JP2003034800A - Article for washing pre-treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an article for washing pre-treatment which can be coated easily and safely to an object to be washed and can give an excellent washing ability when the object is washed after the coating. SOLUTION: The article for washing pre-treatment is a composition which contains (a) 0.05-10 mass.% of a surfactant, (b) an alkaline agent, (c) a chelating agent, and (d) water, and is charged in a bubble discharge container. The above (c) is a chelating agent having a molecular weight of <=1000 and having a calcium capturing capacity 200-600 CaCO3 mg/g and a calcium stability constant of 4-10, which is particularly represented by the general formula I [wherein R is -(CH2 )n -A; A is H, OH, or COOM; M is H, Na, K or NH4 ; and n is a number of 0-5].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an article for pre-washing treatment which is used by applying it to an article to be washed in a foam form. More specifically, it relates to an article for pre-washing treatment, which is applied in a foamy manner to a portion of the article to be washed where stains are concentrated to enhance the washing power in the subsequent washing.

[0002]

2. Description of the Related Art In the case of severe stains on collar sleeves and spilled foods, stains may not be sufficiently removed by ordinary washing, or stains may remain. In general, collar sleeves and stain stains are dealt with by directly applying a detergent to partially increase the detergent concentration.

For example, JP-A-60-101199,
Japanese Unexamined Patent Application Publication No. 10-298599 discloses an applied cleaning agent which is applied to an object to be cleaned and then washed. However, according to the contents disclosed by these, the detergency is insufficient, and especially the detergency against human-derived stains such as collar sleeve stains is insufficient. Moreover, the foaming property was not sufficient.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to easily and safely apply an article to be washed, and by applying a wash to the article to be washed, excellent washing performance can be obtained. The present invention provides a pre-washing treatment article.

[0005]

The present invention provides (a) a surfactant [hereinafter referred to as (a) component] 0.05 to 10% by mass, and (b) an alkaline agent [hereinafter referred to as (b) component]. ,
Article for pre-laundry treatment in which a foam discharge container is filled with a pre-laundry treatment composition containing (c) a chelating agent [hereinafter referred to as (c) component] and (d) water [hereinafter referred to as (d) component]. Regarding

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The article for pre-washing treatment according to the present invention is applied to a portion where stains on an object to be washed such as collar stains, sleeve stains, and stains are concentrated (particularly collar stains and sleeve stains which are stains of human origin). , The contents are applied in the form of foam and used. Effective cleaning can be performed by applying in a foamy form and washing after a certain time. In terms of cleaning performance, it is preferable to wash after 30 seconds or more, more preferably 1 minute or more, still more preferably 5 minutes or more. From the viewpoint of effect and simplicity, 5 hours or less is preferable, 2 hours or less is more preferable, 1 hour or less is further preferable, and 30 minutes or less is particularly preferable.

By applying it in the form of foam, it is safe without being sucked or getting into eyes, and is excellent in retaining property of the pre-washing treatment composition upon application. The foamy form increases the concentration of the surfactant on the surface, facilitates the penetration of the pre-laundry treatment composition into dirt and improves the detergency.

Particularly, the article of the present invention has a bulk density of 50 to 300.
It is preferable that bubbles of g / L can be discharged, and 80 to 250
g / L is more preferable, and 100 to 200 g / L is even more preferable. Further, it is more preferable that 100 mL of foam is allowed to stand, and that the time required for a liquid layer of 10 mL to appear due to natural foam breaking is 1 to 20 minutes, further 3 to 15 minutes, and particularly 5 to 10 minutes.

The bulk density of the foam is 100 at 20.degree.
Using a mL graduated cylinder (inner diameter 27 mm, manufactured by Asahi Techno Glass Co., Ltd.), a mass of 100 mL was obtained. Also,
This was left still, and the time until a 10 mL liquid layer appeared due to spontaneous bubble breaking was determined.

The pre-laundry treatment composition may be filled in a standing pouch, a refill bottle or the like for the purpose of filling the foam pre-washing composition with the foam pre-treatment composition.

[Pre-laundry treatment composition] The pre-laundry treatment composition of the present invention has JIS K 33 in terms of detergency and safety.
62: 1998, the pH at 20 ° C. is 7.5.
It is preferable that it is -12, 8-11 is more preferable, 8.5-11 is more preferable, 9-11 is especially preferable, and 10-11 is the most preferable.

