JP2519953B2 - Liquid detergent composition for imparting flexibility - Google Patents

Description

TECHNICAL FIELD The present invention relates to a softening liquid detergent composition, and more specifically, it can give excellent softness to general cloths to be washed, and particularly to cottons. In particular, it relates to a flexibility-imparting liquid detergent composition capable of imparting excellent flexibility and preventing yellowing usually caused by repeated washing.

BACKGROUND ART Conventionally, when washing textiles such as clothes, it has been known that the use of a cationic surfactant is effective for imparting good flexibility at the time of finishing. Since the cloth to be washed tends to yellow only with an active agent, it has been proposed to use an anionic surfactant in combination (for example, U.S. Pat.Nos. 3,920,563, 3,920,565, and British Patent 1,329,429). Book, JP-A-53-38794
(Japanese Patent Laid-Open No. 53-52799).

However, although the flexibility-imparting detergents in combination with these anionic surfactants have some effect in preventing the yellowing of the cloth to be washed, they have the flexibility-imparting effect originally possessed by the cationic surfactants. It has the drawback of being accompanied by a decrease in

OBJECT OF THE INVENTION The present invention provides a liquid detergent composition capable of imparting excellent flexibility to a cloth to be washed, especially cotton, and preventing yellowing caused by repeated washing. .

Composition of the Invention The flexibility-imparting liquid cleaning composition of the present invention is characterized by containing the following components (A), (B) and (C).

(A) a higher alcohol ethoxylate having an alkyl group having 8 to 20 carbon atoms and an average addition mole number of ethylene oxide of 7 to 30; and an average addition mole of propylene oxide having an alkyl group having 8 to 20 carbon atoms At least 1 selected from the higher alcohol propoxyethoxylates having a number of 1 to 3 and an average number of moles of ethylene oxide added of 8 to 20
Seed nonionic surfactant: 10-40% by weight.

(B) At least one cationic surfactant selected from the quaternary ammonium salts represented by the following general formula (I): 0.1 to 10% by weight.

(Each symbol in the formula indicates the following.

R _1: alkyl group having 12 to 22 carbon atoms, alkenyl or hydroxyalkyl group R _2, R _3: a methyl group, an ethyl group or a benzyl group R _4: an alkyl group, an alkenyl group, hydroxyalkyl group, a methyl group, an ethyl group or a benzyl group X ^-: an anion) (C) the following general formula (II) and (at least one starch derivative of selected from carboxymethyl starch and dialdehyde carboxymethyl starch represented by III): 0.1 to 10 weight %.

(The symbols in the formulas are as follows: p, q, r: degree of etherification, a number of 0 or more, p + q + r = 0.5 to 1.5 m: degree of polymerization, m = 50 to 1000 M: alkali metal or Alkanol-substituted ammonium group) (The symbols in the formula are as follows: s: degree of etherification, s = 0.5 to 1 n: degree of polymerization, n = 50 to 1000 M: alkali metal or alkanol-substituted ammonium group) Will be described in more detail.

As the nonionic surfactant as the component (A), a higher alcohol ethoxylate or higher alcohol propoxytosylate represented by the following general formulas (IV) and (V) is used.

R ₅ —O—CH ₂ —CH ₂ —O ₁ H (IV) (R ₅ : alkyl group having 8 to 20 carbon atoms 1: average number of moles added, 1 = 7 to 30) (R _6: an alkyl group having 8 to 20 carbon atoms m, n: average addition mole number indicates, m = 8~20, n = 1~3 ) in the higher alcohol ethoxylate, average addition mole number of ethylene oxide ( When l) is less than 7, the effect of imparting flexibility to the composition is lowered, while when it exceeds 30, the foaming power of the composition is lowered.

Further, in the higher alcohol ethoxylate, in the general formula (IV), R ₅ is particularly preferably an alkyl group having 9 to 15 carbon atoms.

The higher alcohol ethoxylate has, for example, 8 carbon atoms.
It can be obtained by condensing a primary or secondary alcohol of -20 with polyoxyethylene having an average degree of polymerization of 7-30.

