JP4301061B2 - Anti-fogging article - Google Patents

Description

  The present invention relates to an antifogging article having excellent antifogging performance on the surface of various articles.

  When fine water droplets adhere to the surface of the article, clouding occurs due to light scattering. The present invention relates to prevention of fogging caused by fine water droplets adhering to the surface of an article, particularly an optical article, so-called antifogging performance.

  Conventional methods for imparting antifogging performance to the surface of an article include a method of imparting water absorption to the surface to absorb water droplets, a method of increasing the contact angle of water on the surface to make water droplets difficult to adhere, and heating an article. Examples of methods include evaporating water droplets or increasing the dew point on the surface of the article.

  Among these, as a method of reducing the contact angle to water by imparting hydrophilicity to the surface and spreading water droplets, a method of applying a surfactant to the surface of an article or forming a film containing a surfactant on the surface (For example, refer to Patent Document 1).

  In addition, a method is disclosed in which a large number of recesses of 10 nm to 10 μm are formed on the article surface by a specific method, and the surfactant is continuously filled in the recesses so that the surfactant can flow out (see, for example, Patent Document 2). .

  In addition, as a method of imparting antifogging performance by forming a hydrophilic thin film on the surface of an article, a method of treating the surface with organosilane having a highly hydrophilic sulfonic acid group or sulfuric acid group and / or a hydrolyzate thereof ( For example, Patent Literature 3 and Patent Literature 4) are disclosed.

JP 2001-190471 A (second page) JP 2003-149402 A (second page) US Pat. No. 4,325,638 (pages 3 to 6) JP 2002-60692 A (2nd page)

  However, in order to retain the surfactant on the surface of the article shown in Patent Document 2, as shown in Patent Document 1, the composition of applying a surfactant to the surface of the article or forming a film containing the surfactant on the surface In the structure forming the physical structure, the retention of the surfactant is insufficient, and there is a problem in the durability of the antifogging performance. Further, when the article is an optical article, there is a problem that the reflection characteristics change depending on the film thickness of the film formed on the surface.

  A hydrophilic article obtained by treatment with a sulfonic acid-modified organosilane shown in Patent Document 3, an organosilane containing a sulfonic acid or a sulfonic acid precursor, and / or a hydrolyzate thereof, shown in Patent Document 4 The hydrophilic article obtained by the treatment using the antifogging coating liquid diluted in the hydrophilic organic solvent has a problem that the density of the hydrophilic group is insufficient and high antifogging performance cannot be obtained immediately after the treatment.

  The object of the present invention is to eliminate such conventional problems and provide excellent anti-fogging performance to prevent fogging due to fine water droplets in any use environment, and furthermore, the anti-fogging performance can be maintained over a long period of time. It is to provide a cloudy article.

  As a result of intensive research, the inventors of the present invention contain an anionic surfactant in the base material formed with an organic film containing a sulfur atom on the outermost surface, as described below, or anionic surface activity. By applying an anti-fogging agent containing a surfactant other than the above-mentioned anionic surfactant and the above-mentioned anionic surfactant, it has excellent anti-fogging performance and can prevent fogging due to fine water droplets in any use environment. Has been found that it is possible to produce an anti-fogging article that lasts for a long period of time.

  The clouding phenomenon due to water droplets on an article occurs when water vapor condenses on the surface of the article when the water vapor contained in the atmosphere is below the dew point. In the condensation of water vapor, a large number of places on the surface of the article become nuclei, and minute water droplets generated there grow, and in the process of growing, adjacent water droplets are repeatedly combined to generate fine water droplets.

  In order to impart antifogging properties to the surface of an article, the method of preventing the occurrence of fogging by accelerating the bonding of adjacent water droplets in the process of growing the water droplets and spreading the water droplets uniformly, i.e., making the surface hydrophilic. An imparting method is effective. However, in the structure where a generally known surfactant is applied or a film containing a surfactant is formed on the surface, the initial anti-fogging performance is excellent, but the surface activity is immediately caused by the adhesion of water. There is a problem that the anti-fogging performance is not maintained because the agent falls off and the surface active agent applied to the surface is reduced by cleaning with a cloth or the like. Therefore, in order to maintain the antifogging performance, it is important to maintain the antifogging performance over a long period of time without causing the surfactant component applied to the article surface to easily fall off.

