JP6719121B2 - Textile detergent, soil release agent, and fiber cleaning method - Google Patents

Description

The present invention relates to a detergent for fibers, a soil release agent, and a method for cleaning fibers.

Conventionally, a detergent containing a surfactant has been used as a detergent for textiles such as clothes. In such detergents, the surfactant reduces the physical or electrical interaction between the soil and the fiber in a large amount of water and forms a complex between the soil and the surfactant. , Remove dirt from fibers. This drains the complex formed between the dirt and the surfactant.

Washing with a detergent containing such a surfactant can be performed by (1) approaching the soil or the fiber with the surfactant, (2) adsorbing the surfactant on the soil surface or the fiber surface, and (3) using the surfactant. Dirt forms a complex, and (4) the complex is dispersed and dispersed in water by a four-step mechanism.

In such a cleaning mechanism, the molecular structure or physical structure of the fiber, the molecular structure or physical structure of the soil, the affinity between the soil and the fiber, the affinity or interaction between the surfactant and the soil, and the surfactant. Many factors such as affinity or interaction with fibers, washing method, etc. act in combination.

Currently, liquid detergents are commonly available on the market. Since such a liquid detergent uses a surfactant having a high solubility in water, it cannot be said that the cleaning ability due to the interaction with oily stains is sufficient. Here, a wide variety of stains can be attached to the fiber, but among such stains, stains of hydrophobic substances contained in, for example, mud, food, blood, sebum, oil-based ink, mineral oil, etc. As described above, since the interaction with the surfactant is low, it is difficult to clean, and one kind of surfactant cannot clean the stains due to all hydrophobic substances.

Therefore, in recent years, a plurality of surfactants are often mixed to form a detergent capable of cleaning various types of stains.

For example, in Patent Document 1, (a) polyoxyethylene alkyl ether sulfate or salt thereof, (b) sulfonic acid type anionic surfactant, (c) sulfobetaine, amidobetaine or carbobetaine, and these are specified. It has been reported that the detergent blended in the amount has a high detergency against oil stains derived from food.

Further, in Patent Document 2, (A) a specific amine oxide type surfactant, (B) a specific nonionic surfactant, (C) a specific cationic surfactant, and these are blended in specific amounts. Detergents have been reported to have high detergency against protein stains.

Thus, from the viewpoint of the affinity or the interaction between the soil and the surfactant, it is necessary to combine various surfactants depending on the soil to be treated, and particularly, inorganic solid particles such as mud or foods. It is necessary to add a large amount of surfactant in the case where the substance such as oil and fat contained in is dried and becomes solid.

In addition, from the viewpoint of affinity or interaction between dirt and fibers, for example, a hard surface has unevenness instead of a flat surface, and a plurality of fibers are bundled to form a product such as cloth. To do. When dirt adheres to the fibers, the dirt enters the recesses on the surface of the fibers or the inside of the bundle. The dirt thus entering the inside of the fiber structure may not be sufficiently washed by the action of the surfactant.

More specifically, fibers are defined as "fiber term (raw material section)-Part 1: natural fiber", "fiber term (raw material section)-Part 2: chemical fiber", "fiber" of JIS L0204-1 to -3. As described in "Terms (raw materials sector)-Part 3: Raw materials sector excluding natural fibers and chemical fibers", "constituting units such as threads and fabrics, having a sufficient length compared to the thickness It is easy to bend and bend." In this way, the fibers can be physically changed (folded). Further, since the yarn is made of yarn or the like, voids are formed in the yarn itself that constitutes the fiber, or voids are formed between the yarn and the yarn during spinning, so that the surface of the fiber is also uneven. Also, the chemical characteristics of the yarns that make up the fiber are various, and since the types and molecular weights are diverse, the chemical properties of the fiber surface are not always single (Non-Patent Document 2). As described above, the fiber is physically and chemically different in surface condition from the hard surface such as glass.

From the relationship between fibers and dirt, dirt is ``a foreign matter that adheres to the surface of the fiber from the outside, impairs the aesthetics of the fiber, is unfavorable for maintaining the quality, and is harmful to hygiene and must be removed. "There is" (Non-Patent Document 3). When such a foreign substance adheres to the surface of the fiber, it is not only limited to the surface but also penetrates into the inside of the fiber due to the easiness of bending which is a characteristic of the fiber and the voids due to the constituents.

Dirt not only physically attaches to the fibers, but also chemically. For example, sebum that easily adheres to a collar or a sleeve is an oil and fat, and thus is difficult to dissolve in water, and easily interacts with synthetic fibers composed of a hydrophobic substance. Therefore, it may not be possible to perform sufficient washing only by the action of a surfactant that is easily dissolved in water. As such oily substance stains, sebum, cosmetics, food fats and oils, pigments, mineral oils, etc. are known, and are generally known as oil-soluble stains (Non-Patent Document 3).

The main components such as sweat and urine are classified as water-soluble stains. The water-soluble substance in the water-soluble stain may change into a water-insoluble stain by drying to dryness. In general, substances that change in this way include proteins and starches (Non-Patent Document 3).

On the other hand, there are also stains that are neither oil-soluble nor water-soluble. Called solid particle dirt. This is classified into mud and soot, iron powder, etc. (Non-Patent Document 3).

As described above, since each stain has its own unique chemical and physical characteristics, it may not be possible to sufficiently wash the stain that has entered the inside of the fiber only by the action of the surfactant.

JP, 2005-124337, A JP, 2016-216543, A

Japan Oil Chemists' Society ed. "Interfaces and surfactants-from basic to applied-" Revised 2nd edition 2013 Textile Society of Japan, "Basic knowledge of fiber learning from industry meisters-1 to 19", 2014-2016 Asakura Shoten Second Edition "Encyclopedia of Detergents and Cleaning" 2012

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a new textile detergent having an excellent detergency for hydrophobic substances.

The present inventors have made polycondensation polymer particles having closed vesicles or hydroxyl groups of amphipathic substances that contain water and spontaneously form closed vesicles (vesicles), detergent particles containing them and an oily substance, and The O/W emulsion in which the detergent particles are dispersed has a high cleaning ability for the hydrophobic substance attached to the fibers, they have a soil release ability, the ability to prevent the deterioration of the flexibility of the fibers and the prevention of the deterioration of the water absorption. They found that they have the ability to complete the present invention. Specifically, the present invention provides the following.

(1) A detergent for fibers comprising closed vesicles of amphipathic substances which contain water and spontaneously form closed vesicles, or polycondensation polymer particles having a hydroxyl group.

(2) A detergent for fibers, which is an O/W emulsion and contains polycondensation polymer particles having a closed vesicle or a hydroxyl group of an amphipathic substance that spontaneously forms a closed vesicle, an oily substance and water.

(3) The detergent for fibers according to (2), wherein the oily substance has a melting point of 80° C. or lower.

(4) The textile detergent according to (2) or (3), wherein the oily substance is a polar oil.

(5) The fiber detergent according to any one of (2) to (4), wherein the oily substance has a boiling point of 80° C. or higher.

(6) A fiber detergent comprising closed vesicles of amphipathic substances that spontaneously form closed vesicles, polycondensation polymer particles having a hydroxyl group, and an oily substance.

(7) The detergent for fibers according to (6), wherein an oily substance is surrounded by the closed vesicles or the polycondensation polymer particles to form detergent particles.

(8) The detergent powder for fibers according to (6) or (7), wherein the detergent particles have an average particle diameter of 50 nm or more and 2 μm or less when dispersed in water.

(9) The fiber detergent according to any one of (6) to (8), which is in the form of powder.

(10) The textile detergent according to any one of (1) to (9), which has a soil releasing ability.

(11) The detergent for textiles according to any one of (1) to (10) for partial washing.

(12) The detergent for textiles according to any one of (1) to (10) for washing the whole.

(13) The detergent for textiles according to any one of (1) to (10), which is for washing textile products.

(14) The detergent for textiles according to any one of (1) to (10) for washing clothes.

(15) The detergent for textiles according to any one of (1) to (10), which is for washing without using a softening agent as a treatment after washing the textile with the detergent for textiles.

(16) The textile detergent according to any one of (1) to (10), which is used for washing with a softening agent as a treatment after washing the textile product with the textile detergent.

(17) A method for washing fibers, which comprises washing the fibers with the detergent for fibers according to any one of (1) to (10).

