JP2849041B2 - Detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition containing methylcellulose ether for effectively releasing both mud stains and oil stains adhered to polyester fibers in water at 30 ° C. or lower.

[0002]

BACKGROUND OF THE INVENTION Methylcellulose ethers or detergent compositions or conditioning compositions containing methylcellulose ether are disclosed in U.S. Pat. Nos. 4,000,003 and 4,048,433.
Nos. 4,100,904, 4,136,038, 4,564,463, 4,444,881 and 47.
No. 70666, British Patent No. 1498520 and Japanese Patent Application Laid-Open No. 51-142007, it is known that methylcellulose ether has a soil release effect. However, when washing contaminated polyester fibers in washing water of 30 ° C. or less, high molecular weight methylcellulose releases oily dirt well, but it cannot be said that muddy dirt is sufficiently released, while low molecular weight methylcellulose is Although mud stains can be released, the ability to release oil stains is not sufficient.

[0003] The present invention selectively releases both oil stains and mud stains attached to polyester fibers very well simultaneously with washing water at 30 ° C or less, and has excellent polyester fiber washing power. The present invention relates to a detergent composition containing methylcellulose having a specific viscosity and a specific degree of methylalkyl substitution (methyl DS).

[0004]

That is, the present invention provides (i) 2
A solution having a viscosity of 80 to 120 centipoise (cps) measured at a temperature of 20 ° C. as a weight% aqueous solution and having an average degree of methyl substitution per anhydroglucose (methyl DS).
0.05 to 2% by weight of methylcellulose ether having a surfactant of from about 1.6 to about 2.3, (ii) 25 to 65% by weight of detergent surfactant, (iii) 0 to 20% by weight of bleaching component, and (iv) builder And 30 to 70% by weight of an alkaline substance for use in cleaning polyester fibers.

[0005] The methyl cellulose ether preferably has the following formula:

[0006]

Embedded image (Wherein R represents a hydrogen atom or a methyl group, each R may be the same or different, n represents the degree of polymerization, and the solution viscosity measured at a temperature of 20 ° C. as a 2% by weight aqueous solution is 80%). ~ 120 centipoise (cps).)

The methylcellulose ether used in the present invention has a solution viscosity of 80 to 120 centipoise (cps) measured at a temperature of 20 ° C. as a 2% by weight aqueous solution.
Preferably from 90 to 110 centipoise (cps) and having an average degree of methyl substitution per anhydroglucose (methyl DS) of from about 1.6 to about 2.3, preferably from about 1.7 to about 1.9; More preferably, about 1.8 is used. Such methyl cellulose ether is available, for example, as Metrolose SM100 (manufactured by Shin-Etsu Chemical Co., Ltd.).

When the solution viscosity is lower than 80 cps, it becomes difficult to release oil stains, and when it is higher than 120 cps, it becomes difficult to release mud stains.

If the average degree of methyl substitution is less than about 1.6, the methyl cellulose ether becomes difficult to dissolve in water and organic solvents such as surfactants, and it becomes difficult to release mud stains. When it is larger than 3, the methylcellulose ether becomes difficult to dissolve in water.

[0010] Incidentally, the collection of polymer papers, vol. 39. No. 4
When the viscosity is converted into the molecular weight by the method described in pp. 293-298, April 1982, the solution viscosity measured at 20 ° C. as a 2% by weight aqueous solution at 80 ° C. is 80 to 120 centipoise (cps), preferably 90 to 110 centipoise. Methyl cellulose of (cps) generally has a molecular weight of about 1
It corresponds to about 10,000 to about 150,000, preferably about 110,000 to about 140,000 methylcellulose ethers.

The above methyl cellulose ether is heated at 30 ° C.
At higher temperatures, the solubility is reduced, so that the detergent composition of the present invention is desirably used in washing water at a temperature of 30 ° C. or lower.

