Waterless cleaning wet wipes

Abstract

To provide a wet sheet for waterless cleaning that is suitable for use on lipophilic surfaces, such as resin materials and painted surfaces of automobiles, and on hydrophilic surfaces, such as glass areas of automobiles, and is capable of removing dirt and forming a water-repellent film with excellent durability immediately after and after treatment, regardless of whether it is used on lipophilic or hydrophilic surfaces.SOLUTION: A wet sheet for waterless cleaning that is made of a fibrous sheet impregnated with an impregnation liquid comprising a silicone resin emulsion containing a water-repellent component, and a cationic substance capable of denaturing a hydrophilic surface into a lipophilic surface. The silicone resin emulsion is an emulsion prepared by emulsifying a water-repellent component that is obtained by dissolving trimethylsiloxysilicic acid in dimethylpolysiloxane or a modified product thereof by use of a surfactant. The cationic substance is a cationic surfactant.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a waterless cleaning wet sheet, more specifically, a waterless cleaning wet sheet capable of cleaning the glass surfaces, resin materials and painted surfaces of automobile bodies using only the components such as water in the impregnating liquid of a fibrous sheet without supplying cleaning water from the outside, and capable of removing dirt attached to the glass surfaces, resin materials and painted surfaces by using the sheet, as well as improving the water repellency immediately after treatment and improving the water repellency durability after treatment. [Background technology]

[0002] As a prior example, a wet cloth is known that can remove dirt from a car body by simply wiping the car body 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 emulsifying and dispersing a water repellent component, which is a water repellent component, in a non-volatile oil component such as dimethylpolysiloxane, with a surfactant, and impregnating the water repellent component into a cloth made of a fibrous fabric. 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 water that is repelled by the water repellent film and remains 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, regardless of 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 denaturation or damage to the coating film.

[0003] Meanwhile, in yet another prior art, there is a description of a water-repellent treatment composition for glass that is used by impregnating a fabric (see Patent Document 4). This water-repellent treatment composition for glass contains a fluorine-based alkoxysilane and an acid catalyst or a basic catalyst. It is said that this water-repellent treatment composition for glass can ensure high water repellency and transparency of the glass surface. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 3482517 [Patent Document 2] Patent No. 4583364 [Patent Document 3] Patent No. 4990113 [Patent Document 4] JP 2010-138210 A Summary of the Invention [Problem to be solved by the invention]

[0005] 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 hydrophilic glass 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 resin materials or painted surfaces of automobiles, which are highly lipophilic.

[0006] The present invention has been 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 lipophilic 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 and forming a water-repellent coating that is highly durable immediately after and after treatment, regardless of whether it is used on a lipophilic or hydrophilic surface. [Means for solving the problem]

[0007] 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 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 the hydrophilic surface.

[0008] 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. That is, even if a hydrophilic surface such as a glass surface is directly treated with a lipophilic water-repellent component, the water-repellent component is difficult to fix to the glass surface. However, when a hydrophilic surface such as a glass surface is treated using the waterless cleaning wet sheet according to this invention, the hydrophilic part of the cationic substance having 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 by the action of the cationic substance in this way, 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 to an oleophilic surface by the action of a cationic substance, and the fixation of the oleophilic water-repellent component is expressed to form a water-repellent coating.

[0009] In contrast, when the waterless cleaning wet sheet of the present invention is used to treat a lipophilic surface such as a resin material or a painted surface, the lipophilic water-repellent component adheres directly to the resin material or painted surface, forming a water-repellent coating.

[0010] When the treated surface is wiped, the water and surfactant that separate from the silicone resin in the silicone resin emulsion contained in the impregnating liquid that seeps out of the fibrous sheet becomes the cleaning liquid, and the dirt adhering to the hydrophilic or lipophilic surface floats up from the treated surface and is taken up 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 taken up 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.

[0011] This issue Ming further 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. do.

