JPH0258305B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a naturally crosslinked film-forming composition, which has excellent antifouling durability against lipophilic and hydrophilic contaminants, and has excellent weather resistance. This invention relates to an automotive wax that forms a crosslinked film. [Prior Art] Many antifouling waxes are commercially available for the purpose of preventing contamination of painted metal plates and the like constituting automobile bodies. However, all of these waxes are non-crosslinked and gradually dissolve when exposed to wind and rain, resulting in insufficient antifouling properties.Moreover, the wax film has some tackiness. Depending on the type of contaminants, the adhesion of contaminants may even accelerate contamination. [Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned problems, and its purpose is to develop a completely new type of material that is excellent in weather resistance and has long-term stain resistance. It is an object of the present invention to provide a naturally crosslinked film-forming composition. [Means for Solving the Problems] The composition of the present invention that achieves the above object has: : a trivalent or higher valence metal alkoxide; and : a functional group having reactivity with the alkoxyl group in the alkoxide. An organic polymer having in the molecule, a heated reaction product with, or a heated reaction product of the above component with a fluorine-based or silicon-based reactive surfactant, which is a natural crosslinking product that leaves unreacted alkoxyl groups. The gist is that it contains a type of composition as an active ingredient. [Function] The required characteristics of antifouling water wax include (1) no staining caused by raindrops or water scale, and (2) good film durability. All antifouling waxes are of non-crosslinked type, and it cannot be said that sufficient antifouling durability is obtained due to the stickiness of the wax coating itself or the dissolution of the coating due to wind and rain. The present inventors focused on the above-mentioned circumstances, and from the viewpoint of what characteristics should be considered in order to obtain antifouling properties that surpass those of conventional waxes,
We proceeded with the study without being bound by the characteristics of conventional waxes. As a result, it was concluded that the objective could be achieved if a composition having the following properties could be obtained. It has natural crosslinking properties in the atmosphere and can quickly crosslink after application to form a dense continuous film without pinholes. The coating should be hard and have excellent stain resistance, and should also have appropriate flexibility (no cracks, etc.). The coating must be water and oil repellent. In order to realize this inference, the present inventors evaluated the performance of compositions made from various compounds. As a result, as mentioned above, the unreacted alkoxyl group is a heated reaction product of a trivalent or higher valent metal alkoxide and an organic polymer having a functional group in its molecule that is reactive with the alkoxyl group in the alkoxide. When the remaining composition is left to stand after being applied to automobile exterior panels, unreacted alkoxyl groups react with each other due to the action of moisture in the air and crosslink, forming a cured film with excellent stain resistance and durability. , and above,
In addition to the following ingredients: The composition obtained by heating and reacting a fluorine-based or silicon-based reactive surfactant also has sufficient water-repellent properties as specified in commercially available stain-proofing waxes. It was confirmed that an extremely excellent antifouling film could be formed. That is, when the composition of the present invention is compared with conventional stain-proofing waxes, the latter is a non-curing type that is expected to have stain-proofing function through mere water repellency, whereas the former uses moisture in the atmosphere. It can be said to be completely different in that it is a naturally crosslinked type, and is positioned as a completely new type of antifouling film-forming composition. The metal alkoxide used in the present invention has the general formula (RO) _x M (R is an alkyl group, M is a metal atom,
x represents the valence of the metal atom), among which the most preferred alkyl groups are methyl, ethyl, propyl, butyl, hexyl, heptyl, etc.; Examples of the above metal atoms include boron, aluminum, indium, silicon, germanium, tin, lead, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, etc. Among them, silicon, aluminum, and titanium are most preferred. Of course, it is possible to select and use only one type of these metals, but it is also possible to use two or more types, especially an alkoxide containing the three metals of silicon, aluminum, and titanium,
When these are used together in the following blending ratios, very excellent coating properties are exhibited. Alkoxysilane 40-93 parts by weight Alkoxytitanium 3-35 Alkoxyaluminum 2-23 Next, as an organic polymer having a functional group reactive with the above metal alkoxide in its molecule,
All types of organic polymers (including oligomers) having functional groups such as epoxy groups, isocyanate groups, carboxyl groups, and hydroxyl groups can be mentioned, but the most common are acrylic, epoxy, polyester, and polyurethane polymers. coalescence and its various modifications. Preferably, the organic polymers also include organosiloxane polymers and oligomers that have high reactivity with metal alkoxides. The reaction between the metal alkoxide and the organic polymer is carried out by using an organic solvent such as methyl ethyl ketone and adding a small amount of water in the presence of a catalyst such as an organic tin compound or an organic acid anhydride. The general formula for this reaction is as follows. (In the formula, R, R' are an alkyl group or a proton, M