The detergent surfactant constituting the present invention is selected from an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant and a mixture thereof. The anionic surfactant, secondary C ₁₀ -C ₁₈ alcohol sulfates, linear C ₁₀ -C ₁₈ alkyl benzene sulfonates, alkyl sulfates and alkyl ethoxy sulfates,, alpha-sulfo fatty acid ester salts, fatty acid salts (soaps) and Olefin sulfonates can be mentioned. The nonionic surfactant, C ₁₀ ~ consisting of ethylene oxide is added alcohol
C ₁₆ alcohol ethoxylate, nonylphenol ethoxylate, propylene oxide and ethylene oxide is addition of one alcohol adduct can be fatty acid alkanolamides, sucrose fatty acid esters, alkyl amine oxides and polyhydroxy fatty acid amides exemplified. The detergent surfactant constituting the present invention can also be selected from the description in WO 9218594 (herein incorporated by reference).

As the detergent surfactant constituting the present invention, a mixture of an anionic surfactant and a nonionic surfactant in a weight ratio of 50:50 to 95: 5 is desirable. Among them, the anionic surfactant is preferable. Is more preferably a mixture of linear alkylbenzene sulfonate and alkyl sulfate in a weight ratio of 1:99 to 80:20. or,
The detergent surfactant constituting the present invention is a mixture of an anionic surfactant, a nonionic surfactant and a cationic surfactant, wherein the content of the cationic surfactant is 5% by weight in the mixture. The following are also desirable.

[0014] Bleaching components can optionally be used in the detergent compositions of the present invention. Bleaching ingredients, ^- OOH group source, e.g., sodium monohydrate perborate can be an over sodium tetrahydrate and sodium percarbonate borate.
Sodium percarbonate (2Na ₂ CO ₃ .3H ₂ O ₂ )
It is preferable because it has a dual function of both the HOOH source and the sodium carbonate source. Another useful bleaching component is the formula

[0015]

Embedded image (Wherein R is about 5 to 12 carbon atoms, preferably about 6 carbon atoms)
~ 9 linear or branched alkyl chains, preferably at least one alkyl group is attached to the second or third carbon atom counting from the carbonyl group and Q represents sodium or potassium) Bleaching precursors, for example, nonanoyloxybenzenesulfonate. The bleaching precursor is sodium perborate monohydrate, sodium perborate 4 to produce peracid in the washing solution.
Used in combination with the OOH radical source ^- hydrates, such as sodium percarbonate.

Another bleaching component is the peracid itself, for example of the formula CH ₃ (CH ₂ ) _w —NH—CO— (CH ₂ ) _z CO ₃
H wherein z is 2 to 4 and w is 4 to 10 (compounds of the latter formula wherein z is 4 and w is 8 are represented by N
APAA). The bleaching component contains, as a bleaching component stabilizer, a chelating agent for polyaminocarboxylic acid or polyaminocarboxylate, for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and ethylenediaminedisuccinic acid, and salts thereof with a water-soluble alkali metal. it can.

Builders and alkaline substances that can be used in the detergent compositions of the present invention are, for example, crystalline layered sodium silicate, phosphate and non-phosphate calcium ion scavenging builders, dispersants, and alkaline builders.

The crystalline layered sodium silicate, preferably the following formula _{NaMSi x O 2x + 1 · yH} 2 O ( wherein, M represents sodium or hydrogen, x is 1.
9 to 4, and y is 0 to 20).

