JP2005330472A - Scrub agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a scrub agent that causes less damage to objects, can efficiently scrape out dirts within fine concavity and convexity portions on object surfaces, and has good rinsing property. <P>SOLUTION: The scrub agent is in the shape of a fiber with an average diameter of 3 μm or less. Furthermore, the scrub agent has a fiber length of 0.05 mm or more and 20 mm or less. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a scrub agent with little damage to an object to be cleaned, excellent dirt removal ability, and good rinsing properties during cleaning.

  With the recent development of precision processing technology, precision processing at the nm level is becoming possible. Along with this, a method for cleaning without damaging the surface of a precisely processed object has been demanded. Further, in face washing and body washing applications, it is required to surely remove everything from health and cleanliness to dirt in the skin grooves and pores. On the other hand, the number of patients with atopy and sensitive skin is increasing, and there is a need for a method that is gentle to the skin and can remove dirt reliably.

  Usually, when cleaning an object, it is easy to remove dirt using a detergent, and the dirt is removed with physical force. As this physical force, a fluid such as water flow or high-pressure air may be used, but in many cases, a soft object such as a cloth or a sponge is brought into direct contact with the dirt, and the object is cleaned by scraping. In particular, fabrics made of fibers that are supple and can follow the complicated shape of the surface of the object to be washed are often used.

  In recent years, attempts have been made to make the fibers constituting the cleaning fabric thinner in order to reduce the damage to the cleaning object and improve the followability to the unevenness of the surface of the cleaning object. For example, Japanese Patent Laid-Open No. 61-103428 proposes a wiping cloth characterized by the bulkiness of a fabric made of ultrafine fibers of 0.9 denier (thickness of about 10 μm) or less. Has proposed a wiping cloth using ultra-fine yarn of 0.2 denier (thickness of about 5 μm) or less. However, when the fiber is thinned, its strength is remarkably reduced. Therefore, it is difficult to maintain the form of the fabric, and it is difficult to reduce the fineness beyond a certain level.

  On the other hand, there is also known a method of adding a substance (scrubbing agent) that scrapes off the detergent to give the detergent the physical power to remove the dirt. However, the conventional scrubbing agent is used for hand washing without using a cleaning cloth, or used for obtaining an appropriate stimulus at the time of body washing, and uses a particulate substance having a diameter of 50 to 500 μm such as a pulverized plant shell. That was the mainstream. These scrubbing agents were able to push open skin grooves and pores on the surface by pressing strongly against the skin during use, and scrape dirt inside the skin grooves and pores by entering inside. Depending on the condition, the skin may be too irritating and the skin may turn red or cause rough skin. Further, considering the use for the container, the scrub agent would damage the surface of the object to be cleaned, so it was difficult to use it for cleaning the container.

  In place of these particulate scrub agents, plant-derived cellulose fibers are partly added to detergents (Patent Document 1). However, since such a cellulose fiber is thick and lacks flexibility, damage to the object to be cleaned could not be prevented. In addition, when fine irregularities exist on the surface of the object to be cleaned, the followability to the surface is insufficient and it is difficult to remove dirt inside the irregularities.

As described above, there has been no scrub agent that is less damaging to the object to be cleaned and that can remove even fine dirt inside the surface of the object to be cleaned.
JP-A-8-209199

  SUMMARY OF THE INVENTION An object of the present invention is to provide a scrub agent that is less damaging to an object, can efficiently scrape dirt inside fine irregularities on the surface of the object, and is excellent in rinsing properties.

  The above-mentioned object is achieved by a scrub agent characterized by a fibrous shape having an average thickness of 3 μm or less.

  Since the scrub agent of the present invention is very thin, it is supple and easily deformed, so there is little damage to the object, and it penetrates into fine irregularities such as pores and polishing marks on the glass surface. It is possible to scrape dirt. In addition, since the movement of the scrubbing agent is activated because it has a certain length, the scrubbing agent has improved cleaning properties and excellent rinsing properties. For this reason, the detergent containing the scrub agent of the present invention is gentle to the object, has a high detergency, and has excellent rinsing properties.

  It is important that the scrub agent of the present invention is fibrous. The fibrous form referred to in the present invention indicates a string-like shape having an overwhelmingly large length with respect to the cross-sectional area.

  In addition, it is important that the scrub agent of the present invention has a very thin average thickness of 3 μm or less. If the cross-sectional second moment, which represents the difficulty in bending the object, is proportional to the fourth power of its diameter if the cross-sectional shape is circular, the scrub agent becomes sharp and flexible by reducing the thickness. For example, compared to a commonly used fiber (thickness of about 20 μm), the cross-sectional secondary moment is 1/2000 when the thickness is 3 μm, 1/25 million when the thickness is 0.5 μm, and the thickness is 0. It is reduced to 1/100 million at 2 μm. By being supple in this way, the object to be cleaned is less likely to be damaged. Further, by deforming along the shape of the surface of the object to be cleaned, the cleaning performance is improved because it reaches the dirt inside the irregularities on the surface of the object to be cleaned. Here, if the average thickness of the scrub agent is 0.5 μm or less, the stimulation to the object to be cleaned such as skin and tableware becomes softer, and if it is 0.2 μm or less, the object is almost damaged. It is more preferable because it can be used for cleaning optical components such as precision substrates and lenses.

  Here, the average thickness refers to the average thickness of individual fibrous scrub agents. The fine fibrous material of the present invention may have an aggregated structure in which the fibrous materials are associated with each other in a bundle or entangled with each other. In this case, the aggregate as a whole also functions as a scrub agent, but in the deformation on the surface of the object to be cleaned, the degree of damage to the object to be cleaned is determined by the flexibility of the individual fibrous objects constituting the aggregate. Therefore, in the present invention, even when fine fibrous materials are aggregated, the average value of the thicknesses of the individual fibrous materials is defined as the average thickness.