Therefore, the first invention forms on the outermost surface an organic film containing a dimer or higher condensate of organosilane or / and a hydrolyzate thereof containing at least one sulfur atom in a non-coupling site. An antifogging article comprising an anionic surfactant, or an antifogging agent containing a surfactant other than the anionic surfactant and the anionic surfactant is applied to the substrate. To do.

  According to the first invention, the base material on which the organic film containing sulfur atoms is formed on the outermost surface contains an anionic surfactant, or a surfactant other than the anionic surfactant and the anionic surfactant. When the anti-fogging agent contained is applied, it not only exhibits excellent anti-fogging performance, but the applied anti-fogging agent does not easily fall off even when a physical load such as wiping is applied, and for a long time. It was found that the anti-fogging performance lasts for a long time. This is strongly adsorbed by the ionic interaction between the functional group containing sulfur atoms present on the outermost surface and the anionic surfactant, and the antifogging agent is easily retained without dropping off, We believe that excellent anti-fogging performance will last for a long time.

  The second invention is characterized in that the anionic surfactant in the antifogging agent contains one or more hydrophilic functional groups selected from sulfonic acid, sulfonate, sulfate, and sulfate. An antifogging article according to Item 1, is provided.

  According to the second invention, when the anionic surfactant contains a functional group containing a sulfur atom, that is, a sulfonic acid, a sulfonate, a sulfate ester, or a sulfate ester salt as a hydrophilic functional group, sulfur existing on the outermost surface. It is considered that the durability of the antifogging performance is further increased because of its high affinity with functional groups containing atoms.

  A third invention provides the antifogging article according to claim 1 or 2, wherein the surfactant other than the anionic surfactant is a nonionic surfactant.

  According to the third invention, by using a nonionic surfactant mixed with an anionic surfactant, the movement of the antifogging agent applied to the surface, which occurs when repeatedly used in a high humidity environment, is suppressed. And it discovered that the fall of anti-fogging performance was suppressed. When an anti-fogging article is used repeatedly in a high humidity environment, a water film is formed on the surface of the article, and in the process of drying the water film, the surfactant component moves from a fast drying part to a slow drying part. A phenomenon occurs in which the high concentration portion and the low concentration portion are not uniform. When this phenomenon occurs, it is known that the anti-fogging performance and the durability thereof are lowered at a site where the component concentration is low. By using a nonionic surfactant in combination with an anionic surfactant, aggregation of the polar anionic surfactant itself can be suppressed, and movement of the surfactant component can be suppressed.

  A fourth invention provides an antifogging article according to claim 1 or 2, wherein the surfactant other than the anionic surfactant is an amphoteric surfactant.

  According to the fourth invention, by using the amphoteric surfactant mixed with the anionic surfactant, the movement of the surfactant component can be suppressed as in the third aspect of the invention. In addition, amphoteric surfactants have both cation sites and anion sites in the molecule, and the cation sites are easily adsorbed on the surface. Sustainability is improved.

  5th invention is an aqueous solution whose total amount of the surfactant component which the said antifogging agent contains in an antifogging agent is 0.2 to 30 weight%, Any one of Claims 1-4 characterized by the above-mentioned. An antifogging article according to any one of the above is provided.

  According to the fifth invention, the total amount of the surfactant component contained in the antifogging agent aqueous solution is set to 0.2 to 30% by weight, more preferably 0.5 to 15% by weight. The effect can be further enhanced. When the total amount of the surfactant components is less than 0.2% by weight, the effect as an antifogging agent is insufficient, and when used repeatedly in a high humidity environment, the antifogging performance may be lowered. On the other hand, when the total amount of the surfactant component exceeds 30% by weight, the coating amount on the base material is excessive, which is undesirable in appearance such as white turbidity, and further when formed on the antireflection film of the optical member This is not preferred because it may impair the antireflection performance.

  According to a sixth aspect of the present invention, the organic film containing a sulfur atom is a simple substance or a dimer or more condensate of organosilane containing at least one sulfur atom in a non-coupling site or / and a hydrolyzate thereof. The antifogging article according to any one of claims 1 to 5 is provided.

