JP2003183618A - Antifogging agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifogging agent having good durability of the effect, transparency, slipperiness, applicability, antifreezing property (application at low temperature) and antiblocking property. <P>SOLUTION: The water-based antifogging agent contains a polyacrylic acid salt, a hydrophilic surfactant and an alcohol and has a pH of 4-9 and a viscosity of 10-150 mPas. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mirror, window glass, glasses, goggles, show window, showcase, water tank, surveillance camera, medical instrument such as endoscope, ceramics, or vehicle such as automobile, ship, vehicle and the like. The present invention relates to a fog-preventing agent for aqueous solution, which prevents fogging of glass, plastics, etc. constituting window glass or back mirror.

[0002]

2. Description of the Related Art Mirrors, window glasses, spectacles, goggles, show windows, showcases, water tanks, surveillance cameras, medical instruments such as endoscopes, ceramics, and window glasses or back mirrors for vehicles such as automobiles, ships and vehicles. Glass, plastics, etc. that compose etc. are liable to fog due to water droplets adhering to the surface due to changes in the weather, temperature and humidity, etc. Come here.

In order to prevent such fogging, dry air or hot air is blown onto the object or heat rays are embedded in the object to prevent water vapor from adhering or to evaporate adhering water droplets. Means for preventing the fogging are also provided, and it is also attempted to prevent the fogging by lowering the surface tension of the coagulated water by applying or spraying a surfactant.

Specifically, for example, nonionic (nonionic)
Type anti-fog agent containing sucrose fatty acid ester (JP-A-62-4773), anti-fog agent containing surfactant and polyacrylic acid (JP-A-51-9192)
No. 0, JP-A-52-101680, JP-A-50-81.
No. 985) is known. As an example of observing the characteristics of the coated film in another application field, a surface treatment agent containing sucrose fatty acid ester and high molecular weight sodium polyacrylate (JP-A-5-287097) is described. Further, an antifogging agent containing a surfactant, polyacrylic acid, polyhydric alcohol, etc. (JP-A-56-11129).
No. 84) is known.

[0005]

However, dry air or hot air is blown onto the object or heat rays are embedded in the object to prevent water vapor from adhering or to evaporate the adhering water droplets. However, the method is not general because the use of the device is large and the usage is limited.

On the other hand, the method using a detergent, a surfactant or a hydrophilic antifog agent is not always satisfactory from the viewpoints of the sustainability of the effect and the transparency. Further, the anti-fog agent having a high molecular weight acrylic acid water-soluble polymer is not always satisfactory in terms of workability, coating state and effect. Furthermore, it is not always satisfactory in terms of antifreeze and effect of the anti-fog agent when used in low temperatures such as cold regions and refrigerated showcases. On the contrary, the effect of the antifog agent is not always satisfactory when used in a hot and humid bath or the like. That is, as the performance that the anti-fog agent should have, the effect persistence, the application range ability of temperature and humidity, the transparency (or the coating mark, the whitening, the prevention of the oil film, etc.), the smoothness, the ease of coating (or the non-coating property). (Stringiness, spreadability, etc.)
And the antifreezing property, but they are not always satisfactory in terms of overall performance.

As a result, there is a demand for a simple anti-fog agent which has good workability during application and application state (transparency, etc.) and which can maintain a high anti-fog effect for a long period of time even under conditions of low temperature and low humidity to high temperature and high humidity. Has been done.

[0008]

Therefore, as a result of various investigations by the present inventors, polyacrylate, a hydrophilic surfactant,
Contains alcohols and has a pH of 4-9 and 10-15
An anti-fog agent for an aqueous solution having a viscosity of 0 mPa · s, which does not require a large-scale device and has good durability of the anti-fog effect, transparency and smoothness, and
When a surfactant is used in combination, it is possible to reduce the amount of polyacrylate used while maintaining the sustainability of the effect, transparency and smoothness, and having anti-blocking properties.
The present invention has been completed by finding that when alcohols are added to an aqueous solution of an antifog agent, low temperature specifications can be achieved, and at the same time, ease of application and improvement of transparency can be achieved. That is,
The present invention is

(1) Containing a polyacrylic acid salt, a hydrophilic surfactant and alcohols, and having a pH of 4-9 and 10
An aqueous anti-fog agent having a viscosity of ˜150 mPa · s,
(2) The aqueous fog-preventing agent according to the above (1), wherein the polyacrylic acid salt is a complete polyacrylic acid salt or a partial polyacrylic acid salt, and (3) the polyacrylic acid salt, wherein the carboxylic acid salt is a sodium salt. (4) 0.0, wherein the water-based anti-fog agent according to the above item (1) or (2) comprises at least one selected from the group consisting of:
An aqueous solution having a concentration of 7 M (representing a molar concentration conversion value based on the monomer unit molecular weight) has a viscosity of 10 to 150 mPa · s, p
The aqueous anti-fog agent according to any one of the above items (1) to (3), wherein H is a polyacrylic acid salt having a pH of 4 to 9 and an average degree of polymerization of 120 to 12000, and (5) a hydrophilic surface active agent. The agent according to any one of the above items (1) to (4), wherein the agent is one or more selected from nonionic (nonionic) type surfactants and anionic (anion) type surfactants. And (6) the nonionic (nonionic) type surfactant is sucrose fatty acid ester, and the anionic (anionic) type surfactant is one or more selected from dodecylbenzene sulfonate. Anti-fog agent,
(7) The water-based antifog agent according to any one of the above items (1) to (6), wherein the alcohol is a polyhydric alcohol, and (8) the above item (7), wherein the polyhydric alcohol is propylene glycol. (9) 0.01% to 10% by weight of polyacrylic acid salt, 0.01% to 10% by weight of hydrophilic surfactant, and 10% to 50% by weight of alcohols. The aqueous antifog agent according to any one of claims 1 to 8, (10) the aqueous antifog agent has a pH of 5.5 to 7.5 and a viscosity of 20 to 130 mPa.
The water-based anti-fog agent according to any one of (1) to (9) above, which is s.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous antifog agent of the present invention is an aqueous solution containing a polyacrylic acid salt, a hydrophilic surfactant and alcohols and having a pH of 4 to 9 and a viscosity of 10 to 150 mPa · s. . Usually, one having a pH in the range of pH 4 to 9 is used, but preferably pH 5.5 to 7.
5, more preferably pH 6 to 7. Usually, the viscosity is in the range of 10 to 150 mPa · s, preferably 20 to 130 mPa · s, more preferably 30 to 100 mPa · s.