  The scrub agent of the present invention preferably has a length of 0.05 mm or more. By having such a length, it is easy to receive an external force from a water flow or other objects, and the movement of the scrub agent is activated, so that the cleaning power is enhanced. In addition, the scrub agent is easily washed away by the water flow even during rinsing, and the rinsing property is improved. For this reason, if the length of the scrub agent is 0.05 mm or more, the above effect is more remarkable, which is preferable. However, if the length is too long, the fluidity of the detergent containing the scrub agent is lowered and the usability is deteriorated. Therefore, the length of the scrub agent is preferably 20 mm or less.

  The shape of the scrub agent of the present invention may be linear or branched as long as it is fibrous, but if it does not have a branch, the scrub agent is less likely to be entangled with each other and the dispersibility becomes good. The cross-sectional shape of the scrub agent can be any shape such as a circle, an ellipse, or a three-leaf. Fibers with dents on the surface, such as multi-leaf cross-section fibers, are excellent in scraping off dirt.Since the thickness of the fibers is reduced, the scraping performance is improved. The effect can be sufficiently exerted.

  The thickness and shape of the scrub agent can be confirmed by SEM observation of the scrub agent. Specifically, a liquid in which a scrub agent is dispersed is attached on an observation table to prepare an observation sample.

  This sample is observed with an optical microscope or SEM at a magnification such that about 20 scrubbing agents are present in the visual field, and the thickness and shape of the scrubbing agent are measured. The thickness of the scrub agent is obtained by measuring the width of the scrub agent in the microscopic image. Here, when the width of one scrub agent varies greatly depending on the location, the maximum value and the minimum value of the width inside the microscope image are measured, and the average value is taken as the thickness of the scrub agent. The average thickness of the scrub agent is determined by measuring the thickness of five different scrub agents in one microscopic image and performing this observation at five different locations to obtain a total thickness of 25 scrub agents. The average thickness of the scrub agent is obtained by measuring and obtaining the average value. Here, when observing with an SEM, it is preferable to perform sputtering on the sample with platinum or the like in order to prevent charge accumulation on the sample.

  Here, when the thickness of individual fibrous materials is difficult to discriminate from the side observation due to aggregation of the scrub agent, the scrub agent was embedded in an epoxy resin, and an ultrathin section was prepared using a microtome. Later, the diameter can be measured by observing the cross-sectional shape of the fiber. At this time, when the fiber cross-sectional shape deviates from the circle, the cross-sectional area of the fiber is measured, and the diameter of a circle having the same area as the area is defined as the thickness of the scrub agent. Here, the average thickness of the scrub agent was measured by measuring the thickness of five scrub agents in one field of view, and measuring the thickness of a total of 25 scrub agents by performing this observation at five different locations. The average thickness of the scrub agent is obtained by obtaining the average value.

  The scrub agent of the present invention may be an organic fiber or an inorganic fiber, but in order not to damage the object, it should have a low rigidity and is preferably a more supple organic fiber. In particular, the use of a thermoplastic resin is more preferable because it can be produced using a melt spinning method with high productivity. Examples of the thermoplastic resin that can be used in the scrub agent of the present invention include polyester, polyamide, polyolefin, polyphenylene sulfide (PPS), and the like, and it is possible to use an appropriate one depending on the application. For example, in applications such as household detergents that are discharged into sewers without waste liquid treatment, those with biodegradability such as polybutylene succinate (PBS) and polylactic acid (PLA) are environmental impacts. Is preferable because it becomes smaller. On the other hand, in an environment where waste liquid treatment facilities are complete for industrial use and are recovered and used repeatedly, those having excellent chemical resistance are preferred, and polypropylene (PP) and PPS are preferred. Also, when used or treated at high temperatures, many polycondensation resins typified by polyester and polyamide have a high melting point, and are more preferable. The melting point of the resin is preferably 165 ° C. or higher because the scrub agent has good heat resistance. For example, polylactic acid (PLA) is 170 ° C, PET is 255 ° C, and N6 is 220 ° C. Further, the resin may contain additives such as a flame retardant and an antistatic agent, and other components may be copolymerized as long as the properties of the resin are not impaired. However, when adding particles, the added particles may be deposited on the surface of the scrubbing agent or may be damaged when the particles are removed from the scrubbing agent. Is preferred.

  The scrub agent of the present invention can physically remove dirt even when used alone, but can be combined with a chemical cleaning component to provide a detergent with further enhanced cleaning power. It is. The detergent of the present invention may be solid, creamy or liquid and can be used for industrial substrate cleaning, household dish cleaning and body cleaning.

  It is important that the detergent of the present invention contains a fibrous scrub agent having a thickness of 3 μm or less in addition to a cleaning component such as a surfactant. Thereby, in addition to chemical cleaning power, it becomes the detergent excellent in the cleaning power which had the physical cleaning power of the scrub agent. In particular, by using a scrubbing agent having a thickness of 3 μm or less as a scrubbing agent, it becomes possible to efficiently remove fine dirt inside the object to be cleaned while suppressing damage to the object to be cleaned. And it becomes a detergent excellent in rinsing properties.