(18) A soil release agent comprising closed vesicles of amphipathic substances containing water and spontaneously forming closed vesicles, or polycondensation polymer particles having a hydroxyl group.

(19) A soil release agent, which is an O/W emulsion, containing polycondensation polymer particles having a closed vesicle or a hydroxyl group of an amphipathic substance that spontaneously forms a closed vesicle, an oily substance, and water.

(20) A soil release agent containing a polycondensation polymer particle having a closed vesicle or a hydroxyl group of an amphipathic substance that spontaneously forms a closed vesicle, and an oily substance.

ADVANTAGE OF THE INVENTION According to this invention, the new detergent for textiles which has the outstanding washing|cleaning ability especially with respect to a hydrophobic substance can be provided.

It is a photograph figure of the liquid after washing of Examples 3, 8, 11, and 13 and Comparative Example 3. It is a schematic diagram of the apparatus used for evaluation of water absorption.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments at all, and may be appropriately modified and implemented within a range not changing the gist of the present invention. You can

<Fiber detergent of the first aspect>
The detergent for fibers of this embodiment contains polycondensation polymer particles having a closed vesicle of an amphipathic substance which contains water and spontaneously forms a closed vesicle (vesicle), or a hydroxyl group.

With the closed vesicles of amphipathic substances that spontaneously form closed vesicles or polycondensation polymer particles having a hydroxyl group attached to the dirt on the fiber, apply physical force by hand washing or washing with a machine. Upon addition, the dirt can be pulled away from the fiber with the closed vesicles or polycondensed polymer particles to remove the dirt. Therefore, according to such a mechanism, unlike a conventional detergent for textiles using a surfactant, a high cleaning ability is obtained regardless of the type of stains and even for multi-component stains such as food. Can have.

The closed vesicles and polycondensation polymer particles as described above are known as emulsifiers for so-called three-phase emulsification. Here, “washing” requires higher energy than “emulsification”. More specifically, “emulsification” subdivides the lump of oily substance into a stable dispersion in water, whereas “washing” subdivides the lump of oily substance adhering to the fiber surface and further adhering to the fiber. It is necessary to completely remove the oily substance from the surface, that is, "cleaning" requires more energy to completely remove the oily substance from the surface where the oily substance and the fibers are attached, as compared with "emulsification". Therefore, in order to use the emulsifier for "washing", at least this energy problem must be solved.

Here, the conventional detergent for textiles using a surface-active agent is what separates an oily substance from the fiber surface by lowering the interfacial tension of such an oily substance. However, even if the particles are separated in this way and once become emulsion particles, if the surfactant and the stain have a high affinity, the oily substance again adheres to the fiber surface via the surfactant and the fiber is re-formed. May pollute.

On the other hand, in the present invention, when the closed vesicles or polycondensation polymer particles are used as a detergent for fibers, the interfacial tension does not decrease, and the self-cohesive force of the oil acts and the oil floats. At the same time, closed vesicles or polycondensation polymer particles adhere and fix to the oil-water interface. Particularly, in the fiber detergents of the second and third aspects to be described later, emulsion particles are formed, but there is a small amount of closure between the emulsion particles and between the emulsion particles and hydrated stains on the fiber surface. Since a partition wall composed of cells or polycondensation polymer particles is formed, re-adhesion of oil droplets to the surface of the pollutant hardly occurs. As described above, the closed vesicles or polycondensation polymer particles of the present invention achieve complete peeling of stains from the fiber surface by a mechanism different from that of the conventional fiber detergent using a surfactant. And surprisingly, such a detergent for fibers can prevent recontamination. In the above description of the mechanism, the case where only the oily substance is washed as the target of “washing” in order to clarify the contrast with “emulsification” has been described, but the target of “washing” is not limited to the oily substance, It also includes aqueous substances and solid substances.

(Closed endoplasmic reticulum)
The closed endoplasmic reticulum in the present invention is formed by an amphipathic substance that spontaneously forms the closed endoplasmic reticulum. As the amphipathic substance forming the closed endoplasmic reticulum, a polyoxyethylene hydrogenated castor oil derivative represented by the following general formula 1 or a dialkylammonium derivative (salt) or a trialkylammonium derivative represented by the general formula 2 is used. A tetraalkylammonium derivative, a dialkenylammonium derivative, a trialkenylammonium derivative, or a halogen salt derivative of a tetraalkenylammonium derivative is preferably used.
Derivatives of lysine Na dilauroyl glutamate, decaglyceryl distearate, and POE pentaerythritol dioleate may be used. As the phospholipid and the phospholipid derivative, lecithin (natural lecithin, hydrogenated lecithin, etc.) can also be used. These may use 1 type and may use 2 or more types.

General formula 1

In the formula, E, which is the average added mole number of ethylene oxide, is 3 to 200. From this, the upper limit of E is preferably 100, more preferably 60. The lower limit of E is preferably 5 or more, more preferably 10 or more, further preferably 20 or more, and most preferably 30 or more.

General formula 2

In the formula, R ₁ and R ₂ are each independently an alkyl group or an alkenyl group having 8 to 22 carbon atoms, and R ₃ and R ₄ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms. And X is F, Cl, Br, I or CH ₃ COO.

As the amphipathic substance forming the closed endoplasmic reticulum, phospholipid, phospholipid derivative or the like may be adopted. As the phospholipid, among the constitutions represented by the following general formula 3, DLPC having a carbon chain length of 12 (1,2-Dilauroyl-sn-glycero-3-phospho-rac-1-choline), having a carbon chain length of 14 DMPC (1,2-Dimyristoyl-sn-glycero-3-phospho-rac-1-choline), DPPC (1,2-Dipalmitoyl-sn-glycero-3-phospho-rac-1-choline) having a carbon chain length of 16 Can be adopted.

General formula 3

Further, among the constitutions represented by the following general formula 4, a DLPG having a carbon chain length of 12 (1,2-Dilauroyl-sn-glycero-3-phospho-rac-1-glycerol) Na salt or NH ₄ salt, carbon DMPG chain length 14 (1,2-dimyristoyl-sn- glycero-3-phospho-rac-1-glycerol) Na salt or NH ₄ salt, DPPG (1,2-Dipalmitoyl-sn -glycero carbon chain length 16 It is also possible to employ Na salt or NH ₄ salt of -3-phospho-rac-1-glycerol).

General formula 4

(Polycondensation polymer particles)
The polycondensation polymer is not particularly limited as long as it has a hydroxyl group, and may be either a natural polymer or a synthetic polymer, and can be appropriately selected according to the application. However, it is preferable to use a natural polymer because it is excellent in biosafety and environment and is generally inexpensive, and among them, the sugar polymer described below is more preferable because it has an excellent emulsifying function. In addition, the particles include both a polycondensation polymer formed into a single particle and a continuous particle formed by arranging the single particles, but does not include an aggregate (having a network structure) before being formed into a single particle. .. For example, the "polysaccharide" before being made into single particles is not made into particles, but forms a network structure by hydrogen bonds, so "polycondensation polymer particles" having so-called three-phase emulsification ability. Is clearly different. The polycondensation polymer having a hydroxyl group may be used alone or in combination of two or more.

The sugar polymer is a polymer having a glucoside structure such as cellulose and starch. For example, ribose, xylose, rhamnose, fucose, glucose, mannose, glucuronic acid, those produced by microorganisms with some sugars as constituents from monosaccharides, xanthan gum, gum arabic, guar gum, karaya gum, carrageenan, pectin. , Fucoidan, quince seed gum, tranto gum, locust bean gum, galactomannan, curdlan, gellan gum, fucogel, casein, natural polymers such as gelatin, starch, collagen, sycamore polysaccharide, methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, carboxy Methyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, stearoxy hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, alginic acid propylene glycol ester, cellulose crystal, starch/sodium acrylate graft polymer, hydrophobized hydroxypropyl methyl cellulose, etc. And semi-synthetic polymers of In addition to sugar polymers, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymers, polyacrylates, polyethylene oxide, acrylate/polyethylene glycol type copolymers, (methoxymethacrylate PEG-23/glyceryl methacrylate diisostearate) copolymers, etc. A synthetic polymer or the like can be used. These may be used alone or in combination of two or more.