[0012] In order to cleanly wipe off dirt remaining on the treated surface, which is the resin material or painted surface of the body, which is an oleophilic surface, or the glass surface, which is a hydrophilic surface, the treated surface, such as the resin material, painted surface, or 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 excessively on the treated surface. If the treated surface is in a sufficiently water-repellent state, the water droplets will become finer and will be more likely to separate from the treated surface, and the water droplets of the cleaning solution containing the dirt will be more likely to be collected by the fibrous sheet. Even if the solution of trimethylsiloxysilicate is impregnated into a fibrous sheet, 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 have 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 a modified form thereof as a diluent for trimethylsiloxysilicate.

[0013] The amount of water-repellent component added is preferably 0.1 to 2.0 wt% as the effective component in the impregnation solution. If it is less than 0.1 wt%, the treated surface will not be sufficiently water-repellent, and dirt will reattach 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 easily causing halation on the glass surface. Therefore, an amount of addition less than 0.1 wt% or more than 2.0 wt% is not preferable. If the amount of water-repellent component added is 0.1 to 2.0 wt%, it will be easy to wipe it cleanly, the coating will be uniform, and it will be difficult to cause unevenness or halation on the glass surface.

[0014] This issue Ming further A cationic substance capable of fixing a water-repellent component to a hydrophilic surface is a cationic surfactant. do. In particular, it is desirable for the cationic substance capable of fixing the water-repellent component to a hydrophilic surface to be a quaternary ammonium salt.

[0015] A cationic surfactant, a quaternary ammonium salt surfactant, can be used as a cationic substance that can fix a water-repellent component to a hydrophilic surface. 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 a 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 component becomes familiar with the hydrophobic groups (lipophilic groups), forming a water-repellent coating. Trimethylsiloxysilicate in the water-repellent component does not have a reactive group that reacts with a hydrophilic surface such as a glass surface, 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 resin, which shows lipophilicity, easily becomes familiar and easily adheres uniformly, but silicone resin does not adhere uniformly to glass surfaces whose surfaces are covered with hydrophilic groups. In reality, treating a glass surface with only silicone resin does not allow the formation of a uniform water-repellent coating on the glass surface, and as the dirt-containing cleaning solution does not break down into small droplets, they cannot be collected on the fibrous sheet, resulting in an unsightly finish. Furthermore, even if water is poured onto the surface, it does not form neat droplets.

[0016] The amount of cationic substance added is preferably 0.01 to 1.5 wt% as the effective component in the impregnation solution, and a relatively large amount is required 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 cannot be obtained, and if it exceeds 1.5 wt%, the component is excessively fixed on the treated surface, the water-repellent coating becomes uneven and the water repellency decreases, which is not preferable. If the amount added is 0.01 to 1.5 wt%, it can act on the entire glass surface, so the effect of fixing the water-repellent component sufficiently can be obtained, the water-repellent coating becomes uniform, and the water repellency is less likely to decrease even after treatment.

[0017] As cationic materials capable of attaching water repellent moieties to hydrophilic surfaces, it is preferred to use quaternary ammonium salts, although alkylamine salt type materials can also be used.

[0018] In addition, instead of the quaternary ammonium salt, amino silicone, which is generally used as a water repellent for glass, can be used to obtain a similar effect to that of the present invention, but it has been confirmed that if the fibrous sheet is left at 50°C for about one month while it is impregnated with the amino silicone, the glass surface cannot be made water repellent, and the situation becomes the same as when only silicone resin is 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 make it into an emulsion, but 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 becomes the same as when only silicone resin is blended, so the use of amino silicone in such sheet-type products is not suitable.

[0019] The surfactant for the silicone resin emulsion may be a nonionic surfactant, anionic surfactant, cationic surfactant, or amphoteric surfactant, but a nonionic surfactant is particularly preferable. Nonionic surfactants have high emulsifying and dispersing power and also have cleaning properties, and since the charge is not neutralized with cationic surfactants, the effects of each other are not cancelled out.

