JPS6329911B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aerosol water and oil repellent composition. More specifically, in an aerosol water and oil repellent composition whose main ingredient is a water and oil repellent containing a perfluoro or fluoroalkyl group, the water and oil repellent is uniformly dissolved using a special mixed solvent. This invention relates to an aerosol water and oil repellent composition that has little odor and has excellent water and oil repellency as well as antifouling effects. Fluorine-based water and oil repellents, which are polymers of polymerizable monomers containing perfluoro or fluoroalkyl groups in the molecule, or copolymers with other types of polymerizable monomers, cannot be treated. 0.05 to 2% (0.05 to 2%
OWF), which exhibits excellent water- and oil-repellent and stain-repellent effects even in relatively small amounts, has recently attracted attention as a surface treatment agent for textiles, leather, interior decoration, building materials, etc. On the other hand, when a water and oil repellent composition is commercially used as a surface treatment agent for textiles, leather, interiors, building materials, etc., an aerosol type is most desirable because of its ease of use. In order to effectively carry out surface treatments such as water- and oil-repellent and stain-proofing by spraying, various restrictions are imposed on the composition of the contents. First, the compatibility between the propellant, which is an aerosol propellant gas, and the blended stock solution, the water and oil repellent being uniformly dissolved in the blended stock solution composition, and the ability of the blended stock solution composition to easily wet the surface of the object to be treated. When these conditions are satisfied, the aerosol will be sprayed uniformly and will have uniform water and oil repellency without dusting, whitening, etc.
Antifouling treatment can be performed. Furthermore, it is essential that it has excellent safety, especially that its flammability and explosiveness are within permissible limits, and it is also necessary that it not have an unpleasant odor. In particular, in order to be easily and widely used in general households, it is important that the product be non-hazardous and have a pleasant odor. Now, the stock solution of an aerosol water and oil repellent composition basically consists of a water and oil repellent and its solvent, and the fluorine-based water and oil repellent is a nonvolatile, odorless polymeric substance that can be added in small amounts. It can be said that the above-mentioned various constraints are imposed on the selection of the solvent. However, the solvents for the above-mentioned fluorine-based water and oil repellents are limited, and include ketones such as acetone and methyl ethyl ketone, ethers such as dimethyl ether,
The desired solubility can only be obtained in special solvents such as ethyl acetate esters, chlorinated solvents such as 1,1,1-trichloroethane, and perchlorethylene. These solvents have no problems in solubility or compatibility with propellants, but low boiling point solvents cannot sufficiently wet the surface of the workpiece due to their volatility, and impregnating properties may also be poor. Due to insufficient amount, dusting, whitening, etc. will occur. Additionally, non-chlorinated solvents are highly dangerous to fire. Furthermore, there are some solvents that have a strong dissolving power for fluorocarbon resins, but can dissolve and damage the articles to be treated. Under these circumstances, 1, 1,
1-Trichloroethane is the only solvent actually used. However, this solvent has a unique unpleasant pungent odor that is disgusting to users, and has an extremely large drawback when viewed as a household aerosol product. In view of this situation, the present inventors maintained the basic performance of the aerosol water and oil repellent composition and worked hard to find a solvent with a mild odor. We have discovered an aerosol water and oil repellent composition with excellent basic performance and completed the present invention. That is, unexpectedly, by the presence of a specific volatile solvent and a specific fluororesin non-solvent that were thought to be usable for this technical application,
It has been discovered that an excellent fluorine-based water and oil repellent composition can be obtained even if the amount of 1,1,1-trichloroethane is significantly reduced, and an excellent household aerosol product free of unpleasant irritating odor is provided. It came to this. The present invention provides a fluorine-based water and oil repellent that is a polymer of a polymerizable monomer containing a perfluoro or fluoroalkyl group, or a copolymer with other types of polymerizable monomers, in dichloromethane or 1,
1,2-trichloro-1,2,2-trifluoroethane or a mixture of both, 1,1,1-trichloroethane, and the general formula (1) R-OH (1) (wherein R is the number of carbon atoms 1 to 4 alkyl groups) and _a monohydric alcohol _represented by the general formula (2) (representing an alkyl group, but excluding the case where it is hydrogen at the same time) is dissolved in a mixed solvent with one or more selected from the group consisting of ethylene glycol mono- or dialkyl ethers represented by The present invention provides an aerosol water and oil repellent composition that can be applied by applying the present invention. In the present invention, a polymer of a polymerizable monomer containing a perfluoro or fluoroalkyl group used as a surface treatment agent for water/oil repellency or antifouling, or a combination with other types of polymerizable monomers. There are no particular restrictions on the fluorine-based water and oil repellent, which is a polymer, and those generally used in the technical field can be used. for example, A polymer of unsaturated esters represented by acrylates or methacrylates containing a perfluoroalkyl group having 3 to 20 carbon atoms, or a type of compound that can be polymerized with such unsaturated esters and does not contain a fluoroalkyl group, or Copolymers with two or more types may be mentioned. In this case, examples of polymerizable compounds that do not contain fluoroalkyl groups include ethylene, vinyl acetate, vinyl fluoride, vinyl chloride,
Vinylidene halides, acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, acrylic acid and its alkyl esters, methacrylic acid and its alkyl esters, acrylamide, methacrylamide, diacetone acrylamide, methylolated diacetone acrylamide or methacrylamide , vinyl alkyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, glycidyl acrylate,
Examples include benzyl methacrylate, cyclohexyl methacrylate, and maleic anhydride. By copolymerizing these polymerizable compounds that do not contain fluoroalkyl groups, in addition to the water and oil repellency of the water and oil repellent agent, it also improves stain resistance, dry cleaning resistance, washing resistance, hardness, and texture. It is possible to appropriately improve various properties such as. For example, water and oil repellents made of copolymers of polymerizable compounds containing fluoroalkyl groups, vinyl chloride, and styrenes or alkyl esters of acrylic acid or methacrylic acid have excellent stain resistance. In the present invention, CF ₂ Cl (CF ₂ ) ₁₀ CH ₂ OCOC (CH ₃ )=CH ₂ , H
(CF ₂ ) ₁₀ CH ₂ OCOCH=CH ₂ A water- and oil-repellent base agent made of a polymer or copolymer of a polymerizable compound containing a fluoroalkyl group, such as (CF 2 ) 10 CH 2 OCOCH=CH 2 , may also be mentioned. However, as the water- and oil-repellent main agent, it is preferable to use a polymer or copolymer containing a perfluoroalkyl group as described above. General formula R ^f R〓
OCOCR = CH ₂ and general formula

