JPH08302394A - Detergent for automotive window glass - Google Patents

Abstract

PURPOSE: To obtain a detergent for automotive window glass which is excellent in capability of removing an oil film or a water repellent for glass, does not leave a powder on the surface of glass, can be easily wiped off, does not flow on the surface of glass, and is excellent in workability. CONSTITUTION: An aq. soln. contg. 5-50wt.% colloidal silica stabilized with ammonia or a water-sol. amine and 1-30wt.% glycol having an average mol.wt. of 500 or lower is compounded with 0.1-3wt.% (meth)acrylic acid polymer having an average mol.wt. of 300,000-5,000,000.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a composition for cleaning a window glass of a vehicle, particularly a window glass of an automobile.

[0002]

2. Description of the Related Art Generally, on window glass of automobiles, oil such as wax effluent applied to automobiles, engine oil in exhaust gas and gasoline decomposition products adheres in a thin film form,
A so-called oil film is formed.

If such an oil film adheres to the windshield in particular, the visibility may be deteriorated and the safe driving may be seriously hindered. In particular, when it rains, the oil film causes unevenness in how the glass is wet by rainwater, and at night or the like, lights of oncoming vehicles diffusely reflect, which makes it extremely difficult to drive.

In recent years, a water repellent treatment agent for glass, which imparts water repellency to the glass and repels rainwater attached to the glass, has become popular. Since such a water repellent agent is firmly adhered to the glass, it is difficult to remove it with a general oil film remover even if it is attempted to be removed when it deteriorates.

There are various oil film removing agents as means for removing the oil film, but none of them can be said to be sufficient. Those containing a surfactant as a main component have an insufficient oil film removing ability and cannot remove a strong oil film formed by wax or a strong film formed by a water repellent treatment agent for glass. That is, even if the surface of the oil film becomes hydrophilic due to the surfactant and the water repellency is temporarily lost and the oil film appears to be removed, if the surfactant is washed away, the problem due to the oil film will occur again.

Further, as a detergent for window glass having a strong oil film removing action, for example, those described in JP-A-54-96503 and JP-A-55-7840 are known. This is mainly composed of colloidal silica, and the colloidal silica removes the oil film on the glass surface by polishing.

[0007]

However, in this case, colloidal silica as an abrasive remains white on the glass surface, and if not sufficiently washed, the remaining abrasive remains in the window glass or window frame gaps and stains. there is a possibility.

Further, in the case where a strong alkali is blended in order to enhance the removal property of the oil film, when the cleaning agent remains on the glass surface, the glass surface is attacked by the strong alkali to form spots, and also during the cleaning operation, a strong alkali is generated. The liquid is harmful to the human body.

The present invention has been made in view of the above circumstances, and can strongly remove oil films such as wax and water repellent, and can stain glass and window frames and stain spots on glass. It is an object of the present invention to provide a cleaning agent for window glass, which does not do so.

[0010]

According to the present invention, therefore, 5 to 50% by weight of colloidal silica (silica sol) stabilized with ammonia or water-soluble amines and an average molecular weight of 50 are used.
0.1 to 3% by weight of a polymer of acrylic acid or methacrylic acid having an average molecular weight of 300,000 to 5,000,000 is added to an aqueous solution containing 1 to 30% by weight of glycols of 0 or less. is there.

The colloidal silica in the present invention is
The average particle size is 5 to 50 mμ, preferably 10 to 30
It is preferably mμ. If the particle size is less than 5 mμ, the oil film removing effect is poor, and if it exceeds 50 mμ, white powder remains after washing and it becomes difficult to maintain the dispersion stability of the colloidal silica.

Ammonia or water-soluble amines is used as an alkalizing agent for stabilizing colloidal silica. As the water-soluble amines that can be used in the present invention, in addition to aliphatic amines, morpholines, ethanolamines, amino alcohols and the like are used.

