JP7660872B2 - Waterless cleaning wet wipes - Google Patents

Description

The present invention relates to a waterless cleaning wet sheet. More specifically, the present invention relates to a waterless cleaning wet sheet that can clean the glass surfaces, resin materials and painted surfaces of automobile bodies using only the components such as water in the impregnating liquid of the fibrous sheet without supplying cleaning water from an external source, and that, not only can remove dirt adhering to glass surfaces, resin materials and painted surfaces by using the sheet, but also improves the water-repellent state immediately after treatment and also improves the water-repellent durability after treatment.

As a prior example, a wet cloth is known that can remove dirt from a car body by simply wiping it up, and can also impart water repellency (see Patent Document 1 and Patent Document 2). The wet cloth proposed in Patent Document 1 and Patent Document 2 is made by impregnating a cloth made of fibrous fabric with a water repellent component, which is a non-volatile oil component such as dimethylpolysiloxane, which is a water repellent component, and emulsifying and dispersing the water repellent component with a surfactant. According to this wet cloth, during use, the water repellent component that comes out of the cloth together with water separates from the water and adheres to the coating film, forming a water repellent film, and the remaining water that is repelled by this water repellent film is absorbed back into the cloth. As another prior example, a coating film-protected wet cloth for car washing is known (see Patent Document 3). The wet cloth proposed in Patent Document 3 is made by impregnating a nonwoven fabric with a certain type of silicone resin emulsion containing a water repellent component. According to this, whether the coating film has water-repellent or hydrophilic properties, it is possible to wipe off the coating film and wash the car without causing any changes or damage to the coating film.

Meanwhile, another prior art example describes a water-repellent composition for glass that is used by impregnating a fabric (see Patent Document 4). This water-repellent composition for glass contains a fluorine-based alkoxysilane and an acid catalyst or a basic catalyst. It is said that this water-repellent composition for glass can ensure high water repellency and transparency of the glass surface.

Patent No. 3482517 Patent No. 4583364 Patent No. 4990113 JP 2010-138210 A

However, the wet cloths proposed in the above Patent Documents 1 to 3 are intended for use on the painted surfaces of automobiles, which are lipophilic surfaces, and are not suitable for application to glass surfaces, which are hydrophilic surfaces such as the glass parts of automobiles. In contrast, the water-repellent treatment composition for glass proposed in Patent Document 4 imparts water repellency and transparency to glass surfaces, and is not suitable for application to the resin materials and painted surfaces of automobiles, which are highly lipophilic.

The present invention was made in consideration of the above circumstances, and aims to provide a waterless cleaning wet sheet that does not require the use of cleaning water, is suitable for use on both oleophilic surfaces such as the resin materials and painted surfaces of automobiles, and hydrophilic surfaces such as the glass parts of automobiles, and is capable of removing dirt whether used on oleophilic or hydrophilic surfaces, and of forming a water-repellent coating that is highly durable immediately after and after treatment.

The waterless cleaning wet sheet of the present invention is a waterless cleaning wet sheet intended for use on both lipophilic and hydrophilic surfaces, and is made by impregnating a fibrous sheet with a silicone resin emulsion containing a water-repellent component and an impregnation liquid containing a cationic substance capable of fixing the water-repellent component to the hydrophilic surface.

This invention focuses on the fact that the silicone resin, which is the water-repellent component, exhibits lipophilicity, and that the cationic substance capable of fixing the water-repellent component to a hydrophilic surface has both hydrophilic and lipophilic parts. In other words, even if a hydrophilic surface such as a glass surface is directly treated with a lipophilic water-repellent component, the water-repellent component is unlikely to be fixed to the glass surface. However, when a hydrophilic surface such as a glass surface is treated with the waterless cleaning wet sheet according to this invention, the hydrophilic part of the cationic substance, which has both hydrophilic and lipophilic parts, is fixed to the hydrophilic surface such as a glass surface, and the lipophilic part of the cationic substance is exposed on the surface, and as a result, the hydrophilic surface is apparently modified to a lipophilic surface. When the hydrophilic surface is modified to a lipophilic surface in this way by the action of the cationic substance, the lipophilic water-repellent component is easily fixed to the lipophilic part of the cationic substance, and the lipophilic water-repellent component is fixed to the hydrophilic surface to form a water-repellent coating. In other words, a hydrophilic surface such as a glass surface is modified into an oleophilic surface by the action of a cationic substance, and the adhesion of the oleophilic water-repellent component is expressed, forming a water-repellent coating.

