JP2006077207A - Liquid detergent products and liquid softener products - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid product that has good refill workability over a long period of use, to provide a liquid product that can stably maintain the quality of the composition that is the content, and the composition before the next refill operation It is an object to provide at least one of the liquid products that are easy to store without the product flowing out of the bag.
SOLUTION: A liquid detergent composition or a liquid softener composition having a viscosity at 25 ° C. of 10 to 500 mPa · s, and an openable / closable pouring part are formed, and the liquid detergent composition or liquid softener is formed. It is solved by a liquid product characterized by having a bag for containing the composition.
[Selection figure] None

Description

  The present invention relates to liquid detergent products and liquid softener products.

Conventionally, liquid detergent compositions and liquid softener compositions have been sold as products in containers such as plastic bottles and bags such as polyethylene, polypropylene, and polyethylene terephthalate. In particular, recently, liquid products for refilling stored in simple bottles and bags have been widely distributed, and it has become common to refill the contents into containers that can be used for a long time.
Such refilled liquid products are required to maintain the quality of the contents stably and to have good workability during refilling.

Under such a background, for example, in Patent Document 1, at least one layer is used as a liquid cleaning composition in a storage bag, which is used for refilling purposes and has excellent aroma stability of the liquid cleaning composition during long-term storage. A liquid detergent composition containing an antioxidant is stored in a storage bag made of a multilayer film having two or more ink layers that are colored ink layers other than white and having a total light transmittance of 25% or less. Have been disclosed.
Patent Document 2 describes a material having excellent light-shielding properties, including a light-shielding layer composed of two layers of a white ink layer and a gold-red ink layer as a packaging material for maintaining the quality of the contents. Patent Document 3 discloses a light-shielding packaging material in which at least a white first printing layer, a brown or silver second printing layer is provided on one side of a plastic film, and a sealant layer is provided via a colored resin layer. Is described.
JP 2001-98300 A JP 09-66578 A JP 09-314719 A

  However, the storage bag described in Patent Document 1 is a form in which the spout is formed by cutting the cut portion along the cutting guide line, and once the cut portion is cut, it cannot be resealed. There was a problem. In other words, storage bags and containers used for refill products become waste after the contents are refilled, so from the environmental and cost viewpoints, they can be resealed and contain multiple contents. Although the thing of the form refilled over time is thought to be preferable, in the storage bag described in patent document 1, the contents can be refilled only once in fact.

In addition, for liquid products that refill the contents multiple times, it can be easily refilled from the first refill to the last refill, that is, refillability is good over a long period of use. It is required to be. Specifically, regardless of the remaining amount of contents in the bag, the operator can perform refilling work in a short time while appropriately controlling the amount of liquid to be injected once, and the liquid should not splatter during refilling. Etc. are required.
In addition, it is required that the quality of the contents be stably maintained from the first refill to the last refill. For example, in the case of a content that is easy to form a film, it is important to suppress such inconvenience because a part of the content may solidify each time the number of refills is repeated.
Furthermore, until the next refilling operation, the contents should not be spilled even if they fall out of the bag or fall together with the product, and should be stored for a long time.
However, in Patent Document 1, although the angle and outer diameter of the spout are defined and the ease of refilling is evaluated, refilling workability over a long period, quality stability of contents, ease of storage, etc. Is not described at all. Further, the storage bag described in Patent Document 1 does not have these characteristics.

  In addition, the inventions described in Patent Documents 2 and 3 are mainly intended for packaging food, and are intended to suppress oxidation by light or to suppress deterioration of fragrance of a fragrance. There is no suggestion or description about maintaining the quality of the liquid softener composition in a stable manner, nor is it possible to maintain it stably.

  The present invention has been made in view of the above circumstances, and provides a liquid product that has good refill workability over a long period of use, and a liquid product that can stably maintain the quality of the composition as the contents. That is, at least one of the problems is to provide a liquid product that is easy to store without the composition flowing out of the bag body until the next refilling operation.

The present inventors have intensively studied and appropriately controlled the viscosity and composition of the liquid detergent composition and the liquid softener composition stored in the bag body, and by making the bag body a specific one, the above The present invention has been completed by finding out that the problems can be solved.
That is, the first liquid detergent product of the present invention has a liquid detergent composition having a viscosity of 10 to 500 mPa · s at 25 ° C. and a pouring part that can be opened and closed, and the liquid detergent composition It has the bag body which accommodates. According to this liquid detergent product, the refilling workability is good over a long period of use, and the dispensing part can be freely opened and closed, so that the composition can be easily stored until the next refilling work. Excellent.
The second liquid detergent product of the present invention comprises a liquid detergent composition containing 5 to 50% by mass of surfactant (A) and 1 to 20% by mass of alcohol (B-1), and is openable and closable. A pour-out portion is formed, and the pouch has a bag body for storing the liquid detergent composition. According to this liquid detergent product, the quality of the composition as a content can be stably maintained, and since the pouring part can be opened and closed freely, the composition can be stored until the next refilling operation. Excellent ease.
Further, the first liquid softener product of the present invention comprises a liquid softener composition having a viscosity at 25 ° C. of 10 to 500 mPa · s and a pouring part that can be freely opened and closed. It has the bag body which accommodates. According to this liquid softener product, the refilling workability is good over a long period of use and the dispensing part can be freely opened and closed, so that the composition can be easily stored until the next refilling work. Excellent.
The second liquid softener product of the present invention is selected from the group consisting of a tertiary amine having a long-chain hydrocarbon group and an ester group, a neutralized product of the tertiary amine, and a quaternized product of the tertiary amine. Liquid softener composition containing 3 to 40% by mass of at least one amine-based compound (C) and 0.5 to 10% by mass of alcohol (B-2), and an openable / closable pouring part is formed And a bag for storing the liquid softening agent composition. According to this liquid softener product, the quality of the composition as a content can be stably maintained, and the pouring part can be freely opened and closed, so that the composition can be stored until the next refilling operation. Excellent ease.