The polyacrylic acid salt used in the present invention is usually a complete salt obtained by neutralizing 100% of a carboxylic acid of polyacrylic acid or a part of a salt of carboxylic acid of polyacrylic acid and a free acid. It is a partial salt that is a mixture of forms. The polyacrylic acid salt is preferably one or more salts of carboxylic acid selected from sodium salt, triethylamine salt and triethanolamine salt, and 0.07
An aqueous solution of M concentration (representing a molar concentration conversion value based on the monomer unit molecular weight) has a viscosity of 10 to 150 mPa · s, p
It is preferable that H has a pH of 4 to 9 and an average degree of polymerization of 120 to 12000. The polyacrylic acid salt used in the aqueous anti-fog agent of the present invention can be produced by a method of neutralizing polyacrylic acid or a salt of polyacrylic acid, or by polymerization of acrylic acid salt or copolymerization of acrylic acid and acrylic acid salt. It can be obtained by the method. The degree of neutralization (molar percentage) of the polyacrylic acid salt is 0.07M concentration (representing the molar concentration conversion value based on the monomer unit molecular weight)
There is no particular limitation as long as it is within the range of 4 to 9, but pH is 4.5.
It is preferable that the degree of neutralization is ˜8.5 and the degree of neutralization is 40% to 100%.

The polyacrylic acid salt used in the present invention is completely soluble in water, and there is substantially no precipitate such as a covalently bonded crosslinked structure formed by a crosslinking agent or overheating or a gelled product. Those are preferable.

The average degree of polymerization (hereinafter abbreviated as n) of the polyacrylic acid salt or the like used in the present invention is determined by the GPC-HPLC method (eg, [1] column: TSKgel GMPW × 2,
Solvent: 0.05M or 0.2M sodium nitrate aqueous solution,
Flow rate: 0.5 mL / min, sample concentration: 0.1-0.2
mg / mL, sample amount: 100 μL, detection: RI, column temperature: 40 ° C. or 55 ° C., RI temperature: 40 ° C. or 4
5 ° C, standard: AMERICA POLYMER ST
ANDARDS polyacrylic acid, [2] column:
Asahipak GF-7MHQ × 2, solvent: 0.1
M sodium nitrate aqueous solution, flow rate: 0.8 mL / min, sample concentration: 0.1%, sample amount: 100 μL, detection:
RI, standard: pullulan / pullulan, or [3]
Column: Shodex SB806M, solvent: 0.1M
Disodium phosphate aqueous solution (pH 8.7), flow rate: 1.
0 mL / min, sample concentration: 0.1%, sample amount: 2
0 μL, detection: light scattering method, etc.) is the value obtained by dividing the average molecular weight measured by the molecular weight of the monomer units constituting the polymer. The range of n is usually 120 to 120.
00, but preferably n = 1200-120
00, more preferably n = 2400 to 12000 (or a range of average molecular weight corresponding to n).

The hydrophilic surfactant used in the present invention is usually one or more selected from nonionic (nonionic) type surfactants and anionic (anionic) type surfactants. Preferred nonionic (nonionic) type surfactants are:
The sucrose fatty acid ester, which is preferable as the anionic (anion) type surfactant, is dodecylbenzene sulfonate (sodium salt, triethanolamine salt, etc.). The antifog agent of the present invention can be used in combination with a hydrophilic surfactant to synergistically improve the effect sustainability, transparency and smoothness, and thus the amount of each used can be reduced. . In general, when a surfactant is dissolved in an aqueous solution, the insoluble component of the surfactant or the surfactant is deposited on the surface of the object, and the surface is clouded. It is preferable to use a hydrophilic surfactant which does not cause precipitation of the surfactant. The surfactants may be used alone or in combination of two or more kinds.

The sucrose fatty acid ester is, for example, a saturated fatty acid having 6 to 30 carbon atoms such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid or montanic acid. Sugar ester or carbon number 10 such as linderic acid, palmitooleic acid, oleic acid, elaidic acid, isooleic acid, erucic acid, linoleic acid or linolenic acid
Examples include sucrose esters of unsaturated fatty acids of about 24.

Examples of the anionic surface active agent include tridecanolamine dodecylbenzenesulfonate and sodium dodecylbenzenesulfonate.

In the present invention, when the polyacrylic acid salt and sucrose fatty acid ester are used as the surfactant, the pH of the aqueous antifog agent is pH 5.5 to 5.5 in view of stability.
7.5 is preferred.