In contrast, when the waterless cleaning wet sheet of this invention is used to treat an oleophilic surface such as a resin material or a painted surface, the oleophilic water-repellent component adheres directly to the resin material or painted surface, forming a water-repellent coating.

When the treated surface is wiped, dirt adhering to the hydrophilic or lipophilic surface is removed by wiping the treated surface. The silicone resin in the silicone resin emulsion contained in the impregnating liquid that seeps out of the fibrous sheet is separated from the water and surfactant, which become the cleaning liquid. The dirt floats up from the treated surface and is absorbed into the cleaning liquid. The peeling effect of the water-repellent coating makes it easier for the water droplets of the cleaning liquid that have absorbed the dirt to separate from the treated surface, and the water droplets of the cleaning liquid containing the dirt are collected by the fibrous sheet.

The present invention further provides that the silicone resin emulsion is prepared by emulsifying a water-repellent component, which is a mixture of dimethylpolysiloxane or a modified product thereof and trimethylsiloxysilicate, with a surfactant.

In order to cleanly wipe off dirt remaining on the treated surfaces, which are the resin material and painted surfaces of the body, which are oleophilic surfaces, and the glass surface, which is hydrophilic surfaces, the treated surfaces, such as the resin material, painted surface, and glass surface, must be in a sufficiently water-repellent state. If the treated surface is not in a sufficiently water-repellent state, the water droplets of the cleaning solution containing dirt will become large droplets and remain on the treated surface in excess. If the treated surface is in a sufficiently water-repellent state, the water droplets will become finer and will be easier to separate from the treated surface, and the water droplets of the cleaning solution containing the dirt will be easier to collect on the fibrous sheet. Even if a fibrous sheet is impregnated with a solution of trimethylsiloxysilicate, it will not harden and will remain on the fiber surface, and when the treated surface is wiped, it will properly migrate from the impregnated fibrous sheet to the treated surface, adhere to the treated surface, and form a uniform water-repellent coating, and it has excellent long-lasting performance, so it can be said to be an essential component for wiping off a dirty surface and imparting sufficient water repellency to the treated surface to form a clean surface. Trimethylsiloxysilicate itself is a solid (powder) and cannot be spread evenly on hydrophilic or oleophilic surfaces. For this reason, it can be made into a solution by using dimethylpolysiloxane or its modified form as a diluent for trimethylsiloxysilicate.

The appropriate amount of water-repellent component to be added is 0.1 to 2.0 wt% of the active component in the impregnation liquid. If the amount is less than 0.1 wt%, the treated surface will not be sufficiently water-repellent, and dirt will re-adhere to the treated surface, making it difficult to wipe it clean. If the amount of water-repellent component added exceeds 2.0 wt%, the water-repellent component will be excessively fixed on the treated surface, making the water-repellent coating uneven, causing unevenness, and making it easier to cause halation on the glass surface. Therefore, amounts less than 0.1 wt% and more than 2.0 wt% are not preferable. If the amount of water-repellent component added is 0.1 to 2.0 wt%, it will be easier to wipe it cleanly, the coating will be more likely to be uniform, and it will be less likely to cause unevenness or halation on the glass surface.

In the present invention , the cationic substance capable of fixing a water-repellent component to a hydrophilic surface is a cationic surfactant. In particular, it is preferable that the cationic substance capable of fixing a water-repellent component to a hydrophilic surface is a quaternary ammonium salt.

As a cationic substance that can fix water-repellent components to hydrophilic surfaces, it is possible to use a cationic surfactant, a quaternary ammonium salt surfactant. A cationic surfactant is a compound that has a hydrophobic group (lipophilic group) and a hydrophilic group. The hydrophilic group has a positive charge in an aqueous solution, so that on the negatively charged glass surface, the positively charged hydrophilic group of the cationic surfactant is attracted to the glass surface, and the hydrophobic groups (lipophilic groups) line up on the glass surface toward the outside, and the water-repellent components become familiar with the hydrophobic groups (lipophilic groups) to form a water-repellent coating. The trimethylsiloxysilicate in the water-repellent component does not have a reactive group that reacts with hydrophilic surfaces such as glass surfaces, so it cannot be fixed uniformly to the glass surface by simply applying it to the glass surface. Resin materials and painted surfaces have lipophilic groups (hydrophobic groups) on their surfaces, so silicone resins that show lipophilicity easily become familiar and adhere uniformly, but silicone resins do not adhere uniformly to glass surfaces whose surfaces are covered with hydrophilic groups. In fact, if the glass surface is treated with only silicone resin, a uniform water-repellent film cannot be formed on the glass surface, and the dirt-containing cleaning solution does not break down into small droplets, meaning they cannot be collected on the fibrous sheet, resulting in a poor finish. Also, even if water is poured on the surface, it does not form neat droplets.

