JP2009263459A - Coating composition hardly allowing icing and allowing easy deicing, coating method, and evaluation method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition allowing an object surface, on which a coating film is formed, to suppress icing and to allow easy deicing even in the case of icing in an actual environment over a long period when the coating film is formed on the object surface of various structures in the cold region. <P>SOLUTION: The coating composition, which forms the coating film on the object surface for suppressing icing on the object surface and allowing easy deicing on the object surface, contains a base material resin and reinforcing particles. The coating composition contains a fluororesin-siloxane graft polymer as the base material resin, and at least one of silicone rubber fine particles and silicone rubber surface-modified fine particles, which are obtained by covering the silicone rubber fine particle surfaces with a silicone resin, as reinforcing particles. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a coating composition that suppresses icing on an object surface, such as various structures, or simply removes the icing on the object surface, a coating method, and an evaluation method thereof.

  Conventionally, various problems have arisen due to ice adhering to the surface of various structures such as telecommunications facilities, road traffic signs, traffic lights, geothermal power generation facilities, automobiles, etc. ing. Therefore, as a method for preventing the icing of various structures on the object surface in a cold region, “do not icing” (hereinafter referred to as non-icing property), “suppress icing” (hereinafter referred to as “hard landing”). And the like (hereinafter referred to as “easy deicing ability”) and the like have been proposed.

  Of these, the idea of “no icing” on the surface of objects such as various structures is an ideal icing prevention method. However, if it becomes the concrete means, it has to rely on the system which heats the object surface represented by the electric heating pipe. For this reason, this method has a new problem that the economic burden is high due to the increased energy costs.

  Therefore, as a method for preventing icing on the object surface such as various structures, it is practical to make the object surface “hard icing property” or make the object surface “easy icing removal property”. . Therefore, as a method of imparting a function of “hard icing property” or “easy icing removal property” to the above object surface, a film having “hard icing property” or “easy icing removal property” on the object surface. Development of coating film technology (or coating technology) to be realized by forming the film is energetically performed.

  Here, as a coating composition used for a coating film, for example, a coating composition in which a binder resin and water-repellent fine particles are mixed has been proposed. As the binder resin of the coating composition, for example, solvent-soluble fluororesins, silicone resins, polyurethane resins, polyester resins, and acrylic silicone resins are used. In particular, solvent-soluble fluororesins and acrylic silicone resins are used. Etc. are often used. On the other hand, as the water-repellent fine particles of the coating composition, for example, fluororesin powder (polytetrafluoroethylene, PTFE), silicone resin powder, water-repellent silica powder, graphite fluoride, fluoride pitch, and the like are used. .

  By the way, a method of imparting a function of “hard icing property” or “easy icing removal property” to an object surface of various structures in a cold region using the above-described coating composition is basically the object surface. Based on the idea of forming a coating film with excellent water repellency, thereby reducing the surface free energy of the object surface as much as possible, and minimizing the affinity with water, thereby modifying the object surface to water repellency Yes.

In addition, as a method of evaluating the “hard icing property” or “easy icing removal property” of the surface of the object on which the coating film is formed, water is used to investigate the water repellency of the object surface immediately after the coating film is formed. A method of measuring a “water contact angle” in which a contact angle is measured by dropping on the surface (see, for example, Patent Document 1), or in addition to the measurement of a “water contact angle”, a water droplet is further dropped on the surface of the object. A method of measuring the adhesion force (ice adhesion force) of ice obtained by freezing ice (see, for example, Patent Document 2) has been mainly used.
Japanese Patent Laid-Open No. 10-120941 JP 11-29722 A

  As described above, a number of techniques have been proposed in the past to impart “hard icing resistance” or “easy icing removal performance” to the object surface by forming a coating film on the object surface of various structures. ing. In addition, as an evaluation method of “hard icing property” or “easy icing removal property” of a coating film immediately after the coating is formed on the object surface of various structures, for example, using “water contact angle”, A method of evaluating “ability” or a method of evaluating “hard icing property” and “easy icing removal property” by using “water contact angle” and “icing adhesion” has been used.

  However, when it is desired to impart “hard icing property” or “easy icing removal property” to the object surface of various structures in a cold region using the above-described coating composition, It is dangerous to measure the “water contact angle” or “water contact angle” to evaluate the “hard icing property” or “easy icing removal property” of the coating film. This is because the coating film is known to decrease when exposed to various environmental tests simulating an actual environment for a long period of time. For example, there have been many reports that the “water contact angle” and “freezing adhesion” of coating films after water immersion tests, outdoor exposure tests, and accelerated degradation tests have decreased compared to the performance immediately after film formation. It is clear from Therefore, it is difficult to determine that the performance is maintained for a long time in an actual environment even if the coating film has “hard icing property” or “easy icing removal property” at the time of coating film formation.

  However, it is a social need to impart “hard icing property” or “easy icing removal property” to the object surfaces of various structures in cold regions. Therefore, it is strongly desired to develop a coating composition in which the coating film has “hard icing property” or “easy icing removal property” over a long period in an actual environment. There is also a strong demand for an evaluation method for accurately predicting the long-term stability of a coating composition in an actual environment.

  The present invention has been made starting from solving the problems of the prior art described above. The purpose of the paint is to have a coating with “hard icing resistance” and “easy icing removal performance” over a long period of time when a coating film is formed on the surface of an object of various structures in a cold region. It is to provide a composition and method for coating the same. Another object of the present invention is that when a coating film formed using a coating composition is used in a cold region, the coating film has a long-term “hard-to-icing property” and “easy-to-deicing property”. An object of the present invention is to provide an evaluation method capable of accurately predicting the durability to be passed.

