JPH0124186B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aqueous composition for protecting paint films. Specifically, the present invention relates to an aqueous composition for protecting paint films that is applied to temporarily protect the painted surfaces of automobiles, agricultural machinery, construction machinery, or other machinery and equipment. Products such as automobiles are exposed to wind, rain, humidity, sunlight, air, iron powder,
Painted surfaces are often contaminated by atmospheric pollutants such as bird droppings and soot, and these contaminants impair commercial value. In order to prevent this, various paint film protectants have been developed in recent years. Films developed for this purpose include wax solvent dispersion type (e.g. Japanese Patent Publication No. 50-28534), strippable film type (film type that can be peeled off when no longer needed, e.g. Japanese Patent Publication No. 54-7303). ), wax - solid powder solvent dispersion type (can be removed by hand, for example, JP-A-51-149188 or JP-A-55-
62978), and aqueous emulsion type (wax emulsified and dispersed, for example, Japanese Patent Publication No. 1983-34030). Among these, the currently widely used types are the wax-solvent dispersion type and the wax-solid powder dispersion type, but since most of the solvent is evaporated to form a wax film, in recent years they have become particularly polluting. The disadvantages of solvent-based solvents, such as problems, waste of resources, economy, and safety, have been highlighted. Furthermore, solvent-dispersed wax cannot be removed with steam alone; it is necessary to mix in a small amount of kerosene. In order to improve this drawback, a wax-solid powder dispersion type has been proposed in which wax-solid powder is uniformly mixed to reduce the mechanical strength of the wax film and make it easier to remove by hand wiping. teeth,
It has shortcomings in protection, and it peels off easily when touched by hand.
Another drawback is that it is easily contaminated by acid rain. On the other hand, water-based wax emulsions do not use solvents, so there are no pollution or safety issues, but they do have new performance characteristics that differ from solvent-based ones, such as drying properties and dispersibility in water. required.
Furthermore, the protective film formed by applying this coating must have contradictory properties: it must be strong enough to be impervious to rainwater and moisture, and it must also be easily removable when no longer needed. An aqueous composition that satisfactorily satisfies these requirements has not yet appeared. The object of the present invention is to overcome the above-mentioned drawbacks of the prior art, to form a strong film that is not attacked by rainwater, moisture, sunlight, or atmospheric pollutants without using a solvent, and to provide hot water, steam, etc. after use. An object of the present invention is to provide an aqueous composition for protecting a paint film that can be smoothly removed. The object of the present invention is (a) 10 to 80 parts by weight of a petroleum distillate wax () having a melting point of 50 to 85°C, a melting point of 36 to 120°C, a number average molecular weight of 310 to 1000, and a carbon content of 100 to 1000 carbon atoms. 90 to 20 parts by weight of a polyolefin wax () having a double bond number in the range of 5 to 50, and this mixture
100 parts by weight of an oxygen-containing wax obtained by reacting 3 to 25 parts by weight of an unsaturated polycarboxylic acid or its anhydride under free radical-forming conditions with respect to 100 parts by weight (b) Emulsifier, 7 and (c) an aqueous composition for protecting paint films characterized by emulsifying and dispersing 10 to 400 parts by weight of silicone resin powder as an essential component in water, and (a) having a melting point in the range of 50 to 85°C. Petroleum distillate wax () 10 to 80 parts by weight and polyolefin wax () having a melting point of 36 to 120°C, a number average molecular weight of 310 to 1000, and a number of double bonds per 1000 carbon atoms in the range of 5 to 50. This mixture is mixed with 20 parts by weight.
100 parts by weight of an oxygen-containing wax obtained by reacting 3 to 25 parts by weight of an unsaturated polycarboxylic acid or its anhydride under free radical-forming conditions with respect to 100 parts by weight (b) Emulsifier, 7 An aqueous paint film protection water-based product comprising (c) 10 to 400 parts by weight of a silicone resin powder, and (d) 10 to 200 parts by weight of an organic or inorganic solid fine powder, which are emulsified and dispersed in water as essential components. This is achieved by the composition. Hereinafter, the aqueous composition for protecting paint films according to the present invention will be specifically explained. In the present invention, component (a) refers to 10 to 80 parts by weight of petroleum distillate wax () with a melting point of 50 to 85°C, and
36~120℃, number average molecular weight 310~1000, carbon number 1000
Mixing with 90 to 20 parts by weight of polyolefin wax () having a double bond number of 5 to 50 per piece,
Based on 100 parts by weight of this mixture, 3 parts of unsaturated polyhydric carboxylic acid or its anhydride was added under free radical-forming conditions.