The amount of cationic substance added is preferably 0.01 to 1.5 wt% of the active component in the impregnation solution; a relatively large amount is needed to act on the entire glass surface, but if it is less than 0.01 wt%, the effect of fixing the water-repellent component sufficiently is not obtained, and if it exceeds 1.5 wt%, the component is excessively fixed on the treated surface, causing the water-repellent coating to become uneven and the water-repellent property to decrease, which is not preferable. If the amount added is 0.01 to 1.5 wt%, the entire glass surface can be acted on, so the effect of fixing the water-repellent component sufficiently is obtained, the water-repellent coating becomes uniform, and the water-repellent property is less likely to decrease even after treatment.

As a cationic substance capable of fixing a water-repellent component to a hydrophilic surface, it is preferable to use a quaternary ammonium salt, although alkylamine salt type substances can also be used.

In addition, it is possible to obtain an effect similar to that of the present invention by using amino silicone, which is generally used as a water repellent for glass, instead of quaternary ammonium salt. However, it has been confirmed that if the fibrous sheet is left soaked in the amino silicone for about one month at 50°C, the glass surface will no longer be water repellent, and the situation will be the same as if only silicone resin was blended. This is because amino silicone does not dissolve in water as it is, so it needs to be neutralized by combining with an acid to make it water soluble or to be made into an emulsion. However, since it is not water soluble to begin with, it is thought that the state becomes unstable when it is contained in the fibrous sheet. Therefore, it is adsorbed to the fibrous sheet, which has a stronger lipophilicity than water, and the situation will be the same as if only silicone resin was blended, so amino silicone is not suitable for use in such sheet-type products.

The surfactant for the silicone resin emulsion can be a nonionic surfactant, anionic surfactant, cationic surfactant, or amphoteric surfactant, but nonionic surfactants are particularly preferable. Nonionic surfactants have high emulsifying and dispersing power and also have cleaning properties, and since their charges are not neutralized with cationic surfactants, the effects of each surfactant do not cancel each other out.

In the present invention, the impregnating liquid further includes a silicone resin emulsion to which a modified silicone oil has been added together with the silicone resin emulsion. The modified silicone oil has a hydroxyl group at one or both ends (preferably both ends) . Adding a modified silicone oil having a hydroxyl group at one or both ends improves the initial water repellency and durability of the water repellency on the glass surface. Although this type of modified silicone oil is not very reactive with the glass surface, it is considered that the oil has a hydroxyl group and partially reacts with the hydroxyl group on the glass surface to improve the fixation. The amount of modified silicone oil added is preferably 0.01 to 1.5 wt% in the impregnating liquid as an effective component. If it is less than 0.01 wt%, a sufficient water repellency improvement effect cannot be obtained, and if it exceeds 1.5 wt%, the components are excessively fixed on the treated surface, causing the water repellent coating to become uneven, or the durability of the water repellent coating to decrease due to the excess oil. If the amount added is 0.01 to 1.5 wt%, a sufficient water repellency improvement effect is obtained, and a uniform water repellent coating is formed, improving the durability of the water repellent coating.

The fibrous sheet used in the present invention is preferably a three-layer nonwoven fabric in which hydrophilic fibers as a central layer are sandwiched between lipophilic (hydrophobic) microfibers as an outer layer. In this regard, if short-length (20 mm or less) hydrophilic fibers are used for the central layer, the hydrophilic fibers of the central layer tend to fly off when high-pressure water is applied to cause hydroentanglement, and the fibers tend to come out onto the surface. Furthermore, the presence of hydrophilic fibers on the surface is undesirable, since it not only makes wiping work harder, but also tends to make the water-repellent coating uneven. For this reason, it is desirable to use hydrophilic fibers with a fiber length of 25 mm or more, preferably 30 mm or more, for the central layer.

The microfibers in the outer layer are generally 0.2 to 0.5 denier thick, and are distinct from normal fibers, which are 1.0 to 6 denier thick.