In the higher alcohol propoxyethoxylate of the general formula (V), the addition order of ethylene oxide and propylene oxide is not particularly limited, and these may be any of block addition polymerization, reverse block addition polymerization and random addition polymerization. .

In the general formula (V), the higher alcohol propoxyethoxylate is particularly preferably such that R ₆ is an alkyl group having 9 to 15 carbon atoms.

The nonionic surfactant as the component (A) can be used alone or in combination of two or more kinds, and is 10 to 40% by weight, preferably 20 to 30% by weight in the liquid detergent composition of the present invention.
Be compounded. If the blending amount is less than 10% by weight,
It becomes difficult to uniformly disperse the complex of the cationic surfactant as the component (B) and the starch derivative as the component (C). On the other hand, if the amount is more than 40% by weight, the effect of imparting flexibility to the liquid detergent composition of the present invention is lowered.

As the cationic surfactant as the component (B), a quaternary ammonium salt represented by the general formula (I) is used.

(Each symbol in the formula indicates the following.

R _1: alkyl group having 12 to 22 carbon atoms, alkenyl or hydroxyalkyl group R _2, R _3: a methyl group, an ethyl group or a benzyl group R _4: an alkyl group, an alkenyl group, hydroxyalkyl group, a methyl group, an ethyl group or a benzyl group X ^-: the R ₁ in the anion) formula (I), preferably an alkyl group and alkenyl group of 16 to 20 carbon atoms, especially 16 carbon atoms
-20 tallow alkyl groups are preferred. The X ^- as is,
Halogen ions such as chlorine ion, bromine ion and iodine ion are preferred.

Specific examples of the cationic surfactant as the component (B) include lauryl trimethyl, myristyl trimethyl, palmityl trimethyl, stearyl trimethyl, oleyl trimethyl, cured or uncured tallow alkyl trimethyl,
Dilauryl dimethyl, dimyristyl dimethyl, dipalmityl dimethyl, disateryl dimethyl, di-hardened or uncured alkyl dimethyl, dioleyl dimethyl, di-hardened or uncured tallow alkyl diethyl, hardened or uncured beef tallow alkyl dimethyl benzyl, etc. Examples thereof include salts of quaternary ammonium chloride, bromide, iodide, methosulfate, ethosulfate and the like.

The cationic surfactant as the component (B) can be used alone or in combination of two or more kinds, and is contained in the liquid detergent composition of the present invention in an amount of 0.1 to 10% by weight, preferably 3 to 6% by weight. It When the amount is less than 0.1% by weight, the effect of imparting flexibility to the liquid detergent composition is low. On the other hand, when it exceeds 10% by weight, it becomes difficult to prevent yellowing of the cloth to be washed even if the starch derivative as the component (C) is added.

As the starch derivative as the component (C), carboxymethyl starch [general formula (II)] or dialdehyde carboxymethyl starch [general formula (III)] is used.

(The symbols in the formulas are as follows: p, q, r: degree of etherification, a number of 0 or more, p + q + r = 0.5 to 1.5 m: degree of polymerization, m = 50 to 1000 M: alkali metal or Alkanol-substituted ammonium group) (The symbols in the formula are as follows: s: Degree of etherification, s = 0.5 to 1 n: Degree of polymerization, n = 50 to 1000 M: Alkali metal or alkanol-substituted ammonium group) As carboxymethyl starch When the total etherification degree [p + q + r in the general formula (II)] is less than 0.5, the effect of preventing yellowing of the cloth to be washed is not sufficiently exhibited. On the other hand, when it exceeds 1.5, the anionic property of carboxymethyl starch becomes strong, and the effect of imparting flexibility is deteriorated probably because it strongly forms a complex with the cationic surfactant as the component (B).

If a dialdehyde carboxymethyl starch having an etherification degree [s of the general formula (III)] of less than 0.5 is used, the effect of preventing yellowing of the cloth to be washed is not sufficiently exhibited.

