JPS6115911B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antifogging agent composition, and more specifically, a water-soluble fluorinated surfactant containing a perfluoroalkyl group (hereinafter sometimes simply referred to as a fluorinated surfactant), a hydrophobic group containing a water-soluble fluorinated surfactant, and a hydrophobic group. Water-soluble non-fluorinated surfactants with no fluorine atoms bonded (hereinafter referred to as
It is sometimes simply referred to as a non-fluorinated surfactant. ),
and a novel antifogging agent composition containing anionic polyacrylamide as an essential component. Conventionally, various antifogging agents for glass surfaces have been proposed. For example, aqueous solutions containing surfactants as active ingredients are commercially available in aerosol form. A variety of products have also been proposed that have anti-fogging performance, oil film removing performance, cleaning performance, etc. at the same time. Such conventional antifogging agents are
Although most products are practically satisfactory in terms of anti-fog durability, oil film removal effect, etc., there are some drawbacks in anti-fog performance at low temperatures, and wiping streaks (haze) may occur on the glass surface during the coating process. Or, a whitening phenomenon may be observed after the paint film dries. The present inventor has discovered that it is possible to provide an excellent anti-fog effect even in a wide temperature range, especially at low temperatures, and has excellent anti-fog durability and oil film removal effect, and also does not have drawbacks such as generation of light spots or whitening of the paint film. The present invention was completed as a result of various studies and studies aimed at creating an antifogging agent. That is, the present invention provides water-soluble fluorinated surfactants containing perfluoroalkyl groups (excluding cationic surfactants), water-soluble non-fluorinated surfactants that do not have a fluorine atom bonded to the hydrophobic group (cationic ),
and anionic polyacrylamide as essential components. The antifogging agent of the present invention exhibits various functions in a well-balanced manner due to the combination of three types of essential components, and can be extremely suitably used as a practical antifogging agent for glass surfaces. Firstly, it has good anti-fogging durability, does not generate light spots, and has an excellent oil film removal effect. Furthermore, it exhibits an excellent antifogging effect even at low temperatures of 0° C. or lower, is suitable for use in cold regions, and can be applied over a wide temperature range. Furthermore, when applied to a glass surface, the coating film is transparent without whitening after drying. In the present invention, various examples of the fluorinated surfactant include, without particular limitation, conventionally known or well-known surfactants containing perfluoroalkyl groups. Therefore, such fluorinated surfactants are usually selected from anionic, nonionic, or amphoteric types, taking into consideration their compatibility with the anionic polyacrylamide described below, and cationic types. is undesirable because it reacts with the anionic polyacrylamide, which is another essential component, and inhibits various effects of the present invention. In addition, the perfluoroalkyl group usually has 4 to 4 carbon atoms.
About 20 groups are selected, and perfluoroalkyl groups having 6 to 12 carbon atoms are particularly suitable. Water-soluble fluorinated surfactants containing perfluoroalkyl groups are
The antifogging agent composition of the present invention, which has an excellent ability to lower surface tension, has improved wettability, and in particular, improved oil film removal effect. If the number of carbon atoms in the perfluoroalkyl group is less than 4, the fluorinated surfactant becomes too hydrophilic and wettability decreases, which is not preferable.
If it is more than 20, it is not preferable because it becomes difficult to dissolve in water and the transparency of the antifogging agent decreases. Furthermore, it is important that the fluorinated surfactant has a solubility in water of 0.1% or more, and if it is water-insoluble, the various effects of the present invention will not be achieved. Specific examples of suitable fluorinated surfactants in the present invention include the following.