The pre-laundry treatment composition of the present invention has a viscosity of 1 to 50 at 20 ° C. from the viewpoint of easy discharge from the container at the time of application.
mPa · s (B-type viscometer, 60 r / min) is preferable, 1-30 mPa · s is more preferable, 1-20 mP
a · s is more preferable, and 2 to 15 mPa · s is particularly preferable.

<Component (a)> The laundry pretreatment composition of the present invention contains (a) a surfactant in an amount of 0.05 to 10% by mass. From the viewpoint of cleaning performance and foaming property, 0.1 to 9 mass% is preferable, 0.5 to 8 mass% is more preferable, and 1 to 7 mass%.
Is particularly preferable.

Examples of the surface active agent include nonionic surface active agents, anionic surface active agents, cationic surface active agents and amphoteric surface active agents. Above all, it is preferable to contain an amphoteric surfactant from the viewpoint of cleaning performance and foaming property, and it is more preferable to contain 50% by mass or more of the surfactant.
The content is more preferably 0% by mass or more, and particularly preferably 70% by mass or more.

Examples of the amphoteric surfactant include alkyl betaine, imidazolinium betaine, amine oxide and alkyl alanine. From the viewpoint of cleaning performance, the compound represented by the following general formula (II) or (III) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more in the surfactant. The content of the compound represented by the general formula (II) in the surfactant is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0016]

[Chemical 2]

[Wherein R ¹ is an alkyl group or alkenyl group having 7 to 20 carbon atoms, preferably 9 to 15 carbon atoms, and R ² and R ³ are each an alkyl group or alkenyl group having 1 to 3 carbon atoms, preferably carbon atoms It is an alkyl group of formula 1 or a hydrogen atom. R ⁴ is a hydrogen atom or an alkyl group or an alkenyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl group,
m represents a number of 1 to 5, preferably 3. ]

[0018]

[Chemical 3]

[Wherein R ⁵ is an alkyl group or an alkenyl group having 8 to 20 carbon atoms, preferably 12 to 14 carbon atoms, R ⁶ and R ⁷
Are each an alkyl group or alkenyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 carbon atom or a hydrogen atom, p
Represents a number of 0 to 10, preferably 2 to 4. ].

As the anionic surfactant, a sulfuric acid ester salt of alcohol, a sulfuric acid ester salt of alcohol ethoxylate, an alkylbenzene sulfonate, a paraffin sulfonate, an α-olefin sulfonate, an α
-Sulfo fatty acid salt, α-sulfo fatty acid alkyl ester salt or fatty acid salt. In particular, a linear alkylbenzene sulfonate in which the alkyl chain has 12 to 14 carbon atoms,
An alkyl sulfate ester salt having 12 to 18 carbon atoms is preferable, and as the counter ion, an alkali metal salt or an alkanolamine salt is preferable.

As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, polyoxyethylene polyoxypropylene block polymer, fatty acid alkanolamide. , Alkyl polyglycosides and the like are preferable. Alkyl polyglycosides are particularly preferred.

Examples of the cationic surfactant include quaternary mono long-chain alkyl or di long-chain alkyl ammonium salts.

<Component (b)> The laundry pretreatment composition of the present invention contains (b) an alkaline agent. From the viewpoint of cleaning performance and foaming property, it is preferable to contain 1 to 30% by mass, and 3 to 2
5 mass% is more preferable, 5 to 20 mass% is still more preferable, and 5 to 15 mass% is particularly preferable.

Examples of the component (b) include alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate, alkali metal silicates such as sodium silicate and potassium silicate, orthophosphates and metaphosphates. , Polyphosphates such as pyrophosphate and hexametaphosphate, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine,
Examples thereof include disodium hydrogen phosphate, trisodium phosphate, borate and the like.

From the viewpoint of cleaning performance, the component (b) has a maximum pH of 10 or more (20 ° C.) of an aqueous solution or dispersion of the component (b) having a concentration of 0.025% by mass, and the aqueous solution or dispersion 1 It is preferable that the compound requires 10 ml or more of 0.1 N hydrochloric acid aqueous solution to adjust pH to 9 (20 ° C.). Examples of such compounds include sodium carbonate, potassium carbonate, sodium silicate, trisodium phosphate, monoethanolamine and the like.
Of these, sodium carbonate, potassium carbonate and sodium silicate are more preferable, and sodium carbonate is particularly preferable.

<Component (c)> The laundry pretreatment composition of the present invention contains (c) a chelating agent. From the viewpoint of cleaning performance and foaming property, it is preferable to contain 1 to 30% by mass, 2 to 2
5 mass% is more preferable, 3 to 20 mass% is still more preferable, 3.5 to 15 mass% is especially preferable, and 4 to 12 mass% is the most preferable.