If a strong alkalizing agent such as metal hydroxide is used as the alkalizing agent, the oil film removability is excellent, but if the cleaning liquid remains on the glass surface, the glass surface may be attacked and stains may be produced. So not suitable.

Further, the cleaning agent for vehicle window glass of the present invention is
The pH is preferably 8 to 11, more preferably 9 to 10
Is appropriate. When ammonia or water-soluble amines are used as the alkalizing agent, the pH of colloidal silica stabilized with the alkalizing agent is generally 9 to
It is within the range of 10.

When the pH value is less than 8, the dispersion stability of colloidal silica is lowered and the removability of the oil film is lowered. On the other hand, if the pH value exceeds 11, the removability of the oil film is good, but the surface of the glass may be corroded by the alkali content, and silica is dissolved, and a stable colloid cannot be obtained.

As the colloidal silica stabilized with ammonia, Ludox AS manufactured by DuPont, Snowtex N manufactured by Nissan Kagaku Kogyo Co., Ltd., Cataloid S-20L manufactured by Catalyst Kasei Kogyo Co., Ltd., and Adelite AT-20N manufactured by Asahi Denka Kogyo Co., Ltd.
Are commercially available, and these can be used as they are.

Examples of glycols in the present invention include ethylene glycol, diethylene glycol, polyethylene glycol and the like. The average molecular weight of these glycols is 500 or less. If it has a molecular weight of 500 or more, the viscosity of the cleaning agent becomes high, which makes it difficult to wipe it off the glass surface, resulting in poor practicality.

The amount of these glycols in the detergent depends on the kind of the glycol, but is generally about 1 to 1.
30% by weight is suitable. If the amount is less than 1% by weight, the cleaning agent will dry quickly and the cleaning operation cannot be sufficiently performed. On the other hand, if it is more than 30% by weight, the concentration of colloidal silica in glycol becomes relatively dilute, and the oil film removing effect becomes small.

The (meth) acrylic acid polymer used in the present invention includes polyacrylic acid, polymethacrylic acid,
Copolymers of acrylic acid and methacrylic acid, partially esterified copolymers and the like can be used.

The average molecular weight of these (meth) acrylic acid polymers is preferably 300,000 to 5,000,000. If it is less than 300,000, a suitable thickening effect cannot be obtained, and it is difficult to properly coat it on the glass surface, and if it exceeds 5 million, the solubility of the polymer is deteriorated, which is not suitable.

Although the concentration of poly (meth) acrylic acid varies depending on the type, it is preferably about 0.1 to 3% by weight.
If it is less than 0.1% by weight, a suitable thickening effect for the detergent cannot be obtained, and if it exceeds 3% by weight, the wiping property is deteriorated, which is not suitable.

In the detergent of the present invention, an appropriate surfactant can be mixed in the composition liquid. For example, by adding an anionic surfactant, foamability can be imparted to the composition liquid.

[0023]

In the present invention, the detergent is applied to the glass surface and rubbed with a waste cloth to remove the oil film. At this time, the colloidal silica stabilized by the alkali contained in the detergent mainly removes the oil film on the glass surface.

The action of the colloidal silica at this time has not always been clarified, but it is presumed that the situation is generally as follows. That is, the surfaces of silica particles are bound to hydroxide ions in the alkaline region, and are negatively charged, so that the particles are electrically repelled and stabilized. The presence of a glass surface having a surface potential lower than that of the particle surface and having the same siloxane bond therein reduces the surface energy of silica particles and promotes adsorption to the glass surface.

As a result, the concentration of silica particles in the vicinity of the glass surface becomes high, and the action of physically rubbing in that state is added, and it is considered that the high-concentration silica particles peel off the oil film stain on the glass surface. .

Further, in such an action, the presence of glycols in the cleaning agent prevents the composition liquid from freezing, imparts lubricity during wiping, and prevents the composition liquid of the cleaning agent from being wiped off. Adjust dryness.

