WO2011089839A1

WO2011089839A1 - Multifunctional surface treatment composition

Info

Publication number: WO2011089839A1
Application number: PCT/JP2010/073779
Authority: WO
Inventors: 信重寺本; 久憲寺本; 彪青江
Original assignee: 株式会社テラモト
Priority date: 2010-01-19
Filing date: 2010-12-28
Publication date: 2011-07-28
Also published as: JP2011148717A; JP4611445B1; TW201139653A

Abstract

By means of the disclosed multifunctional surface treatment composition, the occurrence of turbidity and sedimentation occurring during low-temperature storage is prevented, antibacterial properties are imparted, odor-resistance, water repellency and oil repellency are improved, and frictional resistance is reduced. The composition contains: octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride and/or octadecyl dimethyl (3-triethoxysilylpropyl) ammonium chloride, amidoamine oxides and alcohol, and water.

Description

Surface multifunctional treatment composition

The present invention relates to a surface multifunctional treatment composition containing octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride and / or octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride.

In each field, there is a tendency to increase awareness of the importance of hygiene with respect to articles that are touched by people or facilities that are used by people so as to require antibacterial properties.
In medical instruments such as dental instruments, it is known that antibacterial properties need to be imparted to the surfaces of the instruments. In addition, water supplies, toilets, and food containers for buildings that require antibacterial properties as well as medical use There are several known uses such as fish tanks, vases, cleaning tools, clothing, and the like. For this reason, antibacterial properties have been achieved by treating articles with antibacterial agents such as silver and other metals and their compounds, and various antibacterial organic compounds, and blending these antibacterial agents with the materials constituting the articles. Granting has been done widely.

However, these surface treatments require not only coating to give antibacterial properties but also a heat treatment step, and the antibacterial agent gradually peels off during use due to weak adhesion to the surface. Antibacterial properties may not last for a long time, and antibacterial properties may be weakened by washing.
In particular, if antibacterial properties do not last, even if they have antibacterial properties due to antibacterial treatment, they may not already have antibacterial properties when actually used. Not only will it not be used, but it will result in the use of articles that have been propagated by bacteria without the user's knowledge, which may pose a health risk.

Furthermore, when an antibacterial agent such as a metal such as silver or a compound thereof, various antibacterial organic compounds, or an antibacterial agent is added to the material constituting the article, the antibacterial agent is also present inside the article. So you will need more antibacterial agents.
Under such circumstances, it has been known in recent years that a silicon-containing compound for imparting antibacterial properties is used to perform a coating treatment on articles to impart antibacterial properties. Among such silicon-containing compounds, octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride is known.

In Patent Document 1, a foamed glass body coated with silica gel is treated with octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride no methanol solution as a functional compound to form octadecyldimethyl (3-trimethoxysilylpropyl). The immobilization of ammonium chloride is described.
Patent Document 2 describes an antibacterial material characterized in that octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride is immobilized on the surface as a silane compound having an antibacterial substance.
Patent Document 3 discloses that in an antibacterial agent aqueous solution containing octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, the pH of the aqueous solution is adjusted to 3.5 to 2.0. It is described that the storage stability is excellent by making the range, and that this aqueous solution is brought into contact with the surface of the antibacterial material for a certain period of time and then washed and dried.
In Patent Document 4, the antibacterial treatment method of a synthetic resin obtained by immersing a synthetic resin in an aqueous solution of octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, and the contact angle of the treated surface with pure water are as follows: It is described that the angle is 80 to 90 °.
Patent Document 5 discloses a detergent composition containing a silicon-containing compound such as octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, and a denture, toilet, toilet, bathtub, and the like washed with the detergent composition. Bathroom area, tableware, glasses, sink, kitchen area, wash bowl, wash area, textile products and clothes, the detergent composition is excellent in cleaning, antibacterial properties, and antibacterial persistence of these treatments Is described as being excellent.
Patent Document 6 describes an antibacterial separation membrane in which a silane compound having an antibacterial action such as octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride is fixed to the separation membrane.
Patent Document 7 describes an antibacterial film case in which a coating layer containing cellulose acetate as an antibacterial agent is formed on the inner surface of a film case main body.
Patent Document 8 describes an antibacterial tempered glass article in which a solution containing silver or a liquid in which silver fine particles are dispersed is applied to the surface of a tempered glass article and then heated to diffuse silver to the inner surface of the surface layer portion. Yes.
Patent Document 9 describes that seawater used for marine organism cultivation is sterilized in advance.
Patent Document 10 describes a flower stand that accommodates flowers and the like, and that the inner surface of the bottom plate is made of a substance containing an antibacterial metal.

JP 2004-345243 A Japanese Patent No. 3834655 JP 2007-31290 A JP 2007-126557 A JP 2007-146134 A JP 2009-165949 A JP 2003-31626 A JP 11-319042 A JP 2007-44611 A JP 2000-342074 A

As described above, it is known that octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride is a surface treatment compound having an antibacterial action.
However, since the aqueous solution of this compound is inferior in stability, it becomes cloudy or precipitates when it is stored at a low temperature, especially after it is prepared as a surface treatment composition. In some cases, sufficient effects may not be exhibited. Furthermore, the composition may deteriorate during application and drying after preparation, and the object treated in such a state may not exhibit predetermined properties. If the pH is set to 3.5 to 2.0 in order to obtain a uniform solution, it is difficult to treat an object having poor acid resistance as it is.

In addition, simply having antibacterial properties is difficult to use in various applications, and in addition to antibacterial properties, it is necessary to treat the surfaces of water facilities such as toilets, windows, floors and walls. In order to improve the antifouling properties, water and oil repellency needs to be improved in order to improve the antifouling property. In addition, it is necessary to have low friction against the cleaning tool.
Furthermore, if the antifouling property is not excellent, maintenance such as cleaning is frequently performed after the antibacterial treatment, which deteriorates the usability.