That is, C ₈ F ₁₇ COONH ₄ , C ₈ F ₁₇ SO ₄ K, C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) CH ₂ COONH ₄ , C ₁₀ F ₂₁ CONH (CH ₂ ) ₅ COONH ₄ , C ₈ F ₁₇ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂・CH ₂ COO, C ₈ F ₁₇ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂・CH ₂ CH ₂ CH ₂ SO ₃ , C ₈ F ₁₇ CONH (CH ₂ ) ₃ N (CH ₂ ) ₃・CH ₂ CH ₂ COO, Examples include C ₈ F ₁₇ CONH (CH ₂ CH ₂ O) ₁₀ H. Next, in the present invention, it is important to include anionic polyacrylamide as an essential component. If anionic polyacrylamide is not added, the effect of improving antifogging performance at low temperatures will not be achieved, and the antifogging durability will also be insufficient. Such anionic polyacrylamide may be one that is generally used as a paper strength enhancer, such as Polystron 117 (Arakawa Chemical), Hermide B-15 (Harima Kasei), Polyacron ST (Hamano Industries), Star Gum A-15. (Star Photochemistry), etc. Usually, an acrylamide polymer or copolymer with a molecular weight of around 300,000 is anionized by hydrolysis or the like to several mol%. Of course, acrylamide may be anionized by copolymerizing vinyl acetate, acrylic acid, or the like, or anionized by copolymerizing acrylonitrile or the like. Furthermore, the composition of the present invention contains, as an essential component, a non-fluorinated surfactant in which a fluorine atom is not bonded to a hydrophobic group. Examples of the non-fluorinated surfactant include various conventionally known hydrocarbon compounds having both a hydrophilic group and a hydrophobic group in the molecule. Generally, an anionic, nonionic, or amphoteric type is selected, and a cationic type is undesirable because it reacts with the anionic polyacrylamide, which is another essential component, and inhibits various effects of the present invention. Further, it is important that the solubility in water is 0.1% or more, and in the case of water insolubility, the various effects of the present invention cannot be achieved. Preferred specific examples of non-fluorinated surfactants include the following. Namely, sodium alkylbenzene sulfonate, sodium lauryl sulfate, C ₁₂ H ₂₅ (OC ₂ H ₄ )nOSO ₃ Ha, C ₁₂ H ₂₅ N(CH ₃ ) ₂・CH ₂ COO, _{C12H25O ( C2H5O} ) _nH , etc. The antifogging agent composition of the present invention is used in a form in which the above-mentioned essential components are appropriately dissolved or dispersed in a medium. Generally, the form of an aqueous medium composition is preferable, such as an aqueous solution form. The concentration of the above-mentioned essential components is not particularly limited, but is usually 0.01 to 1
% by weight, preferably 0.05-0.3% by weight, water-soluble non-fluorinated surfactant 0.01-10% by weight, preferably 3-6% by weight, anionic polyacrylamide
The concentration is selected from a range of about 0.01 to 10% by weight, preferably about 1 to 5% by weight. In the present invention, it goes without saying that in addition to the above-mentioned essential components and medium, various additives and others may be appropriately added or used in combination. For example, when the composition of the present invention is made into an aerosol form, it can be filled into a container together with an appropriate propellant. Good results can also be obtained by adding various water-soluble solvents, such as alcohol, propylene glycol, ethylene glycol, butyl cellosolve, butyl carbitol, etc., for the purpose of enhancing detergency or lowering the freezing point. Furthermore, fragrances, stabilizers, rust preventives, etc. may be added. The rust preventive of the present invention has excellent, well-balanced performance as described above, so it can be used for a wide range of purposes such as anti-fogging, cleaning, and removing oil films from glass, plastic, and metal surfaces. It can demonstrate sufficient performance on the ground. Including automobile windshields,