Such a crystalline layered sodium silicate is disclosed in Japanese Patent Application Laid-Open Nos.
No. 178398. It is, for example, N
is available as SKS-6 having a chemical formula of a ₂ Si ₂ O ₅ (manufactured by Hoechst AG). Phosphate calcium ion sequestering builders can include sodium tripolyphosphate and sodium pyrophosphate as well as organic phosphonates and aminoalkylene poly (alkylene phosphonates). Organic phosphonates and aminoalkylene poly (alkylene phosphonates) include the alkali metal ethane 1-hydroxydiphosphonate, nitrilotrimethylene phosphonate, ethylenediaminetetramethylenephosphonate and diethylenetriaminepentamethylenephosphonate, Are less preferred when minimization of phosphorus compounds in the composition is desired. Non-phosphate calcium ion sequestering builders include alkali metal aluminosilicates, monomeric polycarboxylates, homopolymer or copolymer polycarboxylic acids or salts thereof (polycarboxylic acids are separated from each other by up to two carbon atoms). (Including at least two carboxyl groups separated), carbonates, silicates, citric acid and mixtures of any of the foregoing. Although a wide range of aluminosilicate ion exchange materials can be used, preferred sodium aluminosilicate zeolites have the unit cell formula Na _r [(AlO ₂ ) _r (SiO ₂ ) _s ] _t H ₂ O where r and s are at least 6 And the molar ratio of r to s is 1.0 to 0.5, and t is at least 5, preferably 7.5 to 276, more preferably 10 to 264). The aluminosilicate material is in a hydrated form and preferably crystalline, with 10% of water in bound form.
It contains 28%, more preferably 18% to 22%. The aluminosilicate ion exchange material has a particle size of 0.1 to
It is further characterized by 10 μm, preferably 0.2-4 μm. As used herein, the term "particle size" refers to the average particle size of a given ion exchange material as measured by conventional analytical techniques, e.g., microscopy utilizing a scanning electron microscope, or by a laser granulometer. . The aluminosilicate ion exchange material is calculated as CaCO
₃ Water hardness at least 200 mg equivalent / g of aluminosilicate and is further characterized by a calcium ion exchange capacity generally ranging from 300 mgeq / g to 352 mgeq / g. The aluminosilicate ion exchange material is aluminosilicate (anhydrous basis) CaCO ₃ at least 130 mg equivalent / l / min / (g / l)
A [2 Glen Ca ⁺⁺ / gallon / minute / (g / gallon)], CaCO ₃ 1 for general calcium ion hardness
30 mg equivalent / liter / minute / (g / liter) [2 grains / gallon / minute / (g / gallon)] to CaCO ₃ 390
mg equivalent / liter / minute / (g / liter) [6gren /
Gallons / minute / (g / gallon)]. The most suitable aluminosilicate for builder purpose is CaCO ₃ at least 260 mg equivalent / l / min / (g / l) [4
[Glen / gallon / min / (g / gallon)]. Aluminosilicate ion exchange materials useful in the practice of the present invention are commercially available and can be naturally occurring materials, but are preferably synthetically derived. The preparation of aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669.
Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material is Zeolite is A and the formula Na _{12 [(AlO 2) 12 (SiO 2} ) 12 ] · xH in ₂ O (wherein, x is 20 to 30, particularly 27).
Formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] · 27
Zeolite X of 6H ₂ O is also of the formula Na ₆ [(AlO ₂ )
₆ (SiO ₂ ) ₆ ] 7.5 H ₂ O, as well as zeolite HS.

Suitable water-soluble monomeric or oligomeric carboxylate builders can be selected from a wide range of compounds, such compounds preferably having a primary carboxyl logarithmic acidity constant (pK ₁ ) of less than 9, preferably Is 2
-8.5, more preferably 4-7.5. The log acidity constant is defined by reference to the equilibrium. H ⁺ + A = H ⁺ A, where A is the fully ionized carboxylate anion of the builder salt. Therefore, the equilibrium constant is: K ₁ = (H ⁺ A) / [(H ⁺ ) × (A)] and pK ₁ = log ₁₀ K.

For the purposes of this specification, the acidity constant is 25
° C, defined as zero ionic strength. Literature values are taken where possible (see Stability Constants of Metal Ion Complexes, Special Publication No. 25, The Chemical Society of London), and where doubt arises, the It is measured by potentiometric titration using

A preferred carboxylate has the formula pK _{Ca ++} = log ₁₀ K _{Ca ++} (where K _{Ca ++} = (Ca ⁺⁺ A) / [(Ca ⁺⁺ ) ×
(A)] can be defined by a calcium ion stability constant (pK _{Ca ++} ) defined similarly to pK ₁ .

Preferably, the polycarboxylate has a pK
_{Ca ++ has} about 2 to about 7, especially about 3 to about 6. once again,
Literature values of stability constants are taken where possible. The stability constant was determined by Anders Ringbomb from Co.
Defined at 25 ° C. and zero ionic strength using a glass electrode assay as described in mplexation (1963). While monomeric polycarboxylates are generally preferred for cost and performance reasons, the carboxylate or polycarboxylate builders can be of the monomer or oligomer type. The monomer and oligomer builders have the general formula

(A)

Embedded image

(B)

Embedded image

Or (c)

