JPH0420960B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a stain removal agent for non-water permeable materials and a stain removal method. More specifically, the present invention provides a stain removal agent for the surface of non-water permeable materials such as structural membranes, tents, waterproof canopies, waterproof clothing, sheets for construction work, etc., and a stain removal agent from the above-mentioned materials. The present invention relates to a method for removing dirt using the method. [Prior Art] Conventionally, waterproof sheets for tent sites, membrane materials for building structures, sheet materials for simple warehouses, truck canopies, waterproof clothing fabrics, etc., have been coated with non-water permeable polymers, for example, on one or both sides of a fiber fabric. A non-water permeable sheet material is used, which is obtained by coating or laminating a thin film such as a polyvinyl chloride resin coating layer or a stretched porous polytetrafluoroethylene coating layer. These materials have the problem of being easily soiled and difficult to remove, for example, due to the hydrophobic and lipophilic nature of the coating material itself, due to its own deterioration, or due to bleeding of additives such as plasticizers. be. Also, sheets for construction work, such as sheets made by coarsely knitting synthetic monofilament, sheets made by covering threads with a synthetic resin material and coarsely knitting the threads, and sheets made by coarsely knitting and weaving threads, and sheets made by coarsely knitting and weaving yarns covered with synthetic resin material, and sheets made by coarsely knitting and weaving the threads, and Resin-coated sheets also have the same staining problem as above. In order to prevent staining of non-water permeable materials such as those mentioned above, there is a method of blending an antifouling agent, such as a silicone compound and a fluorine-containing compound, into the coating polymer, or a method of antifouling treatment of a polymer thin film. For example, methods of coating with antifouling agents or antifouling polymeric materials, such as polyacrylic resins or fluorine-containing polymeric resins, have been practiced. However, products using such antifouling agents or antifouling polymer materials have poor cold resistance,
There are problems such as poor melt sutability, poor adhesion, complicated processing, and/or high cost. In addition, attempts have been made to remove dirt on the surface of non-water permeable materials using ordinary detergents or organic solvents, but this method does not cause deterioration of the material itself.
Practical problems often occur, such as a decrease in waterproofness and dirt seeping into the water-impermeable polymer thin film, and the effects are unsatisfactory, making it difficult to employ. [Problems to be Solved by the Invention] The present invention solves the problems of the conventional dirt removal method described above, does not reduce the quality of the material to be cleaned, and does not cause recontamination or seepage of dirt. With relatively simple operation and relatively low cost,
The object of the present invention is to provide a stain removal agent and a stain removal method that can efficiently remove stains from non-water permeable materials. [Means for Solving the Problems and Their Effects] The stain remover for non-water permeable materials of the present invention contains a water-soluble alkali metal silicate material as a main component. Another stain remover for non-water-permeable materials of the present invention contains a water-soluble alkali metal silicate material and a water-insoluble, highly water-absorbing polymer material as main components. Furthermore, the method for removing stains from a non-water permeable material of the present invention includes a water-soluble alkali metal silicate material which adheres to the surface area of the non-water permeable material in a dry state and which is to be removed. A hydrated stain remover formed by forming a stain remover layer containing as an active ingredient, supplying a water supply agent containing water as a main component to the stain remover layer, and hydrating the alkali metal silicate material. absorbing the soil on the surface area into a layer, and then removing the hydrated soil remover layer absorbing and containing the soil from the surface area. Furthermore, another method of removing stains from non-water permeable materials according to the invention comprises:
A stain remover layer is formed that adheres to the surface area in a dry state and contains a water-soluble alkali metal silicate material and a water-insoluble super-absorbent polymer material as active ingredients; A water-supplying agent containing water as a main component is supplied to hydrate the alkali metal silicate material, and the polymer material absorbs and swells to form a hydrated water-absorbing stain remover layer on the surface area. and then removing the hydrated stain remover layer containing the soil from the surface area. The stain remover of the present invention contains a water-soluble alkali metal salt material as a main component. Water-soluble alkali metal salt materials include sodium silicate (sodium metasilicate (Na ₂ SiO ₃ ) and its hydrates, sodium orthosilicate (Na ₄ SiO ₄ ),