Apply the composition liquid of the cleaning agent to the glass surface,
It is washed by rubbing it with a rag or the like, but if it does not contain glycols, the liquid will spread and the water will evaporate, and the concentration of colloidal silica will become excessively high. In addition to being unable to rub smoothly with, the action of removing the oil film by the silica particles is reduced.

Especially when the temperature is high such as summer or when the glass surface becomes hot under direct sunlight, water alone evaporates rapidly and the oil film cannot be removed properly.

In the present invention, by containing glycols, the volatility of the dispersion medium in the composition liquid is reduced, the concentration of colloidal silica is maintained at an appropriate concentration for a long time, and the composition is rubbed with a waste cloth or the like. In addition to being able to rub against, the oil film can be peeled off sufficiently by rubbing.

Further, in the present invention, since the polymer of (meth) acrylic acid is contained, these polymers react with the alkalizing agent in the composition liquid to form an acrylate salt,
The polymer spreads three-dimensionally in the liquid, and the liquid thickens like a cream.

Therefore, when applied to the window glass of a vehicle or the like, the liquid does not stop on the glass surface and does not flow and drip. Therefore, the liquid can be easily spread on the glass surface, and the oil film can be scraped off by rubbing the liquid on the glass surface with a waste cloth or the like.

Since ammonia and amines are weakly alkaline substances, the pH of the liquid in which a salt with poly (meth) acrylic acid is formed is about 9 to 10, which may adversely affect the glass surface. It is easy to use without causing any serious danger to the human body.

When an alkaline substance such as a metal hydroxide is used, it forms a salt with poly (meth) acrylic acid to give a similar creamy form, but has strong alkalinity and poor wipeability, and also has a glass surface. It is not suitable because it violates.

[0034]

[Example] Colloidal silica,
An aqueous solution of a (meth) acrylic acid polymer is added to a mixed solution of glycols (alcohols) and alkali, and they are sufficiently stirred and mixed. Note that all numbers are% by weight.

[Example 1] Colloidal silica (trade name Ludox AS): 65 Diethylene glycol: 5 Acrylic acid polymer (trade name Carbopol 934): 0.5 Ammonia: 0.5 Water: 29

[Example 2] Colloidal silica (trade name Snowtex N): 50 Diethylene glycol: 3 Acrylic acid polymer (trade name Carbopol 934): 0.5 Ammonia: 0.5 Water: 46

[Example 3] Colloidal silica (trade name Ludox AS): 80 Diethylene glycol: 9 Acrylic acid polymer (trade name Carbopol 934): 0.5 Ammonia: 0.5 Water: 10

Comparative Example 1 Colloidal silica (trade name Ludox AS): 65 Diethylene glycol: 5 Acrylic acid polymer (trade name Carbopol 934): 0.5 Sodium hydroxide: 0.2 Water: 29.3

Comparative Example 2 Colloidal silica (trade name Ludox AS): 65 Ethyl alcohol: 5 Acrylic acid polymer (trade name Carbopol 934): 0.5 Ammonia: 0.5 Water: 29

Comparative Example 3 Colloidal silica (trade name Ludox AS): 65 Diethylene glycol: 5 Polyvinyl alcohol: 0.5 Water: 29.5

[Comparative Example 4] Colloidal silica (trade name: Ludox AS): 65 Diethylene glycol: 5 Carboxymethyl cellulose: 0.5 Water: 29.5

Comparative Example 5 Colloidal silica (trade name Ludox AS): 65 Diethylene glycol: 5 Xanthan gum: 0.5 Water: 29.5

Comparative Example 6 Colloidal silica (trade name Ludox AS): 65 Diethylene glycol: 5 Water: 30

Comparative Example 7 A commercially available oil film removing agent (spray type) was used as it was.

Comparative Example 8 A commercially available glass water repellent remover (abrasive type) was used as it was.