Embedded image Wherein R ₁ is H, C _1-30 alkyl or alkenyl (optionally bonded to a polyethyleneoxy moiety substituted with a hydroxy, carboxy, sulfo or phosphono group or containing up to 20 ethyleneoxy groups) ; R ₂ represents H, C _{1 to 4} alkyl, alkenyl or hydroxyalkyl, or alkaryl, sulfo or phosphono group,; X is a single bond; O; S; SO; SO
_2; or represents NR _1; Y is H; carboxy; hydroxy; carboxymethyloxy; represents or (substituted with hydroxy or carboxy groups optionally) C _{1 to 30} alkyl or alkenyl; Z is H; represents or carboxy; m is an integer from 1 to 10; n is from 3 to 6
P, q are integers from 0 to 6; p + q is from 1 to 6; X, Y and Z each have the same or different when repeated with a given molecular formula; At least one Y or Z contains a carboxyl group], acyclic, alicyclic, heterocyclic and aromatic carboxylates.

Suitable carboxylates containing one carboxy group include lactic acid, water-soluble salts of glycolic acid and Belgian Patent No. 831,368, No. 82.
And ether derivatives thereof as disclosed in US Pat. Nos. 1,369 and 821,370. 2
Polycarboxylates containing one carboxy group include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, and Offenlegensc in Germany
hrift 2,446,686 and 2,44
No. 6,687 and US Pat. No. 3,935,25.
No. 7 and the sulfinyl carboxylate described in Belgian Patent No. 840,623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates and succinate derivatives, for example British Patent 1,3.
No. 79,241, carboxymethyloxysuccinate, lactoxysuccinate according to British Patent 1,389,732, and aminosuccinate according to Netherlands Application 7205873. And oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylate as described in GB 1,387,447. Examples of the polycarboxylate containing four carboxy groups include oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, and 1,1,1 disclosed in GB 1,261,829. Examples include 3,3-propanetetracarboxylate and 1,1,2,3-propanetetracarboxylate. Examples of polycarboxylates containing a sulfo substituent include British Patent Nos. 1,398,421 and 1,398,42.
No. 2, and US Pat. No. 3,936,448, and the sulfonated pyrolysis citrate described in British Patent 1,439,000. Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, ci
s, cis-tetracarboxylate, cyclopentadienidepentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylate,
2,5-tetrahydrofuran-cis-dicarboxylate, 2,2,5,5-tetrahydrofuran-tetracarboxylate, 1,2,3,4,5,6-hexane-hexacarboxylate and sorbitol, mannitol, xylitol and the like A carboxymethyl derivative of a polyhydric alcohol. Aromatic polycarboxylates include melitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB 1,425,343. Among the above, preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxy groups per molecule, more particularly citrates. Mixtures of monomeric or oligomeric polycarboxylate chelating agents with their parent acids or their salts, for example,
Citric acid or a citrate / citric acid mixture is also contemplated as a component of the builder system of the detergent composition according to the present invention. Other suitable water-soluble organic salts are those in which the polycarboxylic acid is at least two amino acids separated from each other by no more than two carbon atoms.
Homocarboxylic or copolymer polycarboxylic acids containing two carboxyl groups or salts thereof. Polymers of the latter type are disclosed in GB 1,596,756. Examples of such salts have a molecular weight of 2000-5.
000 polyacrylates and their copolymers with maleic anhydride, such copolymers having a molecular weight of 2
It has a molecular weight of from 000 to 70,000, especially about 40,000. These substances are usually used in an amount of 0.5 to 10%, more preferably 0.75 to 8%, most preferably 1 to 6% by weight of the composition.

Preferred examples of other copolymer polycarboxylic acids or salts thereof are copolymers of acrylic acid and maleic acid represented by the following general formula (I) or salts thereof.

Formula (I)

[0030]

Embedded image (Where x: y is 3: 7 to 7: 3 and M is a counter ion, preferably sodium or potassium, and the molecular weight of these copolymers is 5000 to 15000.) These copolymers are, for example, Japanese Patent Laid-Open No. 52-451
It can be produced by the method described in No. 0.

