, and 5% by mass of A-type zeolite powder was also used as an auxiliary agent. A bleaching activator granule having an average particle size of 700 μm obtained by supplying and pulverizing. Bleach activator OBS: Bleach activator granules granulated in the same manner as above using sodium dodecanoyloxybenzenesulfonate as a bleach activator. Fragrance composition A to D: Japanese Patent Application No. 2000-346626 Table 1
The composition according to 1 to 18.

[0046]

[Table 1]

[0047]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 3/386 C11D 3/386 3/395 3/395 10/02 10/02 D06H 3/00 D06H 3 / 00 F term (reference) 3B154 AA02 AB20 BA53 BD20 BF12 BF30 CA06 CA21 DA28 4H003 AB03 AB15 AB19 AB21 AB27 AB44 AC08 AC12 AC23 DA01 EA12 EA15 EA16 EA19 EA28 EB09 EB22 EB30 EB32 EC01 EC02 EC03 ED02 FA34 FA43 FA26 FA26

Claims (4)

[Claims] 1. In the following evaluation method, the total amount of low molecular weight fatty acids, aldehydes and ketones generated from fibers exceeds 10 ppb, and / or the low molecular weight sulfur-containing organic compounds and nitrogen-containing organic compounds are When laundering a total of fibers exceeding 1 ppb in an aqueous liquid using a detergent composition, the total amount of low molecular weight fatty acids, aldehydes and ketones generated from the laundered fibers is 1 in the evaluation method.
Laundry of fibers characterized by suppressing the generation of malodor during drying of the above fibers by washing so that the total amount of the sulfur-containing organic compound and the nitrogen-containing organic compound having a low molecular weight of 0 ppb or less becomes 1 ppb or less in total. Method. (Evaluation Method) 1 g of fibers before washing or 1 g of fibers dried indoor after washing are put in a 25 mL vial and left at 40 ° C. for 30 minutes, and the components of the headspace are measured by GC-MS and GC-AED. . 2. In the following evaluation method, the total amount of low molecular weight fatty acids, aldehydes and ketones generated from fibers exceeds 10 ppb, and / or the low molecular weight sulfur-containing organic compounds and nitrogen-containing organic compounds are When laundering fibers exceeding 1 ppb in total in an aqueous liquid using a detergent composition, in the evaluation method, a total of 10 ppb of low molecular weight fatty acids, aldehydes and ketones generated from the laundered fibers are used. Hereinafter, the fibers were washed so that the total amount of the low-molecular-weight sulfur-containing organic compound and the nitrogen-containing organic compound was 1 ppb or less, and the suppression of the generation of malodor from the fibers when the fibers were dried was appealed. A characteristic detergent composition. (Evaluation Method) 1 g of fibers before washing or 1 g of fibers dried indoor after washing are put in a 25 mL vial and left at 40 ° C. for 30 minutes, and the components of the headspace are measured by GC-MS and GC-AED. . 3. A detergent composition comprising an anionic surfactant, a nonionic surfactant, and an enzyme having a bacteriolytic activity value of 80% or more and a casein decomposition specific activity of 90% or more. The washing method according to claim 2 or the detergent composition according to claim 2. 4. The detergent composition contains a bleaching agent and a protease, and further contains 4 mass% or more of an anionic surfactant selected from linear alkylbenzene sulfonates, olefin sulfonates and alkyl sulfates, and soap. The washing method according to claim 1 or the detergent composition according to claim 2, which comprises 5% by mass or more.