  ADVANTAGE OF THE INVENTION According to this invention, the refill workability | operativity can provide a liquid product favorable over a long use period. Moreover, the liquid product which can hold | maintain the quality of the composition which is a content stably can be provided. In addition, it is possible to provide a liquid product that is easy to store without causing the composition to flow out of the bag body until the next refilling operation.

Hereinafter, the liquid detergent product of the present invention will be described in detail.
[First liquid detergent product]
The first liquid detergent product of the present invention has a liquid detergent composition having a viscosity at 25 ° C. of 10 to 500 mPa · s and a pouring part that can be opened and closed, and contains the liquid detergent composition. And a bag body.

(Liquid detergent composition)
The liquid detergent composition used for the first liquid detergent product contains at least one surfactant that increases the permeability of the composition to the object to be washed and has a function of washing the object to be washed. And if the viscosity in 25 degreeC is controlled by 10-500 mPa * s, there will be no restriction | limiting in particular. When the viscosity at 25 ° C. is in the range of 10 to 500 mPa · s, refillability from the first refill to the last refill is good, that is, the refill workability is good over a long period of use. Specifically, regardless of the amount of the composition in the bag, the operator can perform the refilling operation in a short time while appropriately controlling the amount of the injected liquid for one time, and the liquid does not scatter when refilling. When the viscosity at 25 ° C. is less than 10 mPa · s, it is difficult to control the amount of injected liquid for one time, especially when the contents are refilled from a bag containing a composition that can be refilled twice or more. Objects are likely to splatter and spill, and the composition may overflow from the refill container. In addition, even when the remaining amount of the composition in the bag is reduced, the composition is likely to be scattered or spilled. On the other hand, if the viscosity exceeds 500 mPa · s, the refilling operation takes too much time.

  Examples of surfactants include commonly used anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Even if these are used alone, two or more types can be used. You may use together. Although there is no restriction | limiting in particular in content of surfactant in a liquid cleaning composition, Since it expresses sufficient detergency and it is easy to control the viscosity of a composition to the said range, it is 5-50 mass% normally. Preferably it is 5-40 mass%.

Moreover, other arbitrary components can be mix | blended with a liquid cleaning composition as needed other than surfactant.
Examples of other components that can be blended include enzymes (proteases, lipases, cellulases, etc.) and stabilizers (sodium benzoate, citric acid, sodium citrate, etc.) for the purpose of improving cleaning performance and blending stability. Preservatives, hydrotropes, fluorescent agents, dye transfer inhibitors, pearl agents, antioxidants, soil release agents, and the like can be blended.
In addition, a coloring agent and a flavoring agent can be blended for the purpose of improving the added value of the product. As the colorant, pigments and pigments such as Acid Red 138, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Turquoise P-GR, etc. (all trade names) can be used, and the preferred blending amounts thereof are: It is about 0.00005-0.0005 mass%. The fragrance | flavor etc. which are used by the term of "Example" can be used as a fragrance | flavor, The preferable compounding quantity is 0.1-1 mass%.

The method for preparing the liquid detergent composition is not particularly limited, and is prepared by controlling the viscosity within the above range by blending a surfactant, the above optional components as necessary, and further water as necessary. it can.
In addition, the method of use is not particularly limited, but in the case of a liquid detergent composition for clothing, after the article to be washed is put into the washing machine, the washing machine tub is filled with water, and an appropriate concentration is obtained. The composition is added and dissolved so that a washing liquid is obtained, whereby the article to be washed can be washed. In the case of other uses, a normal usage method may be used.