[0020] This issue Ming further The impregnation liquid contains the silicone resin emulsion containing the modified silicone oil in addition to the silicone resin emulsion. nothing. Modified silicone oil has a hydroxyl group at one or both ends (preferably both ends). do.Adding modified silicone oil having hydroxyl groups at one or both ends improves the initial water repellency and durability of water repellency on the glass surface. Although this type of modified silicone oil does not have a strong reactivity with the glass surface, it is considered that the oil has hydroxyl groups and partially reacts with the hydroxyl groups 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 impregnation 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.

[0021] 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 fiber length (20 mm or less) is used for the hydrophilic fibers in the central layer, the hydrophilic fibers in the central layer tend to scatter and come out to the surface when high-pressure water is applied to entangle the fibers. In addition, if hydrophilic fibers are present on the surface, not only will the work of wiping become heavy, but the water-repellent coating will also tend to be uneven, which is undesirable. For this reason, it is desirable to use hydrophilic fibers with a fiber length of 25 mm or more, preferably 30 mm or more, in the central layer.

[0022] Furthermore, the microfibers in the outer layer are basically 0.2 to 0.5d (denier) thick, and are distinguished from normal fibers having a thickness of 1.0 to 6d (denier).

[0023] Generally, nonwoven fabrics composed mainly of microfibers, which have excellent scraping properties, are used to remove dirt. However, fibrous sheets using microfibers in the outer layer have the following drawbacks, although they have excellent dirt-removing properties.

[0024] 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.

[0025] Therefore, 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:normal fiber is preferably about 9:1 to 5:5. In addition, it is also possible to improve the slipperiness during wiping and improve the removability of stuck dirt by making a part of the nonwoven fabric mesh-like. For nonwoven fabrics having mesh parts, the ratio of microfiber: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 amount of impregnation liquid to be contained in the fibrous sheet is preferably 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, the amount of water required for removing dirt will be insufficient, and not only will the cleaning ability decrease, 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 will remain on the painted surface when wiping, causing unevenness and causing the painted surface or glass surface to turn white. In addition, the absorbency of the cloth will approach saturation, making it difficult to remove dirt.

[0026] 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 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 it is known to be 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 is improved, but the uniformity of the water-repellent coating is reduced, resulting in uneven shading, which is not preferable. The amount of addition is preferably 0.1 to 2.0 wt% as the effective component in the impregnation liquid. If it is less than 0.1 wt%, sufficient dilution effect cannot be obtained, and if it exceeds 2.0 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 excess oil. When the amount added is 0.1 to 2.0 wt %, a sufficient dilution effect is obtained, the water-repellent coating tends to become uniform, and a decrease in the durability of the water-repellent coating due to an excess of oil is unlikely to occur.

[0027] 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 caused by dirt. Examples of the wax component include various natural or synthetic waxes or wax-like substances. Specifically, examples of the wax component include fatty acids and their derivatives, plant-based natural waxes such as carnauba wax, candelilla wax, sugar wax, rice wax, wood 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 the scratches caused by washing the car are covered, making the scratches 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, if too much is added to the glass surface, it causes halation, so it is desirable to set the amount to be added small. The amount of the active ingredient in the impregnation liquid is preferably 0.01 to 0.5 wt%, and 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 ingredients 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 ingredients neatly. By adding a dispersion of a wax component, it is possible to improve the slipperiness during wiping work and reduce scratches caused by dirt adhering to the treated surface.The amount of additive is preferably 0.1 to 2.0 wt% as the effective component in the impregnation liquid, and if it is less than 0.1 wt%, the effect of slipperiness during work and prevention of scratches due to dirt cannot be fully exhibited, and if it exceeds 2.0 wt%, the effect of slipperiness during work and prevention of scratches due to dirt is sufficient, but it is not preferable because it tends 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.