From the viewpoint of cleaning performance, the component (c) preferably has a molecular weight of 1,000 or less, more preferably 800 or less,
It is more preferably 600 or less.

The detergency in terms of environmental suitability, calcium trapping amount of component (c) 200~600CaCO ₃ mg / g, more preferably 250~550CaCO ₃ mg / g, is 300~500CaCO ₃ mg / g More preferable. Further, the calcium stability constant is preferably 4 to 10, more preferably 5 to 9, and further preferably 6 to 8,
6.5-8 is especially preferable.

In the present invention, the calcium stability constant and the amount of captured calcium are those determined by the following methods.

(Measurement Method of Calcium Stability Constant) 0.1 mol / liter NH ₄ Cl-NH ₄ O as a buffer solution
Prepare a H (pH 10) solution. Prepare all sample solutions using this buffer. An ion meter 920A manufactured by Orion Co., Ltd. and a Ca ²⁺ ion electrode are used to measure the Ca ²⁺ concentration. First, the relationship between the calcium chloride concentration and the potential of the electrode is obtained, and a calibration curve is created. 5.3 of calcium chloride
A 6 × 10 ⁻² mol / liter solution and a 5.36 × 10 ⁻⁴ mol / liter solution of the chelating agent sample are prepared. Add 1 ml of calcium chloride solution to 100 ml of chelating agent sample solution.
Add ml and stir for 5 minutes. The remaining Ca ²⁺ concentration is measured using a Ca ²⁺ ion electrode. The chelating agent is Ca
^The calcium stability constant (Ca stability constant) is calculated from the following formula, assuming that a chelate complex is formed with ^{2+ in a ratio} of 1: 1.

[0031]

[Equation 1]

(Measuring Method of Calcium Amount) Calcium amount (Ca amount) is described in JP-A-3-277696, page 3, lower right column, line 6 to page 4, upper left column, line 6 (however, (Anionic surfactant is replaced with chelating agent)).

Examples of the component (c) include compounds having 2 to 5, preferably 3 to 5 COOM groups (M is H, Na, K, NH ₄ ) in the molecule. Cleaning performance,
From the viewpoint of environmental suitability, compounds represented by the following general formula (I) are preferable.

[0034]

[Chemical 4]

[Wherein, R is — (CH ₂ ) _n —A, A is H, OH, COOM, and M is H, Na, K, N
H _4, preferably Na, n is a number of 0 to 5. ].

In the present invention, the mass ratio of the component (c), preferably the compound represented by the general formula (I), to the component (a), preferably the amphoteric surfactant is (a) / (c) = 3 /
It is preferably 1 to 1/5, more preferably 2 /
1 to 1/3, more preferably 1/1 to 1/3, particularly preferably 1/1 to 1/2.

<Component (d)> The laundry pretreatment composition for clothes of the present invention contains (d) water in an amount of 50 to 95% by mass. From the viewpoint of cleaning performance and coatability, 55 to 90% by mass is preferable, and 6
0-85 mass% is more preferable, and 65-80 mass% is still more preferable.

<Other Components> The laundry pretreatment composition of the present invention preferably contains 1 to 30% by mass of a hydrotrope agent from the viewpoint of stability at low temperature, foaming property and non-clogging property. 15 mass% is more preferable, and 3-10 mass% is still more preferable.

As the hydrotrope agent, lower alcohol having 1 to 4 carbon atoms such as ethanol, methanol, propanol, glycerin, ethylene glycol, propylene glycol, toluene sulfonic acid or its salt, xylene sulfonic acid or its salt, the following general formula Examples thereof include compounds represented by (IV).

X- (Ph) -O (CH ₂ CH ₂ O) _p (CH ₂ CHRO) _q Y (IV) [In the formula, X represents a hydrogen atom, an alkyl group or an alkenyl group having 1 to 4 carbon atoms, Hydroxyl group or halogen, Y
Is a hydrogen atom, a methyl group, or an ethyl group, and Ph
Is a phenylene group, R is a hydrogen atom, a methyl group,
Or an ethyl group, and p is 1 to 6, preferably 1 to
3, q is 0 to 4, preferably 0 to 2, p + q
Is 1 to 10, preferably 1 to 6. ].

Above all, a lower alcohol having 2 to 3 carbon atoms, p
-Toluenesulfonic acid or its salts are more preferred.