As the sugar polymer, it is preferable to use hydroxyethylcellulose, stearoxyhydroxypropylmethylcellulose, carboxymethylcellulose, carboxymethylcellulose, guar gum, or salts thereof, and more preferable to use hydroxyethylcellulose.

The closed vesicles or polycondensation polymer particles in the present invention preferably have an average particle size of about 8 nm to 500 nm, for example. These preparation methods are conventionally known as disclosed in Japanese Patent No. 3855203, and thus omitted.

The content of the closed vesicles or the polycondensation polymer particles in the detergent can be appropriately set depending on the method of use (partial washing or washing with a machine), the dilution ratio of the detergent, etc., but is not particularly limited, but the total It may be 0.0001 mass% or more.

The property of the detergent for fibers in the present invention is not particularly limited, and may be, for example, powder, gel, liquid or the like. Of these, when it is made liquid, for example, it can be dispersed in an aqueous liquid such as water and the dispersion liquid of closed vesicles or polycondensation polymer particles can be used as a detergent.

<Detergent for fibers of the second aspect>
An O/W containing an oily substance as a third phase of so-called three-phase emulsification, which is a closed vesicle of an amphipathic substance (vesicle) that spontaneously forms a closed vesicle or polycondensation polymer particles having a hydroxyl group. It is also possible to configure a fiber detergent that is a type emulsion.

In such a case, the O/W emulsion forms an emulsified state due to the presence of closed vesicles or polycondensation polymer particles at the interface between the aqueous phase and the oil phase. More specifically, in such an emulsified state, the oily substance (oil phase) becomes a droplet, and the vesicles or polycondensation polymer particles surrounding the oily phase surround one emulsion particle (hereinafter, " Sometimes called "detergent particles"). Then, the emulsion particles are dispersed in water (aqueous phase) to form an O/W type emulsion to form an emulsified state. Such an emulsified state is confirmed by observing the obtained emulsion with a transmission electron microscope (TEM) (for example, Japanese Patent No. 3855203).

In such an O/W type emulsion state, the closed vesicles or the polycondensation polymer particles are not in contact with the oil phase constituting the O/W type emulsion, and the O/W type emulsion is in contact with the dirt, and the fan Adsorbs to the dirt due to the Delwar force. When the stain is an oil-soluble substance, the stain is contacted with the oil phase and then dissolved in the oil phase, so that the stain can be separated from the fiber to the water. When the dirt is an insoluble substance, the dirt is taken into the emulsion and holds a large amount of dirt and suppresses the diffusion again, and when there is a difference in the specific gravity between the emulsion particles and the aqueous phase, the specific gravity Buoyancy and settling force caused by the difference between the two, combined with the externally applied rubbing in the case of hand washing and centrifugal force in the case of washing with a washing machine, and they are separated from the fibers together with the emulsion by a stronger force. Even if the oil-soluble or insoluble stain moves to the oil phase constituting the three-phase emulsified O/W emulsion, the three-phase emulsification enables stable emulsification, so that the stain can be removed without redeposition.

That is, such a fiber detergent has an excellent cleaning ability based on at least the adsorption ability of the closed vesicles or the polycondensation polymer particles to stains. Further, when the oil phase has the ability to dissolve dirt, or when there is a difference in the specific gravity between the emulsion particles and the aqueous phase, as described above, a mechanism different from the adsorption of the closed vesicles or polycondensation polymer particles This makes it possible to wash dirt in a complex manner.

(Emulsion particles)
The emulsion particles are those in which the oily substance (oil phase) is in the form of drops, and the oil phase is surrounded by closed vesicles or polycondensation polymer particles similar to those of the fiber detergent of the first aspect.

The average particle size of the emulsion particles is not particularly limited, but is preferably 2 μm or less, more preferably 1 μm or less, further preferably 900 nm or less, and particularly preferably 800 nm or less. As described above, when the oil phase has the ability to dissolve stains, the larger the oil phase, the more the stains can be dissolved and retained, so the amount of the oil phase was increased, and as a result, the average particle size of the emulsion particles was also increased. It seems that the cleaning efficiency is higher. However, as described above, the dirt enters the inside of the concave portion or the bundle of the fiber, and in order to remove such dirt, it is necessary that the emulsion particles enter the inside of the concave portion or the bundle of the fiber surface. is there. From such a viewpoint, it is preferable that the particle size of the emulsion particles is equal to or smaller than a required value. In this respect, one of the major differences between the detergent of the present invention which performs washing using closed vesicles or polycondensation polymer particles, which are aggregates of molecules, and the conventional detergent using a surfactant which performs washing using molecules. Is one. However, depending on the type of fiber (bundling method, surface chemical properties, etc.), even if the average particle size of the emulsion particles is large, it may easily enter the recesses on the fiber surface or inside the bundle. Since the cleaning efficiency is higher when the amount of the oil phase is increased and the amount of the stain dissolved is increased as described above, the average particle size of the emulsion particles may be more than 2 μm. The average particle diameter of the emulsion particles is preferably 50 nm or more, more preferably 100 nm or more. As a result, when the dirt dissolves in the oily substance, the amount of the oily substance dissolved can be increased. However, the average particle size of the emulsion particles may be 50 nm or less. In this case, the fibers are more likely to enter the recesses on the surface and the inside of the bundle. In the present invention, the “average particle size” means that the dispersion liquid (in the case of emulsion particles, an O/W type emulsion) is measured by a dynamic particle size analyzer FPAR (manufactured by Otsuka Electronics Co., Ltd.). The value of the number distribution value measured by the scattering method and obtained by the Contin analysis is measured three times and averaged. In addition, the detergent for textiles may contain components constituting the emulsion other than the detergent particles, such as a surfactant, but in the case where such components are contained, in the state where such components are also contained. The average particle diameter of

(Closed vesicles and polycondensation polymer particles)
As the closed vesicles and the polycondensation polymer particles, those similar to the fiber detergent of the first aspect can be used.

The content of emulsion particles in the detergent can be appropriately set depending on the method of use (partial washing or whole washing), the dilution ratio of the detergent, and the like, but for example, the total content is 0.01% by mass or more. Good.

The average particle size of the closed vesicles or polycondensation polymer particles is about 8 nm to 500 nm when the emulsion is formed. The polycondensation polymer particles and the closed endoplasmic reticulum may contain either one of them or both of them. If both are included, for example, the emulsified emulsions may be mixed separately.

(Oil substance)
The oily substance constitutes an oil phase which is an internal phase in the O/W type emulsion. The oil phase may be solid, semi-solid, liquid or a mixture, but is preferably liquid at the time of washing. Since the oily substance is liquid, it is possible to dissolve and retain the dirt adsorbed by the closed vesicles or the polycondensation polymer particles. However, even if the oily substance is in a solid state or a semi-solid state, the closed vesicles or the polycondensation polymer particles themselves have the ability to wash the fibers as described above, and thus the washing effect of the present invention is naturally exhibited. ..

The oily substance is not particularly limited, and examples thereof include vegetable oils, hydrocarbon oils, monoester oils, diester oils, triester oils, ether oils, polyoxyethylene polyoxypropylene block polymers, higher fatty acid monoglycerides, glycols and higher. Alcohol etc. can be mentioned. For example, rapeseed oil, di(caprylic acid/capric acid) propanediol (Sarasco PR-85, manufactured by Nisshin OilliO), polyethylene polyoxypropylene glycol (Brownon P-171, Aoki Yushi Kogyo Co., Ltd.), polyoxypropylene glycol (Polyglycol). Industrially available products such as 4000P, manufactured by DOW) can be used.

Among the above, it is preferable to use polar oil. Here, "polar oil" refers to an oil agent composed of polar molecules. For example, many food stains and the like dissolve in polar oil, and an O/W emulsion containing polar oil has a high cleaning action. However, even if the oily substance is a non-polar oil, the closed vesicles or the polycondensation polymer particles themselves have the ability to clean the fibers as described above, and thus the cleaning effect of the present invention is naturally exhibited.