It can be effectively applied in a wide range of fields such as bathroom mirrors and eyeglass lenses. Next, examples of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by such explanations. In addition, in the following Examples and Comparative Examples, various performances were measured as follows. That is, the antifogging durability was measured by the method specified in the Automotive Supplies Industry Standard "Antifogging Agent" JARP212. For the light beam, an anti-fog agent was applied to a cleaned glass plate, and when light from a light bulb was viewed through the glass plate, it was visually determined whether there was any scattering of light. To measure low-temperature haze, place a -5°C ethanol aqueous solution in 10 beakers that have been thoroughly cleaned with an abrasive detergent, coat the outside with an anti-fog agent, and place in a constant temperature, constant humidity room at 20°C and 60% humidity. The rate of clouding that occurred after 24 hours of storage was measured. Anti-fog agent is 10
Apply 15g to the entire outer surface of the beaker and wipe it with a cloth. Further, the fogging rate was determined by the area of the fogging that occurred/the area of the antifogging agent applied x 100 [%] (the area of the entire outer surface of the 10 beakers). The oil film removal effect was determined by the following method. That is, 1 g of antifogging agent is applied to a glass plate (10 cm x 10 cm) contaminated with silicone oil and wiped off with a cloth. When the light from the bulb was viewed through this glass plate, it was visually observed to see if there was any scattering of the light, and if there was no scattering, the oil film removal effect was judged to be "exist." Example 1 Sodium alkylbenzene sulfonate (alkyl group is a mixture of _C4 to _C12 ) 4.0% by weight Sodium alkylbenzene polyoxyethylene sulfonate ( _{polyoxyethylene} group is ( _OC2H4 ) ₃ , alkyl group is _C4 to C12) ₁₂ mixture) 2.0% by weight C ₈ F ₁₇ CONH (CH ₂ ) ₅ COONH ₄ 0.3% by weight Heramide B-15 (Harima Kasei; anionized with a carboxyl modification rate of 5 mol %, molecular weight approx.
50000 polyacrylamide) 2.0% by weight Ethanol 11.0% by weight Water 80.7% by weight Example 2 C ₁₂ H ₂₅ SO ₃ Na 4.0% by weight C ₁₀ F ₂₁ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂・CH ₂ COO
0.3% by weight Heramide B-15 (Harima Kasei) 2.0% by weight Ethanol 12.0% by weight Water 81.7% by weight Comparative Example 1 In Example 1, C ₈ F ₁₇ CONH
Composition excluding (CH ₂ ) ₅ COONH ₄ . Comparative Example 2 The composition of Example 1 except that Heramide B-15 was excluded. Comparative Example 3 A composition in Example 1 except that sodium alkylbenzene sulfonate and sodium alkylbenzene polyoxyethylene sulfonate were excluded. The compositions of Examples 1 to 2 and Comparative Examples 1 to 3 were evaluated for performance, and the results are shown in Table 1 below.

【table】

[Table] Example 3 Same as Example 1 except that the antifogging agent having the same composition as in Example 1 was applied to a transparent plastic plate instead of a glass plate, and was applied to a polypropylene beaker instead of a glass beaker. Measured in a similar way,
Anti-fog durability - 3 times, light beams - none, oil film removal effect -
Yes, condition after coating and drying: Transparent, low-temperature haze: 0%
The results were obtained. Example 4 Measurement was carried out in the same manner as in Example 2, except that the antifogging agent with the same composition as in Example 2 was applied to a metal plate instead of a glass plate, and was applied to a stainless steel beaker instead of a glass beaker. and anti-fog durability - 3 times,
The following results were obtained: light rays: absent, oil film removal effect: present, state after coating and drying: transparent, and low-temperature haze rate: 0%. The light beam and oil film removal effect were determined visually by determining whether there was scattering of light when the light from the bulb was reflected on the metal plate.

Claims (1)

[Scope of Claims] 1. A water-soluble fluorinated surfactant containing a perfluoroalkyl group having 4 to 20 carbon atoms (excluding cationic surfactants), a water-soluble non-fluorinated surfactant in which a fluorine atom is not bonded to a hydrophobic group. Chemically modified surfactants (excluding cationic ones),
and an anionic polyacrylamide as essential components. 2 Water-soluble fluorinated surfactant 0.01 to 1% by weight,
0.01-10% by weight of water-soluble non-fluorinated surfactant and 0.01-10% by weight of anionic polyacrylamide
A composition according to claim 1 containing the essential ingredients at a concentration of .