Water-repellent dry sheet

Abstract

To provide a water-repellency-imparting dry sheet that can be used for both processed faces of a lipophilic face (e.g. a resin material or a coating surface) of an automobile and a hydrophilic face (e.g. a windshield) of an automobile, capable of forming a water-repellent coat being applied and spread over the processed faces by utilizing water droplets left thereon after washing.SOLUTION: A water-repellency-imparting dry sheet includes active ingredients comprising a silicone resin, a cationic substance, and a surfactant that are held in a fibrous sheet. The surfactant has an HLB value of 3-16.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a water-repellent dry sheet. More specifically, it relates to a water-repellent dry sheet intended to wipe away water droplets remaining on a treated surface after washing and to form a water-repellent coating on the treated surface using those water droplets. [Background technology]

[0002] As a prior example, a water-repellent cloth has been proposed that can impart water repellency to the surface of an automobile's paint film simply by wiping it (see Patent Document 1). The water-repellent cloth proposed in Patent Document 1 has a trimethylsiloxysilicate organopolysiloxane solution as its main component, and further impregnates the cloth with a non-volatile component from a treatment agent that contains a trimethylsiloxysilicate derivative having free hydroxyl groups dissolved in an organic solvent or dispersed in water. Patent Document 1 also states that when this water-repellent cloth is used, water repellency is imparted to the surface of an automobile's paint film simply by wiping it, and that the effect is further enhanced if the water-repellent cloth is wet with water, and that the adhesion of the water-repellent coating is improved by the action of trimethylsiloxysilicate and organopolysiloxane. Since this product impregnates the cloth with the non-volatile component from the above-mentioned treatment agent together with an organic solvent or water, the water-repellent cloth is kept in a dry state before use.

[0003] In contrast, there are known wet cloths that can remove dirt simply by wiping the body and also provide water repellency (see Patent Documents 2 and 3). The wet cloths proposed in Patent Documents 2 or 3 are made by dissolving trimethylsiloxysilicate in a non-volatile oil component such as dimethylpolysiloxane, which is a water-repellent component, emulsifying and dispersing this with a surfactant, and impregnating a cloth made of fibrous fabric with it. Because the non-volatile oil component in which trimethylsiloxysilicate is dissolved is contained in the fibrous fabric, the wet cloth is kept in a moist state before use. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 3387852 (0013, 0033, claim 6) [Patent Document 2] Patent No. 3482517 [Patent Document 3] Patent No. 4583364 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, Patent Document 1, mentioned above, only describes the use of a water-repellent cloth on the paint surface of an automobile, which is highly lipophilic, and does not mention its use on a glass surface that is highly hydrophilic, such as an automobile's windshield. Similarly, the wet cloths proposed in Patent Documents 2 and 3 are only described in relation to their use on the paint surface of an automobile, which is highly lipophilic.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a water-repellent dry sheet that can be used on both lipophilic surfaces such as resin materials and coating surfaces of automobiles, and hydrophilic surfaces such as automobile windshields, and in particular, can be used to spread and form a water-repellent film on the treated surface by utilizing water droplets remaining on the treated surface after washing, such as during water washing. Furthermore, the present invention aims to provide a water-repellent dry sheet that is lighter and easier to store than a wet sheet in a wet state. [Means for solving the problem]

[0007] The water-repellent dry sheet according to the present invention is intended for use on both lipophilic and hydrophilic treated surfaces, and is a water-repellent dry sheet for wiping away water droplets remaining on the treated surface after washing to form a water-repellent film on the treated surface, comprising a silicone resin and a cationic substanceNonionic The active ingredient, which includes a surfactant, is held in a fibrous sheet, and the silicone resin is made by dissolving trimethylsiloxysilicate in an oily substance of dimethylpolysiloxane or a modified thereof, or cyclopentasiloxane, and the cationic substance is a cationic surfactant.

[0008] In this invention, silicone resin is a water-repellent component used to impart water repellency to the treated surface. This silicone resin not only imparts water repellency to the treated surface, but also exhibits the effect of subdividing water droplets remaining on the surface after washing, thereby improving the wiping performance by the fibrous sheet. In particular, hydrophilic surfaces such as glass surfaces are highly hydrophilic, and it is known that if the treated surface does not have sufficient water repellency, it is not possible to wipe away water droplets cleanly or achieve a clean finish. Therefore, if silicone resin is included as a water-repellent component, even on such hydrophilic surfaces, the action of the silicone resin subdivides water droplets, improving the wiping performance by the fibrous sheet.

[0009] In this invention, the cationic substance is a component that fixes the silicone resin to a hydrophilic surface. In an aqueous solution, the hydrophilic portion of the cationic substance has a positive charge, and the lipophilic portion has a negative charge. The hydrophilic portion of the cationic substance readily adheres to and fixes to hydrophilic surfaces such as glass surfaces, and the lipophilic portion of the cationic substance fixed to the hydrophilic surface is exposed to the surface, causing the hydrophilic surface, such as a glass surface, to appear to be transformed into a lipophilic surface. When the hydrophilic surface is transformed into a lipophilic surface by the action of the cationic substance, the lipophilic silicone resin readily adheres to and fixes to the lipophilic portion of the cationic substance, and the silicone resin, acting as a lipophilic water-repellent component, is fixed to the hydrophilic surface, such as a glass surface, via the cationic substance.