(Bag)
As an example of a bag body that stores the liquid detergent composition, there is a standing type bag body 10 of FIG.
The bag body 10 is a liquid body which is formed at the center of a bag body 11 formed in a bag shape and the upper end portion 11a of the bag body 11 with the periphery of the resin film closed by heat sealing. It comprises a pouring part 12 for pouring out the cleaning composition. The dispensing portion 12 has a screw portion (not shown) formed on the outer peripheral surface, a resin-made cylindrical member 12a attached to the bag body 11 by heat fusion, and a screw portion formed on the inner peripheral surface. It consists of a cap member (not shown) that is screwed to 12a, and is openable and closable. The lower end portion 11b of the bag body 11 is a bottom formed by forming a folded portion 11c in which a resin film forming the bag body 11 is folded and partially heat-sealing. When the composition is filled therein, the folding portion 11c opens, so that the bag body 10 can stand on its own. In this example, H ₁ = 300 mm, W = 180 mm, H ₂ = 324 mm, H ₃ (bottom folding width) = 50 mm, L ₁ = 26.9 mm, L ₂ = 24.0 mm, L ₃ = 90 mm in the figure. , D = 16 mm, and the capacity of the bag 10 is 1500 ml.

  Here, the resin film forming the bag body 11 is not particularly limited, and may be a single layer film or a multilayer film, but as an inner layer (a layer in contact with the composition), a heat adhesive property having an adhesive property by heat fusion. It is preferable to use a multilayer film including a resin film and an outer layer including a film made of a resin excellent in mechanical, physical, and chemical properties.

Examples of the heat-adhesive resin that forms the inner layer include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene-olefin copolymer, and ethylene-propylene copolymer. Examples thereof include resins such as a polymer, an ethylene-vinyl acetate copolymer, an ionomer resin, an ethylene-acrylic acid copolymer, an ethylene-methyl acrylate copolymer, and an ethylene-methacrylic acid copolymer. You may use individually or in mixture of 2 or more types.
Examples of the resin forming the outer layer include polyester-based, polyamide-based, polypropylene-based, and polyacetal-based resins. Of these, one type may be used alone, or two or more types may be used in combination. Good. The film used for the outer layer may be an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction.

  Further, an intermediate layer for providing gas barrier properties such as oxygen gas and water vapor gas and light shielding properties may be provided between the inner layer and the outer layer. Examples of materials that can provide gas barrier properties and light-shielding properties and are preferably used for the intermediate layer include metal foils such as aluminum, iron, copper, and tin; polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, polychlorinated Films made of vinylidene, etc .; Polyolefins such as polyester, polyamide, polyethylene, polypropylene, ethylene-propylene copolymer, films made of polyvinyl alcohol, etc .: Films made of polyvinyl chloride: Aluminum, silicon oxide, aluminum oxide, oxidized Examples thereof include a film on which an inorganic substance such as indium, tin oxide, and zirconium oxide is deposited. In addition to the gas barrier properties and light shielding properties, the intermediate layer has functions such as mechanical toughness, flex resistance, puncture resistance, impact resistance, cold resistance, heat resistance, chemical resistance, etc. May be provided. In that case, an intermediate layer may be formed by combining a film of polyolefin such as polyester, polyamide, polyethylene, polypropylene, or ethylene-propylene copolymer having these functions and a film having gas barrier properties and light shielding properties. .

There is no restriction | limiting in particular in the thickness of each of the above layers, The inner layer should just be the thickness which can be favorably bonded by heat fusion, However, Preferably it is 100-200 micrometers. The outer layer only needs to have strength and rigidity that can withstand the contents of the liquid detergent composition, but it is preferably 5 to 50 μm. Further, the intermediate layer may have a thickness that exhibits a desired effect, but it is preferably 5 to 50 μm.
Moreover, although there is no restriction | limiting in the total thickness of the resin film which forms the bag main body 11, 100-300 micrometers is preferable from the protection property of a composition and the easiness of a bag body (standing property), More preferably, 140 ˜250 μm.

  The material of the cylindrical member 12a and the cap member constituting the extraction portion 12 is not limited as long as the extraction portion 12 can be formed so as to be openable and closable, but the cylindrical member 12a and the cap member can be easily molded, It is preferable to use a resin of the same material as the inner layer of the bag body 11 because it has excellent liquid-tightness when screwed with the cap member, and excellent heat fusion between the cylindrical member 12a and the inner layer. Moreover, there is no restriction | limiting in the internal diameter (it shows with d in the figure) of the cylinder member 12a, but according to the viscosity of a liquid cleaning composition so that the extraction | pouring speed | rate of a liquid cleaning composition may become an appropriate range. It is preferable to determine, and it is 5-40 mm normally, Preferably it is 5-25 mm. Moreover, although there is no restriction | limiting in particular in the cross-sectional shape of the cylinder member 12a, Usually, it is circular or elliptical. In addition, the inner diameter in the case of an ellipse refers to a major axis here. The cylindrical member 12a of the illustrated bag 10 has a circular cross section and an inner diameter of 16 mm.

  Moreover, you may print on the outer surface of the bag body 10 the design for giving designability, a brand name, etc. suitably. Inks used for printing include metal-containing pigments such as phthalocyanine pigments, titanium-containing pigments, chromium oxide, cobalt, silica, and alumina, and general pigments such as azo pigments, anthraquinone pigments, verinone pigments, and thioindigo pigments. One containing one or more organic pigments can be used. These pigments can be used together with, for example, alcohol solvents, ester solvents, ether alcohol solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ketone solvents, and binder resins. For example, ink can be produced by premixing with a mixer, a kneader or the like and then sufficiently kneading with a roll mill, ball mill, sand mill or the like. Although there is no restriction | limiting in particular as binder resin, The urethane resin excellent in adhesiveness is preferable.