In addition, the parts that come into contact with the object to be cleaned in various cleaning tools such as mops and rags for cleaning by rubbing require more force for cleaning, especially when the frictional resistance is large. As a result, the person who performed the cleaning felt a strong sense of fatigue. In addition, when cleaning various cleaning tools after cleaning, if the cleaning tool itself does not have antifouling properties, dirt attached to the cleaning tool is difficult to remove, making cleaning difficult.
In other fields, food containers, biological culture, cut flower preservation, a cellulose acetate-containing layer on the inner surface of the container, a diffusion layer of antibacterial metals such as silver, etc. Sterilized and used.

As a treating agent composition for solving the above problems, octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride and / or octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride, amidoamine oxides, alcohol and water The surface multifunctional treatment agent composition containing was adopted.
Further, it contains only one of the above-mentioned octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride and octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride, and its concentration is 0.01 to 10% by weight, or octadecyl The total concentration of dimethyl (3-trimethoxysilylpropyl) ammonium chloride and octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride may be 0.01 to 10% by weight.
Further, the amidoamine oxides may be lauramide amidopropyldimethylamine oxides, or the concentration of amidoamine oxides may be 0.01 to 10% by weight. In such a composition, 0.01 to 5% by weight of a polyhexamethylene biguanide compound may be further contained.
The surface multifunctional treatment composition may be one in which the solution is stable in the range of 2 ° C. to 50 ° C. for one week or longer.

The effect of the present invention can be obtained by containing amidoamine oxides in the system even when octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride and / or octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride is stored. The storage stability is remarkably improved, and even if the stability of the obtained solution of the surface multifunctional treatment agent composition is impaired and becomes cloudy, the effect of restoring to the original stable solution by heating is obtained. By being exhibited, the processed object can exhibit a predetermined effect.

Moreover, the further effect that it can use for a processed material after heating as needed can be acquired irrespective of the preservation | save state of a surface multifunctional processing agent composition.
The present inventor treats a treated product with a surface multifunctional treating agent composition containing an amidoamine oxide to not only make the treated product surface an antibacterial surface, but also simultaneously render the treated product surface water-repellent, It was confirmed that a low friction surface was obtained and an effect of imparting a deodorizing effect was also obtained.
Furthermore, antibacterial properties can be further enhanced by adding a polyhexamethylene biguanide compound to the surface multifunctional treatment composition of the present invention.

Furthermore, due to these effects, the multifunctional surface treating agent composition of the present invention is a composition for treating a treated product, and a treated product that needs to be considered in terms of hygiene is maintained in addition to hygiene and cleaning. The surface of the processed material that is required to be cleaned is given the property of reducing the friction required for cleaning, for example, reducing the force required for moping (operation) and preventing the generation of bad odors. The effect that improvement of work efficiency and improvement of environment can be aimed at can be acquired. In addition, since the cleaning tool itself is also reduced in friction by processing a cleaning tool such as a mop, the force required to rub the cleaning tool in close contact with the target surface during use is reduced. It becomes possible.

Moreover, since the surface which has the antibacterial compound couple | bonded with the target object surface can be obtained with the stabilized surface multifunctional processing agent composition, the surface obtained only by means, such as application | coating of an antibacterial substance containing layer Unlike the case, the surface can have antibacterial properties for a long period of time, and there is no need to perform a heat treatment such as when silver is diffused.
Moreover, it is not necessary to sterilize the water with a separate device for the cultivation and breeding of aquatic organisms such as marine organisms.

(Octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride and octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride)
In the surface multifunctional treatment composition of the present invention, these components function as a main component for exerting the effect.
In the surface multifunctional treatment composition, octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride and octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride may be blended alone or in combination. You may mix | blend together.
When these silane compounds are applied to a treated product, the methoxy group or ethoxy group is decomposed, and silicon atoms are bonded to the treated product surface through oxygen atoms, so that these silane compounds are formed on the treated product surface. The compound is fixed.

The concentration in the surface multifunctional treatment composition is 0.01 to 10% by weight, preferably 0.5 to 7% by weight, more preferably 1 to 5% by weight. If these concentrations are lower than 0.01% by weight, a sufficient treatment effect cannot be exerted, and even if the concentration is higher than 10% by weight, the improvement in the effect commensurate with the increase in concentration is not observed. The stability of is inferior.

(Amidamine oxides)
In the surface multifunctional treatment composition of the present invention, amidoamine oxides are components added as a surfactant, and the concentration thereof is 0.01 to 10% by weight, preferably 2 to 8% by weight, Preferably, it is 3 to 7% by weight. When the concentration of amidoamine oxides is lower than 0.01% by weight, the storage stability at each temperature from high temperature to low temperature is deteriorated, and even if it is higher than 10% by weight, no further effect is exhibited as a surfactant. .
Further, even when an amidoamine oxide as a surfactant is added to the surface multifunctional treatment composition, the water repellency and oil repellency of the surface of the object treated with the surface multifunctional treatment composition are not lowered. .

Amidoamine oxides include lauric acid amidopropyl dimethylamine oxide, myristic acid amidopropyl dimethylamine oxide, palmitic acid amidopropyl dimethylamine oxide, oleic acid amidopropyl dimethylamine oxide, stearic acid amidopropyl dimethylamine oxide, palm fatty acid amidopropyl Known amide amine oxides such as dimethylamine oxide, lauric acid amidoethyl dimethylamine oxide, lauric acid amidopropyl diethylamine oxide, lauric acid amidopropyl dihydroxyethylamine oxide, lauric acid amidopropyl dibutylamine oxide can be used.