[0028] In the present invention, other components that are not essential but can be added optionally include dyes, ultraviolet absorbing agents, preservatives, antibacterial agents, and the like. Effect of the Invention

[0029] As described above, the waterless wet sheet according to the present invention does not require the use of washing water, is suitable for use on both lipophilic surfaces such as resin materials and painted surfaces of automobiles and hydrophilic surfaces such as glass parts of automobiles, and can remove dirt and form a water-repellent coating that is excellent in durability immediately after and after treatment, whether used on lipophilic or hydrophilic surfaces. Note that the wet sheet according to the present invention can be used not only on resin materials, painted surfaces, and glass parts (windshields, side windows, etc.) of automobiles, but also on other lipophilic and hydrophilic surfaces, such as 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. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] Below, examples showing the embodiment of the present invention are compared with comparative examples. And reference examples will be explained together.

[0031] [Example , Comparative Example, Reference Example ]

[0032] The raw materials used are as follows: (1) Silicone resin emulsion A Trimethylsiloxysilicate was dissolved in dimethylpolysiloxane to create an emulsion (effective concentration of silicone component: 40 wt%, viscosity of dimethylpolysiloxane used: 350cs, mixing ratio of trimethylsiloxysilicate and 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 4cs, mixture ratio of trimethylsiloxysilicate and cyclopentasiloxane 50:50, nonionic surfactant used as emulsifier: 6.0%). (3) Silicone resin emulsion C Trimethylsiloxysilicate was dissolved in dimethylsilicone with a viscosity of 6cs to create an emulsion (effective concentration 30wt%, viscosity of dimethylsiloxane used was 6cs, mixture ratio of trimethylsiloxysilicate and dimethylpolysiloxane was 50:50, 3% nonionic surfactant was used as emulsifier). (4) Dimethyl silicone emulsion A An emulsion of dimethylpolysiloxane with a viscosity of 10cs (effective concentration of silicone component: 30wt%, 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 with a viscosity of 30cs (effective concentration of silicone component: 30wt%, nonionic surfactant: 3.0%) (7) Dimethyl silicone emulsion B modified with OH at both ends An emulsion of dimethylpolysiloxane modified with OH at both ends and with 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 An emulsion of modified polypropylene wax (effective concentration 35wt%, nonionic surfactant: 4%). (11) Wax emulsion B An emulsion of polyethylene wax (molecular weight approximately 500). (Effective concentration of wax: 30wt% Nonionic surfactant: 5wt%)

[0033] Reference example 1 Silicone resin emulsion A 3.00wt% Cationic surfactant A 1.00wt% Ion-exchanged water 96.00wt% 100.00wt% An impregnation solution 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 / m2) made of nylon / polypropylene microfiber (0.5 denier) cut to 30 x 30 cm. 2 The nonwoven fabric was uniformly impregnated with an impregnation solution equivalent to 2.0 times the weight of the nonwoven fabric to obtain a sample.

[0034] Reference example 2 Silicone resin emulsion B 2.00wt% Dimethyl silicone emulsion B 1.00wt% Cationic surfactant B 1.00wt% Ion-exchanged water 96.00wt% 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 weight: 70 g / m2) made of 80% polyethylene / polyester microfiber (0.5 denier) and 20% polyester (1.7 denier) cut to 30 x 30 cm. 2 ) was uniformly impregnated with the impregnation liquid in an amount equivalent to 2.4 times the weight of the nonwoven fabric to obtain a sample.

[0035] Example 3 Silicone resin emulsion C 2.50wt% Dimethyl silicone emulsion A 0.50wt% Both ends OH modified dimethyl silicone emulsion A 1.00wt% Cationic surfactant A 0.50wt% Ion-exchanged water 95.50wt% 100.00wt% The 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. The nonwoven fabric (total basis weight: 70 g / m) was cut to a size of 30 x 30 cm and was made of microfiber with a middle layer of rayon (2.0 denier) and an outer layer of polyethylene / polypropylene (0.3 denier). 2 The nonwoven fabric was uniformly impregnated with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric to obtain a sample.