As a method for printing on the outer surface of the bag body 10, a normal printing method such as gravure printing, offset printing, screen printing, flexographic printing, or reverse roll coating, floating knife coating, kiss roll coating, spray coating, etc. The usual application method etc. are mentioned. Of these, gravure printing is generally used for general purposes.
If necessary, some printing according to the purpose may be performed on the inner surface of the bag body 10.

  According to such a bag body 10, the openable and closable pouring portion 12 is formed, and when the composition as the contents is to be refilled, the cap member is removed from the tubular member 12a, and the composition is transferred to another container. On the other hand, when storing the composition, the cylindrical member 12a and the cap member are screwed together to close the pouring portion 12 in a liquid-tight manner to prevent the composition from flowing out. it can. Therefore, when the stored composition is refilled several times, the contents do not flow out of the bag until the next refilling operation, or even if the product falls, the composition does not spill. 10 can be securely stored.

Note that the bag body 10 in the illustrated example is a standing type, which is excellent in space saving at the time of display at a store, etc., and is also excellent in appeal to buyers, but the form of the bag body is a standing type. It is not limited and any thing may be sufficient.
In addition, the bag body 10 includes a bag body 11 that is formed in a bag shape in which the periphery of the resin film is closed by heat sealing, but the bag body 11 is not limited to such a heat seal type. It may be sealed with ultrasonic waves or may be formed by other molding methods.
In this example, the pouring part 12 is formed in the center of the upper end part 11a of the bag body 11, and in the case of the standing type bag body 10, it is excellent in usability at the time of refilling. There is no restriction | limiting in particular in the formation position of 12, and you may form in any parts of the bag main body 11, such as the arbitrary parts of the lower end part 11b other than the corner | angular part of the upper end part 11a which is similarly excellent in usability.
Further, the dispensing portion 12 is also composed of a cylindrical member 12a and a cap member, and is not limited to a form in which liquid tightness is expressed by screwing, but a push-in fitting cap type, a hinge cap type, a push-pull type Any form may be used as long as liquid tightness can be exhibited when the pouring part 12 is closed, such as a screw cap type.

[Second liquid detergent product]
The second liquid detergent product of the present invention comprises a liquid detergent composition containing 5 to 50% by mass of surfactant (A) and 1 to 20% by mass of alcohol (B-1), and is openable and closable. A pouring part 12 is formed, and is configured to include a bag body 10 as shown in FIG. 1 that houses the liquid detergent composition.

(Liquid detergent composition)
The liquid detergent composition used for the second liquid detergent product has at least one surfactant (A) that enhances the permeability of the composition into the article to be washed and has the function of washing the article to be washed. ) In an amount of 5 to 50% by mass, preferably 5 to 40% by mass, and the composition is solidified in the form of a film near the pouring part 12 of the bag 10 or the surface of the composition (film forming property). It contains 1 to 20% by mass, preferably 1 to 15% by mass of alcohol (B-1) for preventing water. If the surfactant (A) is less than 5% by mass, the detergency of the composition is insufficient. On the other hand, if the surfactant (A) exceeds 50% by mass, the film-forming property of the composition increases and the fluidity decreases. Inconvenience such as blockage is likely to occur, refillability is reduced, and cleaning power is not improved. Moreover, if alcohol (B-1) is less than 1 mass%, the film forming property of a composition cannot fully be suppressed. As a result, the refillability at the next refilling deteriorates. On the other hand, even if it exceeds 20 mass% and alcohol (B-1) is mix | blended, the inhibitory effect of film formation is saturated and it does not improve.

As the surfactant (A), the surfactants exemplified above in [First Liquid Detergent Product] can be similarly used.
There is no restriction | limiting in particular as alcohol (B-1), Although monohydric alcohol and polyhydric alcohol can be used, it is hard to volatilize even when the extraction | pouring part 12 of the bag 10 is opened many times for refilling. Polyhydric alcohol is preferable because the film-forming property of the liquid detergent composition can be sufficiently suppressed over a long period of time.
Specific examples of such alcohol (B-1) include methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene. Monovalent or polyhydric alcohols such as glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, glycerin, sucrose, sorbitol, phenoxyethanol, butyl carbitol, polyoxyethylene phenyl ether, trialkylene glycol monobutyl ether Of these, one of them may be used alone, or two or more of them may be used in combination. In addition, diethanolamine, polyethylene glycol and the like may be used.

  In addition to the surfactant (A) and the alcohol (B-1), other optional components can be blended in the liquid detergent composition as necessary. As the optional component, [first liquid detergent product] ] Can be used similarly. The method for preparing and using the liquid detergent composition is also the same as in [First liquid detergent product].

(Bag)
The bag used in the second liquid detergent product is not particularly limited as long as it has a pourable portion that can be opened and closed and can store the liquid detergent composition. Of the liquid detergent product] can be suitably used in the same manner.