[Formula] (However, in the formula, R ^f is a linear or branched perfluoroalkyl group having 3 to 20 carbon atoms, and R is a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms. alkylene group, R〓 is hydrogen or methyl group, R〓 is hydrogen or 1-
A water- and oil-repellent base agent consisting of a polymer or copolymer containing as a constituent unit an ester of acrylic acid or methacrylic acid containing a perfluoroalkyl group represented by (representing an alkyl group having 6 carbon atoms) is used. may be particularly advantageous for widespread commercial use. The method for producing the fluorine-based water and oil repellent used in the present invention can be performed by arbitrarily selecting various polymerization reaction methods and conditions, such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, photopolymerization, etc. Any of various polymerization methods can be employed. For example, a method in which a compound to be polymerized is emulsified in water in the presence of a surfactant and the polymerization is carried out while stirring, or a method in which a compound capable of polymerizing as a raw material is dissolved in an appropriate organic solvent and a polymerization initiating source (superposition A method of solution polymerization by the action of a polymerization initiator such as an oxide or an azo compound, or a dispersing radiation (eg, oxidizing radiation) may be employed. The fluorine-based water and oil repellent is preferably blended in an amount of 0.1 to 5% by weight (hereinafter simply abbreviated as %) in the blended stock composition, but the content may exceed this range depending on the application. In the present invention, the mixed solvent that uniformly dissolves the fluorine-based water and oil repellent and imparts various excellent surface treatment effects to the treated object is a mixed solvent containing a main solvent and an auxiliary solvent in a specific range of mixing ratios. The main solvent is dichloromethane, 1,1,2-
Trichloro-1,2,2-trifluoroethane alone or a mixture thereof and 1,1,1-trichloroethane are used. As the auxiliary solvent, one or more selected from the group of solvents represented by the following general formulas (1) and (2) are used. Monohydric alcohol of general formula (1) R-OH (1) (In the formula, R represents an alkyl group having 1 to 4 carbon atoms) Ethylene glycol mono- or dialkyl ether of general formula (2) R'-OCH ₂ CH ₂ OR″ (in the formula, R ¹ and R″ are each hydrogen, carbon number 1 to 4
represents an alkyl group. (However, this excludes the case of hydrogen at the same time) These mixed solvents are included as the main solvent in the blended stock solution composition.
75-99.4% (preferably 80-98.9%), but
Dichloromethane and/or 1,1,2-trichloro-1,2,2-trifluoroethane is 35 to 88.9
%, 1,1,1-trichloroethane must be contained at 10 to 50%, and the co-solvent must be contained at 1 to 10%.
If the mixed solvent is contained in an amount outside of this range, the performance will be affected, particularly dusting and whitening phenomena, which is undesirable. In addition to these essential components, the undiluted solution composition of the aerosol water and oil repellent composition of the present invention contains silicone derivatives, antistatic agents, flame retardants, and optional components to improve iron slippage during ironing. Flavors and the like are optionally and appropriately blended depending on the purpose of blending. In the present invention, it is necessary to fill an aerosol can with a homogeneous solution obtained by mixing these various components into an aerosol can using a conventional method.The propellant used at this time is commonly used Freon gas, LP gas,
Propellant gas such as carbon dioxide can be used. The mixing ratio of the blended stock solution and propellant is 97:3 to 97:3 by weight.
20:80 (preferably 80:20 to 50:50) is good. Various examples of articles that can be surface treated with the aerosol water and oil repellent composition of the present invention are not particularly limited. For example, it can be particularly advantageously applied to textiles, glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters, etc. Therefore, as a textile fabric,
Animal and plant natural fibers such as cotton, hemp, wool, and silk, polyamide, polyester, polyvinyl acetal,
Examples include various synthetic fibers such as polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber and asbestos fiber, and woven fabrics of mixed fibers thereof. Next, examples of the present invention will be described in more detail, but it goes without saying that this description does not limit the present invention. The water repellency and oil repellency shown in the following examples are shown using the following scale. That is, water repellency is expressed by the water repellency number (see Table 1 below) determined by the JIS L-1092 spray method, and water repellent oil is determined by applying a test solution as shown in Table 2 below on a sample cloth. A few drops (approximately 4 mm in diameter) are placed in two locations and judged by the state of penetration after 30 seconds (AATCC-TM118-1966).