[0010] In other words, treated surfaces such as the resin material surfaces and paint film surfaces of automobiles have lipophilic (hydrophobic) groups on the surface, so lipophilic silicone resin adheres easily and adheres uniformly. However, treated surfaces that do not have lipophilic (hydrophobic) groups, such as glass surfaces, do not adhere easily to lipophilic silicone resin and cannot adhere uniformly. Furthermore, since silicone resin does not have reactive groups for glass surfaces, simply applying silicone resin to a glass surface will not allow the silicone resin to adhere uniformly to the glass surface. As a result, even if a glass surface is treated with silicone resin alone, a uniform water-repellent film is not formed, so water droplets are not subdivided, and even wiping with a fibrous sheet does not result in a clean finish. Also, even if water is poured onto a glass surface treated with silicone resin alone, it will not form clean water droplets. In contrast, as described above, if a hydrophilic surface such as a glass surface is modified into a lipophilic surface by the action of a cationic substance, the silicone resin adheres uniformly to that hydrophilic surface as a lipophilic water-repellent component made of silicone resin via the cationic substance.

[0011] In this invention, Nonionic Surfactants are components that not only help to uniformly spread silicone resin on the treated surface, but also help to emulsify the silicone resin.

[0012] In this invention, the fibrous sheet can be a nonwoven fabric with a three-layer structure, in which hydrophilic fibers are arranged in the center and hydrophobic fibers such as PET or PE are arranged in the outer layer. In particular, an airlaid nonwoven fabric, which has excellent moisture absorption and cushioning properties, can be suitably used. This type of fibrous sheet has the advantage of allowing for smooth work due to its good slipperiness on glass surfaces. It is also possible to use microfiber in the outer layer, which improves the ability to wipe away water droplets and remove dirt. In addition, while nonwoven fabrics other than the three-layer structure described above can be used for the fibrous sheet, if the proportion of hydrophilic fibers such as rayon or pulp in the surface layer is high, water droplets tend to remain, and the slipperiness is particularly poor on glass surfaces, causing the sheet to snag and making work difficult. For this reason, if a nonwoven fabric other than the three-layer structure described above is not used, it is desirable to use a ratio of hydrophilic fibers to hydrophobic fibers of 50:50 to 0:100.

[0013] In this invention, the above-mentioned silicone resin and a cationic substance Nonionic As a method for retaining the active ingredient, which consists of a surfactant, on a fibrous sheet, one can use an organic solvent capable of dissolving silicone resin, such as a petroleum-based solvent, or water, such as ion-exchanged water, as a solvent. The active ingredient is dissolved or dispersed in this type of solvent and impregnated into the fibrous sheet. When the fibrous sheet is impregnated with the active ingredient and solvent using this method, it remains in a wet state, so it is necessary to perform a drying treatment afterward to make it dry.

[0014] The drying process for fibrous sheets includes not only the removal of volatile solvent components, but also the removal of water, which is a volatile dispersion medium contained in the emulsified silicone resin. Non-volatile components of the solvent are not removed by this drying process. In other words, volatile components are those that volatilize at temperatures near room temperature and are removed by this drying process, while non-volatile components are those that do not volatilize at temperatures near room temperature and are not removed by this drying process. For example, when using silicone resin emulsion A, which will be described later as an example, silicone resin emulsion A is an emulsion of trimethylsiloxysilicate dissolved in dimethylpolysiloxane, so it contains water. In this case, the water is more of a dispersion medium in emulsification than a solvent, and is a volatile component. Also, if dimethylpolysiloxane is considered as a solvent, even though it is a solvent, dimethylpolysiloxane has extremely low volatility, so it does not volatilize at temperatures near room temperature, and is a non-volatile component that is not removed by the drying process because it does not volatilize. In this invention, the dried fibrous sheet is in a dry state. Therefore, as the fibrous sheet wipes the treated surface, such as a glass surface (hydrophilic surface) or a painted surface (lipophilic surface) where water droplets used for cleaning remain, the sheet absorbs the water droplets remaining on the treated surface. In some cases, the entire fibrous sheet is wet with water and lightly wrung out before use to absorb moisture, which allows the silicone resin in the active ingredient to... Nonionic The surfactant makes it easier for the material to adhere to the treated surface. Silicone resins and cationic substances, Nonionic The active ingredients, such as surfactants, are non-volatile components and remain impregnated into the fibrous sheet as active ingredients even after the fibrous sheet has been dried.

[0015] In this invention, the silicone resin is prepared by dissolving trimethylsiloxysilicate in an oily substance of dimethylpolysiloxane or a modified thereof, or cyclopentasiloxane. In order to cleanly wipe away water droplets remaining on the lipophilic surfaces of automobile resin materials and coatings, or on hydrophilic surfaces such as automobile windshields and other glass surfaces, it is necessary to ensure that the treated surfaces, such as the resin material surfaces, coatings, and glass surfaces, are sufficiently water-repellent. If the treated surface is not sufficiently water-repellent, the water droplets remaining on the surface after washing will be large droplets, causing residue to be left behind. If the treated surface is sufficiently water-repellent, the water droplets will be subdivided and easily absorbed by the fibrous sheet, making it less likely for moisture to remain on the treated surface. Therefore, the silicone resin prepared by dissolving trimethylsiloxysilicate in dimethylpolysiloxane or a modified thereof is a necessary component for wiping the treated surface, imparting sufficient water repellency to the treated surface, and forming a clean, glossy, or water-repellent surface. Since trimethylsiloxysilicate itself is in solid (powder) form, it cannot be uniformly spread on a treatment surface such as a hydrophilic or lipophilic surface as is. Therefore, in this invention, an oily substance such as dimethylpolysiloxane or a modified version thereof is used as the solvent for trimethylsiloxysilicate. In addition to the above-mentioned dimethylpolysiloxane or a modified version thereof, cyclopentasiloxane can also be used as the solvent for trimethylsiloxysilicate, and by doing so, a uniform film of silicone resin as a uniform water-repellent component can be formed on the treatment surface.

