JP2007308598A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition suppressed in the absorption of a gas such as oxygen during storage, slight in the deformation of its container after its storage even in case that a lightweight plastic container with reduced basis weight is used as its container, and impairing no degree of freedom of its container's design. <P>SOLUTION: The liquid detergent composition comprises (a) 20-50 mass% of a nonionic surfactant, (b) 1-20 mass% of a tetra-to-octahydric 5-20C alcohol, (c) 1-10 mass% of a dihydric 2-20C alcohol and/or a trihydric 3-20C alcohol, (d) a phenolic radical-trapping agent, (e) a phosphonic acid-based metal scavenger and (f) water, wherein the mass ratio b/c and the composition's pH(20°C) fall within specific ranges, respectively. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition and a liquid detergent article. In particular, it relates to a liquid detergent composition for clothing and a liquid detergent article for clothing.

A plastic container for storing a liquid cleaning composition is directed to reducing the weight per unit of the plastic container in order to save resources and reduce the weight. Since the plastic container has become thinner due to the reduction in the weight per unit area of the plastic container, the internal pressure of the liquid detergent composition, which is the content, is reduced due to oxygen absorption and the internal pressure is reduced due to the temperature difference between filling and use. There is a problem that the container is easily deformed into a concave shape on both the front side and the back side of the body part or one side, and the appearance of the plastic container is significantly impaired. As a countermeasure against such pressure reduction deformation of a plastic container, it has been proposed that a pressure reduction absorption panel is provided in the body portion of the plastic container to make the deformation due to the internal pressure reduction inconspicuous (for example, Patent Document 1). Moreover, in the blow molded bottle, the surface on the side to be deformed corresponding to the pressure reduction of the internal pressure of the plastic container is intentionally provided by changing the curvature on the front surface side and the curvature on the back surface side of the horizontal section of the container body. A plastic container has been proposed (for example, Patent Document 2).
JP-A-11-208634 JP 2001-199419 A

However, a plastic container with a vacuum absorption panel on the body of the plastic container has a reduced display area and the appearance of the plastic container is reduced when the secondary processing such as printing or labeling is applied. It was a problem because there was a restriction in the degree of freedom in plastic container design.

  On the other hand, the surfactant used in the liquid detergent composition is non-ionic surfactant from the viewpoint of being less affected by water hardness and electrolyte, exhibiting relatively high surface activity at a low concentration, and low foaming properties. Drugs are attracting attention. However, since the liquid detergent composition containing a nonionic surfactant dissolves oxygen in the filled head space in the container, it is necessary to cope with the deformation of the container due to a decrease in the container internal pressure. If the deformation of the container can be suppressed by improving the composition filled in the container, it is desirable in terms of improving the degree of freedom in container design, but a liquid detergent composition that has a sufficient effect has not yet been found.

  The problem of the present invention is that gas absorption such as oxygen during storage is suppressed, and even when a lightweight plastic container with a reduced weight per unit area is used, there is little deformation of the container after storage, and the degree of freedom in container design is not impaired. The object is to provide a liquid detergent composition.

  The present invention includes (a) a nonionic surfactant (hereinafter referred to as component (a)) 20 to 50% by mass, (b) a tetravalent to octavalent alcohol having 5 to 20 carbon atoms [hereinafter referred to as component (b). 1 to 20% by mass, (c) a divalent alcohol having 2 to 20 carbon atoms and / or a trivalent alcohol having 3 to 20 carbon atoms [hereinafter referred to as component (c)] 1 to 10% by mass, (d ) A phenol-based radical trapping agent (hereinafter referred to as component (d)), (e) a phosphonic acid-based metal scavenger (hereinafter referred to as component (e)), and (f) water, (C) It is related with the liquid detergent composition whose mass ratio of a component is 1/1 to 10/1 and whose pH measured at 20 degreeC of JISK3362: 1998 is 4-7.

  The present invention also relates to a liquid detergent article comprising a plastic container having a weight per volume of 100 ml of 3 to 10 g and filled with the liquid detergent composition of the present invention. The weight of the container is a container weight per unit volume (100 ml), and may be referred to as a container weight per unit (unit: g / 100 ml) for convenience.

  Since the liquid cleaning composition of the present invention hardly absorbs the gas inside the container when it is filled in the container, the use of the composition makes it possible to use a thin-walled container with a reduced amount of resin. There is an effect that no deformation or dent occurs. In addition, since it is not necessary to design the container for absorption under reduced pressure, there is an effect that the degree of freedom of the bottle design to be used is improved.