Normally, nonwoven fabrics made primarily of microfibers, which have excellent scraping properties, are used to remove dirt. However, fibrous sheets that use microfibers in the outer layer have excellent dirt-removing properties, but they have the following drawbacks:

First, it is known that good scraping properties result in poor slipperiness, which not only reduces workability but also increases frictional resistance and can damage the painted surface. Second, it is known that nonwoven fabrics made only of microfibers have a high fiber density, which reduces the space between the fibers and reduces the amount of dirt they can hold. And when the space between the fibers becomes large enough, it becomes easier for dirt to be trapped inside the fibers, so the dirt no longer comes into direct contact with the coating film.

For this reason, it is possible to mix in some percentage of normal-thickness fibers, rather than using 100% microfiber fibers. In the conventional 100% plain surface shape, the ratio of microfiber to normal fiber is preferably about 9:1 to 5:5. In addition, it is also possible to improve the slipperiness during wiping and the removability of stuck dirt by making a part of the nonwoven fabric mesh-like. For nonwoven fabrics with mesh parts, the ratio of microfiber to normal fiber is preferably about 10:0 to 8:2. Since the liquid is easily released due to the openings in the mesh part, if the space of the nonwoven fabric is too large, the liquid will remain, which is not preferable. The appropriate amount of impregnation liquid to be contained in the fibrous sheet is about 1.8 to 3.5 times the weight of the fibrous sheet, and more preferably, 2.0 to 2.5 times. If it is less than 1.8 times, not only will the amount of water required for removing dirt be insufficient, resulting in a decrease in cleaning ability, but it will also be difficult to form a water-repellent coating on the paint or glass surface. If the amount exceeds 3.5 times, excess liquid is likely to remain on the painted surface when wiping, causing unevenness and discoloring the painted surface or glass surface. In addition, the absorbency of the cloth approaches saturation, making it difficult to remove dirt.

In the present invention, it is possible to add an emulsion of dimethyl silicone oil to the impregnation liquid as an optional component that is not essential. If an emulsion of dimethyl silicone oil, particularly one with a viscosity of 500 cst or less, is added to the impregnation liquid, even if the water contained in the emulsion evaporates and the concentration of the water-repellent component increases, the dimethyl silicone oil contained in the emulsion acts as a diluent for the water-repellent component, improving the uniformity of the water-repellent coating, improving workability, and serving as an auxiliary agent for finishing cleanly without re-adhering dirt. If a dimethyl silicone oil with a viscosity higher than 500 cst is added, the slipperiness during work will improve, but the uniformity of the water-repellent coating will decrease, resulting in uneven shading, which is not preferable. The amount of the active ingredient in the impregnation solution is preferably 0.1 to 2.0 wt%; if it is less than 0.1 wt%, a sufficient dilution effect is not obtained, and if it exceeds 2.0 wt%, the ingredients will settle excessively on the treated surface, resulting in an uneven water-repellent coating and a decrease in the durability of the water-repellent coating due to excess oil. If the amount is 0.1 to 2.0 wt%, a sufficient dilution effect is obtained, the water-repellent coating is more likely to be uniform, and the durability of the water-repellent coating is less likely to decrease due to excess oil.

In the present invention, it is also possible to add a wax emulsion or dispersion to the impregnation liquid as an optional component that is not essential. The wax emulsion or dispersion is useful for improving the durability of the coating, the slipperiness during work, and the resistance to scratches due to dirt. Examples of wax components include various natural or synthetic waxes or wax-like substances. Specifically, examples include fatty acids and their derivatives, plant-based natural waxes such as carnauba wax, candelilla wax, sugar wax, rice wax, Japan wax, and hardened castor oil, plant-based natural waxes such as beeswax, whale wax, lanolin and its derivatives, petroleum-based natural waxes such as microcrystalline wax and paraffin wax, mineral-based natural waxes such as montan wax, ozokerite wax, and ceresin, and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, and their derivatives. By combining the emulsion of the wax components listed here with the water-repellent component dissolved in dimethylpolysiloxane of trimethylsiloxysilicate or its modified form emulsified with a surfactant, the water-repellent coating becomes thicker, and by covering scratches from car washing, the scratches become less noticeable. In addition, the initial gloss and durability of the gloss are improved. It has been found that the gloss and water-repellent durability during washing are significantly improved. In addition, it is desirable to set the amount of addition to a small amount because adding too much to a glass surface can cause halation. The amount of addition is preferably 0.01 to 0.5 wt% of the active component in the impregnation liquid. If it is less than 0.01 wt%, sufficient gloss and water-repellent durability are not achieved, and if it exceeds 0.5 wt%, sufficient gloss and water-repellent properties are achieved, but the components are excessively attached to the resin material, painted surface, and glass surface, causing unevenness in shading and glare, and the solid content is too excessive, making it difficult to spread the components neatly. By adding a dispersion of wax components, it is possible to improve slipperiness during wiping work and reduce scratches caused by dirt adhering to the treated surface. The amount of additive should be 0.1 to 2.0 wt% of the active ingredient in the impregnation liquid. If it is less than 0.1 wt%, it will not be possible to fully prevent slipperiness during work or scratches caused by dirt, and if it exceeds 2.0 wt%, it will be sufficient to prevent slipperiness during work or scratches caused by dirt, but it is not preferable because it will tend to remain on the treated surface. Note that in the present invention, it is not essential to add a wax emulsion or dispersion to the impregnation liquid.