When the degree of polymerization (m, n) of carboxymethyl starch and dialdehyde carboxymethyl starch exceeds 1000, the viscosity of the aqueous solution becomes high, which is not preferable in practice. Further, if the degree of polymerization is less than 50, the effect of imparting flexibility deteriorates. The preferred degree of polymerization (m, n) is 100
~ 500.

The starch derivative as the component (C) can be used alone or in combination of two or more kinds, and is mixed in the liquid detergent composition of the present invention in the range of 0.1 to 10% by weight, preferably 1 to 5% by weight. To be done. If the content is less than 0.1% by weight, yellowing of the cloth to be washed cannot be sufficiently prevented, while if it exceeds 10% by weight, the effect of imparting flexibility is significantly reduced.

In addition to the essential components (A), (B), and (C) described above, other nonionic surfactants may be added to the flexibility-imparting liquid detergent composition of the present invention as long as the object of the present invention is not impaired. It can also be blended. Examples of such nonionic surfactants include higher fatty acid alkanolamides or alkylene oxide adducts thereof, long-chain ( _C12-14 ) tertiary amine oxides and the like.

Furthermore, if desired, other optional components, for example, viscosity modifiers such as lower or polyhydric alcohols, organic carboxylates, lower alkylbenzene sulfonates; sequestering agents such as ethylenediaminetetraacetic acid, citric acid or salts thereof;
Alternatively, a fluorescent whitening agent, a dye, a fragrance, an antioxidant, an emulsifying agent, an antibacterial agent, an enzyme and the like can be added.

The reason why the liquid detergent composition of the present invention can prevent the occurrence of yellowing of the cloth to be washed without impairing the softness imparting effect which the cationic surfactant originally has, is not necessarily clear, but the washing-rinsing If you repeat the cycle,
In the system in which the starch derivative as the component (C) is used in combination, the yellowing decreases during washing, so that the (C) starch derivative / (B) cationic surfactant complex is adsorbed on the fiber, and iron colloid in water is It is considered that even if they adhere, they fall off together with this complex during washing.

EFFECTS OF THE INVENTION According to the flexibility-imparting liquid detergent composition of the present invention, a specific nonionic surfactant (A), a cationic surfactant (B) and a starch derivative (C) are blended in specific ratios. By doing so, it exerts an excellent effect of imparting flexibility to cotton fibers, protein fibers such as silk and wool, synthetic fibers such as acryl and nylon, which are often washed by heavy washing, and yellow in repeated washing. It is possible to effectively prevent the occurrence of a change.

INDUSTRIAL APPLICABILITY The composition of the present invention is useful as a liquid heavy detergent composition having a softening effect, and can also be used as a light detergent.

Hereinafter, the present invention will be described more specifically with reference to Examples, but prior to this, the evaluation methods used in the Examples will be shown.

(1) Evaluation method of the effect of imparting flexibility In a small-sized reversing type washing machine of about 10 volumes, a washing liquid 5 and a bath ratio of 30
Put the cotton towel cloth so that it doubles and wash it for 10 minutes, dehydrate it, rinse it twice with tap water 5, dry it in the shade, and dry it in a constant temperature and constant humidity room (25 ℃, 65% RH). Two
Left for days. This cleaning cloth was subjected to sensory evaluation by 10 panelists according to the following criteria, and the average value was used as the flexibility evaluation point. It is necessary that the evaluation is 3 points or more.

1 point ... not soft 2 points ... a little soft 3 points ... not soft 4 points ... sufficiently soft 5 points ... very soft (2) Evaluation method of yellowing prevention effect As a cleaning device, Terg-O-Tometer (made by USTesting) Using, use a clean knitted cloth, adjust the bath ratio to 30 times, and wash at 120 rpm at 25 ° C for 10 minutes. As the cleaning liquid, use 900 ml with a cleaning liquid concentration of 0.13 wt% and rinse 900
Performed twice with 3 ml water for 3 minutes. The water used was 3 ° DH hard water containing 2 ppm of iron chloride for both washing and rinsing. After washing, dry in the shade and dry for 1 day. The above operation was repeated 5 times, and 10 panelists visually evaluated the knitted fabric according to the following criteria, and the average was taken as the degree of yellowing.