(alcohol)
The alcohol is preferably methanol and / or ethanol, but other known ethanol that can be dissolved in water and used as a solvent may be used, but the composition of these alcohols is adjusted in consideration of the drying step after the treatment. For this reason, the concentration of alcohol in the surface multifunctional treatment composition may be any concentration within the range where it can be dissolved, but usually octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride or octadecyldimethyl (3-triethoxysilyl). Propyl) ammonium chloride is used as a solvent for the surface multifunctional treatment composition as it is.

(Polyhexamethylene biguanide compounds)
As the polyhexamethylene biguanide compound, for example, polyhexamethylene biguanidine hydrochloride, polyhexamethylene biguanidine acetate can be used, and by adding this polyhexamethylene biguanide acetate compound, the surface multifunctional treatment agent The antibacterial properties of the composition can be further improved.
The concentration in the surface multifunctional treatment agent composition is 0.01 to 5% by weight. When the addition ratio is less than 0.01% by weight, the effect of adding the polyhexamethylene biguanide compound is sufficiently exhibited. In addition, even if 5% by weight or more is added, no further antibacterial effect can be expected.

The surface multifunctional treatment agent composition can contain water. Water as used herein means water contained in the composition and water used for dilution, and the hardness of the water is preferably 300 mg / l or less, more preferably 100 mg / l. l or less.
If hardness is 300 mg / l or more, the mineral content contained in water will precipitate and it will have a bad influence on storage safety. Therefore, it affects the surface modification performance of the composition.
It should be noted that the use of water having a hardness of 100 mg / l or less has no effect on the storage stability and surface modification effect of the present composition, so that the use of low-hardness water is not a problem.
The quality standard of tap water has a hardness of 300 mg / l or less, and the tap water in most regions has a hardness of 100 mg / l or less, so there is no problem in using tap water for dilution or the like.

(Other components that can be added)
As long as the function of the composition is not hindered, known various substances having excellent compatibility and dispersibility can be added to the surface multifunctional treatment composition.
Substances that can be added include other antibacterial and bactericidal agents, other surfactants, viscosity modifiers, acrylic resins as vehicles, resins such as alkyd resins, fillers such as calcium carbonate, resin particles, silicon dioxide And various additives such as pigments such as titanium dioxide and carbon black, inorganic color pigments, organic pigments, dyes, fluorescent materials, ultraviolet absorbers, insect repellents, and fragrances. When other antibacterial agents / bactericides are used, a bactericidal / antibacterial agent that exerts an effect on the bacteria can be selected in order to eliminate problematic bacteria according to the place of use.

When a viscosity modifier, vehicle, or filler is added, the viscosity of the surface multifunctional treatment composition can be controlled, or the thickness of the layer composed of the surface multifunctional treatment composition when it is brought into contact with the object can be adjusted. Therefore, the film layer which consists of a surface multifunctional processing agent composition of the target object surface can be thickened. If it does so, the duration of the effect of a surface multifunctional processing agent composition can be extended and a higher effect can be exhibited.

When pigments, dyes, and fluorescent materials are added, the layer composed of the multifunctional surface treatment agent composition can be visually confirmed when it is peeled off or consumed as the treated object is used, and exhibits various colors. Therefore, the effect on the design can be exhibited.
The ultraviolet absorber can prevent deterioration of the object and the surface multifunctional treatment agent composition layer by ultraviolet rays, and the effect of the surface multifunctional treatment agent composition can be maintained for a longer period of time.

(Adjustment and preservation method of surface multifunctional treatment composition)
The surface multifunctional treatment agent composition is a composition obtained by blending the above-described components, and can be blended at room temperature by a general solution adjustment method regardless of the blending order.
The surface multifunctional treatment composition obtained by the adjustment is stored in a light-shielding container until it is applied to an object imparting antibacterial properties, etc. For example, it may be a normal temperature in a warehouse or the like, and no special care is required unless it is in a severe winter season in a cold region or in an environment where it is particularly heated.
If it is at a temperature of 0 to 50 ° C., it can be stored for 1 month or more while maintaining a sufficient effect. Even if the surface multifunctional treatment composition becomes cloudy during storage, it can be restored to the original cloudless state under relatively mild heating conditions such as heating at 50 ° C. for 2 hours.

(Object to be treated with surface multifunctional treatment composition)
The object that can be treated with the surface multifunctional treatment composition may be any of inorganic materials, organic materials, synthetic materials, natural materials, soft materials and / or hard materials, and any antibacterial material. It is possible to use any object that needs to be imparted with the property, deodorant property, water / oil repellency, and low friction property.
Inorganic materials include metals such as iron and stainless steel, glass, glass fiber, earthenware, tiles, concrete, and stone materials. Organic materials include synthetic resins such as synthetic rubber, polyethylene, polyester, polyvinyl chloride, and polyurethane, and natural materials. Natural products such as rubber, and natural products such as wood, paper, and bamboo may be used.

Regardless of the form of the object, the following various forms can be processed.
Natural fibers such as cotton and silk, organic fibers made of synthetic fibers such as rayon and polyester, inorganic fibers such as carbon fibers and metal fibers, yarns and cloths made of these fibers, clothes made of the cloths, fiber sheets, etc. Various goods.
Sheets and film-like articles such as resin sheets / films, metal sheets / films, paper, glass plates, sheets made of wood and bamboo.
Articles whose surfaces and / or inner surfaces are porous, such as resin foams and inorganic foams.
Furthermore, articles of various shapes such as rod-shaped objects and lump objects made of the various materials described above can be targeted.