As an example of a suitable polycarboxylate, see Australian Application No. It is represented by the following equation as described in PM6108. Polycarboxylate builders having an IR value of 100 or more are also included. IR = BI (binding index) × DI (dispersion index) × 1/10
0 BI = (binding capacity of sample / 0.34) × 100 DI = (dispersion capacity of sample / 2.5) × 100 Method for measuring binding capacity of sample: Prepare the following reagent and polycarboxylate sample solution . [1] Glycine buffer solution 8.85 g of glycine, 6.90 g of sodium chloride and 80 ml of 1N sodium hydroxide are prepared and diluted with deionized water to prepare a 200 ml buffer solution. [2] Calcium solution 2.940 g of calcium chloride dihydrate is diluted to 200 ml with deionized water. (0.100 M) [3] Dilution buffer solution Dilute 20 ml of the glycine buffer solution of [1] with deionized water to make 1 liter. [4] Polycarboxylate sample solution A polycarboxylate sample is diluted with deionized water to obtain a 1% sample solution (as an active ingredient). Prepare the ion meter as follows. Adjust the calcium ion selective electrode (Orion # 93200) according to the manufacturer's instructions. The dilution buffer solution of [3] was added at 20 ° C (± 0.
1 ° C). Ion meter (Orion model 920
A) Double junction reference electrode (Orion # 90)
020) and an ion selective electrode. 50 ml of the correction solution is prepared by diluting the 0.100 M calcium solution of [2] with the dilution buffer solution of [3]. 0.10 mM Ca ⁺⁺ , 0.20 mM Ca ⁺⁺ , 0.3
0 mM Ca ⁺⁺ , 0.40 mM Ca ⁺⁺ and 0.50 mM C
a ⁺⁺ Five 50ml Calibration
n) Prepare the solution. The instrument performs calibration in these five solutions. The sample is measured as follows. 10 g of the polycarboxylate sample solution of [4] was added to 50 ml of 0.50 mM Ca ^++.
, And stirred with a magnetic stirrer (about 600 rpm). Record the calcium concentration of the stirring solution after 3 minutes,
The binding capacity of the sample is calculated as follows. Sample binding ability = 0.5 mM—Calcium concentration after 3 minutes Method for measuring sample dispersion ability: Prepare the following reagent and polycarboxylate sample solution. [1] Glycine buffer solution 67.56 g of glycine, 52.60 g of sodium chloride and 60 ml of 1N sodium hydroxide are prepared and diluted with deionized water to prepare a 600 ml buffer solution. Thereafter, 60 g of the glycine buffer solution is diluted with ion-exchanged water to prepare 1000 g of a dilute buffer solution. [2] Polycarboxylate sample solution A polycarboxylate sample is diluted with the dilute buffer solution of the above [1] to 50 ppm (as an active ingredient).

1 g of soil (Kanto loam) with a radius of 1.3 cm
Into a standard test tube for 100 cc, and pour 100 cc of the sample solution of [2] into the test tube and cover (or paraffin film). The covered test tube is shaken well 20 times to confirm that the soil is not adhered to the bottom of the test tube. The test tube is placed in a test tube stand and left as it is for 20 hours. The photo electrode is calibrated as follows. Photo electrode (DP550)
To a titrator (Mettler DL25).
Ion-exchanged water is placed in a plastic cup, and the photoelectrode is placed in the cup water and left to stabilize for 15 minutes. Thereafter, the potential of the titrator is adjusted to 1000 mV.
The measurement of the sample dispersion is performed as follows.

Mark the midpoint of the vortex solution (5.5 cm from the top of the solution) of the test tube in the test tube stand,
The photoelectrode is placed in the test tube and placed at the position of this mark. When the millivolt (mV) reading (output) is stable, record the millivolt (mV) reading. The dispersion capacity is calculated as follows. Dispersion capacity of sample = -ln (mV / 1000) A dispersion capacity of 2.5 is used as standard. Such IR
Among the polycarboxylate builders having a value of 100 or more, they are particularly represented by the above-mentioned general formula (I). A copolymer of acrylic acid and maleic acid is desirable.

Examples of the dispersant include acrylic acid-maleic acid copolymer, polyaspartic acid, polyacrylate and the like. As an alkaline builder,
Mention may be made of alkali metal silicates such as sodium silicate, alkali metal carbonates such as sodium carbonate and bicarbonates such as sodium hydrogen carbonate. The dosage of the detergent composition of the present invention should be 15 to 45 g, preferably 20 to 30 g per 30 liters of washing water. The detergent composition of the present invention contains, in addition to methylcellulose ether, detergent surfactant, optional bleaching components and builders and alkaline substances, other additives such as a fluorescent whitening agent, a dye transfer inhibitor, a foam inhibitor, Enzymes such as protease, alcalase, cellulase, lipase,
A fabric softener such as a clay or a quaternary ammonium compound may be optionally contained.

