JPH09249895A - Detergent composition having high bulk density - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition containing a surfactant, a specific organic chelating agent, a biphenyl-type fluorescent dye and stilbene-type fluorescent dye, having increased adsorption of the fluorescent dyes to clothes and effective for improving the brightening effect on the cleaned clothes. SOLUTION: This composition contains (A) 10-40% of a surfactant, (B) 3-20% of an imidodisuccinic acid salt of formula I (X1 is an alkali metal ion or hydrogen ion; Y is OH or H), (C) a biphenyl-type fluorescent dye of formula II (X2 is X1 ; R1 and R2 are each H, a lower alkyl, etc.) and (D) a stilbene-type fluorescent dye of formula III (X3 is X1 ; R3 to R6 are each R1 ). The total amount of the components C and D is 0.05-1.5%. The content of anionic surfactant in the component A is preferably larger than that of nonionic surfactant and is preferably 20-50% of the final detergent composition. The weight ratio of C/D is preferably 2/8 to 8/1. The objective composition can be produced e.g. by preparing an aqueous slurry containing the components A to D and having a solid content of 50-70% and converting the slurry into granules having high bulk density.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high bulk density detergent composition, and more particularly, to a high bulk density detergent having improved fluorescent adsorbing ability to a cleaning cloth and improved fluorescent whitening property of the cleaning cloth. It relates to a composition.

[0002]

BACKGROUND OF THE INVENTION Detergent compositions for clothing use fluorescent dyes as whitening agents that emphasize the whiteness of washed clothes.
The whitening effect of the fluorescent dye on clothes is obtained by the adsorption of the fluorescent dye on the fiber surface of the clothes in the washing bath. As such fluorescent dyes, those having various chemical structures are known. However, the general-purpose fluorescent dyes currently used in detergent compositions are not 100% adsorbed on fibers, but are lost to some extent. This is because a surfactant having an adsorptivity to clothes coexists in the detergent composition and the washing bath, and the fluorescent dye competes with these surfactants by adsorption, and this action causes the adsorption of the fluorescent dye to clothes. It is thought that this is due to inhibition.

[0003]

However, the fluorescent dye is
It is expensive among the raw materials for detergent compositions. Therefore, there has been a demand for a detergent composition in which the adsorptivity of a fluorescent dye to clothes is increased, the loss is reduced as much as possible, and the whitening effect of washed clothes is improved. Therefore, the present invention provides a high bulk density detergent composition which increases the adsorptivity of a fluorescent dye to clothes and maintains or improves the whitening effect of a washing cloth even when the amount of the fluorescent dye is reduced. With the goal.

[0004]

According to the present invention, by using a specific organic chelating agent, stains for washing clothes can be removed, and the adsorbability of fluorescent dyes to clothes can be increased, so that the whitening effect of the washing cloth can be improved. By solving or maintaining the above, the above problems are solved. That is, in the present invention, the surfactant is 10 to 40%, the iminodisuccinate represented by the general formula (I) is 3 to 20%, and the general formula (I
Biphenyl type fluorescent dye represented by I) and the general formula (III)
The above problem is solved by a high-bulk density detergent composition containing a stilbene type fluorescent dye represented by the formula (1) and containing the fluorescent dye in a total amount of 0.05 to 1.5%.

[0005]

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[Chemical 6]

(Wherein X ₁ , X ₂ and X _{3, which} may be the same or different, are ions selected from alkali metal ions and hydrogen ions, Y is OH or H, and R ₁ , R < ₂ >, R < ₃ >, R < ₄ >, R < ₅ >, and R < ₆ >, which may be the same or different, are substituents of hydrogen, a lower alkyl group, and an amino group) Hereinafter, the present invention will be described in more detail. .