Other optional ingredients that are not essential in the present invention include dyes, UV absorbers, preservatives, antibacterial agents, etc.

As described above, the waterless wet sheet according to the present invention does not require the use of wash water, is suitable for use on both oleophilic surfaces such as the resin materials and painted surfaces of automobiles, and hydrophilic surfaces such as the glass parts of automobiles, and can remove dirt and form a water-repellent coating that is highly durable immediately after and after treatment, whether used on oleophilic or hydrophilic surfaces. The wet sheet according to the present invention can be used not only on the resin materials, painted surfaces, and glass parts (windshields, side windows, etc.) of automobiles, but also on other oleophilic and hydrophilic surfaces, such as the painted surfaces, resin materials, and glass parts of vehicles other than automobiles, painted materials in the home, resin materials, window glass, mirrors, and glass parts such as ceramics.

Examples showing embodiments of the present invention will be described below together with comparative examples and reference examples .

[Examples , Comparative Examples, and Reference Examples ]

The raw materials used are as follows:
(1) Silicone resin emulsion A
Trimethylsiloxysilicate was dissolved in dimethylpolysiloxane to form an emulsion (effective concentration of silicone component: 40 wt %, viscosity of dimethylpolysiloxane used: 350 cs, mixing ratio of trimethylsiloxysilicate to dimethylpolysiloxane: 30:70, emulsifier: nonionic surfactant + anionic surfactant: 6.0%).
(2) Silicone resin emulsion B
Trimethylsiloxysilicate was dissolved in cyclopentasiloxane to form an emulsion (effective concentration 30 wt %, viscosity of cyclopentasiloxane used 4 cs, mixture ratio of trimethylsiloxysilicate and cyclopentasiloxane 50:50, nonionic surfactant: 6.0% used as emulsifier).
(3) Silicone resin emulsion C
Trimethylsiloxysilicate was dissolved in dimethylsilicone with a viscosity of 6 cs to form an emulsion (effective concentration 30 wt %, viscosity of dimethylsiloxane used was 6 cs, mixture ratio of trimethylsiloxysilicate and dimethylpolysiloxane was 50:50, and 3% nonionic surfactant was used as emulsifier).
(4) Dimethyl silicone emulsion A
An emulsion of dimethylpolysiloxane with a viscosity of 10 cs (effective concentration of silicone component: 30 wt %, nonionic surfactant: 5.0%).
(5) Dimethyl silicone emulsion B
An emulsion of dimethylpolysiloxane with a viscosity of 500cs (effective concentration of silicone component: 30wt%, nonionic surfactant: 3.0%)
(6) Dimethyl silicone emulsion A modified with OH at both ends
An emulsion of dimethylpolysiloxane modified with OH at both ends and having a viscosity of 30cs (effective concentration of silicone component: 30wt%, nonionic surfactant: 3.0%)
(7) Both-end OH-modified dimethyl silicone emulsion B
An emulsion of dimethylpolysiloxane modified with OH at both ends and having a viscosity of 700cs (effective concentration of silicone component: 30wt%, nonionic surfactant: 3.0%)
(8) Cationic Surfactant A
A cationic surfactant containing 30% active ingredient and whose chemical composition is cetyltrimethylammonium chloride.
(9) Cationic Surfactant B
A cationic surfactant containing 50% active ingredient and whose chemical composition is alkylbenzyldimethylammonium chloride.
(10) Wax emulsion A
Modified polypropylene wax emulsified (effective concentration 35 wt %, nonionic surfactant: 4%).
(11) Wax emulsion B
An emulsion of polyethylene wax (molecular weight approximately 500). (Effective concentration of wax: 30 wt% Nonionic surfactant: 5 wt%)

Reference Example 1
Silicone resin emulsion A 3.00 wt%
Cationic surfactant A 1.00 wt%
Ion-exchanged water 96.00 wt%
100.00wt%

An impregnation liquid was prepared by dissolving or dispersing silicone resin emulsion A and cationic surfactant A in ion-exchanged water.
A nonwoven fabric (total basis weight: 70 g/m ² ) made of nylon/polypropylene microfiber (0.5 denier) cut to a size of 30 x 30 cm was uniformly impregnated with an impregnation liquid in an amount equivalent to 2.0 times the weight of the nonwoven fabric to obtain a sample.