[First liquid softener product]
The first liquid softener product of the present invention has a liquid softener composition having a viscosity of 10 to 500 mPa · s at 25 ° C. and a pouring part 12 that can be opened and closed. The bag body 10 as shown in FIG.

(Liquid softener composition)
The liquid softener composition used in the first liquid softener product contains at least one surfactant that imparts flexibility to the fiber product, and has a viscosity at 25 ° C. of 10 to 500 mPa · s. There is no particular limitation as long as it is controlled. When the viscosity at 25 ° C. is in the range of 10 to 500 mPa · s, the refillability from the first refilling to the last refilling is good, and the worker can take one dose regardless of the amount of composition in the bag. The refilling operation can be performed in a short time while appropriately controlling the amount of the injected liquid, and the liquid does not scatter during refilling. When the viscosity at 25 ° C. is less than 10 mPa · s, it is difficult to control the amount of the injected liquid for one time, particularly when the contents are refilled from a bag containing a composition that can be refilled twice or more. Is likely to splatter or spill, or the composition may overflow from the refilled bottle. In addition, even when the remaining amount of the composition in the bag is reduced, the composition is likely to be scattered or spilled. On the other hand, if the viscosity exceeds 500 mPa · s, the refilling operation takes too much time.

  Examples of surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants that are commonly used to impart flexibility. These can be used alone. Or you may use 2 or more types together. Although there is no restriction | limiting in particular in content of surfactant in a liquid softening agent composition, While being able to fully provide a softness | flexibility fully to textiles and being easy to control the viscosity of a composition to the said range, Preferably it is 3 It is 40 mass%, More preferably, it is 5-30 mass%. If the surfactant is less than 3% by mass, sufficient flexibility cannot be imparted to the fiber product unless the composition is used in a large amount, and it is not preferable from the viewpoint of transportation cost. On the other hand, if it exceeds 40% by mass, the film-forming property of the composition is increased, so that inconveniences such as lowering of fluidity and blocking of the spout are likely to occur, and refillability is lowered.

Moreover, other arbitrary components can be mix | blended with a liquid softening agent composition as needed other than surfactant which is an essential component for providing a softness | flexibility.
Optional ingredients include antiseptic / disinfectants, chelating agents for improving the stability of liquid softener compositions, antioxidants, antifoaming agents for suppressing foaming and improving the meterability of softeners, colorants, Examples include flavoring agents. Furthermore, other surfactants, anionic polymer compounds, partially esterified products of hexanoic acid and glycerin or pentaerythritol, water-soluble salts such as sodium chloride, ammonium chloride, calcium chloride, magnesium chloride, potassium chloride, liquid paraffin, Oils such as higher alcohols, urea, hydrocarbons, nonionic cellulose derivatives, UV absorbers, fluorescent brighteners, pH adjusters, and the like may be appropriately blended.

The method for preparing the liquid softener composition is not particularly limited, and is prepared by controlling the viscosity to the above range by blending a surfactant, the above-mentioned optional components as necessary, and further water as necessary. it can.
In addition, the method of use is not particularly limited, but when washing textile products such as clothing, the liquid softener composition is dispersed in the rinsing water at the rinsing stage for processing, or a container such as a tub. And a method of dispersing the composition in water and further immersing the garment. The fiber product may be treated by any method, but the bath ratio (the ratio of the treatment liquid to the fiber product) is preferably 3 to 100 times, particularly preferably 5 to 50 times.

(Bag)
In the first liquid softener product, the bag for storing the liquid softener composition is not particularly limited as long as an openable / closable pouring portion is formed and the liquid softener composition can be stored. The bag 10 illustrated in [First Liquid Detergent Product] can be used in the same manner.

[Second liquid softener product]
The second liquid softener product of the present invention is at least selected from the group consisting of a tertiary amine having a long-chain hydrocarbon group and an ester group, a neutralized product of the tertiary amine, and a quaternized product of the tertiary amine. A liquid softening agent composition containing 3 to 40% by mass of one kind of amine compound (C) and 0.5 to 10% by mass of alcohol (B-2) and an openable / closable pouring part 12 are formed. And a bag body 10 as shown in FIG. 1 for storing the liquid softening agent composition.

(Liquid softener composition)
The liquid softener composition used for the second liquid softener product contains 3 to 40% by mass, preferably 5 to 30% by mass, of the specific amine compound (C) that imparts flexibility to the fiber product. At the same time, 0.5 to 10 mass of alcohol (B-2) for preventing the composition from solidifying into a film shape (film forming property) in the vicinity of the pouring portion 12 of the bag 10 or the surface of the composition. %, Preferably 1 to 5% by mass. Here, if the amount of the amine compound (C) is less than 3% by mass, sufficient flexibility cannot be imparted to the fiber product unless the composition is used in a large amount, and it is not preferable from the viewpoint of transportation cost. On the other hand, if it exceeds 40% by mass, the film-forming property of the composition is increased, so that inconveniences such as lowering of fluidity and blocking of the spout are likely to occur, and refillability is lowered. Moreover, if alcohol (B-2) is less than 0.5 mass%, the film forming property of a composition cannot fully be suppressed. As a result, the refillability at the next refilling deteriorates. On the other hand, when it exceeds 10 mass%, the dispersion stability of a composition will fall.