  As a form of the scrub agent in the detergent, an aggregated state and a dispersed state can be considered. The agglomerated state is a state in which the fibrous scrubbing agent contained in the detergent is aligned in the fiber axis direction and associates in a bundle or is entangled with each other to form a scrubbing agent larger than one fibrous material. Point to. By taking such an agglomerated state, dirt can be taken into the gaps between the fibrous materials, and by removing the taken dirt together with the scrub agent, it is possible to exhibit high dirt removing power. In addition, since the scrub agent of the present invention is composed of extremely thin fibrous materials, it has a very strong holding power for dirt that has been taken in. Become.

  On the other hand, the dispersed state refers to a state in which the fibrous substances contained in the detergent are not aligned in a bundle in the fiber axis direction and are not entangled with each other. Here, since the fibers constituting the scrub agent of the present invention are extremely thin, the uniformity of the detergent is improved by making such a dispersed state, and a smooth feeling of use can be obtained while containing the scrub agent. In addition, the damage to the object to be cleaned is extremely small.

    As described above, if it is in an agglomerated state, it exhibits strong dirt removal power, and if it is in a dispersed state, it can be a detergent that is extremely gentle on the object to be cleaned. It is possible to select according to the purpose of use.

    The dispersion state of the scrub agent in the detergent can be determined by observing optically after the detergent is diluted to a dispersion having a scrub agent concentration of 0.01% by weight or less. First, when the scrubbing agent contained in the detergent has a thickness that can be observed with an optical microscope (thickness of 0.5 μm or more), a scrubbing agent dispersion is dropped on a slide glass and covered with a cover glass. This can be determined by observing the form of the scrub agent with a microscope. At this time, if at least 50 scrub agents are observed, and the ratio of the observed scrub agents in which the scrub agents are aligned in the fiber axis direction and assembled in bundles or entangled with each other exceeds 10%, scrub The agent is considered agglomerated. In addition, if the ratio of the scrub agents that are aligned in the fiber axis direction and associated in a bundle or entangled with each other is 10% or less, it is considered that the scrub agent is dispersed.

    On the other hand, when the scrub agent contained in the detergent cannot be observed with an optical microscope (thickness less than 0.5 μm), the scrub agent dispersion is poured into a glass cell and visually observed. The form can be judged. Here, if the dispersion in the cell is uniform and transparent, this indicates that there is no dispersion having a size that scatters light in the dispersion, and the scrub agent is regarded as being dispersed. On the other hand, if the dispersion in the cell is non-uniform or opaque, the scrub agent is considered agglomerated.

  The content of the scrub agent in the detergent of the present invention varies depending on the form of the detergent, but when the entire detergent is 100 parts by weight, it is 5 to 40 parts by weight for solid detergents and 2.5 to 20 for cream detergents. In the case of parts by weight or liquid detergent, the amount is preferably about 1 to 10 parts by weight. In particular, in the case of a liquid detergent, in order to prevent the scrub agent from separating due to settling or floating, the scrub agent is uniformly dispersed in a dispersion medium using a surfactant, and the viscosity of the detergent is adjusted using a thickener. It is preferable. The surfactant used in the present invention is not particularly limited as long as it is usually used as a soap component of a cleaning agent, and any of anionic, cationic, amphoteric and nonionic surfactants can be used. Examples of the anionic surfactant include fatty acid soaps, polyoxyethylene (POE) alkyl ether carboxylate, POE alkyl allyl ether carboxylate, acyl sarcosine salt, alkane sulfonate, phosphate ester salt, and higher alcohol sulfate. Ester salt, α-olefin sulfonate, higher fatty acid ester sulfonate, dialkyl sulfosuccinate, higher fatty acid amide sulfonate, alkyl allyl sulfonate, secondary alcohol sulfate, POE alkyl ether sulfate, POE Examples thereof include alkyl allyl ether sulfate, higher fatty acid sulfate, higher fatty acid alkylolamide sulfate, acyl glutamate and the like.

  Examples of the cationic surfactant include alkylamine salts, polyamine fatty acid salts, alkanolamine fatty acid salts, alkyl quaternary ammonium salts, and cyclic quaternary ammonium salts.

  Examples of the amphoteric surfactant include amino acid type, betaine type, sulfate ester type, sulfonic acid type, and phosphate ester type.

  Examples of the nonionic surfactant include ether type, ether ester type, ester type, block polymer type, and nitrogen-containing type.

  The thickener used in the present invention is not particularly limited as long as the viscosity can be adjusted by dissolving in the dispersion, and a thickener using a natural polymer and a derivative thereof, or a synthetic polymer thickener may be used. I can do it. Examples of the thickener using the natural polymer include gelatin, casein, collagen, hyaluronic acid, albumin and the like. Examples of the thickener using the natural polymer derivative include cellulose thickeners such as methylcellulose and ethylcellulose. Examples of the synthetic polymer thickener include sodium polyacrylate and polyethylene oxide.

  In addition to the cleaning component and the scrub agent, additives such as antioxidants and preservatives can be added to the cleaning agent of the present invention. In particular, cosmetic ingredients such as humectants and anti-inflammatory agents, and functional ingredients such as fragrances and refreshing agents may be added to the body cleaner.

  Although the manufacturing method of the scrub agent of this invention is not specifically limited, For example, it can manufacture by the following method.

  First, using fibers having different solubility in two or more kinds of solvents, raw fibers in which a hardly soluble resin is dispersed inside an easily soluble resin are produced. By removing the easily soluble resin from the raw fiber with a solvent, it is possible to produce finer ultrafine fibers. At this time, the scrub agent of the present invention can be produced by cutting the raw fiber into an appropriate length in advance or adjusting the length by cutting the produced ultrafine fiber.