[0016] In the present invention, it is desirable that the addition amount of the silicone resin is 0.5 to 20.0 wt% as an active ingredient based on the weight of the fibrous sheet. If the addition amount is less than 0.5 wt%, the treated surface cannot be finished to have a sufficient water-repellent surface, and the water droplets adhering to the treated surface are difficult to be subdivided, making it difficult to wipe them clean. If the addition amount exceeds 20 wt%, the silicone resin as a water-repellent component will be excessively fixed on the treated surface, resulting in a non-uniform or uneven water-repellent film, and particularly causing halation on the glass surface, which is not preferable. When the addition amount is 0.5 to 20.0 wt%, the above-mentioned inconveniences are less likely to occur, and the treated surface can be easily and neatly finished.

[0017] In the present invention, the cationic substance is a cationic surfactant, and particularly, it is desirable that the cationic substance is a quaternary ammonium salt. A cationic surfactant is a compound having a hydrophobic group (lipophilic group) and a hydrophilic group. Since the hydrophilic group has a positive charge in an aqueous solution, on a negatively charged treated surface such as a glass surface, the positively charged hydrophilic group of the cationic surfactant is attracted to the glass surface, and the hydrophobic group (lipophilic group) is arranged outward. It is considered that a water-repellent film is formed by the silicone resin as a water-repellent component being compatible with the hydrophobic group (lipophilic group). The role of this type of cationic substance is to improve the water-repellent state immediately after treatment by strengthening the fixing property of the silicone resin on a negatively charged treated surface such as a glass surface, and also to improve the water-repellent durability after treatment. Further, when the cationic substance is a quaternary ammonium salt, the hydrophilic group part is always positively charged, and this state is stable regardless of the pH of the solution. Examples of the quaternary ammonium salt include diallyldimethylammonium chloride (or bromide, iodide) and alkylbenzalkonium chloride.

[0018] Regarding this point, even if amino silicone, which is generally widely used as a glass water repellent, is used instead of the quaternary ammonium salt, an effect similar to the effect exhibited by the present invention can be obtained. However, if this is left for a certain period of time while impregnated in the fibrous sheet, the affinity between the amino silicone and the fiber progresses, making it impossible to make the negatively charged treated surface such as the glass surface water repellent, and it has been confirmed that the same situation as that of a composition containing only silicone resin occurs. This is presumably because the amino silicone contained in the fibrous sheet becomes unstable in state due to temperature or time-dependent factors and is adsorbed onto the more lipophilic fibrous sheet, resulting in the same situation as that of a composition containing only silicone resin. Therefore, it can be said that the use of amino silicone is not suitable for sheet-type products.

[0019] By the way, as the surfactant as a component for uniformly spreading the silicone resin on the treated surface, a nonionic, cationic or anionic surfactant can be used. The nonionic world surfactant helps to emulsify the silicone resin as a water repellent component. The cationic surfactant may also be able to emulsify the silicone resin as a water repellent component. Also, if the amount of the anionic surfactant is small, it can be used in combination with nonionic or cationic surfactants.

[0020] In addition, in the present invention, it is also possible to adopt a configuration in which the surfactant includes a surfactant added to emulsify the silicone resin as a water repellent component and a surfactant additionally replenished as a component for uniformly spreading the silicone resin as a water repellent component on the treated surface.

[0021] The water-repellent dry sheet according to the present invention is in a dry state in which the active ingredient is held within a fibrous sheet. Therefore, the silicone resin does not exist as an emulsion within the fibrous sheet. On the other hand, in order to adhere the silicone resin contained in the fibrous sheet to the treatment surface, it is required that the water droplets wiped up by the fibrous sheet be quickly dispersed into the active ingredient and spread uniformly on the treatment surface. Considering this, it is desirable that the surfactant in this invention be configured to include a surfactant added to emulsify the silicone resin and a surfactant added as a component to uniformly spread the silicone resin on the treatment surface. In other words, the amount of surfactant added to emulsify the silicone resin alone is insufficient to uniformly spread the silicone resin on the treatment surface, so it is desirable to ensure that there is enough surfactant to spread the silicone resin uniformly on the treatment surface by adding a sufficient amount of surfactant to the treatment solution. Furthermore, adding surfactant to the treatment solution has the advantage of improving the initial water absorption even when using a fibrous sheet with poor initial water absorption from a dry state, such as a highly hydrophobic fibrous sheet.