Sodium disilicate (Na ₂ Si ₂ O ₅ ), sodium tetrasilicate (Na ₂ Si ₄ O ₉ ), potassium silicate (potassium metasilicate (K ₂ SiO ₃ ), potassium disilicate ( KHSi ₂ O ₅ )) and water glass (Na ₂ O.nSiO ₂ , where n is 1 or more, preferably 2 to 4), and other alkali metal silicate salts, such as lithium silicate. etc. can also be used if they are water soluble under the conditions of use. Although alkali metal silicate salts are generally used as cleaning builders, they have not been known to have a cleaning effect by themselves. However, the present inventors discovered for the first time that when it hydrates and absorbs water, it can absorb dirt on the surface of a non-water permeable material, thereby removing the dirt. The antifouling agent of the present invention may contain a water-insoluble, highly water-absorbing polymeric material as a main component together with the alkali metal silicate material. When the water-insoluble superabsorbent polymer material absorbs water and swells, it is thought to strip off dirt on the surface of the non-water-permeable material and absorb it. In this case, the stain prevention effect is significantly enhanced. Although there is no particular limitation on the mixing weight ratio of the alkali metal silicate material and the polymer material in the stain remover of the present invention, it is generally preferably within the range of 0.01:10 to 10:0.01, and 1:10. More preferably, the ratio is within the range of ~10:1. The polymeric material useful as the active ingredient of the stain remover of the present invention is water-insoluble, but absorbs a large amount of water and swells to form a water-absorbing swollen body. Examples of such polymeric materials include starch.
Hydrolyzed (saponified) products of polyacrylonitrile graft polymers, starch-acrylic acid copolymers, starch-acrylate copolymers, and starch
Starch derivatives such as acrylate (e.g. alkali metal acrylate) copolymers; cellulose derivatives such as crosslinked carboxymethylcellulose and hydrolysates of cellulose-polyacrylonitrile graft polymers; and
Hydrolyzate of vinyl acetate-acrylic acid (or salt thereof) copolymer, hydrolyzate of vinyl acetate-acrylic acid ester copolymer, hydrolyzate of vinyl acetate-methtaryl acid (or salt thereof) copolymer, Hydrolyzate of vinyl acetate-methacrylic acid ester copolymer, hydrolyzate of vinyl acetate-α,β-unsaturated dicarboxylic acid ester copolymer, acrylic acid (or its salt)-acrylamide copolymer, polyvinyl alcohol cross-linked products of polyacrylic acid (or its salts), hydrolyzed polyacrylonitrile products, cross-linked products of polyalkylene oxide (e.g. polyethylene oxide), cross-linked products of polyvinylpyrrolidone, cross-linked products of sulfonated polyethylene, vinyl Hydrolyzates of ester-ethylenically unsaturated monomers (e.g., acrylic acid and its salts, methacrylic acid and its salts) copolymers, maleic anhydride-ethylenically unsaturated hydrocarbons (e.g., isobutylene, isoprene, etc.) At least one selected from polymers and chelate crosslinked products of water-soluble polymers having chelate functional groups in their side chains can be used. The above-mentioned water-insoluble/highly absorbent polymer materials are water-soluble polymer materials made water-insoluble by crosslinking, and some of the hydrophilic groups of the water-soluble polymer material are replaced with hydrophobic (lipophilic) groups. This includes things that have been replaced. The water-insoluble, highly absorbent polymer material used in the present invention has the ability to absorb and swell tens to thousands of times more water than its own weight, and this water-absorbing and swollen body can absorb considerable pressure. It has the property of not releasing water even when sprayed on it. To measure the water absorption capacity of polymeric materials, a given weight
A test polymer material of W ₀ was dispersed in ion-exchanged water at room temperature, and this dispersion was stirred slowly to avoid deterioration of the test polymer material (for example, cleavage of weak polymer chains). After standing for 30 minutes, the resulting water-absorbing swollen polymeric material is separated from the water, excess adhering water is removed, and its weight W is measured. The water absorption capacity of this polymeric material is calculated by the following formula. Water absorption capacity = W/W ₀ The stain remover of the present invention contains, in addition to the water-insoluble and highly water-absorbing polymer material, the required amount of preservatives, anti-bacterial agents,
It may contain at least one of a flavoring agent, a coloring pigment, a bleaching agent, and the like. In addition, in addition to the stain remover of the present invention, a surfactant used as a penetrating agent or a hydrophilic agent may be used in combination to improve its water swelling property and to improve its washing removability (washing away) property. You may. The surfactant may be attached to a non-water permeable material surface with a stain remover, or with a water supply agent.