Examples of the alcohols used in the present invention include polyhydric alcohols and lower alcohols. Polyhydric alcohols include propylene glycol, glycerin and ethylene glycol, and lower alcohols include methanol, ethanol and (iso) propanol. ,
Each can be used alone or in combination of two or more. From the viewpoint of safety and toxicity, propylene glycol and glycerin are preferable as the polyhydric alcohol, and ethanol is preferable as the lower alcohol. Polyhydric alcohols are preferred for use as antifog agents under low temperature conditions in cold regions and the like, and propylene glycol is particularly preferred. And applications that require quick drying (glasses, goggles, etc.)
When used for, ethanol is preferred.

Water is used in the present invention. The water used is not particularly limited, but water having a small content of components that adversely affect the polyacrylic acid salt, for example, polyvalent ion components such as iron ions, calcium ions, and magnesium ions is preferable. Examples of preferable water include distilled water, purified water, and tap water.

The composition (percentage by weight) of the aqueous antifog agent of the present invention is generally 0.01% to 10% polyacrylate,
Hydrophilic surfactant 0.01% to 10%, alcohols 1
It contains 0% to 50%. The content of the polyacrylic acid salt in the aqueous antifog agent of the present invention is usually 0.01% to 10%.
However, the range is preferably 0.1% to 5%, more preferably 0.1 to 2%. The content of the hydrophilic surfactant is usually 0.01% to 10%, preferably 0.1% to 5%, more preferably 0.5 to 3%. And the content of alcohols is usually 10% to 5
0%, that is, the sum of polyhydric alcohol and lower alcohol is 10
% To 50%, polyhydric alcohol is 10% to 50%, and lower alcohol is 0% to 30%, preferably the composition of alcohols is 10% to 35%, and polyhydric alcohol is 10% to 30%. , Lower alcohol is 0% to 25%. The content of water in the aqueous anti-fog agent of the present invention is usually 9
It is less than 0%, preferably 50% or more and less than 90%.

The aqueous anti-fog agent of the present invention may contain various additives in the anti-fog agent in order to improve various properties. For example, preservatives, bactericides, plasticizers, antistatic agents, A preservative, an antioxidant, or the like can be contained if necessary. The mixing ratio of these various additives into the antifog agent may be any ratio as long as it is dissolved in the antifog agent of the aqueous solution of the present invention, but is preferably 2% or less, more preferably 1% or less. preferable.

To produce the aqueous antifog agent of the present invention,
For example, it can be obtained by uniformly dissolving the components of the above-mentioned polyacrylic acid salt, hydrophilic surfactant, alcohols, and various additives in water in an arbitrary order.

A preferred embodiment of the aqueous antifog agent of the present invention is an aqueous solution containing a polyacrylic acid salt, a hydrophilic surfactant and a polyhydric alcohol and having a pH of 6 to less than 8.5. As the polyacrylic acid salt, sodium salt or triethanolamine salt is preferable. As the hydrophilic surfactant, sucrose fatty acid ester, dodecylbenzenesulfonic acid triethanolamine salt, and dodecylbenzenesulfonic acid sodium salt are preferable. As polyhydric alcohol,
Propylene glycol is preferred, and ethanol is preferred as the lower alcohol. As described above, the water used is preferably water containing a small amount of components that adversely affect the polyacrylic acid salt.

Examples of objects using the water-based antifog agent of the present invention include mirrors, window glasses, glasses, goggles, show windows, showcases, water tanks, surveillance cameras, medical instruments such as endoscopes, ceramics or automobiles. , A window glass or a back mirror of a vehicle such as a ship or a vehicle.

The method of applying the aqueous antifog agent of the present invention is not particularly limited, and examples thereof include spray coating, brush coating, and cloth coating. The coating amount is not particularly limited, but, for example, when it is used for mirrors, window glasses, show windows, showcases, water tanks, ceramics or window glasses of vehicles such as automobiles, ships and vehicles, it is 0.
It is preferable to use 1 to ²⁰ mg / cm ² , and 0.1 to 1
It is more preferable to use 0 mg / cm ² and 0.1 to 5 m
g / cm ² is particularly preferred. Also, 5 to 20 mg / cm ²
It is also possible to apply it thickly, or apply it thinly and repeat it to increase the number of times. For example, in a high humidity place such as a bath (mirror), a thick coat or a thin coat is repeatedly applied, and in a low humidity place such as a cold district, a thin coat is generally applied.

The aqueous antifog agent of the present invention can be incorporated into a substrate. Examples of the base material include non-woven fabric and paper. The base material may be impregnated with the antifog agent by impregnating the base material. The impregnated base material may be dried. The amount of impregnation may be such that the entire base material becomes wet. A spray type in which the aqueous solution is put in the spray container as it is may be used.

[0027]

EXAMPLES Next, examples of the antifog agent of the present invention will be explained, but the present invention is not limited to these. In addition, unless otherwise described, various evaluations relating to the examples were carried out by the following methods.

(Viscosity of Polyacrylate, etc.) Distilled water was accurately added so that the polyacrylate had a concentration of 0.07 M (representing the molar concentration conversion value based on the molecular weight of the monomer unit), and the mixture was stirred with a stirrer. , Completely dissolve. After completely dissolving, transfer to a constant temperature water bath at 25 ° C., and use a B-type viscometer (digital viscometer DVM-B, manufactured by Tokyo Keiki Co., Ltd.) to keep the temperature constant by using a rotor (rotor No. 1, No. 2 or No.
After rotating at 3 rpm for 180 seconds in 3), the viscosity of the solution was measured. The viscosity of the antifog agent was measured in the same manner as above except for the concentration described in the examples.