Judgment Criteria ○: No yellowing is observed Δ: Somewhat yellowing ×: Clearly yellowing Examples 1 to 10 and Comparative Examples 1 to 11 Primary C ₁₃ alcohol as a nonionic surfactant Ethoxylate (average number of moles of ethylene oxide added EO
= 15) 28% by weight, and 0.15% by weight of Tinopanol 4409 (manufactured by Ciba-Geigy-Akchengezelshaft) described in JP-A-56-8350 as a fluorescent agent, and these concentrations were made constant. As shown in -1, as a cationic surfactant, dioctadecenyldimethylammonium chloride (C ₁₈ DC), and as a yellowing inhibitor, various starch derivatives or anionic surfactants having different etherification degrees and polymerization degrees. Using an activator, these were mixed at various ratios shown in Table 1, and the balance was balanced with water to prepare a liquid detergent composition.

With respect to these liquid detergent compositions, the effect of imparting flexibility and the effect of preventing yellowing were evaluated, and the results are shown in Table 1.

 The abbreviations in the table are as follows.

LAS-Na: C ₁₂ sodium linear alkylbenzene sulfonate AES-Na: C _{12 to} C ₁₃ primary alcohol ethoxy (EO =
3) Sodium sulfate Soap: Sodium oleate C ₁₈ DC: Dioctadecenyldimethylammonium chloride Examples 11 to 21, Comparative Examples 12 to 14 Carboxymethyl starch having a degree of etherification of 0.8 and a degree of polymerization of 200 was used, and the concentration thereof was kept constant at 4% by weight. As shown in Table-2, various nonionic surfactants and cationic surfactants were used, and these were mixed at various ratios shown in Table-2, and the balance was balanced with water to wash the liquid. An agent composition was prepared.

The effect of preventing yellowing and the effect of imparting flexibility to these detergent compositions were evaluated, and the results are shown in Table 2.

 Here, the abbreviations in the table are as follows.

PO: average number of moles of propylene oxide added C ₁₈ DC: dioctadecenyldimethylammonium chloride C ₁₈ MC: octadecyltrimethylammonium chloride BOC: benzylmethyl 4-t-octylphenoxyethoxyethylammonium chloride C ₁₈ BC: octadecyldimethylbenzyl Ammonium chloride

Claims (1)

(57) [Claims] 1. An (A) alkyl group having 8 to 20 carbon atoms,
A higher alcohol ethoxylate having an average addition mole number of ethylene oxide of 7 to 30; and an alkyl group having 8 to 20 carbon atoms, and an average addition mole number of propylene oxide of 1 to 1
3, at least one nonionic surfactant selected from higher alcohol propoxyethoxylates having an average added mole number of ethylene oxide of 8 to 20: 10 to 40% by weight, (B) the following general formula (I) (Each symbol in the formulas represents the following: R ₁ : alkyl group having 12 to 22 carbon atoms, alkenyl group or hydroxyalkyl group R ₂ , R ₃ : methyl group, ethyl group or benzyl group R ₄ : alkyl group , alkenyl group, hydroxyalkyl group, a methyl group, an ethyl group or a benzyl group X ^-: at least one cationic surfactant selected from quaternary ammonium salts represented by anionic): 0.1 to 10 wt % And (C) the following general formulas (II) and (III) (The symbols in the formulas are as follows: p, q, r: degree of etherification, a number of 0 or more, p + q + r = 0.5 to 1.5 m: degree of polymerization, m = 50 to 1000 M: alkali metal or Alkanol-substituted ammonium group) (The symbols in the formula are as follows: s: etherification degree s = 0.5 to 1 n: polymerization degree, n = 50 to 1000 M: alkali metal or alkanol-substituted ammonium group) A softness-providing liquid detergent composition comprising at least one starch derivative selected from methyl starch and dialdehyde carboxymethyl starch: 0.1 to 10% by weight.