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The surfactants used in the present invention are anionic surfactants and nonionic surfactants,
It is preferable that the amount of anionic surfactant is larger than that of nonionic surfactant. As the anionic surfactant, fatty acid methyl ester sulfonate (average carbon chain length 8 to 18), straight chain or branched alkyl (average carbon chain length 8 to 18) benzene sulfonate, long chain alkyl (average carbon chain length 10) ~ 2
0) sulfonate, long-chain olefin (average carbon chain length 10
To 20) sulfonate, long-chain monoalkyl (average carbon chain length 10 to 20) sulfate ester salt, polyoxyethylene (average degree of polymerization 1 to 10) long-chain alkyl (average carbon chain length 1
0-20) ether sulfate ester salt, polyoxyethylene (average degree of polymerization 3-30) alkyl (average carbon chain length 6-
12) Phenyl ether sulfate ester salts, long-chain monoalkyl, dialkyl or sesquialkyl phosphates, polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphates and the like can be mentioned. These anionic surfactants can be used in the form of an alkali metal salt using an alkali metal ion such as sodium ion and potassium ion as a counter ion, an amine salt and an ammonium salt. Further, it may be added in the acid state instead of the salt and used. The content of the anionic surfactant should be 10% by weight or more of the final detergent composition, and preferably 20 to 50% by weight. This is because if it is 10% by weight or less, sufficient cleaning performance cannot be obtained.

Various nonionic surfactants can be used. For example, an EO addition type nonionic surfactant obtained by adding 4 to 50 mol of ethylene oxide on average to a primary or secondary alcohol having 8 to 18 carbon atoms, 8 carbons
18 primary and secondary alcohols with an average of 4 to 50 moles of ethylene oxide and an average of 3 to propylene oxide.
EO-PO-added nonionic surfactant added with 15 mol, sugar-fatty acid ester type nonionic surfactant obtained from fatty acid having 6 to 16 carbon atoms and sugars such as glucose, alcohol having 6 to 16 carbon atoms and glucose It is preferable to use one kind or a mixture of two or more kinds of sugar-alcohol ether type nonionic surfactants obtained from sugars such as.

The amount of the surfactant to be added must be 10% by weight or more of the final detergent composition, and preferably 20 to 50% by weight. This is because if it is 10% by weight or less, sufficient cleaning performance cannot be obtained. The blending amount of the surfactant is more preferably 25 to 40% by weight.

The specific organic chelating agent used in the present invention is the iminodisuccinate represented by the above general formula (I). Examples of the counter ion X ₁ include alkali metal ions such as sodium ion and potassium ion, and hydrogen ion. Of these, sodium ions are preferable in terms of solubility. Examples of Y include OH and H, and OH is preferable from the viewpoint of chelating ability. The high bulk density detergent composition of the present invention contains this iminodisuccinate at 3-20% by weight of the final detergent composition. The reason for setting this range is that if it is less than 3%, the effect of the present invention cannot be obtained, and if it exceeds 20%, the addition effect more than expected cannot be obtained. This range is preferably 5 to 18% by weight, more preferably 7 to 15% by weight.

The fluorescent dye used in the present invention is not limited as long as it has an effect as a whitening agent that emphasizes the whiteness of clothes to be washed. Such fluorescent dyes generally include the following i) and ii). That is, i) a biphenyl type represented by the general formula (II), and ii) a stilbene type represented by the general formula (III).

[0012]

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(In the formula, X ₂ and X _{3, which} may be the same or different, are ions selected from alkali metal ions and hydrogen ions, and are R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ and R _{6, which} may be the same or different, are substituents of hydrogen, a lower alkyl group, and an amino group.)

The high bulk density detergent composition of the present invention contains at least one biphenyl type fluorescent dye represented by the general formula (II) and stilbene type fluorescent dye represented by the general formula (III), and the total thereof. The amount is 0.05 to 1.5% by weight of the final detergent composition
It is better to set the range. The reason why two or more kinds of fluorescent dyes are contained is as follows.
As described above, the fluorescent dye is affected by the competitive adsorption with the surfactant, and the adsorption of the fluorescent dye on the clothing is inhibited. Most of the conventional detergent compositions are 2
A combination of more than one type of surfactant is used. Therefore, detergent compositions containing various surfactants have
The use of more than one type of fluorescent dye reduces the adsorption inhibiting effect of each surfactant. Furthermore, by using two or more types of fluorescent dyes, it is possible to exhibit the effect of exhibiting fluorescent whitening properties for various types of fibers. The total amount of two or more fluorescent dyes is 0.05-1.
The range of 5% by weight is because if the content exceeds 1.5% by weight, the detergent composition itself becomes significantly yellowed and looks bad to the purchaser. If it is less than 0.05%, This is because the whitening effect of the cleaning cloth in the invention cannot be expected. Therefore, the total amount of the above fluorescent dyes is 0.
The content is preferably 1 to 1.2% by weight, more preferably 0.2 to 1.0% by weight. Further, it is preferable that both of the above fluorescent dyes are contained in a ratio of 1/10 to 10/1 (weight ratio), and more preferably 2/8 to 8/1.
(Weight ratio) is preferable.