  In order to achieve the above object, a coating composition according to an embodiment of the present invention has the following configuration. That is, a coating composition for forming a coating film on the object surface so as to suppress icing on the object surface or to easily deice the ice icing on the object surface, the fluororesin-siloxane It includes a graft polymer, and at least one fine particle of silicone rubber fine particles and silicone rubber surface-modified fine particles obtained by coating the surface of the silicone rubber fine particles with a silicone resin.

  Here, for example, the fluororesin-siloxane graft type polymer is formed using a radical polymerizable fluororesin, a radical polymerizable polysiloxane, an alkoxysilyl-containing monomer, a hydroxyl group-containing monomer, and an isocyanate compound that is a crosslinking agent. It is preferred that

  Here, for example, the at least one fine particle is a silicone rubber fine particle, and the silicone rubber fine particle is contained in the coating composition at a ratio of 10 to 70% by weight with respect to the solid content of the fluororesin-siloxane graft polymer. It is preferable that

  Here, for example, the silicone rubber fine particles are preferably silicone rubber fine particles having a predetermined average particle diameter or a mixture of two or more kinds of silicone rubber fine particles having different average particle diameters.

  Here, for example, the at least one fine particle is a silicone rubber surface-modified fine particle, and the silicone rubber surface-modified fine particle is 10 to 70 based on the solid content of the fluororesin-siloxane graft polymer in the coating composition. It is preferably contained in a proportion by weight.

  Here, for example, the silicone rubber surface modified fine particles are preferably silicone rubber fine particles having a predetermined average particle diameter or a mixture of two or more kinds of silicone rubber surface modified fine particles having different average particle diameters.

  Here, for example, the at least one fine particle is a mixture of silicone rubber fine particles and silicone rubber surface-modified fine particles, and the mixture is 10 to the solid content of the fluororesin-siloxane graft polymer in the coating composition. It is preferably contained at a ratio of ˜70% by weight.

  Here, for example, the silicone rubber fine particles are silicone rubber fine particles having a predetermined average particle diameter, or a mixture of two or more types of silicone rubber fine particles having different average particle diameters, and the silicone rubber surface-modified fine particles are It is preferable that the silicone rubber fine particles have an average particle diameter of 2 or more, or a mixture of two or more kinds of silicone rubber surface-modified fine particles having different average particle diameters.

  Moreover, the evaluation method of the coating composition of this invention has the following structures. That is, a method for evaluating a coating composition for forming a coating film on the object surface so as to suppress icing on the object surface or to easily deicing the ice icing on the object surface, The step of exposing the coating film to an environmental test simulating the environment in which the coating is used, and the coating film after being exposed to the environmental test, with a difficult icing property to prevent icing of the coating film and icing A step of performing a plurality of measurement tests for evaluating easy icing removal properties that are easy to deicing, and a comprehensive evaluation that is determined based on each measurement value obtained by the plurality of measurement tests is predetermined. And an evaluation step for comprehensively evaluating the difficult-to-icide property and the easy-to-deice removal property of the coating film after being exposed to the environmental test depending on whether or not the evaluation criteria are satisfied.

  Here, for example, the environmental test includes a water immersion test in which the coating film is immersed in water for a predetermined period, and an outdoor exposure test in which the coating film after the water immersion test is exposed to an outdoor natural environment for a predetermined period. Is preferred.

  Here, for example, in the environmental test, it is preferable to repeat a cycle in which the water immersion test and the outdoor exposure test are one cycle by a predetermined number of cycles.

  Here, for example, the plurality of measurement tests preferably include measurement of a water drop sliding angle, a water contact angle, an icing adhesion force, an icing area ratio, an icing amount, and a water repellency after the environmental test. .

  Here, for example, in the evaluation step, for each measurement test, it is preferable to classify the measured values according to a predetermined evaluation standard to calculate a grade value.

  Here, for example, in the evaluation step, the grade values calculated for each of the measurement tests are the “hard icing ability” ability and the “easy icing removal ability” ability of the coating film after the environmental test. It is preferable to comprehensively evaluate the coating film after being exposed to the environmental test by discriminating which criteria of the comprehensive evaluation criteria for comprehensively evaluating the above.

  The coating method of the present invention has the following configuration. That is, a coating method for forming a coating film of the coating composition on the object surface so as to suppress icing on the object surface or to easily deicing the ice icing on the object surface, Applying an undercoat paint to form an undercoat layer, applying an intermediate coat paint on the undercoat layer to form an intermediate coat layer, and using the coating composition described above on the intermediate coat layer And a step of forming an intermediate coating layer.

  According to the present invention, when a coating film is formed on the surface of an object of various structures in a cold region, the coating film has the performance of “hard icing property” and “easy icing removal property” over a long period of time. The coating composition which has, and its coating method can be provided. In addition, according to the present invention, when the coating film formed using the coating composition is used in a cold region, the coating film has a long-term “hard-to-icing property” and “easy-to-deicing property”. An evaluation method capable of accurately predicting durability can be provided.

  Therefore, a coating film is formed on the object surface of various structures such as telecommunications facilities, road traffic signs, traffic lights, geothermal power generation facilities, automobiles, etc. Then, icing on various structures such as a ship is suppressed, and even if icing is performed, it can be deiced by a simple operation.