is a metal atom, and poly means a polymer or oligomer) Although the raw material itself shown in the above general formula has been publicly known, the resulting copolymer was obtained for the first time by the present inventors. It is a new compound. The blending ratio of the metal alkoxide and the organic polymer can be selected and determined as appropriate, taking into account the types of raw materials to be blended and the required characteristics of the target product, but it is possible to In order to obtain an easy liquid or waxy product, the organometallic alkoxide and the organic polymer are mixed in a ratio of (98-45):(2
It is desirable to use the polymer at a polymerization ratio of ~55). Incidentally, if the amount of organometallic alkoxide is relatively too large, the cured film tends to lack flexibility, while if the amount of organic polymer is relatively too large, the cured film tends to be somewhat lacking in flexibility. Due to insufficient hardness, the cured film is easily damaged by scratching force, etc., and loses its surface protection effect. In addition, suitable reaction conditions for proceeding with the above reaction also vary depending on the types and combinations of raw materials, so they cannot be specified uniformly, but usually 50~
It is selected from the range of 1 to 15 hours at 100°C, more typically 2 to 10 hours at 60 to 80°C. This reaction is
It is controlled by the amount of water added, which acts as a reaction initiator. The reaction product obtained is a liquid containing the reaction solvent and the alcohol produced during the reaction process, and this can be applied as is by brushing, doctor blade painting, or spray painting, or the reaction solvent and alcohol can be distilled off. It can also be made into a liquid or wax form and commercialized in the same form as general antifouling wax. The composition obtained in this way can be coated onto any base material and left in the atmosphere, and the alkoxyl groups contained in the composition will react with moisture in the atmosphere to cause intramolecular or molecular cause a crosslinking reaction between
Forms a coating with high hardness and appropriate flexibility. This film has excellent weather resistance, as well as excellent soot and water stain resistance, making it a completely new type of antifouling film-forming composition used for automobile exterior panels. Demonstrates outstanding functionality as a product. By the way, in many general antifouling waxes for automobiles, water repellency is specified as one of the performance evaluation criteria, and in this type of industry, the premise of suitability evaluation is that it has a minimum water repellency. There seems to be a trend towards this. This is thought to be because the quality of the water repellency can be used to determine, to some extent, the rate of dissolution by rainwater, etc., and, ultimately, the quality of the antifouling durability. On the other hand, the composition of the present invention is a naturally hardening type that is different from conventional waxes, and there is almost no risk of it being dissolved by rainwater, etc. Therefore, adding water repellency to the suitability evaluation criteria is not necessarily beneficial in itself. Although this cannot be said to be the case, it would be better to provide a suitable level of water repellency in order to comply with the trends in the industry as described above. For this purpose, it is sufficient to simply mix an appropriate surfactant into the composition obtained by the above reaction, but with this method, the surfactant gradually dissolves from the coating and loses its water repellency. Moreover, the problem arises that the crosslinking curability or the physical properties of the cured film are inhibited by the incorporation of the surfactant. Therefore, as a result of further research to improve these points, we found that a reactive surfactant was allowed to coexist from the beginning of the reaction or during the reaction when producing the above composition, and these were combined with the metal alkoxide and organic material. It was discovered that if the reaction was carried out together with a polymer, the objective could be successfully achieved, and an antifouling film with appropriate water repellency could be obtained. As the reactive surfactant having such an effect, any reactive surfactant that has a reactive functional group in its molecule and can be cured to impart water repellency can be used, but in particular, fluorine-based and silicon-based surfactants can be used. The reactive surfactant is most suitable because it has excellent stability in itself and also has the additional effect of further improving the stain resistance of the cured film. In order to effectively exhibit the effect of such a reactive surfactant, the preferred blending amount is 1 to 15% by weight, more preferably 2 to 10% by weight of the total solid component including the metal alkoxide and organic polymer. quantity, 1
If it is less than 15% by weight, it will not be possible to impart sufficient water repellency to the cured film, while if it exceeds 15% by weight, the water repellency will not be improved any further, but rather there will be a strong tendency to reduce the film strength, which is not preferable. . Specific examples of fluorine-based and silicon-based reactive surfactants include hydroxyperfluoroalkyl, glycidoxypropyltetramethylsiloxane, perfluorotrimethoxysilane, carboxyalkyldimethylsiloxane oligomer, and aminopropyltetraethoxysilane. Examples include surfactants having reactive functional groups such as hydroxyl groups, epoxy groups, alkoxysilane groups, carboxyl groups, and amino groups. As mentioned above, the film-forming composition according to the present invention itself has a natural hardening property due to moisture in the atmosphere, and the composition can be used alone. are fillers and viscosity modifiers such as abrasive materials, brazing materials, silicone oil, etc.