(Continuity test for anti-fog effect) Three drops (80-120 mg) of anti-fog agent were uniformly applied to a 6 cm × 12 cm area of a 300 ml beaker (1.11-1.1).
67 mg / cm ² ). The dryer is heated to 60 ° C., and the room is sufficiently humidified to have a humidity of 100%. Put 300 ml of ice water in a beaker coated with the antifog agent. Immediately place the coated beaker containing ice water in the dryer for 3 minutes. Observe the degree of cloudiness on the beaker surface.
After 3 minutes, immediately remove from the dryer, quickly dispose of ice water in the beaker, and dry the beaker surface with cold air. Repeat this and record the number of times it started to fog.
Here, the number of times of sustainability indicates the durability of the effect of each antifog agent, for example, n times of sustainability does not cause clouding until the nth time, and n
It means + 1st cloudy.

(Transparency of coating) Antifog agent is applied to a mirror of 7 cm.
Two drops (53 to 80 mg) are dropped on × 7 cm, uniformly spread, dried at room temperature with cold air, and the degree of haze on the surface of the mirror is visually determined. Regarding the evaluation of transparency, ◯ means good transparency, Δ means slightly inferior transparency, and x means no transparency.

(Smoothness) An antifog agent is applied to a mirror of 7 cm × 7 c.
Two drops were dropped on m and the degree of smoothness when uniformly spread was judged by touching the surface of the object with a hand. Regarding the evaluation of smoothness, ⊚ means smooth, ∘ is mostly smooth, but some distortion is observed, Δ means large distortion, and x means that the surface is rough.

(Evaluation Method of Antiblocking Property) Polymer film (made of PET, thickness 100 μm, 7 cm × 10 c)
m) Two sheets are prepared, and one sheet is provided with an antifog agent (55 to 60
mg), and after covering with another one, the films are slid on each other so that the antifog agent sandwiched between the two films becomes uniform. After applying evenly, the two pieces are firmly overlapped. Then, it was put in a poly-made zipper bag, sealed, and after applying pressure (about 0.1 kg / cm ² ) for 4 hours, the peelability of the two films in a wet state was peeled by hand and examined. ("Wet"). Then, 60 ℃ ~
After vacuum drying at 70 ° C. for 2 hours, the peelability of the two films in a dried state was similarly examined (“dry state”). Here, for the evaluation of antiblocking property, ◎ peels at about the same degree as the uncoated film, ○ peels easily, Δ is slightly inferior in peelability or has stringiness, × is difficult to peel or peels Means not to.

The main components of the antifog agents shown in Table 1 below are shown by alphabetical symbols.
In addition,% before the abbreviation represents the content [wt%], [n] following the abbreviation represents the average degree of polymerization, and mPa · s and pH thereafter represent the viscosity mPa · s and pH of the entire antifog agent.

[0034] Table 1  Abbreviated name Official name poly-AA ； Polyacrylic acid poly-AA-1 / 2Na ； Polyacrylic acid partial salt (1/2 sodium) poly-AA-1 / 2TEA; polyacrylic acid partial salt (1/2 triethanolamine) poly-AA-TEA; polyacrylic acid triethanolamine DBS; dodecylbenzene sulfonic acid DBSNA; Sodium dodecylbenzene sulfonate DBSTEA; dodecylbenzenesulfonic acid triethanolamine EGOH; ethylene glycol EtOH; ethanol GCOH; glycerin GCRA; Glycyrrhizic acid PGOH; propylene glycol SFAE sucrose fatty acid ester PVA; polyvinyl alcohol TEA ； Triethanolamine

Example 1 Polyacrylic acid (20.82 g / 289 mM equivalent / average molecular weight 800,000 / average degree of polymerization about 11 thousand / Nippon Shokubai Co., Ltd.) was added to purified water (1800 g) in a 2 L-beaker with stirring. 48% sodium hydroxide (12.04 g)
(/144.5 mM). Next, sucrose fatty acid ester (80 g) was added and dissolved, and the pH was adjusted to about 6.5 with 1N sodium hydroxide, and purified water was added to adjust the total amount to 200.
Adjust to 0 g to make a stock solution. The obtained stock solution (20.00
Propylene glycol (4.00 g) and ethanol (10.00 g) were added to g), and then purified water was added to adjust the total amount to 40.00 g, whereby the anti-fog agent of the present invention (pH 7.1 / viscosity 75 mPa · s) was obtained.

Example 2 Polyacrylic acid (20.82 g / 289 mM equivalent / average molecular weight 800,000 / average degree of polymerization about 11,000 / Nippon Shokubai Co., Ltd.) was added to purified water (1800 g) in a 2 L-beaker with stirring. 48% sodium hydroxide (12.04 g)
(/144.5 mM). Next, sucrose fatty acid ester (80 g) was added and dissolved, and the pH was adjusted to about 6.5 with 1N sodium hydroxide, and purified water was added to adjust the total amount to 200.
Adjust to 0 g to make a stock solution. The obtained stock solution (20.00
Ethylene glycol (4.00 g) and ethanol (10.00 g) were added to g), and then purified water was added to give a total amount of 4
The antifogging agent of the present invention (pH 7.1 / viscosity 75 mPa · s) was obtained by adjusting the amount to 0.00 g.