[Characteristic]
In the present invention, when a coating film having “hard icing property” and “easy icing removal property” is formed on the surface of an object of various structures in a cold region, the long-term durability of the coating film performance is accurately determined. We were able to find a predictable method for evaluating the practicality of the coating film. Therefore, in the present invention, even if a coating film is formed on the surface of an object of various structures in a cold region by applying a method for evaluating the practicality of the coating film, the “hard icing property” and “easy icing removal” of the coating film It was possible to find a coating composition in which the “characteristic” is expected to be maintained for a long time in an actual environment. Hereafter, the evaluation method of the practicality of the coating film of this invention and the outline | summary of the coating composition of this invention are demonstrated.

  First, when the practicality evaluation method of the coating film of this invention is demonstrated, a coating film is exposed to the environmental test which simulated the environment where a coating film is used. Next, the coating film after being exposed to environmental tests is evaluated for "hard icing property" that suppresses icing of the coating film and "easy icing removal property" that can be easily removed even if icing. Therefore, a plurality of measurement tests are performed, and for each measurement test, the measured values are classified according to a predetermined evaluation standard to calculate a grade value. Finally, which criteria of the overall evaluation criteria that the grade value calculated for each measurement test satisfies the overall evaluation of “hard icing property” and “easy icing removal property” of the coating after the environmental test? Is determined. In this way, the practicality evaluation method of the coating film of the present invention comprehensively evaluates the practicality of “hard icing property” and “easy icing removal property” of the coating film after being subjected to an environmental test. Can do.

  Here, when the practicality evaluation method of the coating film of the present invention described above is specifically described with an example, in the environmental test, a water immersion test in which the coating film is immersed in water for a predetermined period (for example, one month), The coating film after the water immersion test is exposed to the outdoor natural environment for a predetermined period (1 month) and the outdoor exposure test is repeated for a predetermined cycle (for example, 6 cycles, 12 months in total). Deteriorate. Next, in the coating test after the environmental test, the “water drop sliding angle”, “water contact angle”, “icing adhesion”, “icing area ratio”, “icing amount”, “ Six performances of “water repellency” are measured. Then, the measured values measured for each measurement test are classified into, for example, 5 grades (5, 4, 3, 2, 1) according to a predetermined evaluation standard. For example, if the evaluation standard of “water drop sliding angle of 20 degrees or less” is defined in advance as “5 (grade)”, the measured value of “water drop sliding angle” of 19 degrees is classified as the evaluation standard “5”. . Next, the grades of the respective grade values classified for each measurement test are classified according to a predetermined evaluation standard and comprehensively evaluated. For example, if the evaluation standard “5” is obtained in all six measurement tests, the overall evaluation standard of the coating film is “●: extremely practical” (“hard icing property” and “easy to wear” of the coating film). If the evaluation criteria “5” is obtained in each of the six measurement tests, the overall evaluation criteria “●” "are categorized. As a result, according to the practicality evaluation method of the coating film of the present invention, by using the comprehensive evaluation described above, the “hard icing property” and the “easy landing” of the coating film when the coating film is used in a cold region. The durability over a long period of “ice removal” can be accurately predicted.

  Next, the outline | summary of the coating composition of this invention is demonstrated. In the present invention, various coating compositions and coating films thereof were prepared, and various coating compositions were evaluated by applying the above-described practicality evaluation method for coating films. As a result, even when a coating film is formed on the surface of an object in various structures in cold regions, the “hard-to-freeze” and “easy-to-removable” properties of the coating are maintained over a long period in the actual environment. It was possible to find a coating composition of the present invention that was predicted to be. The obtained coating composition of the present invention comprises a base resin and reinforcing particles, a fluororesin-siloxane graft type polymer as the base resin, silicone rubber fine particles as the reinforcing particles, and silicone rubber fine particle surfaces. It is characterized in that it contains silicone rubber surface-modified fine particles coated with a silicone resin or both fine particles.

  In particular, the coating composition of the present invention exhibits excellent performance when the reinforcing particles are contained in a proportion of 10 to 70% by weight with respect to the base resin (the solid content of the fluororesin-siloxane graft polymer). is there. Further, the silicone rubber fine particles or the silicone rubber surface-modified fine particles as reinforcing particles have an average particle diameter of several to several tens of μm, and these fine particles can be used alone or in combination. The base resin fluororesin-siloxane graft polymer was formed from a radically polymerizable fluororesin, a radically polymerizable polysiloxane, an alkoxysilyl-containing monomer, a hydroxyl group-containing monomer, and an isocyanate compound as a crosslinking agent. Is.

  The coating composition of the present invention can be dispersed in a solvent and applied by brush coating in the form of a dispersion, or the coating composition of the present invention can be stored in a can or the like and sprayed using a compressed gas. Good. In the case where a coating film of the coating composition is formed on the object surface so as to suppress the icing on the object surface or to make it easy to deiculate the ice icing on the object surface, A coating film may be formed directly on the surface, or a base coating film is previously formed on the surface of the object with a different target coating, and then a coating film by the coating composition of the present invention is formed thereon. May be. The purpose of forming the underlying coating film is various, but examples include rust prevention, smoothing, and coloring of the object surface.