It is an oxygen-containing wax obtained by reacting up to 25 parts by weight, and its specific contents are disclosed by the present inventors in JP-A-54-81306. Petroleum distillate wax (), which is the raw material for component (a) (polyoxygen wax), has a melting point of 50 to 85°C, preferably
It has a temperature range of 50 to 70°C. As the polyolefin wax () which is the raw material for component (a) (oxygen-containing wax), ethylene polymers, propylene polymers, and olefin copolymers containing ethylene or propylene as one of the monomers can be used. Among these, ethylene polymers are particularly preferred. These polyolefin waxes have a melting point of 36 to 120°C, preferably 36 to 90°C, a number average molecular weight of 310 to 1000, preferably 310 to 600, and a number of double bonds of 5 to 50 per 1000 carbon atoms, preferably
It has 10 to 45 pieces. Component (a) (oxygen-containing wax) is 10 to 80 parts by weight of the petroleum distillate wax () and polyolefin wax (2): 90 to 20 parts by weight, preferably 30 to 70 parts by weight: 70 to 30 parts by weight. Mix in the proportion of
Based on 100 parts by weight of this mixture, 3 parts of unsaturated polyhydric carboxylic acid or its anhydride was added under free radical-forming conditions.
It is obtained by reacting ~25 parts by weight, preferably 10 to 20 parts by weight. If the mixing amount of the polyolefin wax () to the petroleum distillate wax () is less than the above range, a product with a sufficiently high acid value cannot be obtained, and a stable wax emulsion cannot be obtained. On the other hand, if it exceeds the above range, it is not preferable because the hue of the product becomes poor. Free radical generation conditions include, for example, wax mixtures.
The conditions are such that 0.2 to 5 parts by weight of an organic peroxide is added to 100 parts by weight. Here, examples of the organic peroxide include ditertiary-butyl peroxide, tertiary-butyl hydroperoxide, dicumyl peroxide, tertiary-butylcumyl peroxide,
cumyl hydroperoxide, 2,5-dimethyl-2,5-di(tertiary-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tertiary-butylperoxy)hexane-3,
Any one kind or a mixture of two or more kinds of methyl ethyl ketone peroxides can be used, and among these, ditertiary-butyl peroxide is particularly preferred. As the unsaturated polycarboxylic acid or its anhydride, maleic acid, itaconic acid, citraconic acid, etc. can be used, and among these, maleic acid is particularly preferred. The amount of unsaturated polyhydric carboxylic acid or its anhydride added to the mixture is extremely important, and the properties of the oxygen-containing wax vary depending on the amount added. If the amount added is less than the above range, the acid value of the product will be low and it will not exhibit sufficient emulsifying properties, and if the amount added exceeds the above range, it will not only have an unnecessarily high acid value but also In some cases, unreacted acid remains, making removal complicated. Although the reaction conditions are not particularly limited, for example, the reaction temperature is 120 to 220°C, preferably 140 to 180°C, and the reaction time is 0.5 to 6.0 hours, preferably 1 to 3 hours. Since the oxygen-containing wax of the present invention thus produced has excellent emulsifying properties, it is possible to reduce the amount of emulsifier when preparing an aqueous composition compared to other petroleum distillate waxes. Therefore, there is no reduction in water resistance, drying properties, weather resistance, etc. Furthermore, since it has a relatively low melting point and does not exhibit stickiness, it can be easily removed using a hot water cleaner or the like. As waxes used in paint film protection compositions, various synthetic waxes are known in addition to mineral waxes, animal and vegetable waxes, and the like. Among these, mineral waxes, specifically paraffin waxes, microcrystalline waxes, etc., do not have sufficient emulsifying properties and can be used in solvent-based compositions without problems, but due to pollution problems and safety concerns, When used in an aqueous composition, a large amount of emulsifier is required, which deteriorates water resistance, drying properties, weather resistance, etc., and is also economically unfavorable. Furthermore, since these mineral waxes have adhesive properties, they have poor removability and may cause discoloration and loss of gloss of automobile paint films. In addition, so-called oxidized waxes, which are made by oxidizing mineral, animal/vegetable, or synthetic waxes to improve their emulsifying properties, can be made into aqueous compositions, but the wax itself is too hard, resulting in cracks in the film. The protective properties of the paint film may be reduced, or the removability may be poor due to the adhesive property, and furthermore, the paint film may become discolored and its gloss may be reduced. Component (b) (emulsifier) of the composition of the present invention can be selected from a wide range of common types, and any of nonionic, cationic and anionic types can be used. Among these, cationic ones are particularly effective in (a) ionizing and activating the acidic groups of the oxygen-containing wax; for example, morpholin is preferred. In the case of nonionic waxes, (a) oxygen-containing waxes with an HLB of 17-18 can be selected; specifically, Kao Atlas Span 60, 80, Twin
Examples include 60, 80, and Emulgen 420 (all trade names). Further, in addition to the cationic type, if an anionic type, such as oleic acid, is added in a smaller amount than the equivalent of the cationic type, the effect will be even greater. (b) The amount of emulsifier added is less than 7 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of (a) oxygenated wax. Component (c) (silicone resin powder) referred to in the present invention can be obtained by reacting silanol groups (≡Si-OH) of methyl silicone condensate powder, dimethyl silicone condensate powder, or silicon dioxide aerosol with dimethyl dichlorosilane. Hydrophobic silica powder obtained by can be used. As an example of methyl silicone condensate powder, M.