The specific gravity of the oily substance is not particularly limited, but the absolute value of the difference in specific gravity (1.00 g/cm ³ ) from water at 25° C. is preferably 0.01 g/cm ³ or more, and 0.02 g / more preferably cm ³ or more, further preferably 0.05 g / cm ³ or more, and particularly preferably 0.10 g / cm ³ or more. When the oily substance is a mixed solvent, it means the absolute value of the difference between the specific gravity of the mixed solvent and the specific gravity of water. That the absolute value is equal to or more than the required value means that there is a difference between the specific gravity of the emulsion particles and the specific gravity of water, which causes the emulsion particles to have buoyancy or sedimentation force. When such a force is generated in the emulsion particles adsorbed on the fibrous soil, the soil is more easily separated from the fiber surface. However, even if the absolute value of the difference between the specific gravity of the oily substance and the specific gravity of water at 25° C. is less than 0.01 g/cm ³ , as described above, the closed vesicles or the polycondensation polymer particles themselves wash the fibers. Since it has a function, the cleaning effect of the present invention is naturally exhibited.

The boiling point of the oily substance is not particularly limited, but is preferably 80° C. or higher under atmospheric pressure, more preferably 100° C. or higher, further preferably 120° C. or higher, and 140° C. or higher. It is particularly preferable that Since the boiling point of the oily substance is the required value or more, unlike the low boiling point volatile oil (fluorine-based solvent which is a general dry cleaning solvent), the safety is higher. However, the boiling point of the oily substance may be less than 80° C. as long as safety is ensured and the temperature of the washing water does not exceed the boiling point of the oily substance. On the other hand, it may be 500°C or lower, 470°C or lower, 450°C or lower, 400°C or lower, 350°C or lower, and 300°C or lower. However, the boiling point of the oily substance may be higher than 500°C.

The melting point of the oily substance is not particularly limited, but may be, for example, −50° C. or higher, −20° C. or higher, 0° C. or higher, 10° C. or higher. However, the melting point of the oily substance may be less than -50°C. On the other hand, the melting point of the oily substance is preferably 80° C. or lower. When the melting point of the oily substance is equal to or lower than the required value, the oil phase in the O/W type emulsion can maintain a liquid state during washing and can act as a solvent for dirt. However, the melting point of the oily substance may be higher than 80°C.

The fiber detergent as described above can be easily emulsified by mixing the raw materials and then using the mixture with a shaker, a stirrer, a homogenizer, or the like.

<Detergent for fibers of the third aspect>
It includes polycondensation polymer particles having a closed vesicle or a hydroxyl group of an amphipathic substance that spontaneously forms a closed vesicle, and an oily substance. In such an emulsified state, the oily substance (oil phase) becomes droplets, and the vesicles or polycondensation polymer particles surround the oil phase, so that one detergent particle may be configured as a detergent for fibers. it can. That is, such a detergent for fibers can be in a solid form such as a powder form or a tablet form. Even if it is solid, the detergent particles contained therein are dispersed in water to form an O/W type emulsion, and as a result, the same effect as that of the fiber detergent of the second aspect is exhibited.

The content of the detergent particles in the detergent can be appropriately set depending on the method of use (partial washing or whole washing) and the dilution ratio of the detergent, but for example, the total content is 0.01% by mass or more. Good.

The average particle diameter of the detergent particles is not particularly limited, but the average particle diameter when dispersed in water is preferably 2 μm or less, more preferably 1 μm or less, and further preferably 900 nm or less. It is preferably 800 nm or less, and particularly preferably. In addition, the detergent for textiles may contain components constituting the emulsion other than the detergent particles, such as a surfactant, but in the case where such components are contained, in the state where such components are also contained. The average particle diameter of

In addition, as the closed vesicles, the polycondensed polymer particles and the oily substance, the same components as those used in the textile detergent of the second aspect can be constituted by the same composition. Further, as the detergent particles constituted by these, the same components as the emulsion particles in the detergent for fibers of the second aspect can be constituted by the same composition.

Such a fiber detergent can be dried, for example, by a conventionally known method such as a dry spray method, a spray drying method, a freeze drying method, or the like of the O/W emulsion in the fiber detergent of the second aspect. In the O/W emulsion in the textile detergent of the second aspect, the oily substance forms a so-called three-phase emulsion structure in which the oily substance is surrounded by the closed vesicles or polycondensation polymer particles. According to such a three-phase emulsified structure, it is possible to obtain a powder in a state in which a fine oil droplet structure maintains a structure surrounded by closed vesicles or polycondensation polymer particles even if water is removed by drying. You can When dried by a dry spray method, an excipient such as starch is included to form a powder.

The fiber detergents of the above-described first to third aspects have the ability to prevent the deterioration of the flexibility of the fibers and the ability to prevent the deterioration of water absorption. Here, the "ability to prevent deterioration in flexibility" refers to the ability to prevent the fibers from being hardened after washing and maintain a soft state. "Ability to prevent lowering of water absorption" refers to the ability to prevent lowering of water absorption of fibers after washing and maintain high water absorption. The present inventors have surprisingly found that the above-described fiber detergents of the first to third aspects have the ability to prevent deterioration in flexibility and the ability to prevent deterioration in water absorption.

For example, many natural fibers such as cotton and hemp are composed of sugar chains. Therefore, a large amount of hydroxyl groups are exposed on the surface. After washing, the fibers may be cured under various drying conditions including sun drying. The reason for this may be that sugar chains on the surface of the fiber are bound to each other during drying, or hydrogen is bonded to the fibers via the moisture adsorbed to the fibers during washing, but generally, the latter moisture is mediated. It is believed that hydrogen bonds between the formed fibers are predominant. The structure formed by this action causes the fibers to lose flexibility and harden. In order to prevent such curing, a softener is usually used. The softening agent contains a highly hydrophobic alkylcationic surfactant, and the alkylcationic surfactant is attracted to a hydroxyl group having a negative charge by its positive charge and surrounds the hydroxyl group. Then, even after rinsing the fibers, such an alkylcationic surfactant remains on the fibers and suppresses hydrogen bonding between the fibers. By such an action, the fiber can be maintained in a flexible state without being cured. However, when such a softening agent is used, a highly hydrophobic alkyl chain is exposed on the surface of the softening agent, resulting in a decrease in water absorption. For example, in a bath towel, a cloth, or the like, it is not preferable to reduce the water absorption because the fibers are required to have the water absorption.

On the other hand, in the detergent of this embodiment, the closed vesicles or polycondensation polymer particles can be adsorbed on the fiber surface by the hydrophobic interaction between the closed vesicles or polycondensation polymer particles and the fiber, whereby the above-mentioned It was found that the bond between hydroxyl groups can be suppressed as in the case of the alkyl cation-based surfactant. Moreover, since the closed vesicles or the polycondensation polymer particles attached to the fiber surface are hydrophilic in this way, the water absorption does not decrease, or the decrease is suppressed to a small extent.

That is, the textile detergents of the first to third aspects also have the above-described ability to prevent deterioration in flexibility and ability to prevent deterioration in water absorption. That is, if the fibers are washed with such a detergent, the above-described effect of preventing the decrease in flexibility can be obtained without using a softening agent as a treatment after washing the fibers. On the other hand, when an ordinary softening agent (for example, one containing a commercially available alkyl cation-based surfactant) is used as the treatment after washing the fiber, the effect of further reducing the flexibility can be obtained, and the closed vesicles or Due to the hydrophilicity of the polycondensation polymer particles, the water absorption does not decrease or the decrease is suppressed to a small extent. That is, when washed with such a detergent for textiles, a softening agent may or may not be used as a post-treatment of the washing. The textile product washed with such a detergent for textiles is resistant to curing under various drying conditions.

(Additive)
The textile detergent according to any one of the first to third aspects of the present invention may include an additive. As the additive, one kind may be used alone, or two or more kinds may be used in combination. Moreover, the additive may not be included.

A hydrophilic surfactant can be used from the viewpoint of improving detergency, rinseability, and stability. As the hydrophilic surfactant, any of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant and a cationic surfactant can be used. However, the hydrophilic surfactant may not be included.

The anionic surfactant is not particularly limited, and examples thereof include sulfuric acid ester salts of alcohols, sulfuric acid ester salts of alcohol alkoxylates, alkylbenzene sulfonates, alkyl sulfate ester salts, paraffin sulfonates, and α-olefin sulfones. Examples thereof include acid salts, α-sulfo fatty acid salts, α-sulfo fatty acid alkyl ester salts and fatty acid salts. In addition, examples of counter ions of these salts include alkali metal salts and amines, and specific examples include sodium, potassium, monoethanolamine, diethanolamine, and triethanolamine.