  According to the sixth invention, an organic film is formed from a simple substance and a condensate of two or more dimers of an organosilane containing at least one sulfur atom at a non-coupling site and / or a hydrolyzate thereof. By forming a high-density and strong bond on the substrate surface and enhancing the durability of the organic film itself, excellent anti-fogging performance can be maintained for a long period of time.

  The seventh invention provides the antifogging article according to any one of claims 1 to 6, wherein the substrate is a lens.

  According to the seventh invention, in the case where the substrate is a lens, particularly a spectacle lens, since maintenance such as wiping off dirt is frequently performed, the durability of the antifogging performance is required at a very high level. The excellent anti-fogging performance and the sustainability that are the features of the invention can be utilized most effectively.

  According to the present invention, it is possible to obtain an antifogging article having excellent antifogging performance, capable of preventing fogging due to fine water droplets in any use environment, and further maintaining the antifogging performance over a long period of time.

  Hereinafter, embodiments of the antifogging article of the present invention will be described, but the present invention is not limited to the following embodiments.

  The base material formed by forming an organic film containing a sulfur atom on the outermost surface of the present invention can be produced, for example, by the following dip coating method.

  The treatment liquid used in the dip coating method contains an organosilane containing at least one sulfur atom at a non-coupling site and / or a hydrolyzate thereof, and the organosilane or / and the hydrolyzate thereof is only a simple substance. It is preferable to contain a dimer or higher condensate. Condensates with a dimer or higher improve the density of hydrophilic groups in the membrane, and organosilane or / and its hydrolyzate present as a simple substance, in addition to fixing the substrate and the membrane, condense the dimer or higher. It plays the role of glue that fills the gap by reacting between condensates of dimers or more with single molecules and between single molecules. Thereby, high adhesiveness with the article surface is expressed, and there is an effect of improving the film strength. Furthermore, the simple substance that acts as a paste also contains a hydrophilic group, and without degrading the hydrophilic group density on the surface of the organic film, excellent antifogging performance and sufficient retention of the antifogging agent applied on it are obtained. It is done.

  Functional groups such as sulfonic acid ester groups, thiol groups, sulfide groups, disulfide groups in organosilanes containing at least one or more sulfur atoms at non-coupling sites and / or their hydrolysates exhibit extremely high hydrophilicity. By converting to a sulfonic acid group, better anti-fogging performance can be imparted. The oxidation of the sulfonic acid ester group, thiol group, sulfide group, and disulfide group may be performed before or after the condensation of organosilane or / and its hydrolyzate, but a general oxidation reaction (sodium permanganate) , Oxidation with potassium dichromate, hydrogen peroxide, ozone-containing gas, etc.).

  Before applying the treatment liquid, in order to further improve the antifogging performance by further increasing the reaction rate between the organosilane containing at least one sulfur atom in the non-coupling site and / or its hydrolyzate and the article surface Further, pretreatment such as plasma treatment, alkali treatment, rubbing treatment, etc. may be performed.

  Examples of organosilanes containing at least one or more sulfur atoms at non-coupling sites include 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxy. Silane, 2-mercaptopropyltriethoxysilane, 2-mercaptopropyltrimethoxysilane, 2-mercaptopropylmethyldimethoxysilane, 2-mercaptopropyldimethylmethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyldimethylmethoxysilane, 2- (2-chloroethylthioethyl) triethoxysilane, mercaptome Rutrimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 2- (2-aminoethylthioethyl) diethoxymethylsilane, dimethoxymethyl-3- (3-phenoxypropylthiopropyl) silane, 3- (2-acetoxyethyl) Thiopropyl) dimethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, 3-trimethoxysilylpropanesulfonic acid isopropyl ester, bis [3- (triethoxysilyl) propyl] tetrasulfide, bis [3- (Triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] sulfide, 3-trimethoxysilylpropylsulfonic acid and the like.

  Subsequently, a dimer or higher condensate of organosilane containing at least one or more sulfur atoms in a non-coupling site and / or a hydrolyzate thereof is formed, and a mixture of a simple substance and a dimer or higher condensate is obtained. The process to do is described.