In addition, specific tools for objects include cleaning tools such as brooms, sponges and blades, wiping materials such as rags, mops and cloths, rags, mops, brushes, resin dust, metal dust, resin and metal Scrap holders, foot mats for footsteps, doormats, footclothes mats, insoles, artificial turf, snowboards, umbrella stands, resin benches, wooden benches, linen-related products (sheets, pillowcases, towels), clothing (underwear) , Shirts, uniforms, socks, hats), sanitary products (masks, diapers, diaper covers), air conditioning filters, water pipe inner surfaces, water purifier inner and outer surfaces, kitchen equipment such as sinks, faucets and other water supply equipment, washbasins Bathroom equipment such as table, stainless steel bathtub, resin bathtub, wooden bathtub, washing toilet seat parts (toilet seat, piping), toilet bowl, baby items (baby bottles, toys), food containers, lighting equipment, etc. Of vending machines for food and drinks, such as furniture such as doors, walls, floors, windows, indoor pipes, household appliances such as washing machines, washing tubs, dishwashers, etc. It can be used for products in various fields such as components, water tanks and vases.
In addition, facilities in facilities that need to be hygienically managed, such as schools, hospitals, kindergartens, nursing homes, facilities used by an unspecified number of people, public transport, interiors of buildings such as houses, various equipment and furniture, etc. Etc. are treated with the surface multifunctional treatment composition of the present invention.

(Treatment method using surface multifunctional treatment agent composition)
As a method of treating each treatment object by bringing the surface multifunctional treatment agent composition into contact with the treatment object, for example, using a general coating apparatus, the surface is directly applied to the treatment object surface by dipping, spraying, or the like. Means for bringing the multifunctional treatment agent composition into contact may be employed, or the surface multifunctional treatment agent composition may be attached to a brush or cloth and spread on the surface of the object to be treated with the brush or cloth. Regardless of which method is employed, it is necessary to treat the entire surface of the processing object. Moreover, after making it contact for a fixed time, a finishing state becomes favorable by wiping off or rinsing off an excess surface multifunctional processing agent composition by water washing, water washing, etc.

In processing by such means, it is necessary to clean the object, and if it is contaminated, there is a possibility that a sufficient processing effect cannot be obtained. Moreover, you may perform surface treatments, such as a corona discharge process and a plasma process, as pre-processing as needed.
Further, the temperature of the surface multifunctional treatment agent composition at the time of treatment may be about room temperature, but it may be about 0 to 50 ° C. If the surface multifunctional treatment agent composition is cloudy, it is heated to become cloudy. It is necessary to use for the treatment after the problem is solved in order to exert a sufficient treatment effect.
When surface treatment is performed by immersion, the surface multifunctional treatment agent composition may be immersed for up to about 30 minutes. In particular, when the treated product is a porous substance, it is necessary to allow the surface multifunctional treating agent composition to permeate the inside in order to perform sufficient treatment.
After contact with the surface multifunctional treatment composition, dry at room temperature to complete the treatment, or after contact for a certain period of time, wipe or wash away excess surface multifunctional treatment composition with water, etc. Complete with things.

Storage stability of surface multifunctional treatment composition of the present invention No. 1 shown in Table 1-1 1 to 10 surface multifunctional treatment compositions according to the present invention in the state of a solution immediately after preparation, storage stability after storage at 50 ° C., 40 ° C. and 20 ° C. for 1 month, 5 ° C. and 2 ° C. for 7 days I saw sex. The solution that was transparent after storage was marked with ◯, and the cloudy solution was marked with △.
And about the solution which became cloudy, reheating was performed at 50 degreeC for 2 hours, and the restorability was observed by seeing the presence or absence of the cloudiness of a solution state. A sample in which the white turbidity disappeared and the solution was transparent was marked with “◯”.

As described in Table 1-1, according to the surface multifunctional treatment composition of the present invention, even when stored at 20 to 50 ° C. for one month, the state of the composition does not change and is good. When stored at -5 ° C for 7 days, white turbidity occurs when the total concentration of octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride and / or octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride is high. However, even in such a case, by heating at 50 ° C. for 2 hours, the cloudiness disappears and returns to the original transparent composition, indicating that the storage stability is good.

Comparative Example 1: Storage stability of treatment composition other than the present invention No. 1 shown in Table 1-2 1 to 8 of the non-inventive treatment composition according to the present invention was stored in the same state as in Example 1 at 50 ° C., 40 ° C. and 20 ° C. for 1 month, and at 5 ° C. and 2 ° C. for 7 days. Later storage stability was observed. A solution that was transparent after storage was marked with ◯, a cloudy solution was marked with Δ, and a solution that produced precipitation was marked with ×.
Then, the solution in which precipitation occurred after testing at 2 ° C. for 7 days was re-heated at 50 ° C., and the restorability was observed by observing the presence or absence of precipitation or cloudiness in the solution state. The case where the precipitate did not disappear was marked with x.

The comparative examples in Table 1-2 are different from the surface multifunctional treatment composition of the present invention in that no amidoamine oxides were added.
The examples of the treating agent compositions 3 to 8 of the comparative examples are those in which a general-purpose surfactant or the like is blended in place of the amine oxide, but in all the treating agent compositions, one month or seven at a temperature of 20 ° C. or less. Precipitation occurred upon storage for days, and in addition to the treatment compositions 6 and 8, examples were white turbid or precipitated immediately after preparation or storage for 1 month at 50 ° C. The solution after testing for 7 days at 2 ° C. was warmed to 50 ° C. Precipitation did not disappear even after heating for several hours, and the storage stability was not good.