[0022] In this invention, it is desirable that the amount of cationic substance added is 0.1 to 2.0 wt% as an effective component relative to the weight of the fibrous sheet. An appropriate amount of cationic substance (for example, a cationic surfactant such as a quaternary ammonium salt) added is 0.1 to 2.0 wt% relative to the weight of the fibrous sheet. If the amount added is less than 0.1 wt%, it becomes difficult to obtain the effect of sufficiently fixing the silicone resin to the glass surface, and if it exceeds 2.0 wt%, the silicone resin will be excessively fixed to the glass surface, resulting in an uneven or streaky water-repellent coating, which is undesirable as it is particularly prone to causing halation on the glass surface. When the amount added is 0.1 to 2.0 wt%, the above-mentioned problems are less likely to occur, and the treated surface can be easily and cleanly finished.

[0023] In this invention, it is desirable that modified silicone oil be added. The modified silicone is preferably one having hydroxyl groups (OH groups) at one or both ends. Adding this type of modified silicone oil improves the initial water repellency after wiping a hydrophilic treated surface, such as a glass surface, and the subsequent water repellency durability. This is thought to be because, although the reactivity with the hydrophilic treated surface is not very strong, the presence of hydroxyl groups in the modified silicone causes a partial reaction with the hydroxyl groups on the hydrophilic treated surface. The desirable amount of modified silicone oil to add is 0.1 to 10.0 wt% relative to the weight of the fibrous sheet. If the amount is less than 0.1 wt%, it is difficult to obtain sufficient water repellency, and if it exceeds 10.0 wt%, the silicone resin as a water-repellent component will be excessively fixed to the treated surface, resulting in an uneven or streaky water-repellent coating, and potentially reducing the durability of the water-repellent coating due to excess oil. Adding an amount of 0.1 to 10.0 wt% makes the above-mentioned problems less likely to occur.

[0024] In this invention, Nonionic It is desirable for the surfactant to have an HLB value of 3 to 16. The HLB value represents the degree of affinity of a surfactant to water and oil (organic compounds insoluble in water), in other words, the degree of balance between hydrophilicity and lipophilicity. The HLB value ranges from 0 to 20, with values ​​closer to 0 indicating higher lipophilicity and values ​​closer to 20 indicating higher hydrophilicity. The properties and applications of a surfactant are determined to some extent by its HLB value. If the HLB value is less than 3, only a portion dissolves in water, and it is almost insoluble. This makes it difficult to wipe and spread the silicone resin cleanly. If the HLB value is greater than 16, the surfactant disperses too much in the water remaining after washing, making it more likely to remain on the treated surface such as resin materials, paint film surfaces, and glass surfaces, reducing the water repellency of the treated surface. If the HLB value is between 3 and 16, the silicone resin can be wiped and spread cleanly without difficulty, and the silicone resin is less likely to remain on the treated surface, thus reducing the reduction in water repellency of the treated surface. An even more preferable range for the HLB value is around 8 to 14.

[0025] In this invention, it is desirable that the amount of surfactant added is 0.01 to 5.0 wt% as an effective component relative to the weight of the fibrous sheet. This range is particularly beneficial when a nonionic surfactant is used as the surfactant in the treatment solution. If the amount added is less than 0.01 wt%, it becomes difficult to spread the silicone resin uniformly on the treated surface, and the initial water absorption when using hydrophobic fibers does not improve. If the amount added exceeds 5.0 wt%, the silicone resin will adhere excessively to the treated surface, resulting in an uneven or streaky water-repellent coating, which may lead to a decrease in the water resistance and durability of the water-repellent coating. When the amount added is between 0.01 and 5.0 wt%, the above-mentioned problems are less likely to occur.

[0026] In the water-repellent dry sheet according to the present invention, wax emulsions and dispersions can be added as optional additives. Wax emulsions and dispersions help to improve the durability of the water-repellent coating. Examples of wax components include various natural and synthetic waxy substances. Specifically, these include plant-based natural waxes such as fatty acids and their derivatives, carnauba wax, candelilla wax, sugar wax, rice wax, wood wax, and hydrogenated castor oil, as well as animal-based natural waxes such as beeswax, whale wax, lanolin, and its derivatives. There are also petroleum-based natural waxes such as microcrystalline wax and paraffin wax, mineral-based natural waxes such as montane wax, ozokerite wax, and ceresin, and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, and their derivatives. By combining emulsions or dispersions of these wax components with a silicone resin, which is made by dissolving trimethylsiloxysilicate in an oily substance such as dimethylpolysiloxane or a modified version thereof, and emulsifying it with a surfactant, the coating becomes thicker, making scratches less noticeable by covering them over car wash scratches. Naturally, the initial gloss and the durability of the gloss are also improved. In particular, the durability of gloss and water repellency during washing is significantly improved. However, on treated surfaces such as glass, adding too much can cause halation, so it is preferable to set the amount to be added in small amounts. The appropriate amount to add is 0.01 to 2.0 wt% relative to the weight of the fibrous sheet (cloth). If it is less than 0.01 wt%, sufficient gloss and water repellency will not be achieved, and if it exceeds 2.0 wt%, sufficient gloss and water repellency will be achieved, but the components will adhere excessively to the paint film surface or glass surface, causing unevenness in color and glare, and the excessive solid content will make it difficult to spread the components evenly.