The detergent composition of the present invention may be prepared by the following method. A detergent slurry is prepared by mixing a detergent surfactant, a builder, an alkaline substance, and the like, and then the detergent slurry is dried to obtain a base granule. If necessary, compression and solidification (compaction) is performed, and then a nonionic surfactant is sprayed on the crushed and granulated base granules, and when coating with zeolite or the like, methylcellulose ether can be added. A moisture or heat sensitive material, such as a bleaching component, a fragrance, an enzyme, a crystalline layered sodium silicate, a dye transfer inhibitor and a foam inhibitor, is added to the base granules and mixed to obtain a detergent composition. Optionally, some of the detergent surfactants and other builders and alkaline materials can be added as dry particles to the base granulate, especially when formulating high density compact detergent products. Also, in some cases, the dried base granules can be milled into smaller particles and agglomerated or recombined to form dense, compact base granules. Examples of such manufacturing methods for dense compact detergent products are disclosed in Japanese Patent Application Laid-Open Nos. 62-169900 and 62-169900.
-161898, JP-A-2-86700, JP-A-4-8
1500 and WO 9206170 (Procter End Gamble Company), Japanese Patent Application Laid-Open No. 60-7 / 1985.
2999 (Kao Soap Co., Ltd.) and US Patent No. 4919
847 (Colgate Palmolive Company).

[0036]

Next, the present invention will be described in more detail with reference to the following examples. [Washing method] National automatic washing machine (NA45Y
In 6), add 48 liters of water at 20 ° C. In 50 liters of water, 5 ppm of methylcellulose ether is put into 500 ml of hot water, stirred for 15 minutes, 500 ml of ion-exchanged water is added thereto, and the methylcellulose ether solution is cooled to 20 ° C. One liter of this methylcellulose ether solution is added to 48 liters of water in the washing machine and stirred for 30 seconds.

Thereupon, 49 g of a base detergent composition having the following composition
And stirred for 15 seconds to form a state in which the detergent composition containing methyl cellulose ether is dissolved in the washing water.

Thereafter, each test cloth was put in for 10 minutes to 12 minutes.
After washing for 3 minutes and dehydrating for 3 minutes, (i) rinse with 49 liters of water at 20 ° C., (ii) rinse for about 2-3 minutes, (ii)
i) Then dehydrate. Steps (i) to (iii) are repeated twice. Then, it is dried with a press.

[Evaluation method] Panelists 3 skilled in evaluation
According to the name, under the light in which the ultraviolet light was blocked, the control was performed by the naked eye as the same kind of stain applied to the same kind of cloth which was washed in the same manner as above except that methylcellulose ether was not added. Evaluate on a scale of scale. +4: Dirt is removed more than the control. +3: Very dirty compared to the control. +2: Dirt is clearly removed as compared to control. +1: It seems that dirt has been removed compared to the control. 0: Same as control. -1: It is considered that dirt is not removed compared to the control. -2: Dirt is not clearly removed compared to the control. -3: Dirt is not much removed compared to the control. -4: Dirt was not removed more than the control. [Test cloth] After the washing (prewashing) before press drying is repeated three times by the above-mentioned washing method, the dried cloth is soaked with muddy water or old motor oil, and the cloth soaked with muddy water is natural. dry.

The stained test cloths AC shown in Table 1 below are prepared. _{Table 1 Type of fabric Dirty} A 100% polyester old motor oil B 100% Mud C Polyester 100% polyester and polyether ^65% mud ^{ester and a blend of 35% cotton} [base detergent Composition C ₁₂ sodium dodecylbenzenesulfonate, C _{14 to 15} sodium alkyl sulfate and A detergent slurry is prepared with an acrylic acid / maleic acid copolymer, and the slurry is then dried to a base granulate. Compression compaction and crush granulation are performed, after which the base granulate is mixed with _C12-14 polyoxyethylene alkyl ether, water, zeolite and optical brightener. The enzyme, bleaching component, and the remaining components are added to the mixture to give the base detergent composition described in Table 2 below.