Results of measurement of the number of viable bacteria on the wash basin After washing the wash basin in advance with a commercially available bleach (Kaito Co., Ltd. kitchen hitter), it was divided into two at the center of the wash basin, and the surface multifunction of the example on one side Treatment composition No. 1 was diluted 5 times with tap water, the solution was applied with a waste cloth, washed for 5 minutes, washed with water, processed for an average of 20 times a day, and a commercially available sterile swab (Heiwa Medic Co., Ltd.) ) Soak a doctor swab) in pure water, shake off excess water, wipe each surface with a cotton swab, and measure the number of viable bacteria. The other side was not processed.
In the following examples, the conditions for each bacterium for measuring the number of bacteria are as follows.
Trichoftton Mentagulfis, Saccharomyces cerevits, Rhizopus stronifel, Cladosporium cladosporioidas, Fusarium gracinearum, Aspergis ochraceus, Aspergis ustus, Candita albicans, Aspergis fumigatus, epicopecrum rotsica 4 days
Escherichia coli ・・・ Aconcee II agar 1 day Culture temperature is 30 ℃ ± 5 ℃.

On one side subjected to the surface multifunctional treatment composition treatment, the number of Trichofteon mentagulfis was 0, and Saccharomyces cerevisiae was 7.6 × 10 ^6, which was reduced to about 1/10. Only the body surface infectious bacteria reached 0, and the sterilization was effectively completed.
On the other hand, on the other side subjected to the treatment with the surface multifunctional treatment composition, Trichofteon mentafifis, which is a body surface-infecting bacterium, remains.

Results of measurement of viable bacteria in the urinal After cleaning the urinal in advance using a commercially available bleach (Kaito Co., Ltd. kitchen hitter), the urinal was divided into two at the center of the urinal. Composition No. 3 is diluted 5 times with tap water, the solution is applied with a waste cloth, and after 5 minutes contact, washed with water and processed, and after one and a half months, a commercially available sterile cotton swab (Doctor Swab manufactured by Heiwa Medic Co., Ltd.) is added to pure water. After soaking and shaking off excess water, wipe each surface with a cotton swab and measure the number of viable bacteria in one and a half months.

On one side subjected to the treatment with the surface multifunctional treatment composition, the numbers of Rhizopus stronifer and Trichoftone mentagulfis were 0, and Saccharomyces cerevisiae was 7.7 × 10 ⁴ and decreased to about 1/10. Since Rhizopus stronifell is a phytopathogenic fungus and Trichofteon mentagulficus is a body surface infectious fungus, it can be understood that the surface treated with the surface multifunctional treatment composition is a cleaner surface.
On the other hand, on the other side where the surface multifunctional treating agent composition treatment is not performed, there is a lot of Rhizopus stronifel and tricofeton mentaffifis, and the surface is not clean.

Results of viable cell count in milk storage Two glass bottles of the same shape with a total volume of 120 ml were prepared, washed with a commercial bleach (Kao Co., Ltd. Kitchen Hiter), and dried thoroughly. Surface multifunctional treating agent composition treatment No. 4 is diluted 5 times by 100ml with tap water, diluted with glass container, left for 10 minutes, rinsed with running water and dried, and unprocessed glass container with commercially available milk (Meiji Dairies) The product was allowed to stand for 5 hours in an unsealed state, brought into contact with airborne bacteria, left at room temperature for 1 week after sealing, and the number of viable bacteria was measured.

The number of bacteria in both Rhizopus stronifell and Cladosporium cladosporioid was reduced when the treatment with the surface multifunctional treatment composition was not carried out, and the propagation of the bacteria could be suppressed by the treatment. .

Results of viable cell count measurement in a breeding aquarium of Himedaka Two tanks of the same shape and capacity were prepared. Dilute 5 5 times with tap water, apply to the inner surface of the aquarium with waste water, leave it for 10 minutes, then wash and dry it, and put 25 medakas into the untreated aquarium for one week at room temperature. The number of viable bacteria in the water after breeding was measured.

The number of bacteria was reduced for both Trichofteon Mentagolfis and Rhizopus stronifel when the surface multifunctional treatment agent composition treatment was performed, and the propagation of the bacteria could be suppressed by the treatment.

Results of viable cell count measurement and storage state test results in the preservation of cut flowers (asters) Two vase glass with the same shape and a total volume of 900 ml were prepared. 3 is diluted 5 times with tap water 50ml, put into a glass container diluent, spread over the inner surface, let stand for 10 minutes, rinsed with running water and dried vase, the same kind in a vase not treated After putting the cut flowers and observing at room temperature for 1 week, the number of viable bacteria was measured.

The number of bacteria was reduced for both Trichofteon Mentagolfis and Rhizopus stronifel when the surface multifunctional treatment agent composition treatment was performed, and the propagation of the bacteria could be suppressed by the treatment. In particular, since the number of phytopathogenic bacteria that quickly wither flowers is reduced to 0, this treatment is suitable for preserving cut flowers.

Results of viable cell count and odor test using towel towels Surface multifunctional treating agent composition treatment no. 3 was diluted 30 times with tap water, immersed for 15 minutes, rinsed thoroughly with tap water and dried. Prepare a Kao Hamming Flare (registered trademark) treatment, wipe the body after bathing (right and left half), leave it for 10 days, and then measure the number of viable bacteria.
Both treatment methods: a. Surface multifunctional treating agent composition No. 1 of Example 1 Soak 3 in a towel for several minutes, wash and dry.
I. Hamming Flare 0.3 g of fluffy essence was diluted with 1 l of tap water every day, soaked for 15 minutes, taken out, squeezed and dried.

Hamming flare treatment is one of the commonly used washing methods, but according to the method of the present invention, all remaining bacteria are also sterilized by the humming flare treatment, so it is extremely useful as a towel that directly touches the human body. It will be hygienic. In addition, the odor is almost undetectable.