  For example, when the coating composition of the present invention is used to suppress icing on the ship surface or to make it easier to deiculate the ice icing on the ship surface, as the undercoat paint, for example, An undercoat layer is formed using an epoxy resin paint, and then an intermediate coat is formed on the undercoat layer, for example, a polyurethane-based paint, and finally the present invention is formed on the intermediate coat layer. The overcoating layer may be formed using the coating composition. In addition, said example is an example and can change the kind and number of layers of a coating material used for an undercoat layer and an intermediate coating layer according to the structure which requires a coating film. In addition, when it is desired to use the coating composition of the present invention after coloring, a pigment having a required color may be added.

  As described above, a coating film is applied to the surface of objects of various structures such as telecommunications facilities, road traffic signs, traffic lights, geothermal power generation facilities, automobiles, etc. If it forms, it will become possible to suppress icing to various structures, such as a ship, and it will become possible to deicing by simple work even if icing. Therefore, by using the coating composition of the present invention, it is possible to improve the safety of various structures including ships in cold regions and reduce economic loss due to their malfunction. it can.

  Next, the coating composition of the present invention described above, the coating method thereof, and the practicality evaluation method of the coating will be described in detail. In the following description, first, a resin selection test for selecting a base resin of the coating composition of the present invention and a reinforcing particle selection test for selecting reinforcing particles of the coating composition of the present invention will be described. Next, the components of the coating composition of the present invention and the characteristics of the optimum blend will be described. In addition, a method for preparing the optimally blended coating composition of the present invention will be described. Next, an environmental test (long-term durability test) of a coating film formed using an optimally blended coating composition and an evaluation test of the coating film after the environmental test will be described. Finally, the evaluation results of the practicality of the coating film using the coating composition of the present invention will be described in comparison with the coating composition of the comparative example.

[Base resin selection test: Fig. 1]
First, the base resin selection test for selecting the base resin of the coating composition of the present invention will be described. In the present invention, in developing the coating composition of the present invention, a base resin selection test was first conducted to select a base resin suitable for the coating composition of the present invention. As the resins used in the base resin selection test, four types of resins that are considered to have “hard icing property” or “easy icing removal property” among pre-selected resins are shown in FIG. A siloxane graft type polymer (R1), a solvent-soluble fluororesin (R2), an acrylic silicone resin (R3), and a polyurethane resin (R4) were selected. The “non-icing property” of the selected resin was evaluated using a simple evaluation that measures “water contact angle”, which is a typical characteristic of water repellency. “Water contact angle” is a test piece of 70 × 150 × 3.2 mmt, then coated with each resin on its surface, and then a deionized water droplet (5 μL) on the coating surface. The water contact angle of the water droplet was measured using an automatic solution contact angle meter (CA-W type manufactured by Kyowa Interface Science Co., Ltd.).

  FIG. 1 shows the results of the base resin selection test. As shown in FIG. 1, the “water contact angles” of the four types of resins used in the base resin selection test were relatively large at 76 to 99 degrees. For this reason, the four selected resins are considered to have excellent “hard icing resistance” by themselves, but among them, the fluororesin-siloxane graft having the largest “water contact angle” of 94 to 99 degrees. Type polymer was used as the base resin of the present invention. Here, the fluororesin-siloxane graft type polymer selected by the base resin selection test is composed of a radical polymerizable fluororesin, a radical polymerizable polysiloxane, an alkoxysilyl-containing monomer, and a hydroxyl group-containing monomer, and an isocyanate compound as a crosslinking agent. It is a resin formed using

[Reinforced particle selection test: Fig. 2]
Next, a reinforcing particle selection test for selecting reinforcing particles to be added to the base resin of the coating composition of the present invention will be described. When added to the selected base resin (fluororesin-siloxane graft polymer), it was decided to select reinforcing particles suitable for improving the “hard icing property” of the base resin. In the reinforcing particle selection test, the “hard icing property” of the coating film of the coating composition obtained by adding reinforcing particles to the base resin was evaluated by “water contact angle”.

  As the reinforcing particles, silicone fine particles having water repellency, impact absorption, cold resistance, and ultraviolet absorption are selected in advance. Next, the silicone shown in FIG. Resin fine particles P1 (cured polyorganosilsesquioxane crosslinked in a three-dimensional network), silicone rubber fine particles P2 (crosslinked structure of linear dimethylpolysiloxane), and silicone rubber surface modified fine particles P3 ( Three types of fine particles obtained by coating the surface of silicone rubber fine particles with a silicone resin were selected and subjected to a reinforcing particle selection test.

  In the reinforcing particle selection test, the coating composition was prepared to the following composition. That is, as a constituent component of the coating composition, a fluororesin-siloxane graft type polymer as a base resin, and 40% by weight of reinforcing particles (silicone resin fine particles P1, silicone rubber fine particles P2, silicone based on the solid content of the base resin) Any of the rubber surface modified fine particles P3), a diluent solvent (xylene / butyl acetate = 1/1), and a polyisocyanate as a curing agent (crosslinking agent) were used. The coating composition is prepared by charging the base resin into a container for dispersion, adding the reinforcing particles with gentle stirring and mixing, then adding a diluent solvent and stirring for 30 minutes, and finally adding a curing agent. And mixed. The coating composition was evaluated using the “water contact angle” as in the base resin selection test.