It may also be applied to the soil remover layer. As surfactants used for this purpose, the following can be used. Namely, sorbitan fatty acid ester, (poly)
Glycerin fatty acid ester, polyethylene glycol monostearate, fatty acid diethanolamide, stearic acid monoglyceride, sorbitan monostearate, sorbitan monooleate,
Polyhydric alcohol fatty acid ester, glycerin monooleate, polyoxyethylene glycerin monostearate, polyoxyethylene sorbitan monooleate, sorbitan monolaurate, sorbitan monovermitate, bentaerythritol fatty acid ester, polyoxyethylene alkyl ether, poly Oxyethylene alkylphenol, polyoxyethylene alkylamine, polyoxyethylene alkylamide, fatty acid polyethylene glycol ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sulbitan ester, fatty acid glycerin ester, alkyl polyethyleneimine, fatty acid amine salt, alkyl phosphate ester salt , polyoxyethylene alkyl phosphate ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl sulfate ester salt, alkyl amine salt, alkyl quaternary ammonium salt, alkylimidazoline derivative, alkyl betaine, alkylimidazoline derivative, N-alkyl β-alanine,
Various higher fatty acid glycerides (however, fatty acids such as lauric acid, myristic acid, valmitic acid,
Stearic acid, montanic acid, oleic acid, linoleic acid, phenic acid, etc. are used, and their mono-, di-, or triglycerides are used. ) Tributyl phosphate, triisooctyl phosphate, tribenzyl phosphate, triphenyl phosphate, phenyldecyl phosphate, diphenyl isodecyl phosphate, triphenyl phosphate, benzenesulfonic acid, para-toluenesulfonic acid or their salts or hydrates, etc.
can be used. The soil removal treatment according to the method of the invention is applied to soiled surface areas of non-water permeable materials. Examples of non-water permeable materials include non-water permeable polymer resins (for example, polyvinyl chloride resins, polyurethane resins, polyolefin resins, polyamide resins, polyester resins, polyacrylic resins, silicone resins, fluorine-containing polymer resins, ethylene/ Synthetic resins such as vinyl acetate copolymer resins, polyethylene-ethylene/vinyl acetate copolymer resins, polyvinyl chloride graft polymers, and ethylene-propylene diene polymers, as well as natural and synthetic rubbers (e.g., chlorosulfone Rubbers such as chlorinated polyethylene, neoprene rubber, chlorinated polyethylene rubber, polynitrile rubber, SBR, isobutylene rubber, butyl rubber, polybutadiene, EPT, acrylic rubber, polyurethane rubber, fluorine-containing rubber, silicone rubber), etc. Materials such as tarpaulins, tent fabrics, membranes for building structures, canopies, sheets for construction work, other waterproof sheets, waterproof clothing covered with expanded porous polytetrafluoroethylene sheets or polyurethane coating layers, waterproof bags These materials do not allow water to seep into the interior of the material.
Generally has a hydrophobic surface. Other non-water permeable materials include tiles,
Made of ceramic materials, concrete, metal, plastic, bamboo, wood, etc., it is difficult for water to seep through.
There are materials that dry quickly, and the present invention can be applied to these materials to efficiently remove stains. In the method of the present invention, a dry coating layer of a stain removal agent containing only an alkali metal silicate material or a water-insoluble, highly water-absorbing polymeric material is applied to the surface of a non-water-permeable material from which stains are to be removed. formed on the area. To form such a dry stain remover layer,
An aqueous solution is prepared by dissolving the alkali metal silicate material in an aqueous medium, or an aqueous dispersion solution is prepared by dissolving the alkali metal silicate material and dispersing the polymeric material used together with it. This aqueous solution or aqueous dispersion may be applied to the surface area of the non-water-permeable material to be cleaned, and the applied layer may be dried. This method allows the stain remover to be applied evenly and
The desired material can be deposited onto the surface area. The dispersion of the stain remover mentioned above can be applied by a conventional method, such as a brush coating method, a spray method, or a dipping method. Although there is no particular limitation on the concentration of the alkali metal silicate material in the aqueous solution of the antifouling agent of the present invention, which contains only the alkali metal silicate material as a main component, it is generally preferable to set the concentration to 1 g/or more.