Surfactants, iminodisuccinates, and 2
The high bulk density cleaning composition of the present invention containing one or more fluorescent dyes can be obtained by the following method. That is, an aqueous slurry containing a surfactant, iminodisuccinate, and two or more kinds of fluorescent dyes is prepared so that the solid content is 50 to 70%. The obtained aqueous slurry is used to obtain a final detergent composition by granulating with high bulk density by the following method. As described in JP-A-60-96698, the slurry is kneaded with a kneader or the like, the kneaded product is crushed and granulated by a crusher such as a cutter mill type, and further mixed with a water-insoluble fine powder. Gives the final detergent composition. The final detergent composition can also be obtained by spray-drying the mixed slurry, kneading the spray-dried product with a nonionic surfactant, etc., pulverizing and granulating.

The detergent composition of the present invention may contain various additives in addition to the above-mentioned anionic surfactant, nonionic surfactant, iminodisuccinate, and two or more fluorescent dyes. As this additive, inorganic builders such as zeolite, sodium sulfate, sodium tripolyphosphate and sodium pyrophosphate; sodium citrate, sodium ethylenediaminetetraacetate, nitrilotriacetic acid salt, sodium polyacrylate, sodium acrylate-sodium maleic anhydride Calcium ion trapping builders such as copolymers and polyacetal carboxylates; sodium carbonate, potassium carbonate alkali builders, alkali builders such as silicates, anti-redeposition agents such as carboxymethyl cellulose and polyethylene glycol;
Rinsing improvers such as soaps; Viscosity modifiers such as paratoluene sulfonate, toluene sulfonate, xylene sulfonate, urea; Proteases, lipases, cellulases,
Examples include enzymes such as amylase (particularly alkaline lipase having an activity in an alkaline atmosphere); softening agents such as quaternary ammonium salts and bentonite; bleaching agents, fluorescent agents, fragrances, and dyes.

In the above manufacturing method, the timing of adding the above various additives is not particularly limited. For example, it may be added to the aqueous slurry or may be added at the time of granulation after spray drying. Also, powder blending may be performed after granulation. However, since the enzyme and the bleaching agent are inactivated or decomposed by heat, it is preferable to add them at the time of granulation or to mix them into powder after granulation. In order to prevent deactivation due to heat, it is more preferable to mix powders after granulation.

[0018]

EFFECTS OF THE INVENTION By using the high bulk density detergent composition of the present invention, the amount of the fluorescent dye adsorbed on the washing cloth can be increased and the whitening effect of the clothes can be improved. Next, the present invention will be specifically described with reference to examples.

[0019]