  At this time, if the thickness of the scrub agent is about 1 μm, a sea-island type composite fiber can be used as the raw fiber. This sea-island type composite fiber uses a composite spinning machine as shown in FIG. 1 to supply two types of resins to one or two separate hoppers, and melt and extrude them using three or four separate extruders. Is produced by merging into a shape as shown in FIG.

  In order to produce ultrafine fibers having a thickness of 1 μm or less, alloy fibers are used as raw material fibers. This alloy fiber can be obtained by kneading two kinds of resins in advance to obtain an alloy resin and fiberizing it using a single component spinning machine as shown in FIG. Here, in order to obtain a nano-sized scrub agent having a thickness of 0.5 μm or less, a combination of resins is important.

First, it is necessary to select so that both solubility parameters (SP value) become an appropriate value. The SP value is a parameter reflecting the cohesive strength of a substance defined by (evaporation energy / molar volume) ^1/2 , and a polymer alloy having good compatibility may be obtained between materials having close SP values. The SP value is known for various polymers, and is described, for example, in “Plastic Data Book” (co-edited by Asahi Kasei Amidus Co., Ltd./Plastics Editorial Department), page 189 and the like. It is preferable that the difference between the SP values of the two polymers is 1 to 9 (MJ / m ³ ) ^{1/2 because} it is easy to achieve both circularization of island domains and ultrafine dispersion due to incompatibility. For example, the difference in SP value between N6 and PET is about 6 (MJ / m ³ ) ^1/2, which is a preferable example. The difference between N6 and PE is about 11 (MJ / m ³ ) ^{1/2 in} SP value. There are some unfavorable examples.

  Further, when the melting point difference between the resins is 20 ° C. or less, particularly when kneading using an extrusion kneader, the difference in melting in the extrusion kneader is unlikely to occur, so it is easy to knead with high efficiency and low during molding. It is preferable because deterioration of the melting point resin can be prevented.

Furthermore, melt viscosity is also important, and if the resin forming the island is set lower, the island resin is likely to be deformed by shearing force, so that the island resin is more likely to be finely dispersed from the viewpoint of making the scrub agent finer. preferable. However, if the island resin is excessively low in viscosity, it tends to be seamed and the blend ratio with respect to the whole fiber cannot be increased. Therefore, the island resin viscosity is preferably 1/10 or more of the sea resin viscosity. At this time, the melt viscosity is a value at a shear rate of 121.6 sec ⁻¹ at the temperature during kneading.

Further, the melt viscosity of the sea resin may greatly affect the spinnability, and it is preferable to use a low-viscosity resin of 100 Pa · s or less as the sea resin because the spinnability at the time of spinning is improved. Since the draft (stretching ratio) at the time of spinning can be increased by improving the spinnability, thinner fibers can be produced. At this time, the melt viscosity is a value at a shear rate of 1216 sec ⁻¹ at the die surface temperature during spinning.

  The above resin is mixed and alloyed and then fiberized. In order to obtain a finer scrub agent, it is preferable to apply a large shearing force during mixing and finely disperse the island resin. In addition, the resin in which the island component is finely dispersed is likely to cause large ballast (a phenomenon in which the resin immediately after ejection becomes thicker than the ejection hole diameter) and scissors (a phenomenon in which the ejected resin is not repeatedly constant in thickness and thickness). . Therefore, it is necessary to perform a base design that reduces the shear stress at the time of discharge, suitability for cooling that quickly cools after discharge, and the like.

  The raw material fiber thus obtained is used to obtain a scrubbing agent raw material by eluting a readily soluble resin with a solvent. In this case, the use of an aqueous solution as the solvent reduces the environmental burden. To preferred. Specifically, it is preferable to use an alkaline aqueous solution or hot water. For this reason, as the easily soluble resin, a resin hydrolyzed by alkali such as polyester or polycarbonate (PC) or a hot water-soluble resin such as polyalkylene glycol, polyvinyl alcohol, or a derivative thereof is preferable.

  At this time, the scrub agent of the present invention can be obtained by cutting the raw fiber into an appropriate length in advance or adjusting the length of the ultrafine fiber by cutting the produced ultrafine fiber. When the raw fiber is a sea-island type composite fiber, the island component is completely continuous, so the cutting length is the length of the scrub agent. In addition, when the raw fiber is an alloy fiber, the hardly soluble resin has a finite length in the raw fiber, but it is sufficiently long compared to the length of the scrub agent of the present invention, so it is almost the cutting length. The length of the scrub agent is determined.

  The scrub agent produced in this way has a plurality of fibers aggregated in a bundle immediately after production. The scrub agent may be used in an agglomerated state, or may be used in a dispersed state after being subjected to a dispersion treatment. When the scrub agent is dispersed, a dispersion process can be performed using a beater such as a beater or a refiner. Thereby, fibrous scrub agents are separated one by one, and a scrub agent that is more friendly to the object to be cleaned can be obtained.

  The scrubbing agent of the present invention and the detergent containing the scrubbing agent can remove dirt on the surface of the washing object while suppressing damage to the object, and also have excellent rinsing properties. However, the present invention is not limited to this, and can be suitably used for cleaning glassware and tableware. Further, by making the scrub agent thinner, it can be used for cleaning a member that does not allow slight scratches on the precision substrate and optical parts.

  Hereinafter, the present invention will be described in detail with reference to examples. In addition, the measuring method in an Example used the following method.

A. Resin melt viscosity The resin melt viscosity was measured by Toyo Seiki Capillograph 1B. The resin storage time from sample introduction to measurement start was 10 minutes.