Reference Example 2
Silicone resin emulsion B 2.00 wt%
Dimethyl silicone emulsion B 1.00 wt%
Cationic surfactant B 1.00 wt%
Ion-exchanged water 96.00 wt%
100.00wt%
An impregnation liquid was prepared by dissolving or dispersing silicone resin emulsion B, dimethyl silicone emulsion B, and cationic surfactant B in ion-exchanged water.
A nonwoven fabric (total basis weight: 70 g/ ^m2 ) consisting of 80% polyethylene/polyester microfiber (0.5 denier) and 20% polyester (1.7 denier) cut to a size of 30 x 30 cm was uniformly impregnated with an impregnation liquid equivalent to 2.4 times the weight of the nonwoven fabric to obtain a sample.

Example 3
Silicone resin emulsion C 2.50 wt%
Dimethyl silicone emulsion A 0.50 wt%
Both ends OH-modified dimethyl silicone emulsion A 1.00 wt%
Cationic surfactant A 0.50 wt%
Ion-exchanged water 95.50 wt%
100.00wt%
An impregnation liquid was prepared by dissolving or dispersing silicone resin emulsion C, dimethyl silicone emulsion A, dimethyl silicone emulsion A modified with OH at both ends, and cationic surfactant A in ion-exchanged water.
A nonwoven fabric (total basis weight: 70 g/ ^m2 ) cut to 30 x 30 cm and consisting of a rayon (2.0 denier) middle layer and a polyethylene/polypropylene (0.3 denier) outer layer made of microfiber was uniformly impregnated with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric to obtain a sample.

Example 4
Silicone resin emulsion C 2.00 wt%
Silicone resin emulsion B 0.50 wt%
Both ends OH-modified dimethyl silicone emulsion A 0.30 wt%
Dimethyl silicone emulsion A 1.00 wt%
Cationic surfactant A 0.70 wt%
Ion-exchanged water 95.50 wt%
100.00wt%
Silicone resin emulsion C, silicone resin emulsion B, dimethyl silicone emulsion A modified with OH at both ends, dimethyl silicone emulsion A in ion-exchanged water
The impregnation solution was prepared by dissolving or dispersing the above.
A nonwoven fabric (total basis weight: 70 g/ ^m2 , central layer 10 g, outer layer 30 g on one side, mesh openings 15%, mesh area 10% of the total, arranged in polka dots) cut to a size of 30 x 30 cm and consisting of a rayon (2.0 denier) middle layer and a polyethylene/polypropylene (0.3 denier) microfiber outer layer was uniformly impregnated with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric to obtain a sample.

Example 5
Silicone resin emulsion C 3.00 wt%
Dimethyl silicone emulsion B 1.00 wt%
Both ends OH-modified dimethyl silicone emulsion B 0.50 wt%
Cationic surfactant A 0.50 wt%
Wax emulsion A 0.50 wt%
Ion-exchanged water 94.50 wt%
100.00wt%
An impregnation liquid was prepared by dissolving or dispersing silicone resin emulsion C, dimethyl silicone emulsion B, dimethyl silicone emulsion B modified with OH at both ends, cationic surfactant A, and wax emulsion A in ion-exchanged water.
A nonwoven fabric (total basis weight: 70 g/ ^m2 , central layer 10 g, outer layer 30 g per side, mesh opening 15%, mesh area 10% of the total, arranged in a wavy pattern) cut to a size of 30 x 30 cm and consisting of a rayon (1.4 denier) middle layer and a polyethylene/polyester (0.6 denier) microfiber outer layer was uniformly impregnated with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric to obtain a sample.