[0027] In the water-repellent dry sheet according to the present invention, other optional components that can be added include dyes, ultraviolet absorbers, preservatives, antibacterial agents (antiviral agents), thickeners, abrasives, and other functional microparticles. [Effects of the Invention]

[0028] As described above, the water-repellent dry sheet according to the present invention focuses on the fact that the silicone resin exhibits lipophilicity, the cationic substance capable of modifying a hydrophilic surface into a lipophilic surface has both a hydrophilic and a lipophilic portion, and that water droplets remaining on the treated surface after washing are absorbed by the fibrous sheet and act as a solvent for spreading the active ingredient onto the treated surface. Therefore, it is suitable for use on both lipophilic surfaces such as the resin material surfaces and paint film surfaces of automobiles, and hydrophilic surfaces such as the windshield of an automobile. Regardless of whether it is used on a lipophilic or hydrophilic surface, it is possible to wipe away water droplets remaining on the treated surface after washing and to form a water-repellent coating with excellent durability immediately after and after treatment. Furthermore, the water-repellent dry sheet according to the present invention can be used not only on the resin material surfaces, paint film surfaces and windshields of automobiles, but also on other lipophilic and hydrophilic surfaces. In addition to water repellency, it can also provide gloss, so it can be used not only on automobiles but also as a polishing sheet for furniture and interior products. However, when imparting water repellency to surfaces such as furniture and interior products where no water droplets are present, it is necessary to wet the fibrous sheet beforehand. In addition, the water-repellent dry sheet according to the present invention has the advantage of being lighter and easier to store compared to a wet sheet in a damp state. [Modes for carrying out the invention]

[0029] The following describes embodiments of the present invention, along with comparative examples. [Examples]

[0030] The raw materials used in the examples and comparative examples are listed below. (1) Silicone resin emulsion A This product is an emulsion of trimethylsiloxysilicate dissolved in dimethylpolysiloxane (effective concentration of silicone component: 40 wt%, viscosity of dimethylpolysiloxane used: 350 cs, mixing ratio of trimethylsiloxysilicate to dimethylpolysiloxane: 30:70, nonionic surfactant + anionic surfactant: 6.0% used as emulsifier). (2) Silicone resin emulsion B This product is an emulsion of trimethylsiloxysilicate dissolved in cyclopentasiloxane (effective concentration of silicone component: 30 wt%, viscosity of cyclopentasiloxane used: 4 cs, mixing ratio of trimethylsiloxysilicate to cyclopentasiloxane: 50:50, nonionic surfactant: 6.0% used as emulsifier). (3) Silicone resin emulsion C Emulsified trimethylsiloxysilicate dissolved in dimethyl silicone (effective concentration of silicone component: 30 wt%, viscosity of dimethylsiloxane used: 6 cs, mixing ratio of trimethylsiloxysilicate to dimethyl silicone: 50:50, nonionic surfactant as emulsifier: 3%) (4) Silicone resin D Trimethylsiloxysilicate dissolved in dimethyl silicone (dimethylsiloxane viscosity used: 6cs, trimethylsiloxysilicate to dimethyl silicone mixture ratio: 50:50, no emulsifier added) (5) Dimethyl silicone emulsion A Dimethylpolysiloxane emulsion (dimethylpolysiloxane viscosity 10 cs, effective concentration of silicone component 30 wt%, nonionic surfactant as emulsifier: 5.0%) (6) Dimethyl silicone emulsion B Dimethylpolysiloxane emulsion (dimethylpolysiloxane viscosity 500 cs, effective concentration of silicone component 30 wt%, nonionic surfactant as emulsifier: 3.0%) (7) End-terminated OH-modified dimethyl silicone emulsion A Emulsified dimethylpolysiloxane with OH-modified ends (viscosity of OH-modified dimethylpolysiloxane: 30 cs, effective concentration of silicone component: 30 wt%, nonionic surfactant as emulsifier: 3.0%) (8) End-ended OH-modified dimethyl silicone emulsion B Emulsified dimethylpolysiloxane with OH-modified ends (viscosity of dimethylpolysiloxane with OH-modified ends: 700 cs, effective concentration of silicone component: 30 wt%, nonionic surfactant as emulsifier: 3.0%) (9) End-terminated OH-modified dimethyl silicone C Dimethylpolysiloxane with OH-modified ends (viscosity of dimethylpolysiloxane with OH-modified ends: 700 cs, no emulsifier added) (10) Cationic surfactant A Active ingredient: 30% Cationic surfactant represented by the chemical composition cetyltrimethylammonium chloride (11) Cationic surfactant B Active ingredient: 50% cationic surfactant, chemically represented as alkylbenzyldimethylammonium chloride. (12) Nonionic surfactant A 100% active ingredient, a nonionic surfactant represented by sorbitan monolaurate as its chemical composition, HLB 8.6 (13) Nonionic surfactant B The active ingredient is 100% dimethylpolysiloxane, a nonionic surfactant which is a silicone-based surfactant in which the side chain is modified with polyether, HLB14. (14) Wax Emulsion B Emulsified polyethylene wax (molecular weight approximately 500) (effective concentration of wax: 30 wt%, nonionic surfactant: 5 wt%)

[0031] Example 1 Silicone resin emulsion A 5.00 wt% Cationic surfactant A 1.00 wt% Nonionic surfactant A 0.50 wt% Ion-exchanged water 93.50 wt% 100.00 wt% A treatment solution was prepared by dissolving or dispersing silicone resin emulsion A, cationic surfactant A, and nonionic surfactant A in deionized water. Nonwoven fabric made of rayon + polyester (blend ratio 40:60) cut into 30 x 30 cm pieces (overall basis weight: 80 g / m²) 2 The nonwoven fabric was uniformly impregnated with a treatment solution equivalent to 2.0 times its weight, and then dried in a constant temperature bath set at 60°C for 5 hours to remove volatile components and obtain a sample.