【table】

[Table] Example 1 Table 3 shows the performance evaluation results of the following aerosol water and oil repellent composition.

[Table] Aerosol composition Mixed stock solution/propellant = 75/25 (weight ratio) Propellant is Freon 12/Freon 11 = 6/4 mixture evaluation method ◎ Evaluation of odor when aerosol is sprayed is 2
The odors of the two types (one of which is a reference product) sprayed in one sensory test chamber are judged by sensory evaluation by 10 expert panelists. The results of the study are shown as the average of the evaluation scores of 10 expert panelists. Evaluation points Evaluation criteria +2 No irritating odor compared to the standard +1 Slightly irritating odor 0 There is an irritating odor similar to the standard -1 Slightly more irritating odor than the standard -2 〃 〃 Strong ◎Regarding aerosol sprayability Evaluation Spray the aerosol from a distance of 20 cm onto the TC blend broad blue cloth or wool/cashmere dark blue cloth so that it is evenly wetted. Visual observation is performed to determine whether powdery whitening occurs immediately after spraying and whether whitening occurs after natural drying, using the following criteria. Judgment Judgment Criteria 〇 Same surface condition as untreated cloth (no whitening) 〇〜△ △ Slight whitening is observed compared to untreated cloth △〜× × Whitening phenomenon is observed Judgment 〇〜△ is the lower limit of tolerance.