The nonionic surfactant is not particularly limited, but examples thereof include higher alcohols, alkylphenols, higher fatty acids, higher fatty acid alkyl esters, higher amines and the like, and polyoxyalkylene type nonionic surfactants obtained by adding alkylene oxides to polyoxyethylene polyesters. Oxypropylene block copolymer, fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or its alkylene oxide adduct, hydrogenated castor oil alkylene oxide adduct, sugar fatty acid ester, N-alkyl polyhydroxy fatty acid amide, alkyl glycoside, etc. Can be mentioned.

The amphoteric surfactant is not particularly limited, and examples thereof include alkylbetaine type, alkylamidobetaine type, imidazoline type, alkylaminosulfonic acid type, alkylaminocarboxylic acid type, alkylamidocarboxylic acid type, amide amino acid type or phosphoric acid. Examples include amphoteric surfactants such as molds.

The cationic surfactant is not particularly limited, and examples thereof include cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylbenzyldimethylammonium salt, alkylpyridinium salt, and ester-type dialkylammonium salt. To be

A builder can be added to the detergent for textiles. Here, the "builder" is a part of the additive, but when it is blended with a detergent, it has a remarkable detergent ability even though it has no detergent power or has only a very weak detergent power. A component that can be improved. Examples thereof include stain redeposition preventing agents, polyvalent metal cation scavengers, enzymes, antibacterial agents or alkaline buffers. In addition, there are also additives having a combination of two or more of these actions. Conventional detergent-based detergent products usually contain additives, but the detergent for textiles of the present invention may not be blended with additives. Also, it may be a small amount.

Examples of the water-soluble inorganic compound include, but are not limited to, phosphates (tripolyphosphate, pyrophosphate, metaphosphate, trisodium phosphate, etc.), silicates, carbonates, sulfates, sulfites, and the like. To be Examples of counter ions of these salts include alkali metal salts and amines, and specific examples include sodium, potassium, monoethanolamine, diethanolamine, and triethanolamine.

The organic compound is not particularly limited, but includes carboxylic acid salts (aminocarboxylic acid salts, hydroxyaminocarboxylic acid salts, hydroxycarboxylic acid salts, cyclocarboxylic acid salts, maleic acid derivatives, oxalic acid salts, etc.), organic carboxylic acids (salts). ) Polymers (acrylic acid polymers and copolymers, polyvalent carboxylic acids (eg maleic acid etc.) polymers and copolymers, glyoxylic acid polymers, polysaccharides and salts thereof, etc.) and the like. Examples of counter ions of these salts include alkali metal salts and amines, and specific examples include sodium, potassium, monoethanolamine, diethanolamine, and triethanolamine.

By including the enzyme, the detergency of the textile detergent of the present invention can be further enhanced. The enzyme has substrate specificity and may be appropriately selected depending on the stain to be washed, but it is not particularly limited as long as it is an enzyme, and examples thereof include protease, amylase, lipase, cellulase and mannanase. In the present specification, the term “enzyme” means an industrially available enzyme product.

An antibacterial agent can be added. The antibacterial agent is a component that has the effect of suppressing the growth of bacteria on the fiber and further suppressing the generation of odor derived from the decomposition products of microorganisms.

The antibacterial agent is not particularly limited, but examples thereof include cationic bactericides such as quaternary ammonium salts (benzalkonium chloride, didecyldimethylammonium chloride), diclosan, triclosan, bis-(2-pyridylthio-1-oxide). ) Zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, polylysine and the like.

The content of the antibacterial agent is not particularly limited, but is, for example, 0.5 mass% or less, 0.1 mass% or less, 0.02 mass% or less, 0.01 mass% with respect to 100 mass% of the fiber detergent. May be: Since the closed vesicles or polycondensation polymer particles of the present invention also have a high antibacterial action and their long-lasting effect, the content of the organic compound may be small or may not be contained.

In addition to the above components, other components usually used in detergents for textiles may be contained.

Other components include, for example, a bleaching agent, a bleaching activator, a water-miscible organic solvent, an antioxidant, a preservative, a texture improving agent, a storage stability improving agent, a fluorescent agent, a pearlescent agent, a flavoring agent, and a coloring agent. Agents, extracts of natural products, defoaming agents and the like.

The content of the additive can be appropriately set according to the method of use (partial washing or total washing), the dilution ratio of the detergent, and the like.

The material of the fiber is not particularly limited, and examples thereof include natural plant fibers such as cotton, flax, ramie, and vein fibers other than the above, and in the case of natural animal fibers, wool, mohair, alpaca, camels. , Cashmere, angora, vicuna, llama, silk, natural fiber down, feather, natural fiber bast fiber. On the other hand, rayon of recycled fiber which is a chemical fiber, cupra of copper ammonia fiber, lyocell of recycled fiber other than the above, acetate of semi-synthetic fiber, triacetate, semi-synthetic fiber other than the above, synthetic fiber nylon which is a chemical fiber, Polyester, polyurethane, polyethylene, vinylon, vinylidene, polyvinyl chloride, acrylic, acrylic, polypropylene, polylactic acid, aramid, synthetic fibers other than the above, natural fibers and synthetic fibers, natural fibers and natural fibers, synthetic fibers and synthetic fibers Examples include blended fibers obtained by combining one or more fibers. Any fiber can be treated as a fiber product, regardless of whether the fiber product quality labeling regulations are specified or not.

The fiber product is not particularly limited as long as it is a fiber product using all or a part of the above-mentioned fiber materials, and for example, a woven fabric, a knit fabric and a lace fabric, a swimwear, an underwear, and a mixed ratio of silk in the composition fiber are 50. % Or more of woven fabric, composition of warp or weft yarn Woven silk, haori, kimono, socks, gloves, obi, tabi, handkerchief, furoshiki, tie, haori string, obi tightening, bedding, futon, table cover, towel, Hand towels, cloths, rags, sweaters, shirts, pants, dresses, home dresses, blouses, skirts, office clothes, work clothes, outerwear, children's overalls, rompers, underwear, sleepwear, haori and kimonos, hats, scarves, scarves, Examples include shawls, aprons, jackets, blankets, knees, tops, duvet covers, bed sheets, curtains, bed spreads, blanket covers, pillowcases and coats.

As described above, the fiber detergents of the first to third aspects have the ability to prevent the deterioration of the flexibility of the fiber. Therefore, even if the textile products used for applications requiring flexibility (for example, applications that come into contact with human skin, more specifically, clothing, underwear, handkerchiefs, towels) are suppressed from curing. The soft state can be maintained.

Further, as described above, the fiber detergents according to the first to third aspects have the ability to prevent the water absorption of fibers from decreasing. Therefore, even if the textile products used for the applications requiring water absorption (for example, towels, hand towels, cloths, rags, etc. among the above-mentioned textile products) are washed, they are It is possible to prevent the decrease and maintain a high water absorption state.

According to the above-described fiber detergent, oil-soluble stains on the fibers such as sebum, cosmetics, food fats, pigments, and mineral oils, water-soluble stains such as sweat and urine, and water-soluble stains It has a high cleaning ability for proteins, starch, etc., which change into water-insoluble stains when water-soluble substances dry out in the dirt, and for dirt, mud, soot, iron powder, etc. which are solid particle dirt. Have. Further, it is considered to be bio- and environmentally safe, and can be preferably used for household detergents.

The textile detergent of the present invention has lower foamability than conventional textile detergents using a surfactant. This is because the closed vesicles and the polycondensation polymer do not cause a decrease in interfacial tension as described above. The foaming action of conventional detergents hinders the washing action on the fiber to be washed, and in laundry washing, the load on the subsequent steps such as rinsing increases, but according to the textile detergent of the present invention, Foaming is suppressed.

<Soil release agent>
The textile detergents according to the first to third aspects described above have a soil release ability. Therefore, it can be used as a soil release agent with the same configuration as the textile detergents of the first to third aspects. Here, the "soil release ability" is one of antifouling properties, and refers to a function of facilitating removal of stains attached to the fibers by attaching the fibers to the fibers. In addition, “similar configuration” refers to an essential configuration of the textile detergent of each aspect. Therefore, it is possible to change the ratio of the additive component and the chemical species/addition amount of each component according to each application.