B. Melting | fusing point The peak top temperature which shows melting | fusing of resin by 2nd run using Perkin Elaer DSC-7 was made into melting | fusing point of resin. The temperature elevation temperature at this time was 16 ° C./min, and the sample amount was 10 mg.

C. Thickness of Scrub Agent Dispersed One drop of the scrub agent dispersed in water was dropped on an observation stage of a scanning electron microscope (SEM), dried, and then a platinum-palladium alloy was deposited to observe the scrub agent. The magnification of the observation is such that about 20 scrubbing agents enter the field of view, the thickness of the 5 scrubbing agents in the field of view is measured, and this is performed at 5 different locations, for a total of 25 scrubbing agent thicknesses. Was obtained by averaging.

SEM apparatus: Hitachi S-4000 type Thickness of Aggregated Scrub Agent The aggregated scrub agent was embedded with an epoxy resin and stained with phosphotungstic acid, and then an ultrathin section having a thickness of 100 nm was prepared using a microtome. This section was observed with a transmission electron microscope (TEM), the cross-sectional area of each scrub agent was measured, and then the diameter of a circle having the same area as that area was calculated to determine the thickness of the scrub agent. The average thickness of the scrub agent was determined by measuring the thickness of five scrub agents in the field of view, performing this at five different locations, and averaging the total thickness of 25 scrub agents.

Example 1
Melt viscosity 296 Pa · s (235 ° C., shear rate 121.6 sec ⁻¹ ), melting point 220 ° C. nylon 6 (N6) (40 wt%) and melt viscosity 91 Pa · s (235 ° C., shear rate 121.6 sec ⁻¹ ) Then, poly-L-lactic acid (PLA) (60% by weight) having a melting point of 170 ° C. was kneaded by a biaxial kneading extruder set at 230 ° C. to obtain an alloy resin. The PLA had a melt viscosity of 52 Pa · s at 225 ° C. and 1216 sec ⁻¹ .

  This alloy resin is put into the melt spinning apparatus shown in FIG. 3, and the melt temperature is 235 ° C., the spinning temperature is 235 ° C. (the base surface temperature is 225 ° C.), the single hole discharge is 0.94 g / min, and the spinning speed is 3500 m / min. Melt spinning was performed. The obtained undrawn yarn was subjected to a drawing heat treatment under the conditions of a drawing temperature of 90 ° C., a draw ratio of 1.4 times, and a heat setting temperature of 130 ° C. After pulling this alloy fiber to 40,000 dtex and winding it around a cocoon, 99% or more of the PLA component in the alloy fiber was hydrolyzed and removed by immersing in a 1 wt% sodium hydroxide aqueous solution at 95 ° C for 2 hours. . Furthermore, after neutralizing with acetic acid, it was washed with water and dried to prepare a microfiber bundle.

  The obtained ultrafine fiber bundle was cut into a length of 0.5 mm to obtain a cut fiber of ultrafine fibers. Thereafter, 23 L of water and 30 g of the cut fiber obtained earlier were charged into a Tappy Standard Niagara Test Beater (manufactured by Toyo Seiki Co., Ltd.), preliminarily beaten for 5 minutes, and then excess water was cut off to collect the fiber. The weight of this fiber was 250 g, and its water content was 88%. 250 g of water-containing fiber was charged as it was into an automatic PFI mill (manufactured by Kumagai Riki) and beaten for 6 minutes at a rotation speed of 1500 rotations and a clearance of 0.2 mm to obtain a scrub agent made of ultrafine fibers.

  4.2 g of the scrub agent is added to a fiber mixer MX-X103 (National) together with 0.5 g of a dispersant (EA-87: manufactured by Daiichi Kogyo Seiyaku) and 500 g of water, and stirred for 5 minutes to disperse in water. The thickness of the agent was measured. As a result, the thickness of this scrub agent was as extremely thin as 0.11 μm.

Example 2
A melt viscosity of 120 Pa · s (260 ° C., 121.6 sec ⁻¹ ), a melting point of 225 ° C. polybutylene terephthalate (PBT) (20 wt%) and a melt viscosity of 140 Pa · s (260 ° C., 121.6 sec ⁻¹ ) Polystyrene (co-PS) (80 wt%) copolymerized with 22% ethylhexyl acrylate was melt-kneaded using a twin-screw kneading extruder at a kneading temperature of 240 ° C. to obtain an alloy resin. The co-PS had a melt viscosity of 60 Pa · s at 245 ° C. and 1216 sec ⁻¹ .

  This alloy resin is put into the melt spinning apparatus shown in FIG. 3 under the conditions of a melting temperature of 260 ° C., a spinning temperature of 260 ° C. (base surface temperature of 245 ° C.), a single hole discharge amount of 1.15 g / min, and a spinning speed of 1200 m / min. Melt spinning was performed. The obtained undrawn yarn was subjected to drawing heat treatment under conditions of a drawing temperature of 100 ° C., a draw ratio of 2.2 times, and a heat setting temperature of 115 ° C. After pulling this alloy fiber to 40,000 dtex, winding it around a kite, and immersing it in trichloroethylene for 1 hour, 99% or more of the co-PS component in the alloy fiber was dissolved and removed. Further, ultrafine fiber bundles were prepared by washing with water and drying.

  The obtained ultrafine fiber bundle was cut into a length of 2.0 mm to obtain a cut fiber of ultrafine fibers. Thereafter, 23 L of water and 30 g of the cut fiber obtained earlier were charged into a Tappy Standard Niagara Test Beater (manufactured by Toyo Seiki Co., Ltd.), preliminarily beaten for 5 minutes, and then excess water was cut off to collect the fiber. The weight of this fiber was 200 g, and its water content was 85%. 200 g of water-containing fiber was charged as it was into an automatic PFI mill (manufactured by Kumagai Riki) and beaten for 6 minutes at a rotation speed of 1500 rotations and a clearance of 0.2 mm to obtain a scrub agent composed of ultrafine fibers.