The antibacterial improvement effect by adding a polyhexamethylene biguanide compound to the surface multifunctional treatment composition of the present invention No. 1 of the surface multifunctional treatment composition of Example 1 No. 1 and No. 1 of the surface multifunctional treatment agent composition. 2 were each diluted 30 times with tap water. A new mop is soaked in each diluted solution for 15 minutes, rinsed thoroughly with running water, dried, and then subjected to surface multifunctional treatment composition no. No. 1 of the mop treated with No. 1 and the surface multifunctional treatment composition. One mop treated by 2 was obtained.
Using these mops, the number of viable bacteria in the mops after the floor surface was wiped daily for one month was measured.

According to the above test results, the No. of the surface multifunctional treatment composition of the present invention containing a polyhexamethylene biguanide-based compound was determined. No. 1 of the surface multifunctional treatment composition of the present invention containing no polyhexamethylene biguanide compound. It can be said that the antibacterial effect is higher than 2.

Measurement results of viable count using socks (Shimamura men's underwear H19 antibacterial deodorization processing) and odor test results Prepare two pairs of the same type of socks.
A. In one foot Example surface multifunctional treatment agent composition processing No. 3 is diluted 30 times with tap water, soaked for 15 minutes, rinsed thoroughly with tap water, and unprocessed.
I. Prepare a pair of Kao Hamming Flare (registered trademark) treated and unprocessed one pair, and measure the viable count of socks worn by the same person for 24 hours.
Both treatment methods: a. The surface multifunctional treatment composition is impregnated with a towel for several minutes, rinsed and dried.
I. Hamming Flare 0.3 g of fluffy essence was diluted with 1 l of tap water every day, soaked for 15 minutes, taken out, squeezed and dried.

According to the processing with the surface multifunctional treatment composition of the present invention, since all the bacteria that existed in the control and the bacteria remaining by the humming flare treatment are sterilized, the bacteria cannot be detected, and the state of clean socks I understand that it was. In addition, the socks used for the test were subjected to antibacterial and deodorizing treatments, and even though antibacterial and deodorizing functions were imparted by the humming flare, there was no effect on bacterial growth and odor suppression.

Results of viable cell count measurement and odor test results in mop used for toilet cleaning Prepare the same type of mop (manufactured by Teramoto Co., Ltd., FX mop replacement yarn (J)), one of which is an example surface multifunctional treatment composition No. 3 is diluted 30 times with tap water, soaked for 15 minutes, rinsed sufficiently with tap water, dried and processed, and the other is treated as a control mop that is not treated for 2 months.
The mop was used for normal cleaning twice a day, followed by washing with water after washing with a detergent for cleaning the floor.

Mops that are not treated have many bacteria such as body surface infectious bacteria, whereas mops that are treated with a surface multifunctional treatment composition can eliminate bacteria even after being used for toilet cleaning for 2 months. It was clean without detection.

Antibacterial measurement results in ceramic tile (Ceramic Cleopatra “Hitech Stone OZ-4600”) Surface multifunctional treatment agent composition treatment method: After washing ceramic tile with detergent and drying, surface multifunctional treatment agent composition of Example Was diluted 5 times with tap water and applied, and after 5 minutes, washed with water and dried.

In this test, the culture conditions for measuring the number of bacteria were Acconkey II agar medium for Escherichia coli and OPA staphylococcal medium for Pseudomonas aeruginosa and Staphylococcus aureus.
The diluted solution was used, dipped on a paper filter, and dried at room temperature to prepare a specimen. 1 ml of the test bacterial solution was transplanted on the specimen, washed out after the culture period of each bacterial species, and the number of viable bacteria was measured.

In the example using the composition of the present invention shown in Table 11, the number of bacteria was 10 or less or 100 or less after treatment for any ceramic tile.
This result means that when the ceramic tile is treated with the composition of the present invention, the antibacterial effect can be surely exhibited, and as is clear from the description of other examples and the like, from various materials other than the ceramic tile. It is clear that the same effect can be exerted on the processed object.
On the other hand, as shown in Table 12 above, the treatment composition No. 1 as a comparative example corresponding to a composition obtained by removing amide propyl dimethylamine oxide, which is an amide amine oxide, from the composition of the present invention was used. When the compositions 1, 4 and 5 are used, they differ somewhat depending on the target bacteria and certainly exhibit a certain degree of antibacterial properties, but are more antibacterial than those according to the composition of the present invention shown in Table 11. It is clear that it is inferior to.

According to these results, it is only the octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride or octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride that the composition of the present invention exhibits antibacterial properties. It is apparent that excellent antibacterial properties are exhibited by including amidoamine oxides instead of.

Test results on water / oil repellency of ceramic tile (Ceramic Cleopatra “Hitech Stone OZ-4600”) Surface multi-functional treatment agent composition treatment method: After washing ceramic tile with detergent and drying, Example surface multi-function treatment Agent composition No. 3 was diluted 5 times with tap water and applied, and after 5 minutes, washed with water and dried. The contact angle of water was measured under the following conditions for the treated ceramic tile and the untreated ceramic tile.

From this result, it can be understood that both the water repellency and the oil repellency were improved on the surface of the ceramic tile formed by applying the surface multifunctional treating agent composition.
* The contact angle was measured at 23 ° C. and 50% RH using a DropMaster 500 image processing type / solid-liquid interface analysis system (manufactured by Kyowa Interface).
Further, as a comparative example, the treating agent composition No. 1 in the above Table 1-2 containing no amidoamine oxides was used. Using 1, 4 and 5, the ceramic tile was similarly treated, and the contact angle with distilled water was measured under the above conditions.