  FIG. 2 shows the results of the reinforcing particle selection test. 2, the “water contact angle” when the silicone resin fine particles P1 are added to the base resin is the same as the “water contact angle” 94 to 99 degrees of the base resin shown in FIG. The “water contact angle” did not increase even when added to the resin. However, when the silicone rubber fine particles P2 are added to the base resin, the “water contact angle” increases to 108 to 113 degrees, and when the silicone rubber surface-modified fine particles P3 are added to the base resin, the “water contact angle” increases. The “angle” increased from 106 to 111 degrees and the “water contact angle” increased. From this, it was found that silicone rubber fine particles P2 and silicone rubber surface-modified fine particles P3 are suitable as reinforcing particles for the base resin (fluororesin-siloxane graft type polymer). Therefore, in the coating composition of the present invention, a fluororesin-siloxane graft type polymer is used as the base resin, and silicone rubber fine particles, silicone rubber surface-modified fine particles, or a mixture thereof is used as the reinforcing particles.

[Composition of components of the coating composition of the present invention: FIGS. 3 to 5]
Next, the optimum coating composition of the present invention comprising the selected base resin (fluororesin-siloxane graft polymer) and reinforcing particles (silicone rubber fine particles, silicone rubber surface-modified fine particles or a mixture thereof) The formulation will be described.

  3 to 5 show examples of the formulation of the coating composition of the present invention. The coating composition of the present invention includes a base resin, reinforcing particles, a diluent, and a curing agent. It is characterized in that the reinforcing particles are contained in a proportion of 10 to 70% by weight with respect to the base resin (solid content of fluororesin-siloxane graft polymer). Hereinafter, the components of the optimum blending of the coating composition of the present invention shown in Examples 1 to 36 will be described in detail.

  First, the base resin will be described. In Examples 1 to 12 shown in FIG. 3, a room temperature curing standard type (trade name ZX-007C) manufactured by Fuji Kasei Kogyo is used as the base resin, and Examples 13 to 13 shown in FIG. 24, a room temperature curing high weather resistance type (ZX-017) manufactured by Fuji Kasei Kogyo as a base resin, and in Examples 25-36 shown in FIG. ZX-022) was used.

  Next, the reinforcing particles will be described. In Examples 1 to 36 shown in FIGS. 3 to 5, silicone rubber fine particles and silicone rubber surface-modified fine particles were used alone or in combination as reinforcing particles. Specifically, two types of fine particles A (average particle size 5 μm: trade name KMP-597) and fine particles B (average particle size 13 μm: trade name KMP-598) manufactured by Shin-Etsu Chemical Co., Ltd. are used as silicone rubber fine particles. Three types of fine particles C (average particle size 40 μm: trade name X-52-875), fine particles D (average particle size 5 μm: trade name KMP-600), fine particles E (average particle size) manufactured by Shin-Etsu Chemical Co., Ltd. 30 μm: trade name KMP-602) was used. Further, xylene / butyl acetate = 1/1 was used as a diluent solvent, and hexamethylene diisocyanurate (trade name: Coronate HX) was used as a polyisocyanate as a curing agent (crosslinking agent).

  3 to 5, the formulation of the coating composition of the present invention is shown as a blending ratio of each component with respect to the base resin 100. For example, in Example 1, the reinforcing particles (silicone rubber fine particles A) are 10, the diluent is 110, and the curing agent is 20 with respect to the base resin (solid content of fluororesin-siloxane graft type polymer). Is contained at a ratio of 10% by weight to the base resin.

[Composition of Comparative Example: FIG. 6]
FIG. 6 shows an example of the composition of the constituents of the coating composition of the comparative example. The coating compositions of Comparative Examples 1 to 7 are the same constituents as the coating compositions of the present invention shown in Examples 1 to 36. The base resin, the reinforcing particles, the diluent, and the curing agent are different from each other in the ratio of the reinforcing particles to the base resin. That is, in Comparative Examples 1 to 7, the reinforcing particles are contained in a proportion of less than 10% by weight or more than 70% by weight with respect to the base resin, and the coating compositions of the present invention shown in Examples 1 to 36 are reinforced. This is outside the proportion of particles (range of 10 to 70% by weight).

  On the other hand, in the case of Comparative Examples 8 to 12, the constituent components of the base resin, diluent and curing agent of the coating compositions of the present invention shown in Examples 1 to 36 are the same, and the reinforcing particles are based on the base resin. The ratio is also the same as the range of 10 to 70% by weight, but the difference is the type of reinforcing particles. That is, in Comparative Example 8, as the reinforcing particles, fluoride pitch (average particle size 40 μm: trade name OGSOL FP-S) is used, and in Comparative Example 9, graphite fluoride (average particle diameter 6 μm: trade name Cefbon CMC) is used. In Examples 10 and 11, polytetrafluoroethylene (average particle size 7 μm: trade name Fluoron 173J) is used, and in Comparative Example 12, water-repellent silica powder (average particle diameter 5 μm: trade name Nipsil SS-70) is used.

[Preparation method of coating composition]
Next, an example of a method for producing the above-described coating composition of the present invention and a coating composition of a comparative example will be described. In manufacture of the coating composition by the mixing | blending shown in Examples 1-36 and Comparative Examples 1-12 demonstrated above, after manufacturing a main ingredient and a hardening | curing agent separately, a hardening | curing agent is added to a main ingredient at the time of use, and a coating composition and did. First, the main ingredient is a fluororesin-siloxane graft type polymer containing an organic solvent as a base resin, charged in a container for dispersion, then reinforcing particles are added and mixed with gentle stirring, and finally a diluent solvent (xylene) / Butyl acetate = 1/1) and stirred for 30 minutes (rotation speed 1,200 rpm). On the other hand, the curing agent was produced by diluting a commercially available polyisocyanate with a solvent (butyl acetate).