  The scrub agent was dispersed in water in the same manner as in Example 1, and the thickness of the scrub agent was measured. As a result, the thickness of this scrub agent was as extremely thin as 0.10 μm.

Example 3
Polypropylene (PP) (20 wt%) having a melt viscosity of 451 Pa · s (220 ° C., shear rate of 121.6 sec ⁻¹ ) and a melting point of 162 ° C. and PLA (80 wt%) used in Example 1 were set to 220 ° C. An alloy resin was obtained by kneading with a twin-screw kneading extruder. The PLA had a melt viscosity of 107 Pa · s at 220 ° C. and 121.6 sec ⁻¹ and a melt viscosity of 86 Pa · s at 215 ° C. and 1216 sec ⁻¹ .

  This alloy resin is put into the melt spinning apparatus shown in FIG. 3, and the melting temperature is 220 ° C., the spinning temperature is 220 ° C. (the die surface temperature is 215 ° C.), the single hole discharge amount is 1.50 g / min, and the spinning speed is 900 m / min. Melt spinning was performed. The obtained undrawn yarn was subjected to drawing heat treatment under conditions of a drawing temperature of 90 ° C., a draw ratio of 2.7 times, and a heat setting temperature of 130 ° C. The alloy fiber was pulled up to 40,000 dtex, wound around a kite, and then immersed in a 1 wt% sodium hydroxide aqueous solution at 95 ° C. for 1 hour to dissolve and remove 99% or more of the PLA component in the alloy fiber. Further, ultrafine fiber bundles were prepared by washing with water and drying.

  The obtained ultra-fine fiber bundle was cut into a length of 1.0 mm to obtain ultra-fine fiber cut fibers. Thereafter, 23 L of water and 30 g of the cut fiber obtained earlier were charged into a Tappy Standard Niagara Test Beater (manufactured by Toyo Seiki Co., Ltd.), preliminarily beaten for 5 minutes, and then excess water was cut off to collect the fiber. The weight of this fiber was 180 g, and its water content was 83%. 180 g of water-containing fibers were directly charged in an automatic PFI mill (manufactured by Kumagai Riki) and beaten for 6 minutes at a rotation speed of 1500 rotations and a clearance of 0.2 mm to obtain a scrub agent made of ultrafine fibers.

  The scrub agent was dispersed in water in the same manner as in Example 1, and the thickness of the scrub agent was measured. As a result, the thickness of this scrub agent was as thin as 0.28 μm.

Example 4
The same N6 and PLA as used in Example 1 were used, PS was put into the hopper 1 of the composite spinning apparatus shown in FIG. 1, and PLA chips were put into the hopper 2, and the extruder 3 was 240 ° C. and the extruder 4 was 220. Each fiber was melted and supplied to the spin pack 5 set at 240 ° C. to obtain a fiber having a cross-sectional shape as shown in FIG. At this time, the amount of the island component relative to the entire fiber was set to 35 parts by weight. The obtained fiber was drawn using a liquid bath drawing machine under conditions of a drawing temperature of 90 ° C., a heat setting temperature of 130 ° C., and a draw ratio of 2.7 times to obtain a composite fiber of 58 dtex and 24 filaments. At this time, the single yarn fineness of the N6 component in the composite fiber is 0.085 dtex. After pulling this composite fiber to 40,000 dtex and winding it around a cocoon, it is immersed in a 3 wt% sodium hydroxide aqueous solution at 95 ° C for 2 hours to obtain 99% or more of the co-PET component in the resin alloy fiber. Hydrolyzed and removed. Further, after neutralizing with acetic acid, washing with water and drying, an ultrafine fiber bundle was produced.

  The obtained ultrafine fiber bundle was cut into a length of 3.0 mm to obtain cut fibers of ultrafine fibers. Thereafter, 23 L of water and 30 g of the cut fiber obtained earlier were charged into a Tappy Standard Niagara Test Beater (manufactured by Toyo Seiki Co., Ltd.), preliminarily beaten for 5 minutes, and then excess water was cut off to collect the fiber. The weight of this fiber was 120 g, and its water content was 75%. 120 g of water-containing fibers were directly charged into an automatic PFI mill (manufactured by Kumagai Riki) and beaten for 6 minutes at a rotation speed of 1500 rotations and a clearance of 0.5 mm to obtain a scrub agent made of ultrafine fibers.

  The scrub agent was dispersed in water in the same manner as in Example 1, and the thickness of the scrub agent was measured. As a result, the thickness of this scrub agent was as thin as 3 μm.

Comparative Example 1
The same N6 as used in Example 1 was used alone and supplied to the spinning device shown in FIG. 3 to obtain a fiber of 75 dtex and 48 filaments. This fiber was drawn at a drawing temperature of 90 ° C., a heat setting temperature of 130 ° C., and a draw ratio of 1.5 times to produce 50 dtex, 48 filament fibers.

  The obtained fiber was cut into a length of 5.0 mm to obtain a scrub agent. The scrub agent was dispersed in water in the same manner as in Example 1, and the thickness of the scrub agent was measured. As a result, the thickness of this scrub agent was 10 μm.

Comparative Example 2
The ground walnut shell was passed through a 60-mesh sieve and further passed through an 80-mesh sieve, and the particles remaining on the sieve were used as a scrub agent. When this scrub agent was observed with an optical microscope and the diameters of 25 particles were measured, the average particle diameter was 200 μm.