Example 3 Polyacrylic acid (20.82 g / 289 mM equivalent / average molecular weight 800,000 / average degree of polymerization about 11 thousand / Nippon Shokubai Co., Ltd.) was added to purified water (1800 g) in a 2 L-beaker with stirring. 48% sodium hydroxide (12.04 g)
(/144.5 mM). Next, sucrose fatty acid ester (80 g) was added and dissolved, and the pH was adjusted to about 6.5 with 1N sodium hydroxide, and purified water was added to adjust the total amount to 200.
Adjust to 0 g to make a stock solution. The obtained stock solution (20.00
g) glycerin (4.00 g) and ethanol (1
0.00g) and then purified water to make a total of 40.0
The antifog agent of the present invention (pH
7.0 / viscosity 82 mPa · s) was obtained.

Example 4 Polyacrylic acid (2.52 g / 35 mM equivalent / average molecular weight 800,000 / average degree of polymerization about 11 thousand / Japan) with stirring in purified water (about 500 g) in 1000 mL-beaker After dissolving the catalyst, 48% sodium hydroxide (1.458)
g / 17.5 mM). Next, sucrose fatty acid ester (10.00 g) was added and dissolved, and propylene glycol (200 g) and purified water were added to adjust the total amount to 1000 g, whereby the antifog agent of the present invention (pH 6.7 /
A viscosity of 43 mPa · s) was obtained.

Example 5 Polyacrylic acid (2.52 g / 35 mM equivalent / average molecular weight 800,000 / average degree of polymerization about 11 thousand / Japan) under stirring in purified water (about 500 g) in 1000 mL-beaker After dissolving the catalyst, triethanolamine (2.61 g /
17.5 mM) is added. Next, sucrose fatty acid ester (10.00 g) was added and dissolved, and then propylene glycol (200 g) and purified water were added to adjust the total amount to 1000 g, whereby the anti-fog agent of the present invention (pH 6.7 / viscosity 69 mPa · s) was prepared. ) Got.

Example 6 Polyacrylic acid (2.52 g / 35 mM equivalent / average molecular weight 800,000 / average degree of polymerization about 11 thousand / Japan) under stirring in purified water (about 500 g) in 1000 mL-beaker After dissolving the catalyst, triethanolamine (2.61 g /
17.5 mM) is added. Then, dodecylbenzenesulfonic acid triethanolamine salt (10.00 g) was added and dissolved, and then propylene glycol (200 g) and purified water were added to adjust the total amount to 1000 g, whereby the antifog agent of the present invention (pH 6.7). / Viscosity 36 mPa · s) was obtained.

Example 7 Polyacrylic acid (2.52 g / 35 mM equivalent / average molecular weight 800,000 / average degree of polymerization about 11 thousand / Japan) under stirring in purified water (about 500 g) in 1000 mL-beaker After dissolving the catalyst, triethanolamine (5.22 g /
35 mM) is added. Next, sucrose fatty acid ester (1
0.00 g) was added and dissolved, and then propylene glycol (200 g) and purified water were added to adjust the total amount to 1000 g to obtain the anti-fog agent (pH 8.2 / viscosity 88 mPa · s) of the present invention.

Comparative Example 1 (Example 1 of JP-A-56-112984) Polyvinyl alcohol (50 g / average degree of polymerization 1750 ± 50) and triethanolamine (20.00 g / 134 mM) in purified water (500 g) with stirring. ), Dodecylbenzene sulfonic acid (10 g / 30 mM) and saponin (glycyrrhizinic acid: 1.0 g / 2.1 mM) are sequentially added and mixed to give a comparative anti-fog agent (however, a suspension liquid containing a large amount of insoluble matter). And its supernatant had a pH of 8.7 and a viscosity of 4 mPa · s).

Comparative Example 2 (Example 2 of JP-A-56-112984) Purified water (224 g) was stirred with polyacrylic acid (10.
00 g / 139 mM equivalent / average molecular weight 800,000 / average degree of polymerization about 11,000 / manufactured by Nippon Shokubai), saponin (glycyrrhizinic acid: 1.40 g / 3.0 mM), sodium dodecylbenzenesulfonate (0.20 g /0.57m
M), ethanol (96.00 g) and glycerin (1
0.00 g) was sequentially added and mixed to obtain a comparative antifog agent (pH 3.3 / viscosity 83 mPa · s).

Comparative Example 3 (Different Composition of Example 2 of JP-A-56-112984) Comparative Example 2 is prepared in the same manner as Comparative Example 2 except that the same amount of purified water is added instead of ethanol. That is, purified water (320 g), polyacrylic acid (10.00 g / 139
mM equivalent / average molecular weight 800,000 / average degree of polymerization about 11,000 /
Nippon Shokubai Co., Ltd., saponin (glycyrrhizinic acid:
A comparative antifog agent consisting of 1.40 g / 3.0 mM), sodium dodecylbenzene sulfonate (0.20 g / 0.57 mM) and glycerin (10.00 g) was obtained.