Appropriate amounts of stabilizers and the like can be added to improve paintability and film properties. In addition, this composition can be used in the same form as conventional antifouling waxes by removing the reaction solvent and making it into a liquid or wax form.
It can be used as a liquid containing reaction solvent, etc.
Furthermore, it is of course possible to once remove the reaction solvent and then dilute with another suitable solvent to form a liquid, or to use a suitable dispersant in combination in place of the aqueous emulsion type. Furthermore, the origin of the present invention is to obtain a high-performance antifouling film-forming composition that can replace antifouling wax for automobiles, and although the composition of the present invention satisfies the required properties, As mentioned above, the cured film that is formed can exhibit outstanding stain resistance while having appropriate hardness and flexibility, and if these characteristics are effectively utilized, it can be applied to various home appliances, office equipment, It can be widely used as an antifouling coating agent for desks, cabinets, etc., and as a functional coating agent. [Example] Example 1 The raw materials shown in (A) to (T) below (all amounts are parts by weight) are dissolved or suspended in a predetermined amount of methyl ethyl ketone, and a predetermined amount of an organotin compound as a catalyst is added thereto. Alternatively, after adding an organic acid anhydride and further adding a predetermined amount of pure water, incubate on a hot water bath at 80°C for 5 to 50 minutes while stirring.
The mixture was refluxed and stirred for 10 hours. After the reaction was completed, the alcohol produced by the reaction with methyl ethyl ketone was distilled off under reduced pressure to obtain liquid and waxy compositions. (A) Tetramethoxysilane 42.9 Tetraethoxytitanium 6.6 Tri-sec-butoxyaluminum 3.3 Acrylic polymer (Note 1) 6.6 Water 0.3 Di-n-butyltin dilaurate 0.7 Methyl ethyl ketone 39.6 100 (B) Tetraethoxysilane 42.9 Tetra-n- Butoxytitanium 6.6 Tri-sec-butoxyaluminum 3.3 Acrylic polymer (Note 1) 6.6 Water 0.3 Methyl anhydride-4-cyclohexene-1,2-
Dicarboxylic acid 0.7 Methyl ethyl ketone 39.6 100 (C) Ethyl silicate oligomer 39.0 Tetra-n-butoxy titanium 6.0 Tri-sec-butoxy aluminum 3.0 Organosiloxane polymer (Note 2) 15.0 Water 0.3 Di-n-butyltin dilaurate 0.6 Methyl ethyl ketone 36.1 10 0 (D) Tetraethoxysilane 31.1 Tetra-n-butoxytitanium 12.4 Tri-sec-butoxyaluminum 6.2 Epoxy polymer (Note 3) 9.3 Water 0.6 Anhydrous methyl-4-cyclohexene-1,2-
Dicarboxylic acid 3.1 Methyl ethyl ketone 37.3 100 (E) Ethyl silicate oligomer 42.9 Tetra-n-butoxy titanium 6.6 Tri-sec-butoxy aluminum 3.3 Acrylic polymer (Note 1) 6.6 Water 0.3 Di-n-butyltin dilaurate 0.7 Methyl ethyl ketone 39.6 100 ( F) Tetraethoxysilane 29.1 Tetra-n-butoxytitanium 2.2 Tri-sec-butoxyaluminum 1.6 Epoxy oligomer (Note 4) 29.1 Water 0.3 Anhydrous methyl-4-cyclohexene-1,2-
Dicarboxylic acid 0.6 Methyl ethyl ketone 37.1 100 (G) Tetraethoxysilane 31.1 Etra-n-butoxy titanium 12.4 Mono-sec-butoxyaluminum diisopropylate 6.2 Polyurethane (Note 5) 9.3 Water 0.6 Di-n-butyltin dilaurate 3.1 Methyl ethyl ketone 37.3 100 (H) Tetraethoxysilane 29.9 Tetra-n-butoxytitanium 12.0 Tri-sec-butoxyaluminum diisopropylate 6.0 Polyester (Note 6) 11.2 Water 0.6 Di-n-butyltin dilaurate 3.0 Methyl ethyl ketone 37.3 100 (I) Ethyl Silicate oligomer 57.6 Tetraethoxytitanium 2.2 Tri-sec-butoxyaluminum diisopropylate 1.5 Acrylic polymer (Note 1) 0.6 Water 0.3 Anhydrous methyl-4-cyclohexene-1,2-