[Environmental test of paint film (long-term durability test)]
Next, the coating composition of the present invention described above and the coating composition of the comparative example are coated on a test piece to form a coating film, and the resulting test piece is an environmental test (long-term durability test) that simulates a cold region. An example in which the coating film is deteriorated by exposure to a predetermined period will be described.

  First, a method for coating the coating compositions of Examples 1 to 36 and Comparative Examples 1 to 12 on test specimens will be described. First, a modified epoxy resin paint with a dry film thickness of 40 is used as an undercoat on a test piece of a predetermined size. Spray with ~ 50 μm and leave for 24 hours. Next, a polyurethane-based paint is spray-coated with a dry film thickness of 25 to 30 μm as an intermediate coat on the undercoat, and left for 24 hours. Finally, after mixing and stirring each main ingredient and each curing agent of the formulations shown in Examples 1-36 and Comparative Examples 1-12 described above as an overcoat on the intermediate coat, the dry film thickness is 20-30 μm. A test piece was prepared by painting with an applicator.

  Next, the test piece which formed the coating film using the mixing | blending of Examples 1-36 and Comparative Examples 1-12 was exposed to the environmental test which simulates a cold region for a predetermined period, and the coating film was deteriorated. That is, in the environmental test of the coating film, the test piece on which the coating film having a three-layer structure of the above-described undercoat (40 to 50 μm) + intermediate coating (25 to 30 μm) + top coat (20 to 30 μm) was formed The water immersion test 1 month + the outdoor exposure test 1 month was taken as 1 cycle, and the coating film surface was deteriorated in an environmental test of 6 cycles (12 months in total) repeated 6 times. Here, the water immersion test was performed by immersing the test piece at a water temperature of about 10 to 25 ° C., and the outdoor exposure test was performed by attaching the test piece to the exposure table at an air temperature of about 1 to 35 ° C.

[Evaluation of coating film after environmental test: FIGS. 7 to 9]
Next, the performance evaluation of the coating film of the composition of Examples 1-36 and Comparative Examples 1-12 after the environmental test of the coating film described above was performed. 7 and 8 show the evaluation results of the durability of “hard icing property” and “easy icing removal property” to the coating films of Examples 1 to 36 after the environmental test. On the other hand, FIG. 9 is an evaluation result of durability of “hard icing property” and “easy icing removal property” for each coating film of Comparative Examples 1 to 12 after the environmental test. In the following description, before describing FIGS. 7 to 9, the evaluation test of the coating film after the environmental test will be described, and finally, the practicality of the coating film using the coating composition of the present invention shown in FIGS. The evaluation test results will be described in comparison with the comparative coating composition.

[Film performance evaluation test]
First, the evaluation test of the coating film after the environmental test will be described. In order to evaluate the durability of “hard icing property” and “easy icing removal property” of the coating composition of the present invention, “hard icing property” and “easy icing removal” of the coating film after the environmental test were conducted. The performance of "sex" must be evaluated correctly. Therefore, in the present invention, as a performance evaluation test for appropriately evaluating the “hard icing property” and “easy icing removal property” of the coating composition, “water drop sliding angle”, “water contact” Evaluation tests that measure the six performances of “corner”, “icing adhesion”, “icing area ratio”, “icing amount”, and “water repellency” were selected, and then obtained in each performance evaluation test. From the measured values, the durability of the “hard icing property” and “easy icing removal property” of the coating film after the environmental test was collectively evaluated by the practicality evaluation method described below.

  That is, in the practicality evaluation method, the coating film after being subjected to an environmental test has “hard icing property” that suppresses icing of the coating film and “easy icing removal property that is easy to deicing even when icing. In order to evaluate the "water drop sliding angle", "water contact angle", "icing adhesion", "icing area rate", "icing amount", "water repellency" measurement test, For each measurement test, the measured value is classified into five levels according to a predetermined evaluation standard to calculate a grade value. Finally, which of the overall evaluation criteria to comprehensively evaluate the “hard icing property” and “easy icing removal property” of the coating film based on the grade value evaluated in five stages for each measurement test? Discriminate and comprehensively evaluate the long-term durability of the “hard icing property” and “easy icing removal property” of the coating film.

[Water drop sliding angle evaluation test]
Next, the above-described six evaluation tests for the coating film after the environmental test will be sequentially described. In the water drop sliding angle evaluation test, a protractor is placed on the back of a 70 × 200 × 0.8 mmt test piece that has been deteriorated in an environmental test. The “water drop sliding angle” was measured by reading the angle of the water drop sliding start. The “water drop sliding angle” of the coating film was evaluated according to the following five levels. That is, the coating film in which water droplets started to slide the earliest at an angle of 20 degrees or less was evaluated as a super water-repellent coating film, and the evaluation standard of “water droplet sliding angle” was set to 5. Similarly, the water-repellent or hydrophilic coating film was evaluated according to Evaluation Criteria 4 to 1 as follows.
Evaluation criteria Water droplet sliding angle coating film evaluation 5 20 degrees or less Super water-repellent coating film 4 21-30 degrees Water-repellent coating film 3 31-40 degrees Water-repellent-hydrophilic coating film 2 41-50 degrees Hydrophilic coating film 1 51 degrees Hydrophilic coating film