Comparative Example 3
Aluminum silicate particles (particle size distribution: 0.2 to 6 μm) manufactured by Moritex Corporation were used as a scrub agent.
<Skin cleaning test>
Draw a 1 cm long line with Blue Magic (Sakura Pen Touch # 36: Sakura Crepas Co., Ltd.) on the back of the subject's left hand, place 10 g of each scrub agent, moisten with tap water, and use the index and middle fingers of the right hand 20 It was washed by rubbing and then rinsed with tap water for 5 seconds. Thereafter, the image was magnified 50 times with a video microscope (VHX-100: Keyence Co., Ltd.), and the magic was removed and the scrub agent was rinsed. In addition, the state of skin and feeling of use after 5 minutes from washing were recorded. Judgment criteria are as follows. The results are summarized in Table 1.
・ Dirt removal: ◎ Dirt inside pores and grooves is removed by 80% or more.
○ 50% or more of dirt inside pores and grooves
△ More than 30% of dirt inside pores and grooves
X The dirt inside the pores and grooves remains in the range exceeding 70%.
Here, if it is △ or more, it is possible to remove most of the dirt by carefully washing, but if it is ×, it is practical because it takes a very long time to remove the dirt. Absent.
・ Rinse properties: ○ No scrub agent is observed
△ There are 10 or less residual scrubbing agents in the field of view.
X 11 or more residual scrubbing agents are observed in the field of view. If it is Δ or more, most scrubbing agents can be removed by a normal cleaning operation, but if x, rinsing for a very long time. Is not preferable.
・ Skin irritation: ○ There is almost no irritation at the time of washing, and no change in skin color is observed after 5 minutes of washing.
△ A slight irritation is felt during washing, but no change in skin color is observed after 5 minutes of washing.
× Pain is felt when washing, and it is observed that the skin color turns red 5 minutes after washing. If it is △ or more, the skin color changes within 5 minutes after washing. It can be judged that the damage of the skin is very small, but if it is x, the discoloration of the skin is not settled even after 5 minutes, and it is judged that substantial damage has occurred.

  As is apparent from Table 1, the conventional particulate scrub agent has insufficient cleaning power when the particle size is large, and the rinsing property is deteriorated when the particle size is small, whereas the scrub agent of the present invention has a skin groove. In addition, it can effectively remove dirt inside the pores and is excellent in rinsing properties. In addition, it can be said that the thinner the scrub agent is, the less irritation to the skin and the gentler to the skin.

  From the above test, it was shown that the scrub agent of the present invention has little damage to the object, is excellent in the ability to remove dirt inside the irregularities on the surface of the object, and is excellent in rinsing properties.

Examples 5 and 6, Comparative Examples 4 to 6
The following tests were performed using the scrub agents of Examples 1 and 4 and Comparative Examples 1 and 3.
<Glass lens cleaning test>
Add 10 parts by weight of scrubbing agent and 10 parts by weight of surfactant (sodium dodecylbenzenesulfonate), add 80 parts by weight of ion exchange water, add to fiber mixer MX-X103 (National), and stir for 5 minutes to scrub the agent. A detergent containing was prepared.

Draw a 1cm long line with blue magic on the spectacle lens and wash it 20 times with a cotton cloth (Kanakin No. 4) soaked with 10g of the detergents of Examples 1, 4 and Comparative Examples 1 and 3, and then for 5 seconds. Rinse with ion exchange water. After cleaning, the surface of the lens was confirmed by observing with a video microscope magnified 200 times. Subsequently, the lens surface was observed at a magnification of 1500 using an SEM (S-4000 model manufactured by Hitachi). The judgment criteria are as follows. The results are summarized in Table 2.
・ Dirt removal: ○ Dirt is completely removed
× Dirt remains on the lens surface. ・ Rinse: No scrub agent is observed.
× Residue of scrubbing agent is observed ・ Lens damage: ○ No damage is observed even by SEM observation
△ Scratches are observed by SEM observation, but scratches are not observed by observation with a microscope.
X Scratches are observed even when observed with a microscope. If Δ or more, there is no substantial decrease in optical performance, but if it is x, an optical performance decrease is undesirable.

  As apparent from Table 2, the detergent that did not contain the scrub agent and the detergent that contained the thick fibrous scrub agent could not remove the dirt that entered the irregularities on the lens surface, whereas the scrub of the present invention. It was shown that the detergent containing the agent can remove dirt inside the irregularities. Further, the conventional detergent containing the particulate scrub agent showed scratches on the lens surface, and the remaining scrub agent was confirmed, whereas the detergent containing the scrub agent of the present invention left the scrub agent residue. No damage was observed on the lens surface, and it was shown that the rinsing property was excellent and the object was less damaged. Further, among the scrub agents of the present invention, when an extremely thin one was used, no scratches were observed on the surface of the object even by SEM, and it was found that the object was very gentle to the object.

  From the above test, it was shown that the detergent of the present invention has little damage to the object, is excellent in the ability to remove dirt inside the unevenness of the object surface, and is excellent in rinsing properties.

Example 7
In the same manner as in Example 1, melt spinning was performed, and after stretching, an alkali treatment was performed to obtain an ultrafine fiber bundle. The obtained ultrafine fiber bundle was cut at intervals of 0.5 mm to prepare a scrub agent. When the cross section of the scrub agent was observed with a TEM, this ultrafine fiber bundle was a very thin fibrous scrub agent having an average thickness of 0.11 μm associated with the bundle. 0.5 g of this scrub agent, 0.5 g of a surfactant (EA-87: manufactured by Daiichi Kogyo Seiyaku), and 99 g of water are added to a fiber mixer MX-X103 (manufactured by National), and sales are expanded for 5 minutes. A detergent containing 5% by weight was prepared. When a part of the prepared dispersion was diluted 5 times and then placed in a glass cell and observed, it was shown that the color tone was uneven and the scrub agent was agglomerated.