[Table] *1 Main solvent dichloromethane/1,1,2-trichloro-1,2,2-trifluoroethane/1,
Example 2 of a mixture of equal amounts of three 1,1-trichloroethane 2 A similar aerosol was produced by incorporating 0.6% of the fluorine-based water and oil repellent of Example 1 into the blended stock solution, and the results of examining the effects of various solvents. are shown in Tables 4 and 5.

[Table] - Equivalent mixture of trichloroethane

[Table] Example 3 Mixed stock solution Fluorinated water and oil repellent ^* 1% Dichloromethane 27% 1,1,2-trichloro-1,2,2-trifluoroethane 27% 1,1,1-trichloroethane 40% Ethanol 5% Aerosol composition Mixed stock solution/Propellant = 70/30 Propellant: Hydrocarbon gas * Fluorine water and oil repellent (a) C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH=
CH ₂ /CH ₂ = CCl-CH = CH ₂ = 1/1 copolymer (b) CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ OCOCH = CH ₂ / chloroprene = 75/25 copolymer (c) CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₄ OCO・CH=CH ₂ /Chloroprene=75/25 copolymer (d) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OCO・CH=CH ₂ /

[Formula] Vinyl chloride = 60/30/10 copolymer (e) CF ₃ (CF ₂ ) ₇ SO ₂ N(CH ₃ ) (CH ₂ ) ₂ OCOCH=
CH ₂ / vinyl chloride / styrene = 85/10/5 copolymer (CF ₃ ) ₂ CF・(CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH=
CH ₂ / vinyl chloride / butadiene = 65/30/5 copolymer All of these have an odor, but compared to conventional commercially available products, there is no noticeable solvent odor, and the water repellency rate is 90 or higher for wool and cashmere cloth. Ta.

Claims (1)

[Scope of Claims] 1. In the blended stock solution, (i) 0.1 to 5% by weight of a fluorine-based water and oil repellent (ii) dichloromethane and/or 1,1,2-trichloro-1,2,2-trifluoro ethane
35-88.9% by weight (iii) 1,1,1-trichloroethane 10-50% by weight (iv) General formula (1) R-OH (1) (wherein R represents an alkyl group having 1 to 4 carbon atoms ) and the general formula (2) R′-OCH ₂ CH ₂ O-R″ (2) (wherein R′ and R″ each represent hydrogen and an alkyl group having 1 to 4 carbon atoms) an aerosol water repellent characterized by containing 1 to 10% by weight of one or more solvents selected from the group consisting of ethylene glycol mono- or dialkyl ethers (excluding hydrogen) Oil composition. 2. The aerosol water and oil repellent composition according to claim 1, wherein the component (iv) is a monohydric alcohol represented by general formula (1). 3. The aerosol water and oil repellent composition according to claim 1 or 2, wherein the fluorine-based water and oil repellent contains a perfluoroalkyl group. 4 The fluorine-based water and oil repellent has the general formula R ^f R〓OCOCR〓=CH ₂ (wherein, R ^f is a linear or branched perfluoroalkyl group having 3 to 20 carbon atoms, and R〓 is a straight chain or branched perfluoroalkyl group having 1 to 20 carbon atoms. 3. The aerosol water and oil repellent composition according to claim 3, which is derived from a monomer represented by 10 linear or branched alkylene groups, R〓 represents hydrogen or a methyl group.