The present inventors have surprisingly found that the textile detergents of the first to third aspects described above have soil release ability. Such soil release ability is obtained by modifying the fiber surface by adsorbing the closed vesicles or polycondensation polymer particles to the fiber surface by hydrophobic interaction between the closed vesicles or polycondensation polymer particles and the fiber, It is considered to be developed by preventing direct contact between the and dirt. Such soil release ability is not found in ordinary surfactants.

That is, since the textile detergents of the first to third aspects have not only the washing ability but also the soil releasing ability, the textile detergent and the soil releasing agent can be used both as one component. In this case, a high cleaning effect is obtained, and at the same time, the washed vesicles have a closed vesicle or a polycondensation polymer attached to the surface thereof, which has an antifouling effect. However, if it is used only as a soil release agent, it may be simply attached, and may be sprayed as a liquid such as an O/W emulsion (second embodiment).

<Method of cleaning fibers>
The fiber cleaning method according to the present invention is a method of performing partial or whole cleaning using any of the above-described fiber detergents. As a specific method of use, it can be used in the same manner as a commercially available fiber detergent.

"Partial washing" mainly refers to the act of directly applying a detergent for textiles to stains that are difficult to remove, such as stains on food spills, regardless of washing methods such as hand washing and washing with a washing machine. It is generally known that when a detergent is directly applied and hand washing is performed, stain removal is higher than in a washing machine.

Also, "whole washing" mainly refers to the act of removing stains from the entire fiber regardless of washing methods such as hand washing and washing with a washing machine. In this case, the detergent is dissolved in a solvent such as water to wash the fibers.

The stains are not particularly limited to organic/inorganic, hydrophilic/hydrophobic, and the like, and oil-soluble stains such as sebum, cosmetics, food oils and fats, pigments, mineral oils, and water-soluble stains such as sweat and urine. In addition, the water-soluble substances in the water-soluble stains become proteins that are insoluble in water when they dry to dryness, such as protein and starch, and solid particles such as soil, mud, soot, and iron powder. You can In particular, the textile detergent of the present invention is advantageous in that it can be washed regardless of the type of dirt. Therefore, for example, stains of a mixture (a plurality of compositions) such as food oil can be removed and cleaned.

(Partially washed)
When performing partial washing, the detergent for fiber may be directly applied to the contaminated portion, or the contaminated portion of the fiber product may be put in water or hot water diluted with the detergent for fiber. Further, in recent years, a device dedicated to partial washing has been sold, and such a device may be used. The fiber detergent of the second aspect constitutes an O/W emulsion. In partial washing, a physical force is applied by a work such as rubbing by hand, but the O/W type emulsion structure is not destroyed and the structure can be maintained.

Further, as described above, since the textile detergent of the present invention has biosafety, it is considered that there is no particular effect on the living body even if it is washed by hand and directly touches the skin.

The water temperature is not particularly limited and is preferably 5°C or higher, more preferably 10°C or higher, further preferably 20°C or higher, further preferably 25°C or higher, 30°C. The above is particularly preferable. From the viewpoint of enhancing the cleanability, the temperature is preferably higher, and may be, for example, 35°C or higher. In the case of hand washing, the user may be in danger if the water temperature is high, so that the temperature may be 40° C. or lower, for example.

The amount of fibers detergent is not particularly limited and may be suitably designed, for example, with respect to the area 1cm per ² dirt, is preferably 1 mg / cm ² or more, with 2 mg / cm ² or more More preferably, it is more preferably 5 mg/cm ² or more, still more preferably 10 mg/cm ² or more. The amount of the detergent for fibers used may be 500 mg/cm ² or less, 100 mg/cm ² or less, and 50 mg/cm ² or less.

(Wash all)
When the whole is washed, a detergent for textiles may be added to the washing tub of the washing machine together with the textiles. Alternatively, the textile may be soaked in water or hot water diluted with a detergent for hand washing.

The water temperature is not particularly limited and is preferably 5°C or higher, more preferably 10°C or higher, further preferably 20°C or higher, further preferably 25°C or higher, 30°C. The above is particularly preferable. The temperature is preferably higher from the viewpoint of enhancing the cleaning property, and may be, for example, 35°C or higher, 40°C or higher, 45°C or higher, 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher. The water temperature may be, for example, 80° C. or lower, 75° C. or lower, 70° C. or lower.

The amount of the fiber detergent used is not particularly limited and may be appropriately designed. For example, it is preferably 0.3 g/L or more, more preferably 0.5 g/L or more, and 1. It is more preferably 0 g/L or more, and particularly preferably 1.5 g/L or more. The amount of the detergent for fibers used may be 3.5 g/L or less, 2.5 g/L or less, and 2.0 g/L or less.

As described above, the fiber detergents of the first to third aspects have the ability to prevent the deterioration of the flexibility of the fiber. Therefore, the softening agent may be used as the treatment after the washing of the textile product with the textile detergent, or the softening agent may not be used.

Hereinafter, the present invention will be described more specifically by showing Examples and Comparative Examples of the present invention. The present invention is not limited to the following examples.

<Cleaning test>
[Preparation of sample]
[Raw material for detergent sample]
(Oil component)
Medium chain fatty acid triglyceride (MASESTER-E6000 or MASESTER-E7000, manufactured by Oleochemical Co., Ltd., hereinafter referred to as "MCT").
Polyoxyethylene polyoxypropylene glycol (Brownon P171, Aoki Yushi Kogyo Co., Ltd., hereinafter referred to as "P171")
Di(caprylic acid/capric acid) propanediol (Sarasco PR-85, manufactured by Nisshin Oillio Co., Ltd., hereinafter referred to as "PR-85")
Oleic acid (manufactured by Oleochemical Co., Ltd., hereinafter referred to as "OA")
Polypropylene glycol (PPG4000, manufactured by DOW Chemical Co., Ltd.)
Isopropyl myristate (NIKKOL IPM-100, manufactured by Nikko Chemicals Co., Ltd., hereinafter referred to as "IPM")
Myristyl alcohol (Hynol 14SS, manufactured by Higher Alcohol Co., Ltd., hereinafter referred to as "MA")
Hexyldecanol (Lisonol 16SP, manufactured by Higher Alcohol Co., Ltd., hereinafter referred to as "HD")
2-octyldodecanol (Lisonol 20SP, manufactured by Higher Alcohol Co., Ltd., hereinafter referred to as "OD")
Liquid paraffin (Moresco White P-55, manufactured by MORESCO Co., Ltd., hereinafter referred to as "LP")
Jojoba oil (NIKKOL Jojoba oil S, manufactured by Nikko Chemicals Co., Ltd., hereinafter referred to as "HO")
(Closed endoplasmic reticulum)
POE hydrogenated castor oil (HCO-60, Nikko Chemicals Co., Ltd.)

[Preparation of detergent sample]
(Examples 1 to 13)
While stirring purified water at 7,000 rpm in a beaker, POE hardened castor oil was added dropwise and stirred. Then, the oily component was dropped and stirred to obtain the detergent samples of Examples 1 to 13. The composition of each sample is shown in Table 1. In addition, in Table 1, a numerical value shows mass %. The emulsion particles of Example 1 had an average particle diameter of 884 nm, and the emulsion particles of Example 8 had an average particle diameter of 664 nm.

(Comparative Example 1: For partial washing test)
Polyoxyethylene monoalkyl ether (9J, manufactured by Maruzen Petrochemical Co., Ltd.) was dissolved in water to prepare a 25 wt% aqueous solution.

(Comparative Example 2: For whole washing test)
Polyoxyethylene monoalkyl ether (9J, manufactured by Maruzen Petrochemical Co., Ltd.) was dissolved in water to prepare a 5 wt% aqueous solution.

(Comparative Example 3: For whole washing test)
A commercially available Farfa liquid detergent clear apple blossom (LOT: C17.11.01D, component: 11% surfactant, alkali agent, anti-redeposition agent, enzyme) was used. The amount used was 0.83 g described as the amount used for the product.

(Comparative Example 4: For whole washing test)
Farfa liquid detergent clear apple blossom (LOT: C17.11.01D), which is a commercially available detergent, was used. The amount used was 3 g, which was the same as in the example.