[Water contact angle evaluation test]
In the water contact angle evaluation test, an automatic solution contact angle meter (CA-W type manufactured by Kyowa Interface Science Co., Ltd.) was added by dropping 5 μl of deionized water onto a 70 × 150 × 3.2 mmt test piece deteriorated in an environmental test. ) Was used to measure the “water contact angle”. The “water contact angle” of the coating film was evaluated in the following five stages. That is, a coating film having a “water contact angle” of 100 degrees or more was evaluated as a water-repellent coating film, and an evaluation criterion of “water contact angle” was set to 5. Similarly, the water-repellent or hydrophilic coating film was evaluated according to Evaluation Criteria 4 to 1 as follows.
Evaluation criteria Water contact angle coating film evaluation 5 100 degrees or more Water repellent coating film 4 90 to 99 degrees Water repellency to hydrophilic coating film 3 80 to 89 degrees Hydrophilic coating film 2 70 to 79 degrees Hydrophilic coating film 1 69 degrees or less Hydrophilic coating

[Ice adhesion test]
In the icing adhesion evaluation test, a hard vinyl vinyl chloride ring (22 mmΦ × 22 mmh, inner diameter 16 mmΦ) is placed on a 70 × 150 × 3.2 mmt test piece deteriorated in an environmental test, and 4 ml of water is placed therein. Then, after freezing in a low temperature test room at −15 ° C. for 5 hours, “ice adhesion” was measured with a push-pull scale manufactured by Imada Corporation at a load load rate of 0.15 / mm. The “icing adhesion” of the coating film was evaluated according to the following five levels. That is, the coating film from which ice is peeled off with the weakest force having an “icing adhesion strength” of 1.0 kg / cm ² or less is evaluated as the coating film having the most “easy icing removal property”, and the evaluation criteria for the icing adhesion strength Was set to 5. Similarly, coating films having an “ice adhesion force” larger than 1.0 kg / cm ² were evaluated according to Evaluation Criteria 4 to 1 as follows.
Evaluation criteria icing adhesion
5 1.0 kg / cm ² or less 4 1.1-2.0 kg / cm ²
3 2.1-3.0 kg / cm ²
2 3.1-4.0 kg / cm ²
1 4.1 kg / cm ² or more

[Icing area rate evaluation test]
In the icing area ratio evaluation test, a 70 × 150 × 1.6 mmt test piece deteriorated in an environmental test was left in a low temperature test room at −15 ° C. for 5 hours and then immersed in supercooled water for 10 seconds. The ice area ratio was measured. The “icing area ratio” of the coating film was evaluated in the following five stages. That is, a coating film having an “icing area ratio” of 10% or less was evaluated as a “hard icing property” coating film, and an evaluation criterion of “icing area ratio” was set to 5. In the same manner, the difficulty of depositing a coating film having an “icing area ratio” larger than 10% was evaluated based on Evaluation Criteria 4 to 1 as follows.
Evaluation criteria icing area ratio
5 10% or less 4 11-20%
3 21-30%
2 31-50%
1 50% or more

[Ice icing amount (residual amount) evaluation test]
In the icing amount (remaining amount) evaluation test, the 70 × 150 × 1.6 mmt test piece deteriorated in the environmental test was left in a low temperature test room at −15 ° C. for 5 hours and then installed at an angle of 30 °. After repeating the water spraying of 100 ml / 5 seconds 5 times for cooling water, the amount of icing remaining when the icing test piece was dropped from a height of 1.5 m was measured as “icing amount (residual amount)”. . The “icing amount (residual amount)” of the coating film was evaluated in the following five stages. That is, a coating film having an “icing amount (residual amount)” of 0.20 g or less was evaluated as the most easily icing coating film, and an evaluation criterion of “icing amount (residual amount)” was 5. Similarly, the “icing amount (residual amount)” of the coating film having an “icing amount (residual amount)” larger than 0.21 g was evaluated according to evaluation criteria 4 to 1 as follows.
Evaluation standard icing amount (remaining amount)
5 0.20 g or less 4 0.21-0.50 g
3 0.51-1,000g
2 1.01-2,000g
1 2.00g or more

[Water repellency evaluation test]
In the water repellency evaluation test, a 70 × 150 × 1.6 mmt test piece deteriorated in an environmental test was placed horizontally, and the manner of repelling water when watering at room temperature was observed. The “water repellency” of the coating film was evaluated according to the following five levels. That is, the coating film that repels water instantly when sprayed was evaluated as the most “water-repellent” coating film, and the “water-repellent” evaluation criterion was set to 5. Similarly, the “water repellency” of the coating film was evaluated according to Evaluation Criteria 4 to 1 as follows.
Evaluation criteria water repellency
5 Repels instantly and no water droplets remain 4 Repels 1 to 10% water droplets 3 Repels 10 to 30% water droplets 2 Repels 30 to 50% water droplets 1 Not repelled but wet

[Comprehensive evaluation of coating durability]
Finally, based on the above-described six evaluation test results, the durability of the coating film after the environmental test (long-term durability test) in terms of “hard icing property” and “easy icing removal property” was comprehensively evaluated. That is, in the evaluation of the six evaluation tests described above, a comprehensive evaluation was given as ● (very practical) with all the evaluation standards in the six evaluation tests being 5 as comprehensive evaluation standards. The comprehensive evaluation of ● indicates that the coating film's “hard icing property” and “easy icing removal property” are maintained at extremely high levels after a long-term durability test. Therefore, when this coating film is used in a cold region, it is predicted that the “hard icing property” and “easy icing removal property” of this coating material will be maintained at a very high level over a long period of time. Is.