Comparative Example 4 (commercially available product) Automotive anti-fogging agent / ingredient: anionic surfactant,
Alkanolamine / weakly alkaline

Comparative Example 5 Polyacrylic acid (2.52 g / 35 mM equivalent / average molecular weight 800,000 / average degree of polymerization about 11,000 / Japan) under stirring in purified water (about 500 g) in 1000 mL-beaker (Catalyst) dissolved, sucrose fatty acid ester (10.00 g)
Was added and dissolved, and then propylene glycol (200 g) and purified water were added to adjust the total amount to 1000 g, whereby a fog inhibitor for comparison (pH 3.3 / viscosity 7 mPa · s)
Got

Comparative Example 6 Polyacrylic acid (20.82 g / 289 mM equivalent / average molecular weight 800,000 / average degree of polymerization about 11,000 / Nippon Catalyst Co., Ltd.) was added to purified water (1800 g) in a 2 L-beaker with stirring. 48% sodium hydroxide (12.04 g)
(/144.5 mM). Next, sucrose fatty acid ester (80 g) was added and dissolved, and the pH was adjusted to about 6.5 with 1N sodium hydroxide, and purified water was added to adjust the total amount to 200.
Adjust to 0 g to make a stock solution. The obtained stock solution (20.00
Purified water was added to g) to adjust the total amount (40.00 g) to give a comparative antifog agent (pH 6.5 / viscosity 63
mPa · s) was obtained.

Table 2 below shows the results of comparison using the anti-fog effect persistence test (2), which is a hot and humid condition.

[0049] Table 2: Comparison of anti-fog effect Sample Main component of antifog agent (water content omitted) Persistence                                                                   test Example 1 0.07M-poly-AA-1 / 2Na [n = 11,000] + 2.0% SFAE + 10% PGOH + 25% EtOH 6 Example 2 0.07M-poly-AA-1 / 2Na [n = 11,000] + 2.0% SFAE + 10% EGOH + 25% EtOH 6-8 Example 3 0.07 M-poly-AA-1 / 2Na [n = 11 thousand] + 2.0% SFAE + 10% GCOH + 25% EtOH 6 to 7 Example 4 0.035M-poly-AA-1 / 2Na [n = 11,000] + 1.0% SFAE + 20% PGOH 6 to 7 Example 5 0.035M-poly-AA-1 / 2TEA [n = 11 thousand] + 1.0% SFAE + 20% PGOH 7-8 Example 6 0.035M-poly-AA-1 / 2TEA [n = 11 thousand] + 1.0% DBSTEA + 20% PGOH 4 Example 7 0.035M-poly-AA-TEA [n = 11 thousand] + 1.0% SFAE + 20% PGOH 7 Comparative Example 1 8.61% PVA [n = 1750,000] + 1.72% DBS + 3.44% TEA + 0.17% GCRA 0 Comparative Example 2 2.93% poly-AA [n = 11 thousand] + 0.06% DBSNA + 0.41% GCRA          ＋ 2.93% GCOH + 28.10% EtOH 2 Comparative Example 3 2.93% poly-AA + 0.06% DBSNA + 0.41% GCRA + 2.93% GCOH 2 Comparative Example 4 (commercially available product) 1 Comparative Example 5 0.035M-poly-AA [n = 11 thousand] + 1.0% SFAE + 20% PGOH 3 Comparative Example 6 0.6% poly-AA-1 / 2Na [n = 11,000] + 2.0% SFAE / 63 mPa · s / pH 6.5 8 to 10

From the results shown in Table 2, the effect of the antifog agent of the present invention is better than that of the antifog agent of JP-A-56-112984 (Comparative Examples 1, 2, 3) and the commercially available product (Comparative Example 4). It can be seen that the lasting antifogging effect is several times superior.

Next, Table 3 below shows the results of testing the transparency and smoothness of the coating.

[0052] Table 3: Transparency, smoothness, spinnability and anti-blocking property of coating Sample Transparency Smoothness Spinnability Antiblocking                                                       Wet / Dry Example 1 ○ ◎ None-/- Example 2 ○ ◎ None-/- Example 3 ○ ◎ None-/- Example 4 ○ ◎ None-/- Example 5 ○ ◎ None ◎ / ◎ Example 6 △ to ○ ◎ None ◎ / ◎ Example 7 ○ ◎ None-/- Comparative Example 1 × to △ ◎ None ◎ / ◎ Comparative Example 2 △ to ○ × to △ None ◎ / △ Comparative Example 4 ○ ○ None − / − Comparative Example 5 ○ ◎ None-/- Comparative Example 6 ○ ◎ None ◎ / ◎

From the results shown in Table 3, the antifog agent of the present invention was
It can be seen that the transparency and smoothness are excellent as compared with the antifog agent of JP-A-56-112984 (Comparative Examples 1 and 2). At the same time, it can be seen that there is no problem in terms of spinnability and blocking resistance.

Table 4 below shows the results of the following freezing prevention test as a model for the cold district of the antifog agent of the present invention.