  The coupling site of the organosilane containing at least one sulfur atom in the non-coupling site and / or its hydrolyzate is slowly hydrolyzed and condensed at a low temperature in a hydrophilic organic solvent and rapidly as the temperature increases. If the temperature is less than 0 ° C., the condensation is slow, and if the temperature exceeds 70 ° C., the condensation proceeds very fast. Therefore, after diluting organosilane or / and its hydrolyzate in a hydrophilic organic solvent, it is preferable to hold at 0 to 70 ° C. for 0.1 to 200 hours. Furthermore, in order to control the degree of condensation more stably, it is preferable to hold at 0 ° C. to 40 ° C. for 2 hours to 200 hours. Moreover, you may use the 1 or more types of catalyst chosen from an acid catalyst, an alkali catalyst, an amine catalyst, and a metal compound catalyst as needed.

Specifically, the acid catalyst includes hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, tartaric acid, citric acid, carbonic acid, and the like, and the alkali catalyst includes sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium compound, and the like. . Amine catalysts include ethylenediamine, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, n-butylamine, triethylamine, guanidine and other amines, glycine and other amino acids, 2-methylimidazole, 2,4 -Diethylimidazole, 2-phenylimidazole, etc. are mentioned. Metal compound catalysts include metal acetylacetonates such as aluminum acetylacetonate, titanium acetylacetonate and chromium acetylacetonate, organic acid metal salts such as sodium acetate, zinc naphthenate and tin octylate, SnC ₁₄ , TiC ₁₄ , ZnC _And Lewis acid such as _{12 and} magnesium perchlorate. The amount of the catalyst is unclear because the effect varies depending on the catalyst, but it is preferably used within a range that does not impair the antifogging performance of the obtained organic film, and is 75% or less based on the solid content in the treatment liquid. Is preferably used.

  The antifogging article forming the organic film is made of a material selected from the group consisting of glass, plastic, oxide, metal, wood, ceramic, cement, concrete, fiber, paper, stone, and leather. anything is fine. In view of the reaction with the coupling component, an oxide surface containing glass is more preferable. In addition, when the article is used for optical applications, the reflective properties of the surface may change depending on the thickness of the organic film formed on the surface, but the organic film of the present invention should have a thickness that does not affect the optical properties. Can do.

  As the solvent used in the treatment liquid, water or a hydrophilic organic solvent is preferable, for example, alcohols such as methanol, ethanol, propanol and butanol, glycols such as ethylene glycol and propylene glycol, glycerin, propylene glycol monomethyl ether and the like. Examples include glycol ethers, ketones such as acetone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane. The hydrophilic organic solvent may be a single type or a mixed solvent of two or more types. Further, a surfactant may be added to the treatment liquid for the purpose of improving the uniformity and appearance of the organic film.

  The antifogging article of the present invention contains, for example, an anionic surfactant on a substrate on which an organic film containing a sulfur atom produced by the above-described method is formed, or an anionic surfactant and the anionic surfactant An antifogging agent containing a surfactant other than the above is applied. Examples of the application method include a dip coating method, a spin coating method, and a spray coating method. As a simple method, a defogging agent is attached to the substrate surface and then wiped with a cloth or paper. An excellent antifogging performance can be obtained by increasing the thickness or applying it using a cloth or paper impregnated with an antifogging agent.

  The surfactant used as a component of the antifogging agent is preferably anionic because of interaction with a functional group containing a sulfur atom present in the organic film, and more preferably the anionic group is sulfonic acid or sulfonic acid. It preferably contains one or more hydrophilic functional groups selected from salts, sulfates and sulfates. Moreover, you may use surfactant, 1 type or in mixture of 2 or more types.

  Specific anionic surfactants include sodium lauryl sulfate, higher alcohol sodium sulfate, lauryl sulfate triethanolamine, alkyl sulfate salts such as ammonium lauryl sulfate, polyoxyethylene lauryl ether sulfate, polyoxyethylene alkyl ether sodium sulfate, Polyoxyethylene alkyl ether sulfate triethanolamine, polyoxyethylene alkyl (or alkylallyl) ether sulfate ester salt such as sodium polyoxyethylene alkyl phenyl ether sulfate, alkylbenzene sulfonate such as sodium dodecylbenzenesulfonate, alkylnaphthalene sulfone Alkylnaphthalene sulfonates such as sodium acrylate, alkyl sulfones such as sodium dialkylsulfosuccinate Alkyl diphenyl ether disulfonates such as succinate, alkyl diphenyl ether disulfonate, alkyl phosphates such as potassium alkyl phosphate, special reaction type anionic surfactant, special carboxylic acid type surfactant, β- Examples thereof include sodium salt of naphthalene sulfonic acid formalin condensate, sodium salt of special aromatic sulfonic acid formalin condensate, special polycarboxylic acid type polymer surfactant, polyoxyethylene alkyl phosphate ester and the like.