There is SP (product name). Further, as an example of hydrophobic silica powder, there is hydrophobic silica R-972 (trade name) commercially available from Nippon Aerosil Co., Ltd. (c) The amount of silicone resin powder added is 10 to 400 parts by weight, preferably 50 to 200 parts by weight, per 100 parts by weight of (a) oxygen-containing wax. If the amount of silicone resin powder added is less than the above range, the protection property will be good but the hot water removability will be poor, while if the amount of silicone resin powder added exceeds the above range, a uniform continuous coating will not be obtained. Although the hot water removability is good, the protective property is lowered, which is not preferable. It is known from JP-A-62978 that the heat resistance and acid resistance of the protective film are improved when silicone resin powder is added to the wax-solid powder solvent-dispersed type. In general, this does not hold true. However, when used in combination with component (a) and in an amount within the above range, it contributes not only to improving heat resistance but also to improving drying properties, which is a problem specific to aqueous emulsions. Component (d) (organic or inorganic solid fine powder) of the composition of the present invention includes, for example, titanium oxide, zinc oxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, silica, diatomaceous earth, calcium stearate, One or a mixture of two or more of zinc stearate, polyethylene, polystyrene, and polyfluorinated ethylene can be used. Among these, one or more of titanium oxide, calcium carbonate, calcium sulfate, polyethylene, and polyfluorinated ethylene can be used. Particularly preferred are mixtures of two or more. When component (d) is added, its amount is 10 to 200 parts by weight, preferably 20 to 100 parts by weight, per 100 parts by weight of (a) oxygen-containing wax. Also, the blending ratio of (c) silicone resin powder and (d) solid fine powder is 90:10 ~
(d) Too much solid fine powder gives good protection but poor hot water removability, and (c) Too much silicone resin powder gives good hot water removability but poor protection. Undesirable. A well-balanced ratio of both performances is 70:30 to 30:70. Each of the components constituting the composition of the present invention has been described in detail above. ) are combined as essential ingredients and are manufactured by emulsifying and dispersing them in water.
Known methods can be used for emulsification and dispersion;
It is suitable to use it in the range of 10 to 45 parts by weight, preferably 10 to 45 parts by weight. In addition to the above-mentioned essential components, the composition of the present invention can be applied to petroleum distillate wax, specifically paraffin wax, microcrystalline wax, or unrefined paraffin wax, such as slut wax, within a range that does not impair its excellent paint film protection properties. , scale wax, etc. may be used in an amount of 50% by weight or less based on (a) oxygen-containing wax, and antioxidants, ultraviolet absorbers, wax dispersants, thickeners, etc. may be added as necessary. . The aqueous composition for protecting paint films of the present invention is (1) an aqueous type that does not use a solvent, so there is no need to worry about pollution or fire, and it is economical because it prevents wastage of resources. (2) Excellent water resistance, heat resistance, weather resistance, and drying properties. (3) Excellent paint film protection. (4) Provides sufficient releasability and can be easily removed with a hot water cleaner. This feature makes it ideal for protecting the paint of automobiles, etc. Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Example 1 (i) Synthesis of oxygen-containing wax Equal amounts of petroleum distillate wax (2) and polyolefin wax (2) were mixed to prepare a synthetic raw material. As petroleum distillate wax, 125% paraffin wax (melting point 52
℃), as a polyolefin wax, it is a low polymer of ethylene with a melting point of 39℃, a penetration rate of 80 or more, an average molecular weight of 320, and a number of double bonds per 1000 carbon atoms of 42, of which 88% are vinyl type and vinylidene type.