[0036] Example 4 Silicone resin emulsion C 2.00wt% Silicone resin emulsion B 0.50wt% Both ends OH modified dimethyl silicone emulsion A 0.30wt% Dimethyl silicone emulsion A 1.00wt% Cationic surfactant A 0.70wt% Ion-exchanged water 95.50wt% 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. The nonwoven fabric (total basis weight: 70 g / m) was cut to a size of 30 x 30 cm and was made of microfiber with a middle layer of rayon (2.0 denier) and an outer layer of polyethylene / polypropylene (0.3 denier). 2 A sample was obtained by uniformly impregnating a nonwoven fabric (10 g for the center layer, 30 g for one side of the outer layer, mesh openings of 15%, mesh area of ​​10% of the total, arranged in polka dots) with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric.

[0037] Example 5 Silicone resin emulsion C 3.00wt% Dimethyl silicone emulsion B 1.00wt% Both ends OH modified dimethyl silicone emulsion B 0.50wt% Cationic surfactant A 0.50wt% Wax emulsion A 0.50wt% Ion-exchanged water 94.50wt% 100.00wt% The 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 were dissolved or dispersed in ion-exchanged water to prepare an impregnation liquid. A nonwoven fabric (total basis weight: 70 g / m) cut to 30 x 30 cm, with a middle layer of rayon (1.4 denier) and an outer layer of polyethylene / polyester (0.6 denier) microfibers. 2 A sample was obtained by uniformly impregnating a nonwoven fabric (10 g for the central layer, 30 g for one side of the outer layer, mesh openings of 15%, mesh area of ​​10% of the total, arranged in a wavy pattern) with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric.

[0038] Example 6 Silicone resin emulsion A 2.50wt% Silicone resin emulsion B 1.00wt% Dimethyl silicone emulsion A 0.20wt% Dimethyl silicone emulsion B 0.20wt% Cationic surfactant B 0.40wt% Both ends OH modified dimethyl silicone emulsion A 0.60wt% Ion-exchanged water 95.10wt% 100.00wt% The 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 both-end OH-modified dimethyl silicone emulsion A 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 weight: 70 g / m2) cut to 30 x 30 cm, with a rayon middle layer and a polyethylene / polyester microfiber outer layer. 2 A sample was obtained by uniformly impregnating a nonwoven fabric (10 g for the central layer, 30 g for one side of the outer layer, mesh openings of 15%, mesh area of ​​10% of the total, arranged in a wavy pattern) with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric.

[0039] Comparative Example 1 Dimethyl silicone emulsion A 4.00wt% Ion-exchanged water 96.00wt% 100.00wt% The impregnation solution was prepared by dispersing dimethyl silicone emulsion A in ion-exchanged water. A nonwoven fabric consisting of polyethylene / polypropylene microfibers cut to 30 x 30 cm (total basis weight: 70 g / m 2 The nonwoven fabric was uniformly impregnated with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric to obtain a sample.

[0040] Comparative Example 2 Silicone resin emulsion A 5.00wt% Ion-exchanged water 95.00wt% 100.00wt% The silicone resin emulsion A was dispersed in ion-exchanged water to prepare an impregnation liquid. A nonwoven fabric consisting of polyethylene / polyester microfiber cut to 30 x 30 cm (total basis weight: 70 g / m 2 The nonwoven fabric was uniformly impregnated with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric to obtain a sample.

[0041] Comparative Example 3 Silicone resin emulsion A 2.00wt% Wax emulsion B 1.00wt% Dimethyl silicone emulsion B 1.00wt% Ion-exchanged water 96.00wt% 100.00wt% Silicone resin emulsion A, wax emulsion B, and dimethyl silicone emulsion B were dispersed in ion-exchanged water to prepare the impregnation liquid. A nonwoven fabric (weight: 70 g / m2) made of a polyester and rayon blend (70:30 blend ratio, nonwoven fabric fiber diameter: 2.0 denier) cut into 30 x 30 cm pieces 2 The nonwoven fabric was uniformly impregnated with an impregnation liquid equivalent to 2.5 times the weight of the nonwoven fabric to obtain a sample.