  As the antifogging agent, a nonionic surfactant can be mixed with an anionic surfactant and used. Specifically, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether such as polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, etc. Polyoxyethylene alkyl aryl ethers, polyoxyethylene derivatives, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, sorbitan distearate Sorbitan fatty acid ester such as rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan Polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate and other polyoxyethylene sorbitan fatty acid esters, tetra Polyoxyethylene sorbitol fatty acid esters such as oleic acid polyoxyethylene sorbitol, glycerol monostearate, glycerol monooleate, glycerin fatty acid esters such as self-emulsifying glycerol monostearate, polyethylene glycol monolaurate, polyethylene glycol monostearate, Polyethylene glycol distearate, polyethylene glycol monooleate, etc. Polyoxyethylene fatty acid esters, polyoxyethylene alkyl amines, polyoxyethylene hardened castor oil, and alkyl alkanolamides.

  Furthermore, for the antifogging agent, an amphoteric surfactant can be mixed with an anionic surfactant. Specifically, alkylbetaine-type amphoteric surfactants such as lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, alkylamide betaine types such as lauric acid amidopropyldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine Amphoteric surfactants, sulfobetaine-type amphoteric surfactants such as lauryl hydroxysulfobetaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, N-lauroyl-N′-carboxymethyl-N′- Examples include imidazolinium betaine-type amphoteric surfactants such as hydroxyethyl imidazolinium betaine, sodium lauryldiaminoethylglycine, sodium laurylaminodiacetate, and lecithin.

  In addition to the surfactant component, an additive may be added as a component of the antifogging agent for the purpose of improving coatability and preventing bacterial growth. Examples of the additive include commonly used preservatives and thickeners, and it is particularly preferable to use alcohols such as ethanol, propanol, and isopropyl alcohol.

  The following Examples and Comparative Examples of the present invention are illustrative, and the present invention is not limited to the following specific examples. Those skilled in the art can make various modifications to the embodiments shown below to fully implement the present invention, and such modifications are included in the scope of the claims of the present application.

(Preparation of treatment liquid)
A 3-mercaptopropyltrimethoxysilane solution (3.9 g dissolved in 60 ml of acetone) was dropped into 200 ml of a 0.4 mol / l manganese peroxide aqueous solution over 1 hour while cooling with ice. After completion of the dropwise addition, the unreacted permanganate was changed to manganese dioxide by stirring at 25 ° C. for 2 hours. Manganese dioxide was filtered off from the reaction solution to obtain a slightly yellowish filtrate. When this filtrate was analyzed by FT-NMR, it was found that the thiol group was oxidized, the methoxy group was hydrolyzed, and potassium trisiloxypropanesulfonate was synthesized. Moreover, it was 3 wt% when solid content concentration of the trisiloxy propane sulfonate potassium solution was measured.

  The obtained potassium trisiloxypropanesulfonate was passed through 100 ml of a strongly acidic cation exchange resin (Amberlite IR-120Na manufactured by Organo Corporation) at a drug speed SV4. The pH of the potassium trisiloxypropane sulfonate solution was 10.5, whereas the pH of the ion-exchanged solution was 1.3, and potassium sulfonate was ion-exchanged to sulfonic acid, and tristrisiloxypropane sulfonic acid It was confirmed that it was in solution. When the solid content concentration of the trisiloxypropanesulfonic acid solution was measured, it was 1.5 wt%.

  This trisiloxypropane sulfonic acid solution was diluted with ethanol so that the solid content concentration became 0.15 wt% to obtain 150 g of a diluted solution. After this diluted solution was stored at 0 ° C. for 72 hours, 100 ppm of sodium dilauryl sulfosuccinate (Nikko Chemicals Corporation Nikkor OTP-100) was added to the total amount of the processing solution to prepare a processing solution.