If a detergent composition containing methylcellulose ether is produced, methylcellulose ether can be added simultaneously with the addition of the above zeolite. Table 2 Surfactant weight% sodium C12 straight chain alkylbenzene sulfonate 19.6 sodium C14-15 alkyl sulfate 5.9 C12-14 polyoxyethylene alkyl ether 3.0 tallow 2.2 builder and alkaline substance acrylic acid / mailen Acid copolymer 4.3 (Molecular weight 6500, molar ratio of acrylic acid and maleic acid = 70: 30, BI = 100, DI = 100, IR = 100 / ML-7 manufactured by Nippon Shokubai Co., Ltd.) Zeolite 9.6 sodium 23.9 sodium silicate carbonate 12.5 bleach component sodium nonanoyloxybenzene sulfonate 3.0 perborate 2.4 enzyme protease 0.6 (trade name Savinase 12.0T by Novo Co.) others Fluorescent whitening agent 0.1 sodium sulfate 4.8 polyethylene glycol (molecular weight 40 0) 0.5 Polyvinylpyrrolidone 0.1 Perfume 0.2 defoamer 0.3 Other components 7.0 Total in 100.0 Table, BI, DI and IR are as described above. Example 1 Using each methyl cellulose ether shown in the following table,
According to the washing method, the test cloth was washed together with about 2.3 kg of other laundry and dried.

According to the evaluation method described above, evaluation was performed.
Was obtained. _{Table 3 Methyl cellulose ether Evaluation type of test cloth Viscosity (cps) Methyl substitution degree A B} Metrolose SM100 80-120 Approx. 1.8 2.58 1.75 Metrolse SM15 13- 18 Approx. 1.8 0.91 1.92 Metrolse SM200 160-240 Approx. 1.8 2.58-Metrolose SM400 350-550 Approx. 1.8 2.66 It represents the solution viscosity (centipoise = cps) measured at a temperature of 20 ° C. as a weight% aqueous solution. Also, Metrolose SM15, Metrolose SM100, Metrolose SM
200 and Metro's SM400 are Shin-Etsu Chemical Co., Ltd.
Is a trade name of Methyl Cellulose Ether manufactured by Toshiba Corporation. Example 2 A test was conducted in the same manner as in Example 1 above, and evaluated according to the evaluation method, and the results in Table 4 below were obtained. Table 4 Methyl cellulose ether Evaluation type of test cloth Viscosity (cps) Methyl substitution degree _{BC Metrol-SM100 80-120 1.8 1.75 1.00 Metrol-SM200 160-240 1.8 -0.17 0.33} The viscosity (cps) in the table represents the solution viscosity (centipoise = cps) measured at a temperature of 20 ° C. using a 2% by weight aqueous solution of methyl cellulose ether, and the degree of methyl substitution is the average degree of methyl substitution per anhydroglucose. Represents Also, Metrolose SM100 and Metrolose SM20
0 is a trade name of methyl cellulose ether manufactured by Shin-Etsu Chemical Co., Ltd.

According to Examples 1 and 2, when polyester fibers are washed in washing water at 30 ° C. or lower in the presence of methyl cellulose ether, high viscosity, that is, high
When methyl cellulose ethers of 60-240 cps and 350-550 cps) are used, oil stains are sufficiently released and removed, but mud stains cannot be said to be sufficiently released and removed, and have low viscosity, that is, low molecular weight (13-18 cp viscosity).
When the methylcellulose ether of (s) is used, mud stains are sufficiently released and removed, but oil stains cannot be said to be sufficiently released and removed. Therefore, the cleaning composition of the present invention (with a degree of methyl substitution of about 1.
8, when methylcellulose ether having a viscosity of 80 to 120 is used), it can be seen that both oil stains and mud stains can be released and removed very well at the same time. Formulations Table 5 shows examples of other detergent compositions of the present invention.

[0044]

[Table 1] In the table, BI, DI and IR are as described above.