[0042] Comparative Example 4 Cationic surfactant A 0.50wt% Dimethyl silicone emulsion B 4.00wt% Ion-exchanged water 95.50wt% 100.00wt% An impregnation solution was prepared by dispersing cationic surfactant A and dimethyl silicone emulsion B in ion-exchanged water. A nonwoven fabric consisting of nylon / polyethylene microfiber cut to 30 x 30 cm (total basis weight: 70 g / m 2The nonwoven fabric (mesh openings are 15%, mesh area is 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.

[0043] Comparative Example 5 Cationic surfactant A 1.00wt% Both ends OH modified dimethyl silicone emulsion A 0.50wt% Dimethyl silicone emulsion B 3.00wt% Ion-exchanged water 95.50wt% 100.00wt% The impregnation solution 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 microfiber cut to 30 x 30 cm (total basis weight: 70 g / m 2 The nonwoven fabric (mesh openings are 15%, mesh area is 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.

[0044] Test Method Using the treated cloth (fibrous sheet) that was created, 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.

[0045] 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 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 down. Next, the windshield was coated with a glass abrasive to remove dirt and the 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 down. At this time, one plot was left untreated as a blank test.

[0046] 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 has been thoroughly removed and a uniform shine has been 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)

[0047] B. Ability to remove dirt from glass 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 is thoroughly removed, there is no residue left behind, and the finish is uniform) ○ 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)

[0048] C. Water-repellent state immediately after treatment (painted surface) Water is poured onto the test surface and the state of water droplets is visually judged. ◎ Water often forms droplets and bounces off ○ There is some water repellency, but the polka dots are deformed. △ Slightly dull repelling × Almost no repelling

[0049] 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. ◎ Water often forms droplets and bounces off ○ There is some water repellency, but the polka dots are deformed. △ Slightly dull repelling × Almost no repelling

[0050] E. Water repellency durability After leaving the vehicle parked outdoors for one month, the vehicle is washed with water and then water is sprayed on the test surface and the state of water droplets is visually judged. ◎ Water often forms droplets and bounces off ○ There is some water repellency, but the polka dots are deformed. △ Slightly dull repelling × Almost no repelling [Table 1]

[0051] The test results in Table 1 show the following: removability of dirt from painted surfaces, removability of dirt from glass surfaces, water repellency immediately after treatment (painted surfaces), water repellency immediately after treatment (glass surfaces), and durability of water repellency (painted surfaces). Reference Examples 1 and 2 and Working Example 3 In Comparative Examples 1 to 6, the evaluation of ◯ or ◯ was given, whereas in Comparative Examples 1 to 5, the evaluation of ◯ was few and the evaluation of △ or × was mostly given. Reference Examples 1, 2 and Working Example 3 In ~6, Reference examples 1 and 2 Although it has a △ rating, Examples 3 to 6was rated as ⊚. In contrast, all of Comparative Examples 1 to 5 were rated as x. From the above, it is clear that the waterless wet sheet according to the present invention exhibits excellent effects in terms of removability of dirt from a painted surface, removability of dirt from a glass surface, water-repellent state immediately after treatment (painted surface), water-repellent state immediately after treatment (glass surface), water-repellent durability (painted surface), and water-repellent durability (glass surface), and is superior to Comparative Examples 1 to 5.

Claims

1. 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 impregnating 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 impregnation 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. A waterless cleaning wet sheet as described in claim 1, wherein the cationic substance capable of fixing a water-repellent component to a hydrophilic surface is a quaternary ammonium salt.

3. A waterless cleaning wet sheet as described in claim 1 or claim 2, in which an emulsion of dimethyl silicone oil is added to the impregnating liquid.

4. A waterless cleaning wet sheet described in any one of claims 1 to 3, wherein the surfactant of the silicone resin emulsion is a nonionic surfactant.

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