It is more preferable to prepare within the range of g/~300g/. In the aqueous dispersion solution of the antifouling agent of the present invention containing an alkali metal silicate material and a polymer material as active ingredients, there is no particular restriction on the concentration of the alkali metal silicate material, but it is generally 1 g/or more. The concentration of the polymer material is preferably 10g/~300g/, and although there is no particular limitation on the concentration of the polymer material, it is generally preferably 0.01g/~50g/, and 0.1g/~20g/. It is more preferable that there be. The aqueous dispersion solution of the stain remover is prepared by adding the stain remover to an aqueous medium, dispersing and dissolving the agent, and stirring the mixture sufficiently to prevent the polymer material from becoming granular or gelling. The aqueous medium may consist only of water, but if the stain remover contains a polymeric material, it may be an aqueous solution containing water as a main component and a swelling regulator for the polymeric material. The swelling regulator is generally preferably selected from volatile, water-soluble, and polar organic solvents such as ethyl alcohol, methyl alcohol, n-propyl alcohol, butyl alcohol, and isopropyl alcohol, and the content thereof is 20 to 700 g. /, generally 50 to 700g/
It is more preferable that the amount is within a certain range. The swelling regulator is
The degree of water absorption and swelling of the polymer material in the aqueous dispersion solution is suppressed and adjusted to prevent its gelation, and the viscosity and coating properties of the aqueous dispersion solution are appropriately adjusted. It is also possible to improve the compatibility with the permeable material surface and thus the adhesion strength of the stain remover. The aqueous medium of the stain remover also contains volatile organic solvents, such as hydrocarbons, halogenated hydrocarbons, alcohols, ethers, acetals, etc.
A medium that does not swell the superabsorbent polymeric material may be included, which is selected from ketone, ester, polyhydric alcohols and their derivatives, fatty acids, phenols, nitrogen compound organic solvents, and the like. The stain remover solution or dispersion coating layer is transformed into a dry stain remover coating (adhesion) layer by drying. This drying is an important step in the method of the present invention, and stain removal cannot be achieved simply by applying the stain remover dispersion. The stain remover coating layer is dried at a temperature range of 0°C to 150°C, and forced drying such as hot air drying or radiation drying may be performed, but generally, the temperature range is 0°C to 100°C.
It is preferable to perform natural drying or low-temperature drying at a temperature of 0°C to 60°C. Such natural or low-temperature drying improves the stain removal effect in the subsequent hydration and water absorption treatment. The content of the alkali metal silicate material contained in the stain remover layer in a dry state is 0.05 g/m ² ~
Preferably within the range of 300g/ ^m2 , 0.5
It is preferably within the range of g/m ² to 200 g/m ² . In addition, the content of polymer material is 0.01g/m ² ~
Preferably within the range of 30g/ ^m2 , 0.05
It is more preferably within the range of g/m ² to 20 g/m ² , and even more preferably within the range of 1 g/m ² to 10 g/m ² . As described above, a water supply agent containing water as a main component is supplied to the stain removal agent layer adhered to the surface area of the non-water permeable material. This water supply agent may consist of only water, or may be an aqueous solution containing the above-mentioned surfactant and/or water-soluble organic solvent. By this operation, the alkali silicate or the alkali silicate and the water-insoluble, highly water-absorbent polymeric material in the stain remover layer are rapidly hydrated or swelled by water absorption, thereby absorbing and enclosing the stain. This