<(A) component>
(A) As a nonionic surfactant of a component, the compound of following General formula (1) is mentioned.
R-O [(EO) _a / (PO) _b ] -H (1)
[Wherein, R represents an alkyl group or an alkenyl group having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms. a is the average number of added moles and is a number from 0 to 20, b is the average number of added moles and represents a number from 0 to 20, except when both a and b are 0. Preferably, the average added mole number of a is 6 to 15, more preferably 7 to 12, and the average added mole number of b is 0 to 10, more preferably 1 to 5, particularly preferably 1 to 3. It is. ]

  In the general formula (1), EO and PO may be arranged in any form of a random copolymer or a block copolymer.

The nonionic surfactant of the present invention is particularly preferably a polyoxyalkylene alkyl ether type nonionic surfactant having an oxyethylene group and an oxypropylene group. The polyoxyalkylene alkyl ether type nonionic surfactant may be arranged in any form of a random copolymer or a block copolymer, and among them, a block copolymer is preferable. As the form of the block copolymer, a compound represented by the following general formula (2) is particularly preferred.
R ¹ −O (EO) _x (PO) _y (EO) _z −H (2)
[Wherein, R ¹ represents an alkyl group or an alkenyl group having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms. x is an average number of added moles and is a number from 1 to 20, y is an average number of added moles and is a number from 1 to 20, and z is an average number of added moles and represents a number from 1 to 20. Preferably, the average added mole number of x is 6 to 15, more preferably 7 to 12, and the average added mole number of y is 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3. The average added mole number of z is 6 to 15, more preferably 7 to 12. ]

  You may mix | blend (a) component as a 2 or more types of mixture. (A) Content of a component is 20-50 mass% in the liquid cleaning composition of this invention, Preferably it is 25-45 mass%, More preferably, it is 30-40 mass%.

<(B) component>
(B) Examples of the 4- to 8-valent polyhydric alcohol having 5 to 20 carbon atoms as the component include aliphatic polyols, for example, alkane polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, and the like or Examples include intramolecular or intermolecular dehydrates of alkanetriol; and saccharides such as sucrose, glucose, mannose, fructose, and methylglucoside. Preferably, sorbitol, mannitol and glucose are used. (B) Content of a component is 1-20 mass% in the liquid detergent composition of this invention, Preferably it is 3-15 mass%, More preferably, it is 5-15 mass%.

<(C) component>
Among the components (c), the dihydric alcohol having 2 to 20 carbon atoms (hereinafter referred to as the component (c1)) is an aliphatic diol such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4. -Alkylene glycols such as butanediol, 1,6-hexanediol, neopentyl glycol; and alicyclic diols such as cycloalkylene glycol such as cyclohexanediol.

  In addition, among the components (c), the trivalent alcohol having 3 to 20 carbon atoms (hereinafter referred to as the component (a2)) includes aliphatic triols such as glycerin, trimethylolpropane, trimethylolethane, and hexanetriol. Alkanetriol is mentioned.

  (C) As a component, ethylene glycol, propylene glycol, and glycerin are preferable.

  In addition, it is preferable to use the component (c1) and the component (c2) together in terms of suppressing the amount of gas absorption, and the mass ratio in this case is (c1) / (c2) = 10/1 to 1/2, Further, 5/1 to 1/1 is preferable.

  (C) Content of a component is 1-10 mass% in the liquid detergent composition of this invention, Preferably it is 2-8 mass%, More preferably, it is 3-7 mass%.

  In the liquid detergent composition of the present invention, from the viewpoint of suppressing gas absorption during storage and suppressing container deformation after storage, the mass ratio of the component (b) / (c) is 1/1 to 10/1. The ratio is preferably 3/1 to 8/1, more preferably 2/1 to 5/1.

<(D) component>
As the phenolic radical trapping agent as component (d), compounds having a phenolic OH group, and derivatives such as ester derivatives and ether derivatives thereof are preferred. Suitable examples include dimethoxyphenol, catechol, hydroquinone, methoxyphenol, phenolsulfonic acid, dibutylhydroxytoluene (BHT) and the like. (D) Content of a component is 0.1-5 mass% in the liquid detergent composition of this invention, Furthermore, 0.3-3 mass%, Especially 0.5-2 mass% is preferable.

<(E) component>
As the phosphonic acid-based metal scavenger of the component (e), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonate, 1-hydroxyethane-1,1-diphosphonic acid, ethanehydroxy- Examples include organic phosphonic acid derivatives such as 1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid, and the like. . These can be used alone or in combination of two or more. Of these, 1-hydroxyethane-1,1-diphosphonic acid, ethylenediaminetetrakismethylenephosphonic acid and the like are preferable. (E) As for content of a component, 0.1-5 mass%, 0.3-3 mass%, and 0.5-2 mass% are preferable in the liquid cleaning composition of this invention.