A white wax-like material was used that was 11% and 4% internal vinylene type. Maleic anhydride 13 to 100 parts by weight of mixed raw materials in equal amounts
While heating and stirring at 150° C., a solution of 1 part by weight of ditertiary-butyl peroxide dissolved in 5 parts by weight of xylene was added. After continued stirring for an additional 30 minutes, volatile materials were removed under reduced pressure and filtered under pressure to obtain a pale yellow oxygenated wax. This oxygen-containing wax has a melting point of 52℃.
The penetration was 20, and the acid value and saponification value were both 90. (ii) Emulsification of oxygenated wax 10g of oxygenated wax synthesized by (i)
The mixture was heated and stirred at 100°C, and 0.1 g of oleic acid and then 0.1 g of morpholine were added. While stirring the mixture vigorously, 86 ml of water at 95°C was slowly added to obtain a white, uniform emulsion. Transfer this emulsion to a Manton-Gaulin homogenizer at 200 kg/cm ²
A good white wax emulsion was obtained. (iii) Production of aqueous composition for protecting paint film Titanium oxide (Tipaque R-780 Ishihara Sangyo Co., Ltd.) pre-dispersed in 80 g of the wax emulsion described in (ii) above; calcium carbonate (Hakuenka cc Shiroishi Calcium) 12g of 50% paste with a weight ratio of 5:1
Then, 10 g of methyl silicone powder was added and stirred to obtain an aqueous composition. The viscosity of this composition was 230 centipoise (25° C.) and a specific gravity of about 1.0, and no sediment or change in altitude was observed after it was left at room temperature for two weeks. Examples 2 to 10 Adding (c) silicone resin powder or (d) solid to the oxygenated wax emulsion obtained by methods (i) to (ii) in Example 1 at the blending ratio shown in Table 1. Fine powder was added to produce a paint film protection composition.
These compositions were evaluated for performance as described below. These results are shown in Table 1. All of the compositions of the present invention showed excellent performance in all performance evaluations such as the strength of the protective film, removability, and drying properties.

[Table] Comparative Examples 1 to 6 Comparative Example 1 shown in Table 2 is an aqueous composition in which the (a) oxygen-containing wax of the present invention is emulsified by the method (ii) of Example 1. (a) Since it uses oxygen-containing wax, it has good emulsifying properties, but (c) Since it does not contain silicone resin powder, it has poor performance in terms of film condition in accelerated weather resistance, removability in outdoor weather resistance, and drying properties. was insufficient. Comparative Examples 2 and 3 were manufactured by emulsifying the oxygen-containing wax (a) of the present invention by the method (ii) of Example 1, and further adding titanium oxide in the blending ratio shown in Table 2 by the method (iii). Both of these aqueous compositions had insufficient removability in outdoor weather resistance. Comparative Example 4 is an example in which paraffin wax was used as the wax, but since the emulsifying property was insufficient, the amount of emulsifier was reduced by the method (ii) of Example 1.
Even if 7 parts by weight is added to 100 parts by weight, a stable emulsion cannot be obtained, and nonionic emulsifiers cannot be added to the wax.
It was necessary to use 10 parts by weight per 100 parts by weight. Furthermore, the emulsion thus produced was insufficient in water resistance, heat resistance, and acid resistance. That is, compositions made by adding a large amount of emulsifier to paraffin wax or a similar non-emulsifying wax to form an aqueous emulsion exhibit a noticeable lack of water resistance, weather resistance, etc. due to the emulsifier. Comparative Example 5 uses oxidized microwax NPS-6010 (trade name, manufactured by Nippon Seiro Co., Ltd., melting point 79) as the wax.
℃, acid value 14, and saponification value 36), emulsifying properties are improved, but the melting point is too high and it is sticky, so removability in accelerated weathering and outdoor weathering is insufficient. It was hot. Comparative Example 6 uses beeswax (melting point 60~
67℃, acid value 5 to 9, saponification value 80 to 100), the film was hard, the removability of both (4) and (5) was poor, and accelerated weathering was used. The chemical film test was also poor.