【Example】

1) Each component excluding the nonionic surfactant, PEG, a part of zeolite, a part of sodium carbonate, an enzyme, and a fragrance from the detergent composition shown in Table-1 (Example) and Table-2 (Comparative Example). Was used to prepare a detergent slurry having a solid content of 60%, which was prepared to have an appropriate viscosity with tap water. The detergent slurry was heated at a hot air temperature of 270 ° C. using a countercurrent spray drying tower.
It was dried to a water content of 5% to obtain a spray-dried product. Next, this dried product, nonin surfactant, PEG and water were introduced into a continuous kneader (KRC Kneader # 2, manufactured by Kurimoto Iron Works) to obtain a dense and uniform kneaded product. The discharge port of this kneader has a perforated plate with 80 holes of 5 mm diameter (10 m thick).
m) was installed and the kneaded material was made into a cylindrical pellet of about 5 mmφ × 10 mm. The pellets were introduced into a pulverizer (Speed Mill ND-10 type, Okada Seiko Co., Ltd.) together with twice the amount of 15 ° C. cooling air. The crusher has four stages of cutter cloth with a length of 15 cm, rotates at 3000 rpm, the screen is made of punching metal 360 degrees, and the hole diameter is 2
mmφ, aperture ratio 20%. Table 1 and Table-
A detergent composition having the composition shown in 2 and a bulk density of 0.8 to 0.95 g / cc was obtained. 2) Evaluation method of fluorescent whitening property As a wash cloth for judgment, unfluorescent plain-woven cotton cloth (20 × 20
cm) was used. Two tank type U. S. Testing Company Terg-O
-Use Tometer, put 5 pieces of evaluation cloth on it, and 120rp
m, washed at 25 ° C for 10 minutes. As the cleaning liquid, use 900 ml of detergent composition concentration 0.066% and rinse 900
Performed for 3 minutes with ml of water. The rinse was repeated twice. The water used was 3 ° DH. In order to prevent the decomposition of the fluorescent dye during a series of operations, each solution was shielded from light, and the judgment cloth was air-dried in the shielded state. In addition, the cloth was kept in a light-blocking box until the judgment was completed. The color difference meter (Nippon Denshoku Industries Co., Ltd., Σ90 type) was used for the determination, and the cloth surface 3
The surface color of the portion of 0 mmφ was measured and expressed using the reflectance Z value.

[0020]

[Table 1] Table-1Example Composition (wt%) 1 2 3 4 5 6 7 (A) Surfactant α-SF 12 12 12 12 5 12 AOS 8 8 8 8 2 2 8 8 AES − − − − − 5 − AS − − − − 10 5 − LAS 10 10 10 10 20 20 10 10 AE 3 3 3 3 2 3 3Soap 3 3 3 3 3 3 3 3 (B) HIDS 5 5 5 5 5 5 5 15 (C) Fluorescent agent Fluorescent agent 1 0.1 0.25 0.4 0.1 0.1 0.1 0.1 0.1 Fluorescent agent 2 0.4 0.25 0.1 0.7 0.7 0.4 0.4 0.4 Other additives Zeolite 15 15 15 15 15 15 15 5 Polyacrylic acid 2 2 2 2 2 2 2 2 Sodium sulfite 1 1 1 1 1 1 1 1 1 PEG ---- 2--Sodium carbonate 25 25 25 25 25 25 25 25 25 Enzyme 1 1 1 1 1 1 1 1 Perfume 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Sodium sulfate balance Fluorescent whitening (Z value) 94 95 96 95 95 96 95 94 α-SF: α-sulfofatty acid (average carbon chain length 8 to 18) methyl ester sodium AOS: C₁₄~ C₁₈Sodium α-olefin sulfonate AES: alkyl (C₁₂~ C₁₃) Ether (EO (ethylene oxide) = 3) Sodium sulfate AS: Alkyl (average carbon number 12-18) Sodium sulfate LAS: Linear alkyl (C_Ten~ C₁₄) Sodium benzenesulfonate AE: C₁₂~ C₁₃EO = 7 mol adduct of primary alcohol HIDS: sodium hydroxyiminodisuccinate Fluorescent agent 1: 4,4-bis (sulfostyryl) biphenyl disodium (Tinopearl CBS) Fluorescent agent 2: 4,4-bis [(4 -Toluidino-6-morpholino-1,3,5-triazin-2yl) amino] stilbene-2,2-disulfonic acid 2 sodium (Whitetex SA)) PEG: polyethylene glycol enzyme: protease (sabinase 6.0T) ) Fragrance: A mixed fragrance having a composition containing the components shown in Table 3

[0021]