  Here, the amine compound (C) includes a tertiary amine having a long chain hydrocarbon group and an ester group, a neutralized product of the tertiary amine with an organic acid or an inorganic acid, and a quaternized product of the tertiary amine. 1 type chosen from a group can also be used, and 2 or more types of mixtures can also be used. Examples of the tertiary amine having a long-chain hydrocarbon group and an ester group include ester amines represented by the following general formulas (1) to (7). These are cationic surfactants, and when they are used in a mixture, all of R of each compound may be the same or different.

In the formula, R is a long-chain hydrocarbon group, which is a residue obtained by removing a carboxyl group from a fatty acid having 10 to 24 carbon atoms, and is a group derived from any of a saturated fatty acid, an unsaturated fatty acid, a linear fatty acid, and a branched fatty acid It is. Here, when an ester amine having a group derived from an unsaturated fatty acid is used, the unsaturated fatty acid has a cis / trans isomer mass ratio of 25/75 to 100/0. It is preferable to use those of 40/60 to 80/20.
As fatty acids having 10 to 24 carbon atoms, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), partially hydrogenated beef tallow fatty acid (iodine value) 10-60) etc. are mentioned, Among these, you may use individually by 1 type, or may mix and use 2 or more types. Among them, stearic acid, palmitic acid, myristic acid, oleic acid and elaidic acid are combined in a predetermined amount, the saturation / unsaturation ratio is 95/5 to 50/50 (wt / wt), and the cis / trans mass ratio is 40. / 60 to 80/20, the iodine value is 10 to 50, the ratio of 18 carbon atoms is 80 mass% or more, the fatty acid having 20 carbon atoms is 2 mass% or less, and the fatty acid having 22 carbon atoms is 1 mass% or less. It is preferable to use the fatty acid composition adjusted as described above.
At this time, in order to improve the flexibility of the fiber product, the mass ratio of the ester amine having two or three R is preferably 50% or more in the fatty acid composition.

Examples of the acid used for neutralizing the tertiary amine include hydrochloric acid, sulfuric acid, and methyl sulfuric acid. As a neutralization method, the tertiary amine may be neutralized with an acid in advance and dispersed in water, or the tertiary amine may be dispersed in water in advance and an acid may be added thereto. Alternatively, the tertiary amine may be charged into the acid aqueous solution in liquid or solid form. Of course, a tertiary amine and an acid component may be added simultaneously.
Examples of the quaternizing agent used for the quaternization of the tertiary amine include methyl chloride and dimethyl sulfate.

  As the amine compound (C) used in the liquid softener composition, a tertiary amine, a neutralized product thereof, a quaternized product of a tertiary amine can be used as described above, and a mixture thereof can also be used. Among these, it is preferable to use one containing at least a quaternized product.

The ester amines of the general formulas (1) and (2) can be obtained as a mixture by a condensation reaction between a fatty acid composition or a fatty acid methyl ester composition corresponding to the fatty acid composition and methyldiethanolamine. At that time, from the viewpoint of improving the dispersion stability, the abundance ratio of the ester amines of the general formulas (1) and (2) is (1) / (2) = 99/1 to 50/50 in mass ratio. It is preferable to synthesize.
When the quaternized product is used, methyl chloride, dimethyl sulfate or the like is used as a quaternizing agent. However, methyl chloride is more preferable in that it has a low molecular weight and requires a small amount of quaternizing agent. preferable. At that time, the abundance ratio of the quaternized product of the ester amines represented by the general formulas (1) and (2) is also the quaternized product of (1) / (2) by mass ratio from the viewpoint of dispersion stability. It is preferable to synthesize such that = 99/1 to 50/50. Further, when the ester amines of the general formulas (1) and (2) are quaternized, an ester amine that is not quaternized remains after the quaternization reaction. In that case, it is preferable that the ratio of the quaternized / non-quaternized ester amine is a mass ratio of 99/1 to 70/30 in terms of mass ratio from the viewpoint of hydrolysis stability of the ester group.

The ester amines of the general formulas (3), (4) and (5) can be obtained as a mixture thereof by a condensation reaction of a fatty acid composition or a corresponding fatty acid methyl ester composition and triethanolamine. . At that time, from the viewpoint of improving the dispersion stability, the abundance ratio of these ester amines is [(3) + (4)] / (5) = 99/1 to 50/50 in mass ratio. It is preferable to synthesize.
When the quaternized product is used, methyl chloride, dimethyl sulfate or the like is used as a quaternizing agent, and dimethyl sulfate is more preferable from the viewpoint of reactivity. At that time, the abundance ratio of the quaternized product of the ester amine was also expressed in terms of mass ratio from the viewpoint of improving the dispersion stability. It is preferable to synthesize so that the graded product = 99/1 to 50/50. Moreover, when quaternizing the ester amine of General formula (3), (4), (5), the ester amine which is not quaternized generally remains after quaternization reaction. In that case, it is preferable that the ratio of the quaternized / non-quaternized ester amine is a mass ratio of 99/1 to 70/30 in terms of mass ratio from the viewpoint of hydrolysis stability of the ester group.