<(G) component>
The liquid detergent composition of the present invention preferably contains a monohydric alcohol having 1 to 4 carbon atoms as the component (g). Examples of the component (g) include methanol, ethanol, isopropanol, and phenyl polyoxyethylene alcohol. (G) Content of a component is 0.1-10 mass% in the liquid detergent composition of this invention, Furthermore, 0.5-5 mass% is preferable.

<(H) component>
The liquid detergent composition of the present invention preferably contains, as component (h), a sulfonic acid having 4 to 10 carbon atoms in the molecule and having aromaticity or a salt thereof. Examples of the component (h) include paratoluenesulfonic acid or a salt thereof, paraxylenesulfonic acid or a salt thereof. The content of the component (h) is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass in the liquid detergent composition of the present invention.

<(I) component>
The liquid detergent composition of the present invention preferably contains a boron compound as component (i). Examples of the component (i) include at least one compound selected from boric acid, borax, and borate. Examples of borates include sodium borate, potassium borate, ammonium borate, sodium tetraborate, potassium potassium borate, and ammonium ammonium borate. (I) Component content is 0.05-10 mass% in the liquid cleaning composition of this invention from a viewpoint of stabilization of pH, Furthermore, 0.5-5 mass% is preferable.

<Other ingredients>
In addition to the nonionic surfactant (a) component, the liquid detergent composition of the present invention is disclosed in the Patent Office's “Known and Conventional Techniques (Clothing Detergent for Clothing)” Japan Patent Office, March 26, 1998. JP, P4-22, may contain a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.

  In addition, the liquid detergent composition of the present invention may contain optional components such as silicones, bactericides, fluorescent dyes, enzymes, and fragrances. The liquid detergent composition of the present invention contains (f) water, and usually the balance of the composition is water.

  The liquid detergent composition of the present invention has a pH of 4 to 7, preferably 4 to 6, more preferably 4 to 5 measured at 20 ° C. described in JIS K3362: 1998. PH adjusting agents for adjusting to such pH include inorganic acids such as hydrochloric acid and sulfuric acid, or acids such as organic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid and maleic acid. Or alkali agents such as sodium hydroxide, potassium hydroxide, ammonia and derivatives thereof, amine salts (monoethanolamine, diethanolamine, triethanolamine, etc.), sodium carbonate, potassium carbonate, etc. may be used alone or in combination. It is particularly preferable to use an acid selected from hydrochloric acid and sulfuric acid, or an alkali agent selected from sodium hydroxide and potassium hydroxide.

  The object of the liquid detergent composition of the present invention is preferably a textile product such as clothing, and most preferably applied to a textile product such as clothing that is washed using a washing machine.

<Container>
The liquid detergent composition of the present invention is suitable for filling a container into a liquid detergent article. In particular, it is preferable to fill a plastic container having a weight per unit volume of 3 to 10 g / 100 ml, preferably 3 to 9 g / 100 ml, more preferably 4 to 8 g / 100 ml.

  The container used in the present invention is preferably composed of a single layer or a laminate made of a resin. Examples of the resin include an ethylene resin, a propylene resin, a styrene resin, an ester resin, and a polyamide resin. Alternatively, a mixture of these resins can be used. Preferably, an ethylene homopolymer, an ethylene copolymer can be used as the ethylene resin, and a propylene homopolymer or a propylene copolymer can be used as the propylene resin. Particularly preferably, polyethylene, ethylene / α-olefin copolymer containing at least one α-olefin (preferably having 4 to 10 carbon atoms), propylene / ethylene copolymer, ethylene / vinyl acetate copolymer, ethylene・ (Meth) acrylic acid copolymer, zinc (Zn), sodium (Na), calcium as metal (Ca) at least one kind of ethylene / (meth) acrylic acid copolymer metal salt partial neutralized product (sometimes referred to as ionomer resin), ethylene / (meth) acrylic acid alkyl ester copolymer, polystyrene, A styrene-type copolymer is mentioned. A container containing the liquid cleaning composition of the present invention preferably does not have a vacuum absorbing means, for example, a vacuum absorbing panel (a circumferential polyhedral wall or a plurality of curved surfaces undulating in the axial direction of the barrel), etc. Used for.