[0032] Example 2 Silicone resin emulsion B 5.00 wt% Dimethyl silicone emulsion B 1.00 wt% Cationic surfactant B 1.00 wt% Nonionic surfactant A 0.50 wt% Ion-exchanged water 92.50 wt% 100.00 wt% A treatment solution was prepared by dissolving or dispersing silicone resin emulsion B, dimethyl silicone emulsion B, cationic surfactant B, and nonionic surfactant A in deionized water. A nonwoven fabric made of 80% polyethylene / polyester microfiber (0.5 denier) and 20% polyester (1.7 denier), cut into 30 x 30 cm pieces (total basis weight: 80 g / m²). 2 The nonwoven fabric was uniformly impregnated with a treatment solution equivalent to 3.0 times its weight, and then dried in a constant temperature bath set at 60°C for 5 hours to remove volatile components and obtain a sample.

[0033] Example 3 Silicone resin emulsion C 4.00 wt% Dimethyl silicone emulsion A 1.00 wt% End-ended OH-modified dimethyl silicone emulsion A 3.00 wt% Cationic surfactant A 1.50 wt% Nonionic surfactant B 0.30 wt% Ion-exchanged water 90.20 wt% 100.00 wt% A treatment solution was prepared by dissolving or dispersing silicone resin emulsion C, dimethyl silicone emulsion A, OH-modified dimethyl silicone emulsion A, cationic surfactant A, and nonionic surfactant B in deionized water. A nonwoven fabric cut to 30 x 30 cm, consisting of a pulp middle layer and a polyethylene / polypropylene (1.2 denier) outer layer (overall basis weight: 80 g / m²). 2 The nonwoven fabric was uniformly impregnated with a treatment solution equivalent to 2.5 times its weight, and then dried in a constant temperature bath set at 60°C for 5 hours to remove volatile components and obtain a sample.

[0034] Example 4 Silicone resin emulsion C 4.00 wt% Silicone resin emulsion B 1.50 wt% End-ended OH-modified dimethyl silicone emulsion A 2.00 wt% Dimethyl silicone emulsion A 1.00 wt% Cationic surfactant A 1.50 wt% Nonionic surfactant B 0.50 wt% Ion-exchanged water 89.50 wt% 100.00 wt% A treatment solution was prepared by dissolving or dispersing silicone resin emulsion C, silicone resin emulsion B, terminally OH-modified dimethyl silicone emulsion A, dimethyl silicone emulsion A, and nonionic surfactant B in deionized water. A nonwoven fabric cut to 30 x 30 cm, with a middle layer made of pulp and an outer layer of polyethylene / polypropylene microfiber (0.5 denier) (total basis weight: 80 g / m²). 2 The nonwoven fabric was uniformly impregnated with a treatment solution equivalent to 3.0 times its weight, and then dried in a constant temperature bath set at 60°C for 5 hours to remove volatile components and obtain a sample.

[0035] Example 5 Silicone resin emulsion C 6.00 wt% Dimethyl silicone emulsion B 1.00 wt% End-ended OH-modified dimethyl silicone emulsion B 2.50 wt% Cationic surfactant A 1.50 wt% Wax Emulsion A 0.50 wt% Nonionic surfactant A 0.70 wt% Ion-exchanged water 87.80 wt% 100.00 wt% A treatment solution was prepared by dissolving or dispersing silicone resin emulsion C, dimethyl silicone emulsion B, OH-modified dimethyl silicone emulsion B, cationic surfactant A, wax emulsion A, and nonionic surfactant A in deionized water. A nonwoven fabric cut to 30 x 30 cm, consisting of a pulp middle layer and a polyethylene / polypropylene (1.2 denier) outer layer (overall basis weight: 80 g / m²). 2 The nonwoven fabric was uniformly impregnated with a treatment solution equivalent to 3.0 times its weight, and then dried in a constant temperature bath set at 60°C for 5 hours to remove volatile components and obtain a sample.

[0036] Example 6 Silicone resin emulsion A 2.50 wt% Silicone resin emulsion B 2.00 wt% Dimethyl silicone emulsion A 0.50 wt% Dimethyl silicone emulsion B 0.50 wt% Cationic surfactant B 1.50 wt% Nonionic surfactant B 1.00 wt% End-ended OH-modified dimethyl silicone emulsion A 3.50 wt% Ion-exchanged water 88.50 wt% 100.00 wt% A treatment solution was prepared by dissolving or dispersing silicone resin emulsion A, silicone resin emulsion B, dimethyl silicone emulsion A, dimethyl silicone emulsion B, cationic surfactant A, nonionic surfactant B, and terminally OH-modified dimethyl silicone emulsion A in deionized water. A nonwoven fabric cut to 30 x 30 cm, with a middle layer made of rayon and an outer layer of polyethylene / polyester microfiber (overall basis weight: 70 g / m²). 2 A treatment solution equivalent to 3.0 times the weight of the nonwoven fabric was uniformly impregnated into the central layer (10g) and one side of the outer layer (30g), and then dried in a constant temperature bath set at 60°C for 5 hours to remove volatile components and obtain the sample.