[Table 2] Table-2 Comparative composition (wt%) 1 2 3 4 5 (A) Surfactant α-SF 12 12 12 5 AOS 8 8 8 8 2 2 AES − − − − 5 AS − − − 10 5 LAS 10 10 10 20 20 10 AE 3 3 3 2 3 Soap 3 3 3 3 3 (B) HIDS-2 5 5 5 (C) Fluorescent agent Fluorescent agent 1 0.1 0.1 0.3- Fluorescent agent 2 0.4 0.4-0.6- Other additives Zeolite 15 15 15 15 15 15 Polyacrylic acid 2 2 2 2 2 Sodium sulfite 1 1 1 1 1 Sodium carbonate 25 25 25 25 25 25 Enzyme 1 1 1 1 1 1 1 Fragrance 0.2 0.2 0.2 0.2 0.2 Sodium sulfate balanced fluorescent whitening property (Z value) 90 90 91 91 88 α-SF: α-sulfo fatty acid (average carbon chain length 8-18) Methyl ester sodium AOS: C ₁₄ ~C ₁₈ α- olefin sul Sodium phosphate AES: alkyl (C ₁₂ -C ₁₃₎ ether (EO (ethylene oxide) = 3) sulfate AS: alkyl (average carbon number 12 to 18) Sodium sulfate LAS: linear alkyl (C ₁₀ -C ₁₄₎ benzene sodium sulfonate AE: C ₁₂ -C ₁₃ 1 primary EO = 7 mole adduct of an alcohol HIDS: hydroxy iminodiacetonitrile sodium succinate fluorescent agent 1: 4,4-bis (sulfostyryl) biphenyl disodium (Tinopal CBS) fluorescent agent 2: 4,4-bis [(4-toluidino-6-morpholino-1,3,5-triazin-2yl) amino] stilbene-2,2-disulfonate 2 sodium (Whitetex SA)) Enzyme: Protease (Sabinase 6.0T) Perfume: Compounded perfume having a composition containing the components shown in Table-3

[0022]

TABLE 3 Table 3: perfume compositions (Part 1) The amount Ingredient (parts by weight) 3,7-dimethyl-1,6-octadiene-3-ol 80 3,7-dimethyl-1,6-octadiene - 3-yl-acetate 60 3,7-dimethyl-6-octen-1-ol 40 β-phenylethyl alcohol 50 p-tert-butyl-α-methylhydrocinnamic aldehyde 70 α-methyl-p-isopropylphenylpropionaldehyde 60 α-n-amylcinnamic aldehyde 20 α-n-hexylcinnamic aldehyde 60 7-acetyl-1,1,3,4,4,6-hexamethyl 80 tetrahydronaphthalene 3- (5,5,6-trimethyl- Norbornane-2-yl) 20 cyclohexane-1-ol bertfix 30 2-ethyl-4- (2 , 2,3-Trimethyl-3-cyclopenten 10-1-yl) -2-butan-1-ol 10% α, α-dimethyl-p-ethylhydrocinnamic aldehyde 40 2,4-dimethyl-3-cyclohexene- 1-Carboxyaldehyde 10 cis-3-hexenol 10 2-trans-3,7-dimethyl-2,6-octadiene-1-ol 30 n-decylaldehyde 5 ────────────── ──────────────────────

[0023]

Table 4 Table 3: perfume compositions (Part 2) The amount Ingredient (parts by weight) 10-undecene-1-al 5 methyl nonyl acetaldehyde 5 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene 30-1-Carboxaldehyde naphthalene-2-acetyl-1,2,3,4,6,7,8 30-octahydro-2,3,8,8-tetramethyl 5- (2-methylene-6,6- Dimethyl-cyclohexyl) 50-4-penten-3-one 2-methoxy-4-propenylphenol 20 allylcyclohexanepropionate 10 6,7-dihydro-1,1,2,3,3-pentamethyl 5-4 (5H ) -Indanone p-propenyl phenyl methyl ether 5 methyl-2-aminobenzoate 5 lemon oil 30 orange oil 0 Lavandin oil 20 Patchouli oil 10 3,7-Dimethyl-2,6-octadienal 30 Methyl dihydrojasmonate 50 ──────────────────────── ─────────────

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C11D 3:33 3:40)

Claims (1)

[Claims] 1. A surfactant is 10 to 40%, an iminodisuccinate represented by the general formula (I) is 3 to 20%, and a biphenyl type fluorescent dye represented by the general formula (II) and a general formula (III). ) A stilbene type fluorescent dye represented by the formula (1) is contained, and the total amount of the fluorescent dye is 0.05 to 1.5%. Embedded image Embedded image Embedded image (In the formula, X ₁ , X ₂ , and X _{3, which} may be the same or different, are ions selected from alkali metal ions and hydrogen ions, Y is OH or H, and R ₁ ,
_{R 2, R 3, R 4} , R 5, and R _6, which may be the same or different, hydrogen, a substituent of a lower alkyl group and amino group)