[Contaminated cloth sample]
As the material of the cloth, three kinds of cotton, blended fiber and chemical fiber were used. As dirt, assuming clay dirt, mineral oil dirt, food dirt, blood dirt and curry dirt, clay-contaminated cloth, mineral oil-contaminated cloth, colored rice starch red-contaminated cloth, blood-contaminated cloth and curry-contaminated cloth, respectively. Was used. Specifically, it is as shown below. Regarding curry stains, according to the method described in JP 2011-126939 A, a curry solution was prepared using a commercially available curry roux, and cotton (JIS L 0803 compliant attached white cloth cotton (Kanakin No. 3) was prepared therein. )), mixed spinning (T/C twill) or chemical fiber (polyester tropical (Teijin)) was added and cooked to obtain each contaminated cloth sample.
(Clayy (yellow) contaminated cloth)
Cotton (C-S-40, CFT)
Chemical fiber (PS-40, manufactured by CFT)
(Blood-contaminated cloth)
Cotton (C-S-01, manufactured by CFT)
Chemical fiber (PS-01, manufactured by CFT)
(Colored rice starch red stain cloth)
Cotton (C-S-28, CFT)
Chemical fiber (PS-28, manufactured by CFT)
(Cloth contaminated with mineral oil)
Cotton (C-S-65, manufactured by CFT)
Chemical fiber (PS-65, manufactured by CFT)

[Evaluation]
[Partial washing test]
First, the reflectance of a contaminated cloth sample and a cloth not contaminated with the same material as the contaminated cloth sample was measured using a white photometer TC-6DS/A (manufactured by Tokyo Denshoku Co., Ltd.).

Next, 0.3 ml per contaminated cloth was applied to each contaminated cloth sample (area 25 cm ² ) moistened to such an extent that water did not drip to the extent that the detergent samples of Examples 1 to 12 and Comparative Example 1 did not flow out. Dropped. After washing the contaminated cloth sample by rubbing it, it was rinsed with running water for 3 minutes using tap water. Then, it was dehydrated, flat-dried, and air-dried.

The reflectance of the contaminated cloth sample after drying was measured using a white photometer TC-6DS/A (manufactured by Tokyo Denshoku Co., Ltd.). The clay-contaminated cloth and the curry-contaminated cloth were measured for reflectance at a wavelength of 460 nm. The reflectance at a wavelength of 550 nm was measured for the mineral oil-contaminated cloth, the colored rice starch red-contaminated cloth, and the blood-contaminated cloth.

[Whole washing test]
First, the reflectance of a contaminated cloth sample and a cloth not contaminated with the same material as the contaminated cloth sample was measured using a white photometer TC-6DS/A (manufactured by Tokyo Denshoku Co., Ltd.).

Next, about 270 mg of calcium chloride dihydrate (hardness component) specified in hard water JIS K 8122 was dissolved in generated water, and the volume was adjusted to 1000 mL to obtain a hard aqueous solution. On the other hand, after dissolving 3 g of each detergent sample in 990 mL of purified water, 10 mL of the hard aqueous solution prepared as described above was added to obtain a total detergent solution of 1000 mL.

For each of the detergent samples of Examples 1 to 3, 6 to 8 and 13 and Comparative Examples 2 to 4, 5 pieces of the same soil and same material soiled cloth sample were immersed in 1000 mL of the cleaning solution adjusted to 30° C., and stirred. It wash|cleaned for 10 minutes at the rotation speed of 100 +/-5min< ^-1 > using the detergency tester (Tergometer).

After completion of washing, dehydration was performed for 1 minute using a dehydrator so that the water content was 200% or less by mass fraction, and the resultant was placed in 1000 mL of tap water adjusted to 30° C. Rinsing for 3 minutes at a rotation speed of 5 min ^-1 .

Then, it dehydrated for 1 minute using the apparatus which has a dehydration function, air-dried, and ironed. Note that the blood-contaminated cloth was only air-dried because the blood was denatured.

The reflectance of the contaminated cloth sample after drying was measured using a white photometer TC-6DS/A (manufactured by Tokyo Denshoku Co., Ltd.). The clay-contaminated cloth and the curry-contaminated cloth were measured for reflectance at a wavelength of 460 nm. The reflectance at a wavelength of 550 nm was measured for the mineral oil-contaminated cloth, the colored rice starch red-contaminated cloth, and the blood-contaminated cloth.

[Calculation of cleaning rate]
With respect to each combination of the material of the cloth and the type of stain, the cleaning rate of each of the five pieces of cloth was calculated by the following formula (1) and determined, and the average value was used as the cleaning rate of each contaminated cloth. The cleaning rate is an index showing the ratio of stains that can be removed by cleaning, and the larger the value, the higher the cleaning performance.

...(1)
In the formula (1), K/S is a value calculated by the following formula (2).

...(2)
In Formula (2), R is the reflectance (%) of each cloth. The reflectance means a value measured by a white photometer TC-6DS/A manufactured by Tokyo Denshoku Co., Ltd.

〔result〕
[Partial washing test]
Table 2 shows the results of the partial washing test for the clay-contaminated cloth, the blood-contaminated cloth, and the colored rice starch red-contaminated cloth. In Table 2, the numerical value shows the cleaning rate (%).

As shown in Tables 2 to 4, the detergent samples of Examples 1 to 12 tended to show higher cleaning ability than the detergent samples of Comparative Example 1. Although not shown in Tables 2 to 4, the detergent samples of Examples 1 to 12 also showed excellent cleaning ability against mineral oil-contaminated cloth and curry-contaminated cloth.

[Whole washing test]
The results of the overall washing test for the clay-contaminated cloth, the blood-contaminated cloth, the colored rice starch red-contaminated cloth and the curry-contaminated cloth are shown in Tables 5-8. In addition, in Tables 5-8, a numerical value shows a cleaning rate (%).

As shown in Tables 5-8, the detergent samples of Examples 1-3, 6-8, and 13 which do not use surfactant are equivalent to or the same as the detergent samples of Comparative Examples 2-4 constituted by the surfactant. There was a tendency to show the above cleaning ability. Although not described in Tables 5 to 8, the detergent samples of Examples 1 to 3, 6 to 8 and 13 also showed the washing ability with respect to the mineral oil contaminated cloth.

<Soil release ability test>
[Preparation of sample]
[Preparation of soil release agent sample]
The samples of Examples 1 and 11 were used as the soil release agent samples.

[Cloth sample]
As the material of the cloth, the following two kinds of chemical fibers and a mixed spinning of chemical fibers were used.
Chemical fiber (Polyester tropical (Teijin), purchased by Shikiso Co., Ltd.)
Blending of chemical fibers (polyurethane/polyester (=15/85) mixed knitting, purchased by Color Dye Company)

[Evaluation]
3 g of the detergent samples of Examples 1 and 11 were added to 1000 mL of tap water. A 5×5 cm cloth sample was dipped in the detergent sample aqueous solution (Examples 1 and 11) or tap water (Comparative Example 5), and stirred at 30° C. for 100 rpm for 5 minutes. Then, it was taken out and dehydrated for 1 minute. The cloth sample that underwent this treatment was dried at 20° C. under 65 RH% for 12 hours or more to prepare a sample-immersed cloth. As Comparative Example 5, a cloth not subjected to the above treatment was used.

JIS C9606 Electric washing machine's "Appendix 4 Contaminated cloth preparation method (2) Material and amount of contaminated liquid" of artificial dirt except red-yellow soil and carbon black among artificial dirt ( Oleic acid:triolein:cholesterol oleate:liquid paraffin:squalene:cholesterol=mixture in the ratio of 18:10:8:2:2:1) was prepared, and the oil red concentration thereof was 0. An artificial soil oil of 95% by weight was prepared. Next, while stirring the aqueous gelatin solution using a homogenizer, artificial soil oil was added to the aqueous gelatin solution so that the oil red concentration was 0.03 mass% in the total amount, and the mixture was stirred to prepare an organic soil solution. ..

0.5 g of an organic dirt solution was dropped on a sample dipping cloth or a tap water dipping cloth and dried at 20° C. and 65 RH%. The cloth was dropped into 1000 mL of a solution containing 3 g of a 5% polyoxyethylene alkyl ether aqueous solution in tap water, and the cloth was dropped. The mixture was stirred at 30° C., 100 rpm for 10 minutes using a tergotometer, dehydrated for 1 minute, and air dried. The reflectance of the contaminated cloth sample after drying was measured at a wavelength of 550 nm using a white photometer TC-6DS/A (manufactured by Tokyo Denshoku Co., Ltd.).