In addition to the laundry pretreatment composition of the present invention,
(1) Polyacrylic acid or its salt, polymaleic acid or its salt, carboxymethylcellulose, acrylic acid-maleic acid copolymer or its salt, maleic anhydride-diisobutylene copolymer or its salt, maleic anhydride-methyl vinyl ether Copolymer or salt thereof, maleic anhydride-isobutylene copolymer or salt thereof, maleic anhydride-vinyl acetate copolymer or salt thereof, and claims 1 to 21 (1) of JP-A-59-62614.
P. 3, col. 5 to p. 3, col. 4, line 14) Organic polyvalent carboxylic acids and / or salts thereof such as polymers 0.01 to 10
%, (2) 0.01 to 10% by weight of a redeposition preventing agent and a dispersant such as polyethylene glycol having an average molecular weight of 5,000 or more and a naphthalenesulfonate formalin condensate.
(3) Color transfer inhibitor 0.01 such as polyvinylpyrrolidone
10% by mass, (4) 0.01 to 2% by mass of foaming agent such as silicone and silica, (5) 0.01 to 200% of antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium hydrogen sulfite. 2% by mass, (6) colorant, (7) amylase, protease,
Enzymes such as lipase and cellulase, (8) enzyme stabilizers such as calcium chloride, calcium sulfate, formic acid and boric acid (boron compound), (9) fragrances, (10) antibacterial preservatives and the like can be added.

[Foam Discharge Container] As the foam discharge container, a trigger type foam discharge container, a pump type foam discharge container used by pressing the head of a cap equipped with a pump mechanism with fingers, and a body part of a soft container Examples of the squeeze former used by pressing with a finger, an aerosol, and the like, a trigger-type spray container and a squeeze-former are more preferable from the viewpoint of usability, economy, environmental compatibility, etc., and a trigger-type spray container is particularly preferable. . In the case of a trigger type spray container, the discharge amount per discharge is 0.5 to 1 g in terms of usability.
Is preferred.

[0044]

[Examples] Examples 1 to 7 and Comparative Examples 1 to 3 The pre-laundry treatment composition shown in Table 1 was prepared. The pH of each of the compositions of Examples obtained at 20 ° C. was 10 to 11. In addition, the compositions of the examples all have a viscosity of 2 to 15 mP.
It was a · s (B type viscometer, 20 ° C., 60 r / min).

A commercially available trigger type foam discharge container (250 mL of a cleaner around the family sink,
Kao Co., Ltd.) was filled to obtain an article for pre-washing treatment. The foam discharged from the article for pre-washing treatment of the obtained example is
All have a bulk density of 50 to 300 g / L, 100 mL that has been left stationary
1 to 20 times from the appearance of bubbles to the appearance of a 10 mL liquid layer
It was a minute.

With respect to these, the cleaning power and the foam discharge property were evaluated by the following methods. The results are shown in Table 1.
Shown in.

<Evaluation of Detergency> (Preparation of collar cloth) A collar cloth described in JIS K3362: 1998 is prepared.

(Washing conditions and evaluation method) JIS K3362: in a washing tub of an automatic two-tub type washing machine (Toshiba Galaxy 3.6)
Put 40L of water as described in 1998, 1.4k
g cotton underwear and 0.6 kg cotton / polyester blended shirt. Furthermore, JIS K
3362: 1998, 53 g (anhydrous equivalent) of an index detergent for detergency determination (without addition of an optical brightening agent) is added. Furthermore, 4 g of the pre-laundry treatment composition was applied from the article for pre-washing treatment to one piece of the above-mentioned collar-lining cloth, and the collar-lining cloth 6 was left standing for 5 minutes.
Put a sheet (2 pieces of 3 grade stains) in the washing tub and wash normally for 10 minutes. Then dehydrate for 1 minute, 15 L / m for 8 minutes
Rinse with running water. Then, it is dehydrated for 5 minutes and naturally dried in the room.

A blank obtained by performing the same operation without applying the pre-laundering treatment composition was used as a blank, and a pair was visually compared, and evaluated according to the following criteria.

Evaluation Criteria ⊚: The stains are clearly removed from the blanks in all three grades of stains. ◯: Stain is slightly removed from the blank in all of the three levels of stains. X: There is almost no difference from the blank in all the three levels of stains, or the stain removal is poor. -: Cannot be evaluated because it was not discharged from the container.

<Evaluation of Foam Dischargeability> Five people having a grip strength of 25 to 30 kg actuated the trigger of the article for pre-washing treatment to discharge the pre-washing agent composition. The operability at that time was evaluated according to the following criteria.