【table】

[Table] <Performance evaluation method> (Application) The test piece was a 150 mm x 70 mm (1 mm thick) mild steel plate coated with black aminoalkyd resin, and the emulsion was sprayed from a nozzle and left at room temperature for 24 hours. Dry. The average thickness of the wax coating was 15 μm when calculated from the weight. (Test) (1) Appearance of protective film (2) Heat resistance test Place the test piece vertically in a thermostat and leave it at 80℃ for 96 hours. Dripping, cracking, and other changes in the wax coating were observed. Furthermore, the wax coating was rinsed with warm water and detergent in the sink and wiped with gauze, and the alkyd painted surface was observed for gloss, blistering, and other changes. The results are displayed in three stages: ◯ (no change), △ (slight change), and × (some change). (3) Water resistance test A test piece was immersed in pure water maintained at 40°C for 240 hours, and the wax coating and the painted surface after the wax coating was removed were observed for blistering, peeling, and other changes.
The results were evaluated according to (2). (4) Accelerated weathering test <Removability test> Spray 1Kg/cm ² G water vapor for 10 seconds from a distance of about 50mm through a nozzle with a hole diameter of about 3mm.
The diameter of the circular trace where the wax coating was removed was measured. The result is a removed trace diameter of 20mm
The above was rated as ◎, 15 mm to 20 mm in diameter as ○, 8 mm to 15 mm as △, and less than 8 mm as ×. <Film test> The product was placed in a Sunshine weather meter manufactured by Toyo Rika Kogyo Co., Ltd. and tested for 250 hours at 63°C while pouring cold water for 18 minutes every 2 hours. Observations were made for scarring, dullness, and other changes. Evaluation of the results is (2)
It was carried out in accordance with. (5) Outdoor weather resistance test The sample was exposed outdoors for one month in summer, and after one month, a removability test was conducted using the method described in (4). The evaluation criteria are the same as in section (4). (This composition was easily removed using a hot water cleaner after being exposed outdoors for 3 months through a car door.) (6) Iron powder spreading test The sample was sufficiently sprinkled with iron powder, and heated at 80°C for 5 hours.
After drying in a constant temperature bath, leave it at room temperature for 1 hour, then
After holding for 24 hours in the salt spray test specified in JISZ2371, the iron powder and coating were soaked in hot water after being left for 24 hours.
Rinse with detergent and check the painted surface for rust and scratches caused by iron powder. The results were evaluated as: ○ No rust occurred on the paint film, × Rust occurred. (7) Sulfuric acid resistance Drop a 0.1ml spot of 6% sulfuric acid onto the film, leave it at room temperature for 24 hours, and after the test, soak the film in warm water.
Wash off with detergent, air dry, and examine the scar for discoloration and erosion. The results were evaluated as: ○ No scar and discoloration, △ Slight scar and discoloration, and × Clear scar and discoloration. (8) Hydrochloric Acid Resistance 0.1 ml of N/10 hydrochloric acid was spotted onto the film of this composition, left to stand at room temperature for 24 hours, and after the test, the film was washed off with warm water and detergent in the sink, air-dried, and the scar was removed. Check for discoloration and erosion. The results were evaluated according to (7). (9) Drying test The sample was applied with a glass spray nozzle, immediately placed in a semicircular drying box with a diameter of 10 cm and a length of 20 cm, and air was blown with a hair dryer to dry it. When the coating stops blistering or peeling, this is considered the drying time (room temperature, wind speed approximately 4 m/sec). The results were evaluated as ○ those that dried within 3 minutes, and × those that dried within 3 minutes.

Claims (1)

[Claims] 1 (a) 10 to 80 parts by weight of a petroleum distillate wax () having a melting point in the range of 50 to 85°C and a melting point in the range of 36 to 120°C and a number average molecular weight of 310 to 1000 carbon atoms per 1000 carbon atoms. 90 to 20 parts by weight of a polyolefin wax () having a double bond number in the range of 5 to 50, and this mixture
(b) an emulsifier; 1. An aqueous composition for protecting a paint film, characterized in that less than 7 parts by weight and (c) 10 to 400 parts by weight of silicone resin powder are emulsified and dispersed in water as essential components. 2 (a) 10 to 80 parts by weight of a petroleum distillate wax () with a melting point of 50 to 85°C, a melting point of 36 to 120°C, a number average molecular weight of 310 to 1000, and a double bond number of 5 to 1000 carbon atoms. This mixture is mixed with 90 to 20 parts by weight of polyolefin wax () in the range of 50
(b) an emulsifier; (c) 10 to 400 parts by weight of silicone resin powder, and (d) 10 to 200 parts by weight of organic or inorganic solid fine powder as essential components emulsified and dispersed in water. Aqueous composition for use.