Dicarboxylic acid 0.6 Methyl ethyl ketone 37.2 100 (J) Ethyl silicate oligomer 29.1 Tetraethoxy titanium 19.5 Tri-sec-butoxyaluminum diisopropylate 12.7 Organosiloxane polymer (Note 2) 0.6 Water 0.3 Anhydrous methyl-4-cyclohexene-1,2 −
Dicarboxylic acid 0.6 Methyl ethyl ketone 37.2 100 (K) Tetramethoxysilane 37.2 Tetraethoxy titanium 5.7 Tri-sec-butoxyaluminum 2.9 Acrylic polymer (Note 1) 5.7 Hydroxyl group-containing fluorine-based oligomer (Note 7) 2.9 Carboxyalkyldimethylsiloxane oligomer 1.7 Water 0.3 Di-n-butyltin dilaurate 0.6 Methyl ethyl ketone 43.0 100 (L) Tetraethoxysilane 37.2 Tetra-n-butoxytitanium 5.7 Tri-sec-butoxy aluminum 2.9 Acrylic polymer (Note 1) 5.7 Hydroxyl group-containing fluorine-based oligomer (Note 7) 2.9 Carboxyalkyldimethylsiloxane oligomer 1.7 Water 0.3 Di-n-butyltin dilaurate 0.6 Methyl ethyl ketone 43.0 100 (M) Ethyl silicate oligomer 31.5 Tetra-n-butoxy titanium 4.8 Tri-sec-butoxy aluminum 2.4 Organosiloxane polymer (Note 2) 12.2 Methoxysilane group-containing fluorine-based oligomer (Note 8) 4.8 Water 0.2 Di-n-butyltin dilaurate 0.5 Methyl ethyl ketone 43.6 100 (N) Ethyl silicate oligomer 37.2 Tetra-n-butoxy titanium 5.7 Tri-sec-butoxy aluminum 2.9 Acrylic polymer (Note 1) 5.7 Hydroxyl group-containing fluorine-based oligomer (Note 8) 2.9 Carboxyalkyldimethylsiloxane oligomer 1.7 Water 0.3 Di-n-butyltin dilaurate 0.6 Methyl ethyl ketone 43.0 100 (O) Tetraethoxysilane 24.9 Tetra-n-butoxytitanium 10.0 Tri-No. Secondary butoxyaluminum 5.0 Epoxy polymer (Note 3) 7.5 Hydroxyl group-containing fluorine-based oligomer (Note 7) 2.5 Aminopropyltetraethoxysilane 2.5 Water 0.5 Methyl anhydride-4-cyclohexene-1,2-
Dicarboxylic acid 2.5 Methyl ethyl ketone 44.6 100 (P) Tetraethoxysilane 24.9 Tetra-n-butoxytitanium 10.0 Tri-sec-butoxyaluminum 5.0 Epoxy oligomer (Note 4) 7.5 Hydroxyl group-containing fluorine-based oligomer (Note 7) 2.5 Glycidoxypropyl tetra Methylsiloxane 2.5 Water 0.5 Methyl anhydride-4-cyclohexene-1,2-
Dicarboxylic acid 2.5 Methyl ethyl ketone 44.6 100 (Q) Tetraethoxysilane 18.8 Tetra-n-butoxytitanium 7.5 Mono-sec-butoxyaluminum diisopropylate 3.8 Polyurethane (Note 5) 15.0 Hydroxyl group-containing fluorine-based oligomer (Note 8) 1.9 Aminopropyl Tetraethoxysilane 1.9 Water 0.4 Methyl-4-cyclohexene-1,2-dicarboxylic anhydride 1.9 Methyl ethyl ketone 48.8 100 (R) Tetraethoxysilane 23.7 Tetra-n-butoxytitanium 9.5 Tri-sec-butoxyaluminum diisopropylate 4.7 Polyester (Note 6) 11.8 Hydroxyl group-containing fluorine-based oligomer (Note 8) 2.4 Carboxyalkyldimethylsiloxane 2.4 Water 0.5 Di-n-butyltin dilaurate 2.4 Methyl ethyl ketone 42.6 100 (S) Ethyl silicate oligomer 52.7 Tetraethoxytitanium 1.7 Tri-sec-butoxy Aluminum diisopropylate 1.1 Acrylic polymer (Note 1) 0.6 Fluorine-based oligomer containing methoxysilane (Note 9)
0.6 Water 0.6 Di-n-butyltin dilaurate 0.3 Methyl ethyl ketone 42.4 100 (T) Ethyl silicate oligomer 22.7 Tetraethoxy titanium 19.8 Tri-sec-butoxyaluminum diisopropylate 13.0 Organosiloxane polymer (Note 2) 0.6 Hydroxyl group-containing fluorine-based Oligomer (Note 8) 0.6 Water 0.6 Di-n-butyltin dilaurate 0.3 Methyl ethyl ketone 42.4 However, (Note 1) to (Note 8) shown in the above ingredients are as follows. (Note 1): Acrylic polymer product name manufactured by Dainippon Ink & Chemicals Co., Ltd. (Findyk Series, Acrydik Series); product name manufactured by Mitsubishi Rayon Co., Ltd. (Dianal).