  When a part of this treatment solution was diluted 20 times with pure water and analyzed by LC / MS, the presence of a dimer or higher condensate was confirmed, and the ratio was 10 wt% in the total solid content. It was confirmed.

(Formation of organic film on lens surface)
A plastic lens for spectacles (Seiko Super Sovereign manufactured by Seiko Epson Corporation) having a hard coat film and an antireflection film (the outermost layer is a SiO ₂ film) is plasma-cleaned, immersed in a treatment solution for 1 minute, and then pulled at a constant speed. The coating was carried out at a lifting speed of 20 cm / min with an apparatus. The plasma cleaning conditions were as follows: processing pressure: 0.1 Torr, introduced gas: dry air, distance between electrodes: 24 cm: power output: DC 1 KV, processing time: 15 sec.

  The lens to which the treatment liquid was applied was held at 60 ° C. for 4 hours in a hot-air circulating thermostatic chamber to complete the reaction with the base material to obtain an organic film-forming lens.

(Preparation of antifogging agent)
Anionic surfactant: 5 g of sodium polyoxyethylene lauryl ether sulfate (Nikko Chemicals Nikkor SBL-4N) was dissolved in 95 g of water to prepare an antifogging agent.

(Application of antifogging agent to organic film-forming lens substrate)
One drop (about 0.02 g) of the antifogging agent was dropped onto the organic film forming lens, and spread with tissue paper, and at the same time, the excessively adhered components were wiped off. The contact angle of the lens thus obtained with respect to pure water was 5 ° or less, and no defects in appearance such as cloudiness were confirmed. The reflectance did not change before and after treatment.

(Preparation of antifogging agent)
Anionic surfactant: Polyoxyethylene lauryl ether sodium sulfate (Nikko Chemicals Nikkor SBL-4N) 8 g, Nonionic surfactant: Polyethylene glycol monolaurate (Nikko Chemicals Nikkor MYL-10) 2 g, Ethanol 5 g Dissolved in 85 g of water to obtain an antifogging agent.

(Application of antifogging agent to organic film-forming lens substrate)
One drop (about 0.02 g) of the antifogging agent prepared above is dropped onto the organic film-forming lens produced in the same manner as in Example 1, and spread with tissue paper, and at the same time, the extra attached component Wiped off. The contact angle of the lens thus obtained with respect to pure water was 5 ° or less, and no defects in appearance such as cloudiness were confirmed. The reflectance did not change before and after treatment.

(Preparation of antifogging agent)
Anionic surfactant: 8 g of sodium polyoxyethylene lauryl ether sulfate (Nikko Chemicals Nikkor SBL-4N), amphoteric surfactant: 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine (Nikko Chemicals) Nikkor AM-101) (2 g) and 20 g of ethanol were dissolved in 70 g of water to obtain an antifogging agent.

(Application of anti-fogging agent to organic film-forming lens substrate)
Two drops (about 0.04 g) of the antifogging agent prepared above are dropped and impregnated into the tissue paper, and the antifogging agent is immersed in the organic film forming lens produced by the same method as in Example 1. The remaining components were wiped off using a tissue paper and wiped off. The contact angle of the lens thus obtained with respect to pure water was 5 ° or less, and no defects in appearance such as cloudiness were confirmed. The reflectance did not change before and after treatment.

(Preparation of antifogging agent)
Anionic surfactant: 1 g of sodium lauryl sulfate (Nikko Chemicals Corporation Nikkor SLS), Nonionic surfactant: 1 g of polyethylene glycol monolaurate (Nikko Chemicals Corporation Nikkor MYL-10), 40 g of methanol are dissolved in 58 g of water. Antifogging agent was used.

(Application of antifogging agent to organic film-forming lens substrate)
The antifogging agent prepared above was applied to the surface of the organic film forming lens produced by the same method as in Example 1 by the dip coating method. The dip coating conditions were an immersion time of 10 seconds and a lifting speed of 10 mm / min. The contact angle of the lens thus obtained with respect to pure water was 5 ° or less, and no defects in appearance such as cloudiness were confirmed. The reflectance did not change before and after treatment.