The ester amines of the general formulas (6) and (7) are known from J. Org. Chem., 26, 3409 (1960) based on the fatty acid composition described above and an adduct of N-methylethanolamine and acrylonitrile. It can be synthesized by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized by the method. In that case, it is preferable to synthesize | combine so that the abundance ratio of the ester amine of General formula (6) and (7) may be (6) / (7) = 99 / 1-50 / 50 by mass ratio.
Further, when the quaternized product is used, it is quaternized with methyl chloride. The abundance ratio of the quaternized product of the ester amine is quaternized product of (6) / (7) quaternized product = 99 / It is preferable to synthesize so that it may become 1-50 / 50. Further, when the ester amines of the general formulas (6) and (7) are quaternized, the ester amine that is not quaternized remains after the quaternization reaction. In that case, it is preferable that the ratio of the quaternized / non-quaternized ester amine is a mass ratio of 99/1 to 70/30 in terms of mass ratio from the viewpoint of hydrolysis stability of the ester group.

There is no restriction | limiting in particular as alcohol (B-2) used for a liquid softening agent composition, Although monohydric alcohol and polyhydric alcohol can be used, what is the extraction part 12 of the bag 10 for refilling? Polyhydric alcohols are preferred because they are less likely to volatilize even when they are released, and the film-forming properties of the liquid softener composition can be sufficiently suppressed over a long period of time.
As such alcohol (B-2), what was previously illustrated as alcohol (B-1) in [2nd liquid detergent product] is used individually by 1 type or in mixture of 2 or more types. it can.

  In addition to the surfactant, which is an essential component for imparting flexibility, the liquid softener composition may contain other optional components as necessary. As the optional component, those exemplified in [First Liquid Softener Product] can be used in the same manner. Further, the preparation method and the usage method of the liquid softening agent composition are the same as those in [First liquid softening agent product].

(Bag)
In the second liquid softening product, the bag body for storing the liquid softening composition is not particularly limited as long as an openable / closable pouring part is formed and the liquid softening composition can be stored. The bag 10 illustrated in [First Liquid Detergent Product] can be used in the same manner.

EXAMPLES Hereinafter, although an example is given and this invention is demonstrated concretely, this invention is not limited at all by these examples.
[Liquid detergent products]
(Test Examples 1-31)
In each example, a liquid detergent composition was prepared in the same manner except that the blending composition was changed, and 1500 ml of the composition was filled in a bag 10 having the shape of FIG. 1 to obtain a liquid detergent product and evaluated. . Tables 1 to 5 show the composition of each example, the type of bag used, and the evaluation results. The unit of the blending amount in the table indicates mass%. In the compositions of each example, an appropriate amount of sulfuric acid or sodium hydroxide was added as a pH adjuster and the amount of water was adjusted so that the total of all components was 100% by mass and the pH shown in the table was reached. ing.

  The surfactants (a-1) to (a-15) used in Test Examples 1 to 31 are listed in Table 6, the alcohols (b-1) to (b-15), the optional components in Table 7, and the fragrances A to A Table 8 shows D. Moreover, it shows in Table 9 about the structure of the multilayer film which forms the bag body 10 used in each example.

(Evaluation methods)
1) Refilling speed From the liquid detergent product obtained in each example, the liquid detergent composition as the contents was refilled by half (750 ml) into two 800 ml containers, and the time required for refilling was measured. The measurement was performed 5 times, and the average value was obtained. The symbols in the table indicate the following contents.
○: 2 minutes or less △: 2 to 3 minutes ×: 3 minutes or more

2) Spattering property From the liquid detergent product obtained in each example, the liquid detergent composition as the contents was refilled into two 800 ml containers by half (750 ml), and the scattering property at that time was visually evaluated. . The symbols in the table indicate the following contents.
○: No splattering △: Slightly splattered ×: Splattered

3) Viscosity The temperature of each liquid detergent composition was adjusted to 25 ° C., and a Brookfield type viscometer (BL type viscometer, manufactured by Tokyo Keiki Co., Ltd.) was used. The number of rotations is 60 for one rotor (10 mPa · s or less). 2 rotors with 30 rotations (10 to 1000 mPa · s) or No. Viscosity after 1 minute was measured at 30 rotations (1000 mPa · s or more) with 3 rotors.