hydration and water absorption treatment is preferably carried out at a temperature of 0°C to 100°C, more preferably carried out generally at a temperature of 10°C to 60°C. Moreover, it is preferable that the hydration and water absorption treatment be carried out for 1 to 30 minutes as much as possible. The hydrated or hydrated water-absorbing soil remover layer containing the soil is then removed from the non-water permeable material surface by washing with water or by wiping. The stain remover and stain removal method of the present invention achieve the desired stain removal through the mechanism described above. Therefore, the surface of the material to be soiled may be smooth or rough, as long as it is capable of forming a soil-removing agent layer thereon and is washable. It may be a surface or may be a complexly deformed surface, and the present invention can efficiently extract from these surfaces,
Dirt can be removed. In the method of the present invention as described above, a stain preventive agent is used in combination with a stain remover to perform adhesion/drying treatment and water absorption swelling stain removal treatment, during which stain prevention treatment is applied to the surface of the non-water permeable material. It's okay. As a stain prevention agent, silicone water repellent,
A fluorine-containing compound (polymer) water repellent or the like can be used. [Examples] The present invention will be further explained below using Examples. Examples 1 to 9 and Comparative Examples 1 and 2 In each of Examples 1 to 9 and Comparative Examples 1 to 2, polyester fiber spun yarn plain woven fabrics having the following structure: 20S/1×20S/1/92 yarns/2.54cm× 55 pieces/2.54cm, basis weight: 195g/m ² were scoured and dried in a conventional manner to obtain a base fabric for a waterproof sheet. Separately, a resin composition with the following composition: Ingredient parts by weight : Polyvinyl chloride resin 100 DOP (plasticizer) 75 Titanium dioxide (white pigment) 8 Antimony trioxide (flame retardant) 5 Zinc stearate (stabilizer) 3 Calendar The mixture was kneaded and formed into a film with a thickness of 0.1 mm. This polyvinyl chloride resin film was superimposed on both sides of the base fabric and bonded under heat and pressure.
The obtained waterproof sheet had a thickness of 0.58 mm, and had a white surface with noticeable dirt. This white waterproof sheet is vertically 1m long and horizontally 5m long.
It was stretched and fixed on the frame of M. This soil exposure test sample was fixed on the roof of a 3-story building in an urban area at a height of 1 m from the roof surface, facing south at an angle of 30 degrees from the vertical plane, and exposed to the roof for 3 months. did. The exposed samples were quite noticeably contaminated. A stain removal treatment liquid having the composition shown in Table 1 was applied to the soiled surface area of this soiled sample at a temperature of 20°C.
Air dried at ~25°C. Water is gently exposed to the dried stain remover layer, and the alkali metal silicate and polymeric material in the layer are sufficiently absorbed and swollen, and left in this state for 10 minutes. The stain remover layer was rinsed off with a strong shower of water. Thereafter, the cleaned surface of the sample was observed and the stain removal effect was evaluated. The results are shown in Table 1.

【table】

〔Effect of the invention〕

The stain removal agent and stain removal method of the present invention can clean the soiled surface of a non-water permeable material, which has conventionally been difficult to remove stains, with a simple operation and extremely efficiently. In addition, the stain removal agent and stain removal method of the present invention can be applied not only to various sheet materials but also to automobiles, houses, washrooms, toilets, baths, sinks, restrooms, kitchens, etc.
As described above, a wide range of non-water permeable materials such as floors and exterior walls of buildings can be efficiently cleaned.