Example 6
Silicone resin emulsion A 2.50 wt%
Silicone resin emulsion B 1.00 wt%
Dimethyl silicone emulsion A 0.20 wt%
Dimethyl silicone emulsion B 0.20 wt%
Cationic surfactant B 0.40 wt%
Both ends OH-modified dimethyl silicone emulsion A 0.60 wt%
Ion-exchanged water 95.10 wt%
100.00wt%
An impregnation liquid was prepared by dissolving or dispersing silicone resin emulsion A, silicone resin emulsion B, dimethyl silicone emulsion A, dimethyl silicone emulsion B, cationic surfactant B, and dimethyl silicone emulsion A modified with OH at both ends in ion-exchanged water.
The above components were dissolved or dispersed in 94.8 wt % ion-exchanged water to prepare an impregnation solution.
A nonwoven fabric (total basis weight: 70 g/ ^m2 , central layer 10 g, outer layer 30 g per side, mesh opening 15%, mesh area 10% of the total, arranged in a wavy pattern) cut to a size of 30 x 30 cm with a rayon middle layer and a polyethylene/polyester microfiber outer layer was uniformly impregnated with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric to obtain a sample.

Comparative Example 1
Dimethyl silicone emulsion A 4.00 wt%
Ion-exchanged water 96.00 wt%
100.00wt%
Dimethyl silicone emulsion A was dispersed in ion-exchanged water to prepare an impregnation solution.
A nonwoven fabric (total basis weight: 70 g/m ² ) made of polyethylene/polypropylene microfibers cut to 30×30 cm was uniformly impregnated with an impregnation liquid in an amount 2.5 times the weight of the nonwoven fabric to obtain a sample.

Comparative Example 2
Silicone resin emulsion A 5.00 wt%
Ion-exchanged water 95.00wt%
100.00wt%
Silicone resin emulsion A was dispersed in ion-exchanged water to prepare an impregnation liquid.
A nonwoven fabric (total basis weight: 70 g/m ² ) made of polyethylene/polyester microfiber cut to 30×30 cm was uniformly impregnated with an impregnation liquid in an amount 2.5 times the weight of the nonwoven fabric to obtain a sample.

Comparative Example 3
Silicone resin emulsion A 2.00 wt%
Wax emulsion B 1.00 wt%
Dimethyl silicone emulsion B 1.00 wt%
Ion-exchanged water 96.00 wt%
100.00wt%
Silicone resin emulsion A, wax emulsion B, and dimethyl silicone emulsion B were dispersed in ion-exchanged water to prepare an impregnation liquid.
A nonwoven fabric (basis weight: 70 g/ ^m2 ) made of a polyester and rayon blend (blended ratio 70:30, nonwoven fabric constituent fiber diameter 2.0 denier) cut to a size of 30 x 30 cm was uniformly impregnated with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric to obtain a sample.

Comparative Example 4
Cationic surfactant A 0.50 wt%
Dimethyl silicone emulsion B 4.00 wt%
Ion-exchanged water 95.50 wt%
100.00wt%
An impregnation liquid was prepared by dispersing a cationic surfactant A and a dimethyl silicone emulsion B in ion-exchanged water.
A nonwoven fabric consisting of nylon/polyethylene microfibers cut to 30 x 30 cm (total basis weight: 70 g/ ^m2 , mesh openings: 15%, mesh area: 8% of the total, arranged in polka dots) was uniformly impregnated with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric to obtain a sample.

Comparative Example 5
Cationic surfactant A 1.00 wt%
Both ends OH-modified dimethyl silicone emulsion A 0.50 wt%
Dimethyl silicone emulsion B 3.00 wt%
Ion-exchanged water 95.50 wt%
100.00wt%
An impregnation liquid was prepared by dispersing cationic surfactant A, dimethyl silicone emulsion A modified with OH at both ends, and dimethyl silicone emulsion B in ion-exchanged water.
A nonwoven fabric consisting of nylon/polyethylene microfibers cut to 30 x 30 cm (total basis weight: 70 g/ ^m2 , mesh openings: 15%, mesh area: 8% of the total, arranged in polka dots) was uniformly impregnated with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric to obtain a sample.

Test method: Using the treated cloth (fibrous sheet) prepared, the water-repellent state of a painted surface immediately after treatment, the water-repellent state of a glass surface immediately after treatment, the dirt removability of a painted surface, and the dirt removability of a glass surface were investigated.

The evaluation test was carried out as follows.
The bonnet and windshield of a 2010 Toyota Corolla Fielder ("Toyota", "Toyota Corolla", "Corolla" and "Fielder" are registered trademarks) painted black were used for the test. The bonnet was coated with a cleaner wax to remove dirt, and the remaining wax coating was removed with an aliphatic solvent. The bonnet was then left outdoors for two weeks, and the naturally soiled bonnet was used as the test surface. This test surface was divided into 12 sections (each section was approximately 25 x 40 cm square), and each sample was used to wipe it. Next, the windshield was coated with a glass abrasive to remove dirt and water-repellent coating, and the remaining oil film was removed with IPA. The bonnet was then left outdoors for two weeks, and the naturally soiled bonnet was used as the test surface. This test surface was divided into 12 sections (each section was approximately 25 x 40 cm square), and each sample was used to wipe it.
At this time, one section was left untreated as a blank test.