[0037] Example 7 Silicone resin D 6.00 wt% End-ended OH-modified dimethyl silicone C 3.00 wt% Cationic surfactant A 1.50 wt% Nonionic surfactant A 1.50 wt% Mineral spirits 30.00 wt% Ion-exchanged water 58.00 wt% 100.00 wt% After dissolving silicone resin D, hydroxyl-modified dimethyl silicone C, and nonionic surfactant A in mineral spirits, ion-exchanged water was added while stirring in a homomixer to form a W / O type emulsion. Then, cationic surfactant A was added and uniformly dispersed to prepare the treatment solution. A nonwoven fabric cut to 30 x 30 cm, consisting of a pulp middle layer and a polyethylene / polypropylene (1.2 denier) outer layer (overall basis weight: 80 g / m²). 2 The nonwoven fabric was uniformly impregnated with a treatment solution equivalent to 2.0 times its weight, and then dried in a constant temperature bath set at 60°C for 5 hours to remove volatile components and obtain a sample.

[0038] Comparative Example 1 Dimethyl silicone emulsion A 4.00 wt% Ion-exchanged water 96.00 wt% 100.00 wt% Dimethyl silicone emulsion A was dispersed in ion-exchanged water to prepare a treatment liquid. A non-woven fabric composed of rayon + polyester (blending ratio 40:60) cut into 30×30 cm (total basis weight: 80 g / m 2 ) was uniformly impregnated with a treatment liquid corresponding to 4.0 times the weight of the non-woven fabric, and then dried in a thermostatic bath set at 60°C for 5 hours to remove volatile components and obtain a sample.

[0039] Comparative Example 2 Silicone resin emulsion A 5.00 wt% Ion-exchanged water 95.00 wt% 100.00 wt% Silicone resin emulsion A was dispersed in ion-exchanged water to prepare a treatment liquid. A non-woven fabric composed of cotton + polyester (blending ratio 40:60) cut into 30×30 cm (total basis weight: 80 g / m 2 ) was uniformly impregnated with a treatment liquid corresponding to 2.0 times the weight of the non-woven fabric, and then dried in a thermostatic bath set at 60°C for 5 hours to remove volatile components and obtain a sample.

[0040] Comparative Example 3 Silicone resin emulsion A 6.00 wt% Wax emulsion B 1.00 wt% Dimethyl silicone emulsion B 1.00 wt% Nonionic surfactant B 1.00 wt% Ion-exchanged water 91.00 wt% 100.00 wt% Silicone resin emulsion A, wax emulsion B, dimethyl silicone emulsion B, and nonionic surfactant B were dispersed or dissolved in ion-exchanged water to prepare a treatment liquid. A non-woven fabric composed of a polyester and rayon blended product (blending ratio 80:20, fiber diameter of the constituent fibers of the non-woven fabric is 2.0 denier) cut into 30×30 cm (basis weight: 70 g / m2 The nonwoven fabric was uniformly impregnated with a treatment solution equivalent to 3.0 times its weight, and then dried in a constant temperature bath set at 60°C for 5 hours to remove volatile components and obtain a sample.

[0041] Comparative Example 4 Cationic surfactant A 1.00 wt% Dimethyl silicone emulsion B 5.00 wt% Nonionic surfactant A 1.00 wt% Ion-exchanged water 93.00 wt% 100.00 wt% A treatment solution was prepared by dispersing or dissolving cationic surfactant A, dimethyl silicone emulsion B, and nonionic surfactant B in deionized water. A nonwoven fabric cut to 30 x 30 cm, consisting of a pulp middle layer and a polyethylene / polypropylene (1.2 denier) outer layer (overall basis weight: 80 g / m²). 2 The nonwoven fabric was uniformly impregnated with a treatment solution equivalent to 3.0 times its weight, and then dried in a constant temperature bath set at 60°C for 5 hours to remove volatile components and obtain a sample.

[0042] Comparative Example 5 Cationic surfactant A 1.00 wt% End-ended OH-modified dimethyl silicone emulsion A 0.50 wt% Dimethyl silicone emulsion B 3.00 wt% Nonionic surfactant B 1.00 wt% Ion-exchanged water 94.50 wt% 100.00 wt% A treatment solution was prepared by dispersing or dissolving cationic surfactant A, terminally OH-modified dimethyl silicone emulsion A, methyl silicone emulsion B, and nonionic surfactant B in deionized water. A nonwoven fabric cut to 30 x 30 cm, consisting of a pulp middle layer and a polyethylene / polypropylene (1.2 denier) outer layer (overall basis weight: 80 g / m²). 2The nonwoven fabric was uniformly impregnated with a treatment solution equivalent to 3.0 times its weight, and then dried in a constant temperature bath set at 60°C for 5 hours to remove volatile components and obtain a sample.

[0043] Comparative Example 6 Silicone resin D 6.00 wt% Nonionic surfactant A 1.50 wt% Mineral spirits 30.00 wt% Ion-exchanged water 62.50 wt% 100.00 wt% After dissolving silicone resin D and nonionic surfactant A in mineral spirits, ion-exchanged water was added while stirring with a homomixer to form a W / O type emulsion. Then, cationic surfactant A was added and uniformly dispersed to prepare the treatment solution. A nonwoven fabric cut to 30 x 30 cm, consisting of a pulp middle layer and a polyethylene / polypropylene (1.2 denier) outer layer (overall basis weight: 80 g / m²). 2 The nonwoven fabric was uniformly impregnated with a treatment solution equivalent to 2.0 times its weight, and then dried in a constant temperature bath set at 60°C for 5 hours to remove volatile components and obtain a sample.