series) (Note 2): Organosiloxane polymer Shin-Etsu Chemical Co., Ltd. product name (X-40-175, -
9740) (Note 3): Product name manufactured by Epoxy Polymer Shell Epoxy Co., Ltd. (Epicoat)
Series) Product name manufactured by Asahi Denka Kogyo Co., Ltd. (ADEKA Resin series) (Note 4): Epoxy oligomer Product name manufactured by Asahi Denka Kogyo Co., Ltd. (ADEKA ED series) (Note 5): Polyurethane Product name manufactured by Nippon Polyurethane Industries Co., Ltd. (Yuukiast series) ) Product name manufactured by Asahi Denka Kogyo Co., Ltd. (ADEKA BONTITER series) (Note 6): Polyester product name manufactured by Dainippon Ink Chemical Co., Ltd. (Betsucosol series) (Note 7): Reactive surfactant manufactured by Dainippon Ink Chemical Co., Ltd. , hydroxyl group-containing perfluoroalkyl (trade name
DEFENSA series) (Note 8): Reactive surfactant manufactured by Shin-Etsu Chemical Co., Ltd., methoxysilane group-containing fluorine-based oligomer (product name KP series) (Note 9): Reactive surfactant manufactured by Toshiba Silicon Co., Ltd., epoxy Silicon-based oligomers containing silicone groups, carboxyl groups, and amino groups (trade names: TSL series, YF series) From the obtained reaction product, the solvent and the alcohol produced by the reaction were distilled off under reduced pressure to obtain a wax-like composition. . Each of the obtained wax-like compositions was applied thinly to the surface of a painted steel plate for automobile exterior panels (using melamine/alumide, melamine/acrylic/urethane type paint) using a cloth, wiped off until it was sufficiently glossy, and left in the air at room temperature. After leaving to stand for 24 hours to form a cured film, the surface hardness, water repellency, and antifouling durability were examined using the following methods. Surface hardness: Find the surface hardness using Mitsubishi Uni, B, HB, H1-5. Water repellency: One day after applying the sample, spray water onto the painted surface and observe the state of the water droplets on the painted surface. A nearly spherical state is considered good. ○...Condition of commercially available solid wax △...Poorly spherical condition than commercially available solid wax ×...Condition where no water droplets are seen at all Antifouling durability: After each sample steel plate was exposed outdoors for one month, the surface was wiped with a cloth. It was wiped clean and the degree of dirt was visually judged. 〇...No discoloration or stains at all △...Slightly yellowish stains ×...Significant stains in some areas The results are summarized in Table 1.

【table】

〔Effect of the invention〕

The present invention is constructed as described above, and it cures under the action of moisture in the atmosphere to form a cured film with excellent hardness, flexibility, and antifouling properties, thus creating a completely new type of antifouling wax composition. As a result, it exhibits antifouling properties that cannot be obtained with conventional non-curing waxes. In addition, the cured film formed by the composition of the present invention not only has excellent mechanical properties as described above, but also has excellent weather resistance, so it can be used as an antifouling film for various exterior members. It is extremely useful as it can be used as a topcoat paint, a functional coating material, and the like.

Claims (1)

[Scope of Claims] 1: A heated reactant of: a trivalent or higher valent metal alkoxide; and: an organic polymer having a functional group in its molecule that is reactive with the alkoxyl group in the alkoxide, which is an unreacted product. A film-forming automotive wax characterized by containing a reaction product that leaves an alkoxyl group as an active ingredient. 2: A heating reaction between a trivalent or higher-valent metal alkoxide, an organic polymer having a functional group in its molecule that is reactive with the alkoxyl group in the alkoxide, and a fluorine-based or silicon-based reactive surfactant. 1. A film-forming wax for automobiles, which contains as an active ingredient a reaction product that leaves unreacted alkoxyl groups.