The ingredients indicated by trade names in each of the above examples are as follows. Ludox AS: DU PONT, ammonia stabilized colloidal silica aqueous solution, particle size: 13-14 mμ, sol concentration 30% Snowtex N: Nissan Chemical Industries, ammonia stabilized colloidal silica aqueous solution, particle size: 10-20 mμ, sol concentration: 20 -21% Carbopol 934: BFGOOD RICH, acrylic acid polymer, molecular weight 3 million

[Washing test] Preparation of test piece 1. A commercially available solid wax is uniformly applied to a glass plate (30 mm x 30 mm), and wiped with a dry waste cloth so as not to cause unevenness. A glass plate was created. 2. A commercially available glass water repellent was uniformly applied to a glass plate (30 mm × 30 mm), and wiped and spread according to the method of use of the water repellent to form a glass plate with the glass water repellent evenly.

Oil film removal test 1. Each of the above test pieces was fixed on a horizontal table, and a wooden pad (10 mm x 10 mm) wrapped with a soft clean cloth was used.
About 1 g of the cleaning agent was evenly applied to the wiping surface (wet surface) of the above, and a reciprocation of 20 mm was repeated 10 times while applying a load of about 1 kg to evaluate the removability of the oil film and the water repellent on the glass surface. The evaluation method was to examine the change in water repellency (contact angle) of the glass before and after the test.

In addition, the powder residue and the wiping-off property during the above-mentioned work were evaluated by visually observing the work condition. The cleaning agent is dropped onto a clean glass in spots, and the temperature is maintained at 50 ° C for 30
After leaving it for a minute to dry, it was wiped with a clean waste cloth, and it was visually evaluated whether or not a stain was generated on the glass surface.

2. A windshield of a passenger car (manufactured by Nissan Motor Co., 1994, Bluebird) is coated with the oil film and the water repellent, and the cleaning agent of each of the examples and comparative examples is used to apply the oil film and the water repellent. It was removed, and the appearance was visually evaluated for its removability.

[Test Results] Table 1 shows the test results.

[0052]

[Table 1]

[0053]

As is clear from the results of Table 1, according to the present invention, the removability of the oil film and the water repellent is excellent,
No powder is left on the glass surface, and it has good wiping-off properties and excellent workability. Further, not only in the table test using the test piece but also in the test using the actual vehicle, excellent results are obtained in workability and removability of the oil film and the like.

On the other hand, in Comparative Example 1 using sodium hydroxide as a stabilizer for colloidal silica,
The strong alkali causes stains on the glass surface, and the ability to wipe from the glass surface is poor.

Further, in Comparative Example 2 in which ethyl alcohol having a low boiling point is used instead of glycols, the oil film removal property is poor because the drying is fast, and the wiping property from the glass surface is poor, and the workability is poor.

Further, in Comparative Examples 3 to 5 in which other polymer substances were used in place of the (meth) acrylic acid polymer, the wiping properties were poor, and the (meth) acrylic acid polymer was a detergent. It can be seen that it is essential in the present invention to form a smooth creamy form, which improves the wiping property from the glass surface.

In Comparative Example 6 containing no (meth) acrylic acid polymer, excellent results which are almost the same as those of the examples of the present invention were obtained in the table test, but in the actual vehicle test, the inclined front surface was used. When the cleaning agent is applied to the glass surface, the liquid flows down the glass surface, so it is not possible to sufficiently apply the cleaning agent to a specific part of the glass surface and rub it, resulting in sufficient oil film removability. Absent.

Claims (3)

[Claims] 1. 1 to 50% by weight of colloidal silica (silica sol) stabilized with ammonia or a water-soluble amine, and 1 to 1 of glycols having an average molecular weight of 500 or less.
An aqueous solution containing 30% by weight has an average molecular weight of 300,000 to 5
A cleaning agent for vehicle window glass, characterized by containing 0.1 to 3% by weight of a polymer of (meth) acrylic acid of, 000,000. 2. The average particle diameter of the colloidal silica is 5
The cleaning agent for vehicle window glass according to claim 1, characterized in that 3. The cleaning agent for vehicle window glass according to claim 1, having a pH of 8-11.