(Preparation of treatment liquid)
2.9 g of 3-trimethoxysilylpropanesulfonic acid isopropyl ester is dissolved in 60 ml of glacial acetic acid, and 35 g of 30% hydrogen peroxide solution is added dropwise over 1 hour while maintaining the liquid temperature at 25-30 ° C. After the dropwise addition, the mixture was stirred at 25 ° C. for a whole day and night. When this liquid was analyzed by FT-NMR, it was found that the sulfonic acid ester group was oxidized, the methoxy group was hydrolyzed, and trisiloxypropanesulfonic acid was synthesized. Moreover, it was 4 wt% when solid content concentration of the trisiloxypropanesulfonic acid solution was measured.

  This trisiloxypropanesulfonic acid solution was diluted to 0.2 wt% with ethanol to 150 g. N-aminoethylethanolamine 0.1g was mixed here, and it stirred at 30 degreeC for 2 hours. Here, 50 ppm of sodium lauryl sulfate (Nikko Chemicals Nikkor SLS) was added to the total amount of the processing solution to prepare a processing solution.

  When a part of this treatment solution was diluted 20 times with pure water and analyzed by LC / MS, the presence of a dimer or higher condensate was confirmed, and the ratio was 40 wt% of the total solid content. It was confirmed.

(Formation of organic film on article surface)
After immersing the optical components for projectors, which have been immersed in 1.6N potassium hydroxide solution at 40 ° C. for 3 minutes and thoroughly washed with pure water for 1 minute, with a constant speed lifting device at a lifting speed of 10 cm / min. Coated.

  The projector optical component coated with the treatment liquid was held in a hot-air circulating thermostat at 120 ° C. for 1 hour to complete the reaction with the substrate to obtain an organic film-forming projector optical component.

(Preparation of antifogging agent)
Anionic surfactant: 5 g of sodium polyoxyethylene lauryl ether sulfate (Nikko Chemicals Nikkor SBL-4N) was dissolved in 95 g of water to prepare an antifogging agent.

(Application of antifogging agent to organic film-forming lens substrate)
The antifogging agent prepared above was applied to the surface of the obtained optical component for an organic film forming projector by a dip coating method. The dip coating conditions were an immersion time of 10 seconds and a lifting speed of 10 mm / min. The contact angle of the optical member for projector thus obtained with respect to pure water was 5 ° or less, and no defects in appearance such as cloudiness were confirmed. The reflectance did not change before and after treatment.

[Comparative Example 1]
(Application of antifogging agent to organic film-forming lens substrate)
One drop (about 0) of the antifogging agent prepared in Example 1 was applied to a plastic lens for spectacles (Seiko Super Sovereign manufactured by Seiko Epson Corporation) having a hard coat film and an antireflection film (the outermost layer being a SiO ₂ film). .02 g) The solution was dropped and spread with tissue paper, and at the same time, the excessively adhered components were wiped off. The contact angle of the lens thus obtained with respect to pure water was 5 ° or less, and no defects in appearance such as cloudiness were confirmed.

[Comparative Example 2]
(Preparation of antifogging agent)
Nonionic surfactant: 5 g of polyoxyethylene monostearate (Nikko Chemicals Nikkor MYS-40) was dissolved in 95 g of water to prepare an antifogging agent.

(Application of antifogging agent to organic film-forming lens substrate)
One drop (about 0.02 g) of the above antifogging agent was dropped on the organic film-forming lens produced in Example 1 and spread with tissue paper, and at the same time, the excessively adhered components were wiped off. The contact angle of the lens thus obtained with respect to pure water was 5 ° or less, and no defects in appearance such as cloudiness were confirmed. The reflectance did not change before and after treatment.

[Comparative Example 3]
(Preparation of antifogging agent)
Cationic surfactant: 5 g of cetyltrimethylammonium chloride (Nikko Chemicals Nikkor CA-2350) was dissolved in 95 g of water to prepare an antifogging agent.

(Application of antifogging agent to organic film-forming lens substrate)
One drop (about 0.02 g) of the above antifogging agent was dropped on the organic film-forming lens produced in Example 1 and spread with tissue paper, and at the same time, the excessively adhered components were wiped off. The contact angle of the lens thus obtained with respect to pure water was 5 ° or less, and no defects in appearance such as cloudiness were confirmed. The reflectance did not change before and after treatment.