Claims (1)

[Scope of Claims] 1. A stain remover for non-water permeable materials containing a water-soluble alkali metal silicate material as an active ingredient. 2. The stain remover according to claim 1, wherein the water-soluble alkali metal silicate material comprises at least one selected from sodium silicate, potassium silicate, and water glass. 3 Water-soluble alkali metal silicate and water-insoluble
A stain remover made of non-water-permeable materials containing a super-absorbent polymeric material as an active ingredient. 4. The water-insoluble and highly water-absorbing polymeric material is a starch-polyacrylonitrile graft polymer hydrolyzate, starch-acrylic acid copolymer, starch-acrylate copolymer, starch-acrylate copolymer, carboxylic acid Crosslinked methylcellulose, hydrolyzate of cellulose-polyacrylonitrile graft polymer, hydrolyzate of vinyl acetate-acrylic acid (or its salt) copolymer, hydrolyzate of vinyl acetate-acrylic acid ester copolymer, acetic acid Hydrolyzate of vinyl-methacrylic acid (or its salt) copolymer, hydrolyzate of vinyl acetate-methacrylic acid ester copolymer, vinyl acetate-
Hydrolyzate of α,β-unsaturated dicarboxylic acid ester copolymer, acrylic acid (or salt)-acrylamide copolymer, crosslinked product of polyvinyl alcohol,
Crosslinked products of polyacrylic acid (or its salts), hydrolyzed products of crosslinked polyacrylonitrile, crosslinked products of polyalkylene oxide, crosslinked products of polyvinylpyrrolidone, crosslinked products of sulfonated polyethylene,
A hydrolyzate of a vinyl ester-ethylenically unsaturated monomer copolymer, a chelate crosslinked product of a water-soluble polymer having a chelate functional group in its side chain, and
The stain remover according to claim 3, which comprises at least one selected from maleic anhydride-ethylenically unsaturated hydrocarbon copolymer. 5. The stain remover according to claim 3, wherein the mixing weight ratio of the alkali metal silicate material and the polymer material is in the range of 0.01:10 to 10:0.01. 6. Forming a stain removal agent layer on the surface area of the non-water permeable material from which stains are to be removed, which adheres to the surface area in a dry state and contains a water-soluble alkali metal silicate material as an active ingredient; supplying a water supply agent containing water as a main component to the stain remover layer to absorb and incorporate the stains on the surface area into the hydrated stain remover layer formed by hydration of the alkali metal silicate material; A method for removing stains from non-water permeable materials, the method comprising: then removing a hydrated stain remover layer absorbing and containing the soil from the surface area. 7. In the formation of the dry stain remover layer, an aqueous solution of the stain remover is applied onto the surface area of the non-water permeable material to be soil removed, and the aqueous solution coated layer is dried. The method described in scope item 6. 8. In the dry stain remover layer, the amount of the alkali metal silicate material is 0.05 g/m ² -
Claim 6 within the range of 300g/m ²
The method described in section. 9. Removal of the hydrated stain remover layer is by washing with water,
The method according to claim 6. 10. The method of claim 6, wherein the removal of the hydrated stain remover layer is by wiping. 11. The method of claim 6, wherein the hydration treatment is carried out within a temperature range of 0°C to 100°C. 12. On the surface area of the non-water-permeable material to be soiled, it adheres to the surface area in a dry state and contains a water-soluble alkali metal silicate material and a water-insoluble/super absorbent polymer material as active ingredients. forming a stain remover layer containing the stain remover layer, supplying a water supply agent containing water as a main component to the stain remover layer to hydrate the alkali metal silicate material and cause the polymer material to absorb water and swell; absorbing and incorporating the stains on the surface area into the formed hydrated water-absorbing stain remover layer;
A method for removing stains from non-water permeable materials, comprising: removing stains from said surface area. 13 In forming the dry stain remover layer, dissolve the alkali metal silicate material in an aqueous medium, disperse the polymer material, and use the resulting dispersion solution to remove stains on the non-water permeable material. 13. The method of claim 12, wherein the dispersion layer is applied onto the surface area to be removed and the dispersed solution layer is dried. 14 In the dry stain remover layer, the amount of the alkali metal silicate material is 0.05 to 300.
g/m ² and the amount of said polymeric material is within the range of
13. The method of claim 12, wherein the amount is within the range of 0.01 to 30 g/ ^m2 . 15. The method according to claim 13, wherein the aqueous medium of the stain remover consists only of water. 16. The method according to claim 13, wherein the aqueous medium of the stain remover comprises an aqueous solution containing a swelling degree modifier for the polymeric material. 17 The swelling degree regulator is ethyl alcohol,
17. The method according to claim 16, comprising at least one member selected from methyl alcohol, propyl alcohol, butyl alcohol and isopropyl alcohol. 18. The method of claim 12, wherein the hydration and water absorption treatment is carried out within a temperature range of 0°C to 100°C. 19. The method according to claim 12, wherein said hydrated water-absorbing stain remover layer is removed by washing with water. 20. The method of claim 12, wherein the removal of the hydrated stain remover layer is by wiping.