[0055] Table 4: Freezing prevention Sample freezing point Anti-fog effect at low temperature Examples 1 to 3 ◎ ○ to ◎ Examples 4 to 6 ○ ○ Example 7 ○ ○ Comparative Example 1 △ △ Comparative Example 2 ◎ ○ Comparative Example 3 △ △ Comparative Example 4 x to Δ x to Δ Comparative Example 5 ○ ○ Comparative Example 6 x to Δ x to Δ

(Evaluation Method of Freezing Prevention Effect by Freezing Point) 5
Cooling agent bath (dry ice + carbon tetrachloride: −23 ° C./or dry ice + acetonitrile:
The freezing point is measured by cooling at -41 ° C. Regarding the evaluation of the antifreezing effect by the freezing point, ◎ is -20
± 3 ° C or less, ○ means −10 ± 3 ° C, Δ means 0 to −5 ° C, and × means 0 ° C or more (note that those showing intermediate freezing points are, for example, in the case of a freezing point of −15 ° C. Represented by ○ ~ ◎). (Evaluation method of anti-fog effect at low temperature) 300 ml-A part of the outer surface of the beaker (6 cm x 12 cm) was coated with 3 anti-fog agents.
Apply drops (80-120mg) (1.11-1.67m)
g / cm ² ) and then transferred to a dry box at a temperature of about 25 ° C. and a relative humidity of about 21% (100% relative humidity at a temperature of 0 ° C.). Next, a coolant prepared in advance (100 to 150 m
L / about −10 ° C./prepared with dry ice cooled carbon tetrachloride, etc.) into a coating beaker. Beaker temperature-
The antifog effect was observed for 5-10 minutes at 10 ± 3 ° C.
Regarding the evaluation of the anti-fog effect, compared to a beaker tough coated surface where the cooling agent is not in contact, ◎ is clear to the same degree, ○ is the same degree in the early stage of cooling, but slightly inferior in the latter half,
Δ is slightly inferior, but is clearer than the uncoated cooled portion, and × is equivalent to the uncoated cooled portion (note that in case of intermediate effects between these, represented by both symbols Δ to ◯).

From the results shown in Table 4, the antifog agent of the present invention was
Antifog agent disclosed in JP-A-56-112984 (Comparative Example 1,
2, 3), commercially available products (Comparative Example 4), and Comparative Example 6 are better in terms of the freezing point and the antifreezing effect at the low temperature.

As an actual model of the anti-fog agent of the present invention, the performance of the anti-fog agent using the mirror (under non-sunlight) of the unit bath dressing room and the window glass facing south in the room (under sun light) (anti-fog effect, Table 5 below shows the results of observation of transparency (paint marks, whitening, oil film, etc.) and ease of application.

[0059] Table 5: Antifogging agent performance in actual model                   Under the sun under the sun Sample Sustainability / Transparency Sustainability / Transparency / Ease of application / * Note Example 5 ≧ 21 days / ○ to ◎ ≧ 14 days / Δ to ◯ / ○ / * 1 Comparative Example 1 4 to 21 days / △ 3 days / x (paint marks) / ○ / * 2 Comparative Example 2 13 days / ○ 2 days / △ 〜 ○ / × 〜 △ * 2 Comparative Example 4 ≧ 4 days / Δ to ◯ ≧ 7 days / × (oil film) / ◯ / * 2 Comparative Example 6 ≧ 14 days / × to Δ ≧ 14 days / × to Δ / × / −

(* Note) Whitening and the like are observed on the coated surface over time, but when the surface is lightly wiped with a chemical rag, mop, etc., * 1 shows almost the effect is maintained and * 2 shows the effect is reduced.

(Evaluation method for sustaining effect and transparency under non-sunlight and low humidity) Unit bath dressing room mirror (W100c
m × H125 cm), sprayed with anti-fog agent and then uniformly applied with a water-squeezed nonwoven fabric (0.4 ± 0.1 mg / c
m ² ). After application, take a bath (2 times each in the morning and evening / about 30 minutes x
4 times) to confirm the effect. Record the number of bathing days the day before the mirror began to cloud. At the same time, the transparency (coating marks, whitening, oil film, etc.) was visually observed when the coated surface was dried, and the evaluation was as follows: ⊚: very good transparency, ◯: good transparency, Δ:
In part, whitening and the like are observed, but almost good, and in X, coating marks, whitening, oil film, etc. are clearly observed.

(Persistence effect under sunlight and low humidity, transmission
Evaluation method of lightness and ease of application) South window illuminated by sunlight
Anti-fog agent on the inner glass (W57cm x H75cm) of
After spraying, apply evenly with a non-woven cloth (0.4
± 0.1 mg / cm ²) Do. 1 hour or more has passed since application
After that, steam cleaner (Made in Italy / Distributor Japan
・ International Commerce / Model No. 725
64 / Steam Cleaner Deluxe) with steam
(7 ± 3 mg / cm²) Is sprayed onto the coated surface and then clouded.
Check the effect of anti-locking. The day before the glass began to cloud
Record the number. Also, when the coated surface is dried, it is transparent (paint marks, white
(Oilization, oil slick, etc.) is visually observed and
Indicates very good transparency, ○ indicates good transparency, Δ indicates partially white
Almost good, but there are clear marks and white
Deterioration, oil film, etc. are observed. In addition, anti-fog agent on the object
When applying evenly with a non-woven fabric squeezed after spraying
Compare the smoothness and the spread of the liquid agent. Its evaluation
Regarding ○, ○ means good, △ means that the liquid agent spreads but is applied smoothly.
No, x does not spread easily and cannot be applied smoothly.

From the results shown in Table 5, the antifog agent of the present invention was
Antifog agent disclosed in JP-A-56-112984 (Comparative Example 1,
It can be seen that the performance of the actual model is better than that of 2) or the commercial product (Comparative Example 4).

Further, in order to confirm the transparency, the results of measuring the transmittance of the antifog agent with a spectrophotometer (visible light 900 to 400 nm) are shown in Table 6 below.