The liquid cleaning composition of Table 1 was prepared and the following evaluation was performed. The results are shown in Table 1.
(1) Measuring method of gas absorption
Water was filled up to the top of the opening of a 500 ml conical stoppered conical flask (total volume of about 555 ml) shielded with aluminum foil, and then the surface of the water after removing 105 ml of water with a pipette was marked. Water was discarded and the liquid detergent composition was poured up to this position. After standing for 30 minutes in a thermostatic bath at a temperature of 20 ° C, the portion of the thread in the glass tube with a grounding stopper (length equal to or larger than the grounding is 100 cm, length below the grounding is 15 cm and has a uniform inner diameter) Apply a thin layer of silicon grease and insert it into the flask (be careful that the meniscus part is at the top of the tap). After confirming that the grease had spread all around the slot plug, it was fixed using a spring or rubber band. The plug portion was covered with aluminum foil, and the position of the meniscus was recorded after being left in a thermostatic bath at a temperature of 20 ° C. (the water level of the thermostatic bath is the opening of the flask) or in a thermostatic chamber for 2 hours. At the same time, the position of the meniscus was recorded in the same set with ion-exchanged water. Both the liquid detergent composition and ion-exchanged water were allowed to stand at 50 ° C. for 60 days and then stored at 20 ° C. for 1 day. The change in each meniscus was measured, and the gas absorption was calculated according to the following equation.
Gas absorption (ml / 450ml) = (x -x 0) π (d / 2) 2
x = amount of change in meniscus of liquid detergent composition (cm)
x ₀ = Change in meniscus of ion exchange water (cm)
d = Inner diameter of glass tube (cm)

(2) Bolt dent measurement 150 ml of liquid detergent composition is filled into a polyethylene cylinder bottle (full volume 280 ml, container weight 23 g / 100 mL), the cap is sealed at 20 ° C, and stored at 50 ° C for 60 days. After that, it was stored at 20 ° C. for 1 day, and the dent of the bottle was measured at that temperature and evaluated according to the following criteria.
○: No change ○ to Δ: Deformation exceeding 0 mm and 3 mm or less Δ: Deformation exceeding 3 mm and deformation of 5 mm or less ×: Deformation exceeding 5 mm

The components in the table are as follows. The pH adjustment amount of sodium hydroxide is such an amount that the pH in the table is reached.
A-1: Softanol 70H (manufactured by Nippon Shokubai Co., Ltd.): Ethylene oxide adduct having an average addition mole number of 7 of linear secondary alcohol having 12 and 14 carbon atoms)
A-2: Emulgen 120 (manufactured by Kao Corporation): an ethylene oxide adduct having an average addition mole number of 12 of linear primary alcohol having 12 and 14 carbon atoms
_{· A-3: CH 3 -} (CH 2) k -O- (C 2 H 4 O) l - (C 3 H 6 O) m - (C 3 H 6 O) n -H (k 11 and 13 And l, m and n represent the average number of added moles of 5, 2 and 3, respectively)
E-1: Dequest 2010 (manufactured by Solusia): ethane-1-hydroxy-1,1-diphosphonic acid LAS: alkylbenzene sulfonic acid having 12 and 14 carbon atoms in the alkyl group AOS: sodium α-olefin sulfonate (Carbon number 14)
Amine oxide: Amphital 20N (manufactured by Kao Corporation): amine oxide having a total carbon number of 12

Claims (6)

(A) 20-50% by mass of a nonionic surfactant, (b) 1-20% by mass of a 4-8 valent alcohol having 5-20 carbon atoms, (c) a divalent alcohol having 2-20 carbon atoms, and / or Or 1 to 10% by mass of a trivalent alcohol having 3 to 20 carbon atoms, (d) a phenol radical trapping agent, (e) a phosphonic acid metal scavenger, and (f) water, / (C) The liquid detergent composition whose mass ratio of a component is 1 / 1-1 / 10/1 and whose pH measured at 20 degreeC of JISK3362: 1998 is 4-7. The liquid detergent composition according to claim 1, further comprising (g) a monohydric alcohol having 1 to 4 carbon atoms. The liquid detergent composition according to claim 1 or 2, further comprising (h) a sulfonic acid having 4 to 10 carbon atoms in the molecule and having aromaticity or a salt thereof. Furthermore, the liquid cleaning composition in any one of Claims 1-3 containing (i) boron compound. The liquid detergent article | item formed by filling the liquid detergent composition in any one of Claims 1-4 in the plastic container whose weight per 100 ml of capacity | capacitance is 3-10g. The liquid detergent article according to claim 5, wherein the plastic container is a container having no vacuum absorbing means in the container body.