While the contact angle with respect to distilled water of the surface of the ceramic tile treated with the composition of the present invention described in Table 13 is 96 °, amidopropyldimethyl laurate which is one of the amidoamine oxides described in Table 14 Treatment agent composition No. containing no amine oxide. The contact angle of the ceramic tile surface using 1, 4, and 5 with distilled water remains at most 90 °.
This result shows that the water repellency effect obtained by the present invention is not simply the effect of blending octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride or octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride, Furthermore, it shows that it is an effect obtained by blending amidoamine oxides.

Test results on water repellency in cleaning load test Three glass plates of the same kind were prepared, one was untreated, and the surface multifunctional treatment composition No. A solution obtained by diluting 3 with tap water 5 times was applied to the other two glass plates, and after 5 minutes, washed with distilled water and dried. Measure the water contact angle on the coated surface of one of the two glass plates obtained, and perform the following cleaning addition test on the other sheet, and measure the water contact angle on the coated surface after the test. did.

According to this result, it can be understood that the water repellency is improved and the durability of the effect is high by applying the surface multifunctional treatment agent composition of the present invention to the glass plate.
Furthermore, looking at the numerical value of the contact angle after the cleaning load test, the contact angle on the surface of the glass plate shows a high value of 87 ° even after a severe test of reciprocating the white pad 7000 times. The treatment with the surface multifunctional treatment agent composition of the present invention can maintain high water repellency even after repeated washing.
* The cleaning load test is for the purpose of simulating the durability (friction) of the surface multifunctional treatment composition. JIS K3920 Floor Polish Test Method, 19, Detergent Resistance C) Using a cleaning tester, Sumitomo A white pad made of 3M was attached, and it was driven 7000 reciprocations while a suitable amount of water was occasionally dripped at a speed of 37 reciprocations / minute with a pressing mass of 1000 g.

Friction coefficient measurement results for ceramic tiles (using electrical resistance measurement tester)
Test results on coefficient of friction measurement in ceramic tile (Ceramic Cleopatra “Hitech Stone OZ-4600”) Surface multifunctional treatment agent composition treatment method: After washing ceramic tile with detergent and drying, Example surface multifunctional treatment agent composition Item No. 3 was diluted 2.5 times with tap water and applied, and after 5 minutes, washed with water and dried.

In the ceramic tile (treated product) treated with the surface multifunctional treatment agent composition, both the static friction coefficient and the dynamic friction coefficient were decreased, and the surface slipperiness was improved. This improvement in slipperiness means that, for example, the slipperiness with a cleaning tool such as a mop is improved when cleaning the surface of a ceramic tile. The effect of reducing will be demonstrated. Moreover, when it treats with a surface multifunctional processing agent composition, even if it gives washing durability load, it can understand the high durability by the friction coefficient not becoming high.
* The coefficient of friction was measured by attaching a cotton cloth to the surface property measuring instrument HEIDON-14 ASTM flat indenter, and moving speed: 75 mm / min, load: 500 g.
For the purpose of evaluating the durability (friction) of the surface multifunctional treatment composition in a pseudo manner, JIS K3920 Floor Polish Test Method, 19, Detergent Resistance C) Using a cleaning tester, a white pad made by Sumitomo 3M It was mounted and driven at a speed of 37 reciprocations per minute with a pressing mass of 1000 g and 7000 reciprocations while occasionally dropping a suitable amount of water.

Each example shown in Table 17 corresponding to the comparative example shows similar static friction coefficient and dynamic friction coefficient with respect to the example of the present invention shown in Table 16 before applying the treatment product durability load. After applying the product durability load, the static friction coefficient and the dynamic friction coefficient are higher than before applying the load.
This indicates that when using a ceramic tile surface treated with the composition of the present invention, less force is required to rub even if the ceramic tile is repeatedly cleaned. Conversely, from the results shown in Table 17, when a composition that is not the composition of the present invention is adopted, a cleaning tool such as a mop that rubs the surface of the ceramic tile when the ceramic tile is cleaned as it is repeatedly washed. It can be understood that the applied force increases.
In the present invention, by adding amidoamine oxides in addition to octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride and octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride, the static friction coefficient and the dynamic friction coefficient of the treated surface can be obtained. Is prevented from increasing even if the use is continued, and the cleaning of the treated surface becomes easy.

Result of friction coefficient measurement on glass plate (using electrical resistance measurement tester)
Surface multifunctional treating agent composition treatment method: After washing and drying the glass plate with a detergent, Example surface multifunctional treating agent composition No. 3 was diluted 20 times with tap water and applied, and after 5 minutes, washed with water and dried.

In the glass plate treated with the surface multifunctional treatment composition, the surface electrical resistance value decreased, and both the static friction coefficient and the dynamic friction coefficient decreased, and the surface slipperiness was improved. This improvement in slipperiness means, for example, that the slipperiness with cleaning tools such as rags is improved when cleaning the glass surface, thus reducing the power required for cleaning work in combination with water and oil repellency effects. The effect of doing will be demonstrated.
* The coefficient of friction was measured by attaching a cotton cloth to the surface property measuring instrument HEIDON-14 ASTM flat indenter, and moving speed: 75 mm / min, load: 500 g.

Friction coefficient measurement results for floor tiles (using electrical resistance measurement tester)
Surface multifunctional treating agent composition treatment method: After washing floor tile (manufactured by Tajima Co., Ltd., Genius Plain, GE-1100) with detergent, Example surface multifunctional treating agent composition No. 3 is diluted 5 times with tap water and applied, and after 15 minutes, washed with water and dried.

Also for floor tiles, those treated with the surface multifunctional treatment composition can reduce the accumulation of static electricity and contribute to the reduction of trouble due to static electricity because the surface electrical resistance ground is lowered.