[0044] Test method We investigated the ability to remove dirt from the paint film surface and glass surface immediately after treatment using the fabricated fibrous sheet (cloth).

[0045] The evaluation test was conducted as follows: For testing, the hood and windshield of a 2010 Toyota Corolla Fielder (product name), painted black, were used. The hood was cleaned with cleaner wax to remove dirt, and any remaining wax film was removed with an aliphatic solvent before being used as the test surface. This test surface was divided into 12 sections (each approximately 25 x 40 cm square), and then water was evenly applied to the hood surface using a shower nozzle before wiping with each sample. Next, the windshield was cleaned with glass polishing compound to remove dirt and the water-repellent coating, and any remaining oil film was removed with IPA before being used as the test surface. This test surface was also divided into 12 sections (each approximately 25 x 40 cm square), and then water was evenly applied to the hood surface using a shower nozzle before wiping with each sample. One section was left untreated for a blank test.

[0046] Removal of water droplets remaining on the coating surface Each sample was folded into quarters, and the entire test surface was wiped back and forth 10 times to evaluate its water droplet removal ability. ◎ Excellent (Water droplets have been completely removed, and the surface has a uniform shine) ○ Good (Water droplets have been neatly removed, but there are slight variations in color intensity.) △ Normal (Water droplets remain slightly as streaks after wiping) × Poor (Water droplets cannot be wiped away, leaving uneven, streaky residue of water-repellent components)

[0047] Removal of water droplets remaining on the glass surface Each sample was folded into quarters, and the entire test surface was wiped back and forth 10 times to evaluate its water droplet removal ability. ◎ Excellent (Water droplets are completely removed, leaving no residue or glare, resulting in a uniform finish) ○ Good (Water droplets have been neatly removed, but there are some slight variations in color intensity.) △ Normal (The number of water droplets has decreased, but streaks of water-repellent components remain in some areas.) × Poor (Water-repellent components remain in streaks across the entire test surface)

[0048] Water-repellent state immediately after treatment (coating surface) Water was poured onto the test surface, and the state of the water droplets was visually inspected. ◎ It repels water well by forming droplets. ○ It repels water, but the droplets are slightly deformed. △ The water droplets are somewhat dull, and the droplets are quite deformed. × It hardly ever hits.

[0049] Water-repellent state immediately after treatment (glass surface) Water was poured onto the test surface, and the state of the water droplets was visually inspected. ◎ It repels water well by forming droplets. ○ It repels water, but the droplets are slightly deformed. △ The water droplets are somewhat dull, and the droplets are quite deformed. × It hardly ever hits.

[0050] Water-repellent durability After leaving the vehicle parked outdoors for a month, it was washed with water, and then water was poured onto the test surface and the water droplet pattern was visually inspected. ◎ It repels water well by forming droplets. ○ It repels water, but the droplets are slightly deformed. △ The water droplets are somewhat dull, and the droplets are quite deformed. × It hardly ever deflects.

[0051] [Table 1]

[0052] According to the evaluation test results shown in Table 1, in Examples 3 to 7, which contain a fibrous sheet containing a silicone resin as a water-repellent component, a cationic surfactant to enhance adhesion, and a nonionic surfactant to spread the silicone resin as a water-repellent component on the treated surface, all items received an excellent rating (◎). In Examples 1 and 2, some items received a △ rating, but the remaining items received a ○ rating. Furthermore, there were no cases in Examples 1 to 7 that received an × rating in any of the above items. In contrast, in Comparative Examples 1 to 6, no excellent ratings were obtained in any of the above items, and although there were some cases that received a ○ rating, many items received a △ or × rating. From this, it can be said that the water-repellent dry sheet according to the present invention surpasses Comparative Examples 1 to 6 in terms of the ability to remove water droplets remaining on the coating surface and glass surface, and the water-repellent state and water-repellent durability immediately after treatment on the coating surface and glass surface.

Claims

1. A water-repellent dry sheet that is used on both lipophilic and hydrophilic treated surfaces, and is used to wipe away water droplets remaining on the treated surface after washing, thereby forming a water-repellent coating on the treated surface. The active ingredients, which include silicone resin, a cationic substance, and a nonionic surfactant, are held in a fibrous sheet. The silicone resin is prepared by dissolving trimethylsiloxysilicate in an oily substance of dimethylpolysiloxane or a modified thereof, or cyclopentasiloxane. A water-repellent dry sheet characterized in that the cationic substance is a cationic surfactant.

2. A water-repellent dry sheet according to claim 1, wherein the amount of silicone resin added is 0.5 to 20.0 wt% as an effective component relative to the weight of the fibrous sheet.

3. A water-repellent dry sheet according to claim 1 or claim 2, wherein the cationic surfactant is a quaternary ammonium salt.

4. A water-repellent dry sheet according to any one of claims 1 to 3, wherein the amount of cationic substance added is 0.1 to 2.0 wt% as an effective component relative to the weight of the fibrous sheet.

5. A water-repellent dry sheet according to any one of claims 1 to 4, wherein a modified silicone oil is added.

6. A water-repellent dry sheet according to any one of Claims 1 to 5, wherein the HLB value of the nonionic surfactant is 3 to 16.

7. A water-repellent dry sheet according to any one of Claims 1 to 6, wherein the amount of nonionic surfactant added is 0.01 to 5.0 wt% as an effective component relative to the weight of the fibrous sheet.

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