Example 8
In the same manner as in Example 1, melt spinning was performed, and after stretching, an ultrafine fiber bundle was produced by performing alkali treatment. The obtained ultrafine fiber bundle was cut into a length of 0.5 mm to obtain a cut fiber of ultrafine fibers. Thereafter, 23 L of water and 30 g of the cut fiber obtained earlier were charged into a Tappy Standard Niagara Test Beater (manufactured by Toyo Seiki Co., Ltd.), preliminarily beaten for 5 minutes, and then excess water was cut off to collect the fiber. The weight of this fiber was 250 g, and its water content was 88%. 250 g of water-containing fiber was directly charged into an automatic PFI mill (manufactured by Kumagai Riki) and beaten for 6 minutes at a rotation speed of 1500 rotations and a clearance of 0.2 mm.

  Subsequently, 4.2 g of the beaten fiber was added to a fiber mixer MX-X103 (National) together with 0.5 g of a surfactant (Charol AN-103: manufactured by Daiichi Kogyo Seiyaku) and 95.3 g of water, and stirred for 5 minutes. Thus, a detergent containing 0.5% by weight of a scrub agent was prepared. When a part of the prepared dispersion was diluted 5 times and then placed in a glass cell and observed, it became a uniform translucent liquid, indicating that the scrub agent was dispersed.

Comparative Example 7
Without adding a scrubbing agent, 0.5 g of a surfactant (Charol AN-103: manufactured by Daiichi Kogyo Seiyaku) and 99.5 g of water are added to a fiber mixer MX-X103 (manufactured by National). Produced.

Comparative Example 8
A detergent was prepared in the same manner as in Comparative Example 7 except that 0.5 g of the scrub agent of Comparative Example 2 was added.

Comparative Example 9
A detergent was prepared in the same manner as Comparative Example 7 except that 0.5 g of the scrub agent of Comparative Example 3 was added.
<Skin cleaning test>
Draw a 1 cm long line with Max Factor 501 Aqua Rush Waterproof Mascara (Black) (trademark) on the back of the left hand of the subject, drop 3 cc of the detergents of Examples 7 and 8 and Comparative Example 7 with the finger of the right hand. And then rinsed with tap water for 5 seconds. After that, the video microscope (VHX-100: Keyence Co., Ltd.) was used to observe the image by magnifying it 50 times, and the mascara was removed and the scrub agent was rinsed. In addition, the usability during cleaning was recorded. The results are summarized in Table 3.
・ Dirt removal: ◎ Dirt inside pores and grooves is removed by 80% or more.
○ 50% or more of dirt inside pores and grooves
△ More than 30% of dirt inside pores and grooves
X The dirt inside the pores and grooves remains in the range exceeding 70%.
Here, if it is △ or more, it is possible to remove most of the dirt by carefully washing, but if it is ×, it is practical because it takes a very long time to remove the dirt. Absent.
・ Rinse properties: ○ No scrub agent is observed
△ There are 10 or less residual scrubbing agents in the field of view.
X 11 or more residual scrubbing agents are observed in the field of view. If it is Δ or more, most scrubbing agents can be removed by a normal cleaning operation, but if x, rinsing for a very long time. Is not preferable.
・ Skin irritation: ○ There is almost no irritation at the time of washing, and no change in skin color is observed after 5 minutes of washing.
△ A slight irritation is felt during washing, but no change in skin color is observed after 5 minutes of washing.
× Pain is felt when washing, and it is observed that the skin color turns red 5 minutes after washing. If it is △ or more, the skin color changes within 5 minutes after washing. It can be judged that the damage of the skin is very small, but if it is x, the discoloration of the skin is not settled even after 5 minutes, and it is judged that substantial damage has occurred.

  Conventional detergents using a particulate scrub agent deteriorate in rinsing properties when the particle size is small, and the skin irritation becomes too strong when the particle size is large. Further, the cleaning power was not satisfactory. On the other hand, the detergent containing the scrub agent of the present invention has a high detergency and a rinsing property. In addition, although the detergent containing the agglomerated scrub agent has a slight irritation to the skin, the testimony expressed that the subject feels that the dirt has been removed. On the other hand, it was expressed that the detergent containing the dispersed scrub agent is very gentle on the skin and can be used with peace of mind.

Compound spinning device Sea-island type composite fiber cross section Single component spinning machine

Explanation of symbols

1: Sea component resin hopper 2: Island component resin hopper 3: Sea component resin extruder 4: Island component resin extruder 5: Composite spinning pack 6: Chimney 7: Converging oiling guide 8: Yarn 9: Take-up roller 10: Winding yarn 11: Alloy resin hopper 12: Alloy resin extruder 13: Single component spinning pack

Claims (6)

  A scrub agent characterized by being in a fibrous form having an average thickness of 3 μm or less.   The scrub agent according to claim 1, wherein the fiber length is 0.05 mm or more and 20 mm or less.   The scrub agent according to claim 1 or 2, wherein the scrub agent comprises a thermoplastic resin.   A detergent comprising the scrub agent according to any one of claims 1 to 3.   5. The detergent according to claim 4, wherein the scrub agent is dispersed in the detergent.   The detergent according to claim 4, wherein the scrub agent in the detergent is contained in an aggregated state.

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