Test results on deodorization (Part 1) [Results with urine applied to porcelain tiles]
Processing method:
A. The porcelain tile was washed with a neutral detergent, then washed with water and dried.
I. After washing 90mm square porcelain tile with detergent and drying, Lion Co., Ltd.
Made of 1g gauze of manufactured and clean mist (registered trademark), and with ultrasonic cleaner (BRANSONIC B1200) containing tap water,
It was washed for a minute, washed with water and dried.
C. After washing the porcelain tile, Example surface multifunctional treatment composition No. 3 was diluted 5 times with tap water, 1 g was applied, 10 minutes later, washed with water and dried.
D. After washing the porcelain tile, Example surface multifunctional treatment composition No. 3 was diluted 5 times with tap water, 1 g was applied, and after 10 minutes, the porcelain tile washed with water and dried was washed with an ultrasonic cleaner (BRANSONIC) containing tap water.
B1200), washed at 30 ° C. for 30 minutes, washed with water and dried.

When treated with a clean mist manufactured by Lion Corporation, there is no change from the control, but when treated with the surface multifunctional treatment composition of the present invention, it does not change much depending on the presence or absence of ultrasonic cleaning. Compared with clean mist treatment, ammonia concentration decreased.
In addition, the treatment with the surface multifunctional treatment composition of the present invention has the same ammonia concentration for up to 24 hours as compared with the control, but after standing at room temperature for 10 days, the ammonia concentration Was low.
* Apply urine over the surface of these porcelain tiles with 2ml gauze, leave it in the room for 6 hours, and then place the porcelain tile with urine in a polyethylene container with a total capacity of 1800ml and made by Gastec Co., Ltd. , Ammonia no. Insert a 3D gas detector tube (passive dodge tube) and read the ammonia concentration in the detector tube.

[Results with urine in a glass bottle]
Surface multifunctional treatment agent composition treatment method: Prepare two wide-mouthed mayonnaise bottles with a total volume of 450 ml. 3 was diluted 5 times with tap water, 5 ml was put in contact with the inner surface, left to stand for 10 minutes, rinsed with running water and dried, and the other was rinsed with running water and dried. 3 ml of urine was put in a bottle and left in the room for 6 hours, and then sealed, and ammonia no. Insert a 3D gas detector tube (passive dodge tube) and read the ammonia concentration in the detector tube.

In the case of treatment with the surface multifunctional treatment composition of the present invention, although there is no particular short-term effect due to the high temperature period for the control, it is left for 10 days and 14 days at room temperature. Can exhibit the effect that the ammonia concentration is suppressed lower than that of the control and the generation of malodor is suppressed.

Wax mop friction coefficient measurement test results Test method: A test piece (90 × 70 mm) is placed on HEIDON (surface property measuring machine), and the load is measured at 0.5 kg and 150 mm / min. As a test piece, two kinds of mop, flat mop (manufactured by Hanwa Co., Ltd.) and wax mop of Teramoto Co., Ltd., were adopted.
Surface multifunctional treating agent treatment method: Example surface multifunctional treating agent No. 3 was diluted 5 times with tap water, impregnated with mop for 10 minutes, washed and dried.
Dry is when drying.
The floor polish to be impregnated into the mop was measured by impregnating the mop with an amount equivalent to 15 ml / m ^{2 of} Raster VX manufactured by Suisho Oil Chemical Co., Ltd.

As shown in Tables 22-1 and 22-2, when the two types of mops are both rastered, the static friction coefficient and the dynamic friction coefficient increase compared to the other types, and when the mop is impregnated with wax, the friction coefficient increases. It can be seen that it takes considerable force to push the mop during use.
However, it can be understood that the two types of mops subjected to the surface multifunctional treatment treatment according to the present invention have lower static friction coefficient and dynamic friction coefficient in both dry and raster treatments than in the untreated ones. As a result, the mop treated with the surface multifunctional treatment agent of the present invention can be used with a smaller force, whether it is dry or rasterized. In addition to the friction coefficient measurement test described above, six people actually experienced the application test using these mops using the actual floor surface. It was also confirmed that the applied mop can feel lighter and can be applied to a larger area if the amount of floor polish applied is constant.

Anti-fouling test results on the floor polish application surface 300 mm x 150 mm floor tiles (manufactured by Tajima Co., Ltd., Genius Plain, GE-1100) were washed with a detergent, then washed with water and dried, manufactured by Suisho Yuka Kogyo Co., Ltd. Raster VX is applied 3 times with gauze in an amount equivalent to 15 ml / m ² . The surface multifunctional treatment composition No. 3 is diluted 50 times with tap water, an amount corresponding to 15 ml / m ^{2 is} applied with gauze, washed with water after 10 minutes and dried. Then, in accordance with JIS K3920 2009 floor polish test method 16: heel mark property test, a comparison is made with an untreated floor material.

As shown in Table 23, it can be understood that adhesion of heel mark marks (black stains on the heels of shoes) is reduced on the surface of the floor polish treated with the surface multifunctional treatment agent. This is very useful for floor maintenance because it makes it possible to remove dirt and extend the life of the floor polish.

Claims

0.01 to 10% by weight of octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride and / or octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride, 2 to 8% by weight of amidoamine oxide as a surfactant, A surface multifunctional treatment composition containing 0.01 to 5% by weight of a polyhexamethylene biguanide compound and alcohol and water (excluding an algae generation inhibitor that suppresses the generation of algae).
The surface multifunctional treatment agent composition according to claim 1, wherein the amidoamine oxides are amidopropyldimethylamine oxide laurate.
3. The surface multifunctional treatment composition according to claim 1 or 2, which is further stable for 1 week or more in the range of 2 ° C to 50 ° C.