[0065] Table 6: Transmittance of antifog agent [%]  Sample 900nm 800nm 700nm 600nm 500nm 400nm Average value Example 5 100% 101% 100% 99% 98% 97% 99.2% Comparative Example 1 94% 94% 91% 88% 81% 66% 85.7% Comparative Example 2 100% 101% 100% 98% 93% 80% 95.3% Comparative Example 4 100% 100% 99% 98% 96% 89% 97.0% Purified water 100% 101% 100% 99% 98% 98% 99.3% (blank)

(Measurement Method of Transmittance of Antifog Agent) Sample room of spectrophotometer (Hitachi 200-20 type double beam spectrophotometer) warmed up (adjusted to 0% T and 100% T) at a visible wavelength of 900 nm. REFERENCE side and SA
Cells (2 cells) containing purified water are placed on both sides of the MPLE side and adjusted to 100% T (transmittance). Then SA
After taking out the cell on the MPLE side and drying the cell, after adding an undiluted aqueous solution of an antifog agent, each visible wavelength (900 nm, 8 nm
00 nm, 700 nm, 600 nm, 500 nm, 40
The transmittance of the antifog agent is measured at 0 nm). The evaluation of the transmittance is made by comparing the average value of all the transmittances (6 points).

From the results shown in Table 6, the antifog agent of the present invention was
It can be seen that the transmittance is better than that of the anti-fog agent of JP-A-56-112984 (Comparative Examples 1 and 2) and the commercially available product (Comparative Example 4).

In addition, the thermal stability of the antifog agent (80 ° C /
Table 7 below shows the results of comparison using the appearance and anti-fogging effect persistence test (2) for 3 days).

[0069] Table 7: Thermal stability Sample appearance Persistence test Example 5 ○ (Maintaining transparency) 8 (Maintaining sustainability) Example 6 ○ to ◎ (maintaining transparency) 4 (maintaining sustainability) Example 7 x to Δ (strong turbidity) 5 (decreased sustainability) Comparative Example 5 × (strong turbidity, insoluble matter precipitation) 3 (maintaining sustainability)

(Evaluation Method of Thermal Stability) The antifog agent (about 50 mL) in a plastic container was put in an incubator at 80 ° C.
The appearance of 1 to 3 days was compared with that of the sample before heating, and changes such as transparency and turbidity were observed. Further, a sustainability test (2) of the anti-fog effect after 80 ° C./3 days was conducted. Regarding the appearance evaluation, ⊚ maintains transparency, ○ maintains almost transparency,
Δ represents turbidity, and X represents strong turbidity or insoluble matter precipitation.

From the results of Table 7, Example 7 and Comparative Example 5
Of the anti-fogging agent solution, turbidity appeared, and particularly in Comparative Example 5, insoluble matter was deposited. In addition, the sustainability of the effect of Example 7 dropped from 7 times to 5 times. From this,
From the viewpoint of thermal stability, it is understood that the polyacrylic acid salt used in the antifog agent of the present invention is more preferably a partial salt than a complete salt.

[0072]

EFFECTS OF THE INVENTION The water-based antifog agent of the present invention does not cause fogging and can effectively prevent fogging when it is attached to the surface of objects such as glass, plastics and ceramics used for various purposes. In addition, the effect of anti-fog is maintained, the effect of transparency and smoothness of the surface of the object is observed, and the blocking resistance is excellent, and the transparency and coating property are also excellent. In addition, it has an antifreezing effect by lowering the freezing point, so it can be used as an antifog agent in low temperature conditions such as in cold regions, and its moisturizing effect improves the transparency (whitening prevention etc.) of the coating surface. Since it has the property of lubricating oil, it can be applied smoothly.

Claims (10)

[Claims] 1. A polyacrylic acid salt, a hydrophilic surfactant and alcohols, and having a pH of 4-9 and 10-15.
Aqueous anti-fog agent having a viscosity of 0 mPa · s. 2. The aqueous antifog agent according to claim 1, wherein the polyacrylic acid salt is a complete polyacrylic acid salt or a partial polyacrylic acid salt. 3. The aqueous antifog agent according to claim 1 or 2, wherein the carboxylic acid salt of the polyacrylic acid salt is at least one selected from sodium salt, triethylamine salt and triethanolamine salt. 4. An aqueous solution having a concentration of 0.07 M (representing a molar concentration conversion value based on a molecular weight of a monomer unit) is 10 to 150 m.
Pa · s viscosity, pH pH 4-9, average degree of polymerization 12
The water-based antifog agent according to any one of claims 1 to 3, which comprises a polyacrylate of 0-12000. 5. The hydrophilic surfactant is one or more selected from nonionic (nonionic) type surfactants and anionic (anionic) type surfactants. The water-based anti-fog agent described. 6. The aqueous solution according to claim 5, wherein the nonionic (nonionic) type surfactant is one or more selected from sucrose fatty acid ester and the anionic (anionic) type surfactant is selected from dodecylbenzene sulfonate. Antifog agent. 7. The aqueous antifog agent according to any one of claims 1 to 6, wherein the alcohol is a polyhydric alcohol. 8. The aqueous antifog agent according to claim 7, wherein the polyhydric alcohol is propylene glycol. 9. A polyacrylic acid salt of 0.01% by weight to 10% by weight, a hydrophilic surfactant of 0.01% by weight to 10% by weight,
The aqueous antifog agent according to any one of claims 1 to 8, which comprises 10% by weight to 50% by weight of alcohols. 10. The pH of the aqueous antifog agent is 5.5 to 7.5.
And the viscosity is 20 to 130 mPa · s, the aqueous antifog agent according to any one of claims 1 to 9.