4) Film-forming property 20 g of the liquid softening agent composition prepared in each test example was placed in a 50 ml beaker and left to stand in a constant temperature room at 20 ° C. for 3 hours, and then visually judged.
○: A film is not formed ×: A film is formed or solidified

ＬＬＤＰＥ：直鎖状低密度ポリエチレン
ＯＮＹ：ポリアミド
ＯＰＰ：ポリプロピレン樹脂
ＥＶＯＨ：エチレン―酢酸ビニル共重合体ケン化物
ＰＥＴ：強化ポリエチレンテレフタレ−ト

LLDPE: linear low density polyethylene ONY: polyamide OPP: polypropylene resin EVOH: saponified ethylene-vinyl acetate copolymer PET: reinforced polyethylene terephthalate

[Liquid softener products]
(Test Examples 32-54)
In each example, a liquid softening agent composition was prepared in the same manner except that the blending composition was changed, and each was filled in a bag to obtain a liquid softening product, which was evaluated in the same manner as in Test Examples 1 to 31. The compounding composition of each example and the kind of used bag body are shown to Tables 10-12. The unit of the blending amount in the table indicates mass%. In the composition of each example, the following components were blended as common components, and the amount of water was appropriately adjusted so that the total of all components was 100% by mass.
(Common ingredients)
Calcium chloride (manufactured by Tokuyama Corporation): 0.3% by mass
Partially cured beef tallow fatty acid (beef tallow 45 ° cured fatty acid HFA, manufactured by Nippon Oil & Fats Co., Ltd.): 1% by mass
Isothiazolone solution (Caisson CG / ICP, manufactured by Rohm & Haas): 100 ppm
2-Bromo-2-nitro-1,3-propanediol (Protectol BN, manufactured by BASF Japan Ltd.): 50 ppm

The amine compounds (c-1) to (c-3) used in each example are shown.
(C-1):
A cationic surfactant was produced by the method described in Example 1 of JP-A No. 2003-12471 (however, ethanol was not added after completion of the reaction), and this was used as an amine compound (c-1). Used as. The obtained cationic surfactant is a mixture containing the compounds represented by formulas (8) to (18). The composition (parts by mass) is shown in Table 13. In the formula, R is derived from any alkyl group or alkenyl group of methyl stearate, methyl oleate, methyl palmitate, or methyl elaidate.

(C-2):
A cationic surfactant was produced by the method described in Example 4 of JP-A-2003-12471 (however, ethanol was not added after completion of the reaction), and this was converted to an amine compound (c-2). Used as. The obtained cationic surfactant is a mixture containing the compounds represented by formulas (8) to (18). The composition (parts by mass) is shown in Table 13. In the formula, R is derived from any alkyl group or alkenyl group of methyl stearate, methyl oleate, methyl palmitate, or methyl elaidate.

Synthesis of (c-3):
N- (2-hydroxyethyl) -N-methyl-1,3 synthesized by a known method described in J. Org. Chem., 26, 3409 (1960) from an adduct of N-methylethanolamine and acrylonitrile. -66 g of propylenediamine and 284 g of hardened beef tallow fatty acid were charged into a four-necked flask equipped with a stirrer, a thermometer and a dehydrating tube, and the temperature was raised to 180 ° C. As a result of heating for about 10 hours while distilling off generated water, 300 g of a reaction product (c-3) was obtained.
As a result of measuring the acid value, saponification value, hydroxyl value, total amine value, tertiary amine value of the obtained reaction product and examining the composition of the reaction product, 86% by mass of the dialkyl product and 10% of the monoalkylamide product were obtained. The mass% and unreacted fatty acid were 4 mass%. Moreover, from the analysis by gas chromatography, 0.1 mass% of unreacted N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine was contained in the reaction product. Other detailed synthesis conditions and the like conform to JP-A-5-230001.

  Table 14 shows the alcohols (b-20) to (b-27) used in Test Examples 32 to 54, and Table 15 shows the optional components (d-1) to (d-10). The fragrance is as shown in Table 8.

  From the result of each test example, when the viscosity of the composition stored in the bag body 10 is less than 10 mPa · s, the liquid scatters at the time of refilling, whereas when the viscosity exceeds 500 mPa · s, it takes time to refill. Became clear. In addition, it was found that a composition to which a specific amount of alcohol was not added easily formed and solidified a film.

It is (a) top view which shows an example of the bag body used by this invention, (b) Side view, (c) Front view.

Explanation of symbols

10 Bag body 11 Bag body 12 Extraction part

Claims (4)

A liquid detergent composition having a viscosity at 25 ° C. of 10 to 500 mPa · s;
A liquid detergent product comprising: a pouch that is openable and closable, and has a bag for containing the liquid detergent composition. A liquid detergent composition containing 5 to 50% by mass of surfactant (A) and 1 to 20% by mass of alcohol (B-1);
A liquid detergent product comprising: a pouch that is openable and closable, and has a bag for containing the liquid detergent composition. A liquid softener composition having a viscosity at 25 ° C. of 10 to 500 mPa · s;
A liquid softener product, characterized in that the liquid softener product has a pouch part that is openable and closable and contains the liquid softener composition. At least one amine compound (C) 3-40 selected from the group consisting of a tertiary amine having a long-chain hydrocarbon group and an ester group, a neutralized product of the tertiary amine, and a quaternized product of the tertiary amine A liquid softener composition containing, by weight, 0.5% to 10% by weight of alcohol (B-2),
A liquid softener product, characterized in that the liquid softener product has a pouch part that is openable and closable and contains the liquid softener composition.

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