Evaluation criteria ◯: Foam was discharged without any problem. Δ: Discharged in a mixed state of foam and liquid. X: Not ejected.

[0053]

[Table 1]

Amphoteric surfactant 1: lauramidopropyl
Amine oxide (Softofazoline LAO-C, Kawaken Phi
Chemical Co., Ltd., net amount equivalent) Amphoteric surfactant 2: dimethyllaurylamine oxai
De (Amphitor 20N, Kao Corporation, net content conversion) Amphoteric surfactant 3: lauryl (2-hydroxy-3-
Sulfopropyl) dimethyl betaine (Amphitol 20
HD, Kao Corporation, net conversion) ・ Nonionic surfactant 1: Decyl glucoside (Mido
Le 10, Kao Corporation, net conversion) -Nonionic surfactant 2: straight chain first having 10 to 14 carbon atoms
8 mol of ethylene oxide on average in primary alcohol
Pyrene oxide with an average of 2 moles randomly added ・ Anionic surfactant 1: coconut oil fatty acid sodium salt -Anionic surfactant 2: alkyl having 10 to 14 carbon atoms
Straight chain sodium alkylbenzene sulfonate having a group -Chelating agent 1: Methylglycine diacetate trisodium
(Trilon M, BASF Japan Ltd., net conversion)
(Ca capture amount 430CaCO₃mg / g, Ca stability determination
(Number 6.1) -Chelating agent 2: aspartic acid-N, N-diacetic acid tetra sodium
Thorium (Ca capture amount 328CaCO₃mg / g, Ca
Stability constant 6.7) -Chelating agent 3: trisodium serine diacetate (Ca capture
Amount 347CaCO₃mg / g, Ca stability constant 6.5) -Chelating agent 4: tetrasodium glutamate diacetate (C
a Capture amount 305CaCO ₃mg / g, Ca stability constant
5.8) ・ Chelating agent 5: Ethylglycine diacetate trisodium
(Ca capture amount 419CaCO₃mg / g, Ca stability determination
(Number 5.7) -Carboxylic acid-based polymer: JP-A-10-60476
Phenoki synthesized by the method described on pages 116 to 13 of the report
Si polyethylene glycol, acrylic acid, maleic acid
Polymer (weight average molecular weight 10,000, solid content 51.2)
amount%) Enzyme: Evalase 16.0L-EX (protease,
(Novozymes) ・ Dye: coconut on orange (10ppm in the composition
(Mass ratio) addition)

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 17/04 C11D 17/04 17/08 17/08 D06L 1/16 D06L 1/16 (72) Inventor Kazutoshi Ide 1334 Minato Minato, Wakayama City, Kao Co., Ltd. (72) Inventor Hiroshi Nishimura 1334 Minato Minato, Wakayama City, Wakayama Prefecture F Term in Kao Co., Ltd. EB13 EB22 EB30 EC02 ED02 ED28 ED29 FA07 FA12 FA17 FA26 FA28

Claims (6)

[Claims] 1. A foam pre-treatment container is provided with a laundry pretreatment composition containing (a) a surfactant of 0.05 to 10% by mass, (b) an alkali agent, (c) a chelating agent and (d) water. Pre-washed pre-washed articles. 2. (c) is a calcium capture amount of 200 to 6
00CaCO ₃ mg / g and calcium stability constant 4 to
The pre-laundry article according to claim 1, which is a chelating agent having a molecular weight of 1,000 or less and having a molecular weight of 10. 3. The article for pre-laundry treatment according to claim 2, wherein (c) is a compound represented by the following general formula (I). [Chemical 1] [Wherein, R is - (CH _{2) n} -A, A is H, OH, C
OOM, M is H, Na, K, NH ₄ , and n is a number from 0 to 5. ] 4. In (b), the maximum pH of an aqueous solution or dispersion having a concentration of 0.025% by mass is 10 or more (20 ° C.), and 1 liter of the aqueous solution or dispersion is adjusted to pH 9
To obtain (20 ° C), add 0.1N hydrochloric acid solution to 10m
The article for pre-laundry treatment according to any one of claims 1 to 3, which is a compound that requires 1 or more. 5. The laundry pretreatment article according to claim 1, wherein 50% by mass or more of (a) is an amphoteric surfactant. 6. A bulk density of 50 to 300 g / L, which was allowed to stand 1
The pre-laundry article according to any one of claims 1 to 5, which is capable of discharging foam having a time from 1 to 20 minutes until a liquid layer of 10 mL appears from 00 mL of foam.