The antifogging articles obtained in Examples and Comparative Examples were evaluated by the following evaluation methods. The results are shown in Table 1.
<Method of evaluation>
Initial antifogging property:
The sample stored at 20 ° C. was transferred to an environment maintained at a temperature of 40 ° C. and a relative humidity of 90%, and the occurrence of cloudiness on the surface was visually observed. Visual haze was evaluated in the following four stages.
◎ ・ ・ ・ No clouding ○ ・ ・ ・ Slightly cloudy but no problem in practical use △ ・ ・ ・ Fog disappears after 2 minutes (problem in practical use)
× ... Cloudy does not disappear even after 2 minutes

Anti-fog durability:
The sample stored at 20 ° C. was held in an environment maintained at a temperature of 40 ° C. and a relative humidity of 90% for 3 minutes, and then transferred to an environment maintained at a temperature of 20 ° C. and a relative humidity of 35% to remove moisture adhering to the surface. After drying, this series of operations was repeated several times as one cycle. The antifogging performance at that time was evaluated in the following four stages.
◎ ... No clouding even after 6 cycles ○ ... Clouding occurs in the 3rd to 5th cycles, but no problem in practical use △ ... Clouding occurs in the 2nd cycle × ... Clouding in the 1st cycle Occurs

Anti-fog durability:
The surface of the article was subjected to a load of 200 g with cloth (cotton) and rubbed 5,000 times, and then washed with pure water and dried. After storing this sample at 20 ° C., it was transferred to an environment maintained at a temperature of 40 ° C. and a relative humidity of 90%, and the occurrence of cloudiness on the surface was visually observed. Visual haze was evaluated in the following four stages.
◎ ・ ・ ・ No clouding ○ ・ ・ ・ Slightly cloudy but no problem in practical use △ ・ ・ ・ Fog disappears after 2 minutes (problem in practical use)
× ... Cloudy does not disappear even after 2 minutes

Comprehensive evaluation:
From the evaluation of initial antifogging property, antifogging durability, and antifogging durability, the overall antifogging performance was evaluated in the following three stages.
○ ・ ・ ・ No problem in practical use △ ・ ・ ・ There is an anti-fogging effect but there is a problem in practical use × ・ ・ ・ Not practical

  From the results of Table 1, the base material formed with an organic film containing sulfur atoms on the outermost surface contains an anionic surfactant or contains a surfactant other than the anionic surfactant and the anionic surfactant. The antifogging articles obtained by applying the antifogging agent (Examples 1 to 5) obtained practically sufficient performance in all of the initial antifogging performance, antifogging durability and antifogging durability. . However, an antifogging article (Comparative Example 1) in which an organic film containing a sulfur atom is not formed on the outermost surface, and an antifogging article not containing an anionic surfactant as an antifogging agent (Comparative Examples 2-3) In particular, the anti-fogging sustainability was at a level that causes a practical problem.

The present invention relates to a lens for glasses / cameras having anti-fogging performance, or an optical article such as a window glass, a car windshield, a helmet shield, underwater glasses, or a mirror used in a bathroom.

Claims (7)

To a base material formed on the outermost surface an organic film containing a condensate of a dimer or higher of an organosilane containing at least one sulfur atom at a non-coupling site or / and a hydrolyzate thereof ,
An antifogging article comprising an anionic surfactant or an antifogging agent containing an anionic surfactant and a surfactant other than the anionic surfactant.   The antifogging agent according to claim 1, wherein the anionic surfactant in the antifogging agent contains one or more hydrophilic functional groups selected from sulfonic acid, sulfonate, sulfate, and sulfate. Sex goods.   The antifogging article according to claim 1, wherein the surfactant other than the anionic surfactant is a nonionic surfactant.   The antifogging article according to claim 1, wherein the surfactant other than the anionic surfactant is an amphoteric surfactant. The total amount of the surfactant component contained in the antifogging agent in the antifogging agent is an aqueous solution of 0.2 to 30% by weight, according to any one of claims 1 to 4. Anti-fogging article.   The organic film containing a sulfur atom is composed of a simple substance or a dimer or more condensate of organosilane containing at least one sulfur atom at a non-coupling site and / or a hydrolyzate thereof. The anti-fogging article according to any one of claims 1 to 5.   The antifogging article according to any one of claims 1 to 6, wherein the substrate is a lens.