The stain residual ratios of five pieces of the same type of cloth were calculated by the following equation (3), and the average value was defined as the stain residual ratio (%) of each contaminated cloth. The stain residual ratio is an index showing the ratio of stains remaining on the cloth sample even after washing, and the smaller the value, the greater the effect of soil release capability.

...(3)

〔result〕
Table 9 shows the results of the soil release test of artificial dirt. Incidentally. In Table 9, the numerical values indicate the contamination residual rate (%).

From Table 9, when the soil release agent samples of Examples 1 and 11 were used, there were fiber species in which the residual contamination rate was lower than in Comparative Example 5 in which no treatment was applied to the cloth sample. It has a soil release ability for such fibers.

<Foamability test>
[Preparation of sample]
The samples of Examples 3, 8, 11, 13 and Comparative Example 3 were used as the samples for the foamability test.

[Evaluation]
Hard water Approximately 270 mg of calcium chloride dihydrate (hardness component) specified in JIS K 8122 was dissolved in generated water, and the volume was adjusted to 1000 mL to obtain a hard aqueous solution. On the other hand, after dissolving 3 g of each detergent sample in 990 mL of purified water, 10 mL of the hard aqueous solution prepared as described above was added to obtain a total detergent solution of 1000 mL.

For each of the detergent samples of Examples 3, 8, 11, 13 and Comparative Example 3, 50 mL of the washing solution was placed in a candle bottle, and the candle bottle was shaken up and down by hand for 30 seconds, and the washing solution after standing for 10 seconds. The bubble height was observed.

〔result〕
FIG. 1 is a photograph of the post-washing liquids of Examples 3, 8, 11, 13 and Comparative Example 3. The post-washing solutions of Examples 3, 8, 11, and 13 had less foaming than the post-washing solutions of Comparative Example 3.

<Flexibility reduction prevention test>
[Preparation of sample]
[Preprocessing]
15 sheets of commercially available cotton towels (manufactured by Lipos Co., Ltd., trade name: F/T Lipos Gold 350, white border 34×80) were used as a pretreatment detergent (NS Furfa Japan Co., Ltd.; polyoxyethylene lauryl ether ( EO: 9 mol) 25% solution) was used to perform treatment 3 times using a fully automatic washing machine (Hitachi BW-7MV) (detergent standard usage (25 g/30 L), tap water (normal temperature), After 50 L of water, 12 minutes of washing, then 3 times of water rinsing, 9 minutes of dehydration), the same process (tap water (normal temperature), 50 L of water, 15 minutes of washing, then water rinsing) without using the pretreatment detergent It was dried three times and once for 9 minutes) and dried at room temperature.

[Flexibility reduction prevention processing]
0.5 kg of the pretreated washed cotton towel was treated with the sample of Example 14 or a commercially available detergent for 10 minutes using a two-tub washing machine (PS-H35L manufactured by HITACHI) (10 g of sample of Example 14, water). After performing 10 L and tap water (normal temperature), dehydration was performed for 1 minute. Then, the cotton towel treated with each detergent was treated with a commercially available softening agent (Farfa Trip Dubai, Y16.08.10) for 5 minutes (softening agent 3.33 g, water 10 L, tap water (normal temperature)). After that, dehydration was performed for 1 minute. After these treatments, it was dried under constant temperature and humidity conditions of 20° C. and 65% RH.

[Evaluation of sample]
In the above "treatment for preventing deterioration of flexibility", a cotton towel treated with a commercially available detergent was used as a control, and the judgment was made by a pairwise comparison of 5 specialized panelists. The evaluation criteria of each panelist are as follows, and the average of the scores of 5 people is taken, and if it is 0.5 points or more in terms of commercial value, it has the ability to prevent the deterioration of flexibility of the fiber. Can be said to be. The results are shown in Table 10 below.

(Evaluation criteria)
+2: Clearly better than commercial detergents.
+1: Slightly better than commercial detergent.
0: Almost the same as a commercially available detergent.
-1: The commercially available detergent is slightly better.
-2: Commercial detergent is obviously better.

<Water absorption reduction prevention test>
[Preparation of sample]
[Pretreatment method for evaluation cloth]
Fifty sheets of commercially available cotton gold width (Kin width No. 3) were washed with a pretreatment detergent (NS Farfa Japan Co., Ltd.; polyoxyethylene lauryl ether (EO: 9 mol) 25% solution) fully automatic washing machine (HITACHI BW7MV). ) Was used 3 times (standard detergent usage (25 g/30 L), tap water (normal temperature), water volume 50 L, washing for 12 minutes, then water rinsing 3 times, dehydration 9 minutes), and pretreatment only The same steps (tap water (normal temperature), water amount 50 L, washing 15 minutes, then water-rinsing 3 times, dehydration 9 minutes) were performed once without using a detergent, and dried at room temperature.

[Water absorption reduction prevention treatment]
Using a two-tank type washing machine (PS-H35L manufactured by HITACHI), 6.0 g of the pretreated and washed cotton wire width was treated with the sample of Example 14 or a commercially available detergent for 10 minutes (composition 10 g, water 10 L, tap water). After performing water (normal temperature), dehydration was performed for 1 minute. Then, the cotton rag treated with each detergent was treated with a commercially available softener (Farfa Trip Dubai, Y16.08.10) for 5 minutes (softener 3.33 g, water 10 L, tap water (normal temperature)). After that, dehydration was performed for 1 minute. After these treatments, it was dried under constant temperature and humidity conditions of 20° C. and 65% RH.

[Evaluation of water absorption]
A test piece having a size of about 200 mm×25 mm was taken from the pretreated sample. Next, after fixing the test piece with a pin on a horizontal bar supported on the water surface of a water tank containing water, lower the horizontal bar and adjust so that the lower end 20 mm ± 2 mm of the test piece is immersed in water. Then, it was left as it was for 10 minutes. After standing, the height at which the water rose due to the capillary phenomenon was measured on a scale. FIG. 2 is a schematic diagram of an apparatus used for evaluation of water absorption.

In the above "water absorption lowering prevention treatment", the same test was conducted on a gold width (hereinafter referred to as "blank") treated under the same conditions except that nothing was added, and the water level at which the blank rose for 10 minutes was increased. As a control (100%), N = 2 times the average height was taken, and the value when the blank was 100% was taken as the water absorption.

Claims (17)

Spontaneously closed saw including a polycondensation polymer particles and the oily substance having a closed vesicle or a hydroxyl group of the amphiphilic material forming the vesicles,
A detergent for fibers, wherein the oily substance is surrounded by the closed vesicles or the polycondensation polymer particles to form detergent particles . The textile detergent according to claim 1, further comprising water, which is an O/W emulsion. In powder form, fiber detergent of claim 1. The detergent for fibers according to claim 1, wherein the melting point of the oily substance is 80° C. or lower. The detergent for textiles according to any one of claims 1 to 4 , wherein the oily substance is a polar oil. The boiling point of the oily substance is 80 ° C. or higher, the fibers detergent according to any one of claims 1-5. The detergent particles have an average particle diameter of when dispersed in water is 50nm or more 2μm or less, the fibers detergent according to any one of claims 1-6. Having soil release ability, fiber detergent according to any one of claims 1-7. The detergent for textiles according to any one of claims 1 to 9 for partial washing. The detergent for textiles according to any one of claims 1 to 9 for washing the whole. The detergent for textiles according to any one of claims 1 to 9 for washing textiles. The detergent for textiles according to any one of claims 1 to 9 for washing clothes. Without using a softener as treatment after cleaning of textiles by the textile detergents, for performing the cleaning, textile detergent according to any one of claims 1-8. The detergent for textiles according to any one of claims 1 to 9 for washing using a softener as processing after washing of textiles with the detergent for textiles. Using fibers detergent according to any one of claims 1-8 for cleaning the fibers, fiber cleaning method. Including polycondensation polymer particles having a closed vesicle or a hydroxyl group of an amphipathic substance that spontaneously forms a closed vesicle and an oily substance,
A soil release agent in which the closed vesicles or the polycondensation polymer particles surround the oily substance to form detergent particles . The soil release agent according to claim 16, further comprising water, which is an O/W type emulsion.