[0045]

As is clear from the results of the above embodiment,
(i) A solution having a solution viscosity of 80 to 120 centipoise (cps) measured at a temperature of 20 ° C. as a 2% by weight aqueous solution and having an average degree of methyl substitution per anhydroglucose (methyl D
0.05% to 2% of methylcellulose ether wherein S) is from about 1.6 to about 2.3; (ii) 25% of detergent surfactant
(Iii) 0% to 20% of the bleaching component, and (iv)
According to the present invention, there is provided a detergent composition used for cleaning polyester fibers, comprising 30% to 70% of a builder and an alkaline substance. Both oil stains and mud stains are released very well at the same time and the polyester fibers can be washed effectively.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C11D 1/83 1:22) (C11D 1/86 1:22) (C11D 3/60 3:22 3:39 3 : 395 3:10 3:37 3:12 3:08) (73) Patent holder 592043805 ONE PROCTER & GANB LE PLAZA, CINCINNATI, OHIO, UNITED STATS OF AMERICA (72) Inventor Allen, Dee, Claus Hyogo 5-15-901 Naka-cho, Higashi-Nada-ku, Kobe, Japan (56) References JP-A-63-35700 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C11D 3/22 C11D 1/22 C11D 1/83 C11D 1/86 C11D 3/60

Claims (10)

(57) [Claims] (1) A solution having a solution viscosity of 80 to 120 centipoise (cps) measured at a temperature of 20 ° C. as a 2% by weight aqueous solution and having an average degree of methyl substitution per anhydroglucose (methyl DS) of about 80 to 120 centipoise (cps). 1.6 to about 2.3, and the following formula: (Wherein R represents a hydrogen atom or a methyl group, each R may be the same or different, n represents the degree of polymerization, and the solution viscosity measured at a temperature of 20 ° C. as a 2% by weight aqueous solution is 80%). 0.05 to 2% by weight of methylcellulose ether represented by: (ii) 25 to 65% by weight of a detergent surfactant, and (iii) 0 to 20% by weight of a bleaching component. %, And (iv) 30 to 70% by weight of a builder and an alkaline substance, for use in cleaning polyester fibers. 2. A solution having a solution viscosity of 90 to 1 measured at a temperature of 20 ° C. as a 2% by weight aqueous solution of methyl cellulose ether.
The detergent composition according to claim 1, which is 10 centipoise (cps). 3. An average degree of methyl substitution (methyl DS) per anhydroglucose of methyl cellulose ether is about 1.
The detergent composition of claim 1, wherein the composition is between 7 and about 1.9. 4. A solution having a solution viscosity of 90 to 110 centipoise (cps) measured at a temperature of 20 ° C. as a 2% by weight aqueous solution of methylcellulose ether and anhydrous glucose 1
The detergent composition according to claim 1, wherein the average degree of methyl substitution per piece (methyl DS) is from about 1.7 to about 1.9. 5. The detergent surfactant is selected from an anionic surfactant, a nonionic surfactant, a cationic surfactant and a mixture thereof, and the bleaching component is sodium perborate monohydrate, sodium percarbonate. , in the wash solution ^- bleach precursor in the presence of OOH ions to produce a peracid is selected from peracetic acid, and mixtures thereof, sodium builder and alkaline material is carbonate, sodium bicarbonate, of acrylic acid and maleic acid 5. The detergent composition according to claim 4, wherein the composition is selected from copolymers, zeolites, sodium silicate, crystalline layered sodium silicate and mixtures thereof. 6. The detergent composition according to claim 4, wherein the detergent surfactant is a mixture of an anionic surfactant and a nonionic surfactant in a weight ratio of 50:50 to 95: 5. 7. An anionic surfactant wherein the weight ratio of linear alkylbenzene sulfonate to alkyl sulfate is 1: 9.
The detergent composition according to claim 6, which is a mixture of 9 to 80:20. 8. The detergent surfactant is a mixture of an anionic surfactant, a nonionic surfactant and a cationic surfactant, wherein the content of the cationic surfactant in the mixture is 5% by weight or less. The detergent composition according to claim 4, wherein 9. An average degree of methyl substitution (methyl DS) per anhydroglucose of methyl cellulose ether is about 1.
The detergent composition according to claim 1, which is 8. 10. The detergent composition according to claim 1, which is used in washing water at a temperature of 30 ° C. or lower.