A. Ability to remove dirt from painted surfaces Each sample was folded into four and the entire test surface was wiped back and forth 10 times to evaluate the ability to remove dirt. ◎ Very good (dirt was completely removed and a uniform shine was achieved)
○ Good (dirt has been completely removed, but there is some unevenness in the shade)
△ Normal (there is less dirt, but some streaks of dirt remain)
× Poor (streaks of dirt remain on the entire test surface)

B. Removability of stains from glass surfaces Each sample was folded into four, and the entire test surface was wiped back and forth 10 times to evaluate the removability of stains. ◎ Very good (stains were completely removed, with no residue or glare, leaving a uniform appearance)
○ Good (dirt has been completely removed, but there is some unevenness in the color)
△ Normal (there is less dirt, but some streaks of dirt remain)
× Poor (streaks of dirt remain on the entire test surface)

C. Water repellency immediately after treatment (painted surface)
Water is poured onto the test surface and the state of water droplets is visually judged.
◎ The water often forms dots and bounces off. ○ The water bounces off, but the polka dots are deformed.
△ Slightly slow repelling × Almost no repelling

D. Water-repellent state immediately after treatment (glass surface)
Water is poured onto the test surface and the state of water droplets is visually judged.
◎ The water often forms dots and bounces off. ○ The water bounces off, but the polka dots are deformed.
△ Slightly slow repelling × Almost no repelling

E. Water-repellent durability After leaving the vehicle parked outdoors for one month and then washing the vehicle with water, water was sprayed on the test surface and the state of water droplets was visually evaluated.
◎ The water often forms dots and bounces off. ○ The water bounces off, but the polka dots are deformed.
△ Slightly slow repelling × Almost no repelling

From the test results in Table 1, in terms of the removability of dirt on a painted surface, the removability of dirt on a glass surface, the water-repellent state immediately after treatment (painted surface), the water-repellent state immediately after treatment (glass surface), and the durability of water-repellent (painted surface), Reference Examples 1 and 2 and Examples 3 to 6 were rated as ⊚ or ◯, while Comparative Examples 1 to 5 were rated as few ◯ and more △ or x. In terms of the durability of water-repellent (glass surface), Reference Examples 1 and 2 and Examples 3 to 6 were rated as △, while Examples 3 to 6 were rated as ⊚. On the other hand, Comparative Examples 1 to 5 were all rated as x. From the above, it can be seen that the waterless wet sheet according to the present invention exhibits excellent effects in terms of the removability of dirt on a painted surface, the removability of dirt on a glass surface, the water-repellent state immediately after treatment (painted surface), the water-repellent state immediately after treatment (glass surface), the durability of water-repellent (painted surface), and the durability of water-repellent (glass surface), and is superior to Comparative Examples 1 to 5.

Claims (4)

A waterless cleaning wet sheet having both a lipophilic surface and a hydrophilic surface,
A wet cleaning sheet is obtained by impregnating a fibrous sheet with an impregnation liquid containing a silicone resin emulsion containing a water-repellent component and a cationic substance capable of fixing the water-repellent component to a hydrophilic surface,
The silicone resin emulsion is prepared by emulsifying a water-repellent component, which is a mixture of dimethylpolysiloxane or a modified product thereof and trimethylsiloxysilicate, with a surfactant,
The cationic substance capable of fixing the water-repellent component to the hydrophilic surface is a cationic surfactant,
The waterless cleaning wet sheet is characterized in that the impregnating liquid contains a silicone resin emulsion to which a modified silicone oil has been added together with the silicone resin emulsion, and the modified silicone oil has a hydroxyl group at one or both ends . 2. The waterless cleaning wet sheet according to claim 1 , wherein the cationic substance capable of fixing the water-repellent component to the hydrophilic surface is a quaternary ammonium salt . 3. The waterless cleaning wet sheet according to claim 1 , wherein an emulsion of dimethyl silicone oil is added to the impregnating liquid . 4. The waterless cleaning wet sheet according to claim 1, wherein the surfactant in said silicone resin emulsion is a nonionic surfactant .