  Similarly, in each of the six evaluation tests, each evaluation criterion of 5 or 4 was comprehensively evaluated as ○ (high practicality) as a comprehensive evaluation criterion. In the case of a comprehensive evaluation, the “hard icing property” and “easy icing removal property” of the coating film are maintained at a high level even after the long-term durability test. Therefore, when this coating film is used in a cold region, the “hard icing property” and “easy icing removal property” of this coating film are expected to be maintained at a high level over a long period of time. Is.

Similarly, in each of the six evaluation tests, each evaluation criterion was 4 or 3, and the overall evaluation criterion was Δ (low practicality). What was comprehensively evaluated as Δ was that the “hard icing property” and “easy icing removal property” of the coating film were low after the long-term durability test. Moreover, it evaluated comprehensively as x (very practically low) by making each evaluation criterion 3 or 2 in six evaluation tests into a comprehensive evaluation criterion. The comprehensive evaluation of “x” indicates that the “hard icing property” and “easy icing removal property” of the coating film are extremely low after the long-term durability test.
Comprehensive evaluation of the comprehensive evaluation criteria coating film
All evaluation criteria are all 5: Very practicality Each evaluation criterion is 5 or 4 ○: High practicality Each evaluation criterion is 4 or 3 Δ: Low practicality Each evaluation criterion is 3 or 2 ×: Practicality Is extremely low

[Evaluation results of coating film in environmental test: FIGS. 7 to 9]
Next, the evaluation result of the coating film after the environmental test (long-term durability test) of the coating film produced using the coating compositions having the formulations shown in Examples 1 to 36 and Comparative Examples 1 to 12 will be described.

[Evaluation results of Examples]
First, the evaluation result after the environmental test (long-term durability test) of the coating film formed with the coating composition (FIGS. 3-5) shown in Examples 1-36 is demonstrated using FIG. 7, FIG.

  As shown in FIGS. 7 to 8, “water droplets after an environmental test of a coating film formed from the coating composition of the present invention shown in Examples 3, 6, 10, 12, 13, 15, 18, 20, 24. Each of the evaluation criteria showed a maximum rating of 5 for “sliding angle”, “water contact angle”, “icing adhesion”, “icing area ratio”, “icing amount”, and “water repellency”. Therefore, the coating compositions of these formulations were comprehensively evaluated as ● (very practical) as a comprehensive evaluation standard. In the case of the comprehensive evaluation, ●, the “hard icing property” and “easy icing removal property” of the coating film are maintained at a very high level after the long-term durability test. Therefore, when the coating composition of the present invention shown in Examples 3, 6, 10, 12, 13, 15, 18, 20, and 24 is used in a cold region, its “hard icing property” and “easy icing” “Removability” is expected to be maintained at a very high level over a long period of time.

  On the other hand, "water droplets" after an environmental test of a coating film formed from the coating composition of the present invention shown in Examples 1, 2, 4, 5, 7-9, 11, 14, 16, 17, 19, 21-23 "Sliding angle", "Water contact angle", "Icing adhesion", "Icing area ratio", "Icing amount", and "Water repellency" are the 5th or 2nd rating with the highest rating. 4 was shown. Therefore, the coating compositions of these formulations were comprehensively evaluated as ○ (high practicality) as a comprehensive evaluation standard. A comprehensive evaluation of “◯” indicates that the “hard icing property” and “easy icing removal property” of the coating film are maintained at a high level after a long-term durability test. Therefore, when the coating composition of the present invention shown in Examples 1, 2, 4, 5, 7 to 9, 11, 14, 16, 17, 19, 21 to 23 is used in a cold region, the It is predicted that “iceability” and “easy-ice removal” will be maintained at high levels over a long period of time.

  Thus, the coating compositions of the present invention having the formulations shown in Examples 1 to 36 all have a comprehensive evaluation of ● (very practical) or ○ (high practicality), and coating after environmental testing It was found that the film has excellent “hard icing property” and “easy icing removal property”.

  As described above, according to the practicality evaluation method of the coating film of the present invention, by using the comprehensive evaluation described above, the “hard icing property” of the coating film when the coating film is used in a cold region and The long-term durability of “easy icing removability” could be accurately predicted. In the coating composition of the present invention, the coating composition of the present invention has an extremely high or high level of “hard icing property” and “easy icing removal property” after a long-term durability test. It is predicted to be retained. Here, the coating composition of the present invention comprises a fluororesin-siloxane graft type polymer as a base resin, silicone rubber fine particles as reinforcing particles, and silicone rubber surface modified fine particles obtained by coating the surface of the silicone rubber fine particles with a silicone resin. Of fine particles. The coating composition of the present invention exhibits particularly excellent performance when the reinforcing particles are contained in a proportion of 10 to 70% by weight with respect to the base resin (the solid content of the fluororesin-siloxane graft type polymer). I understood it.

[Evaluation results of comparative example]
Next, the evaluation result of the coating film after the environmental test of the coating film formed by the coating composition (FIG. 6) shown in Comparative Examples 1 to 12 will be described with reference to FIG.

  First, the evaluation result of the coating film after the environmental test of the coating compositions of Comparative Examples 1 to 7 will be described. Although the coating composition of Comparative Examples 1-7 is comprised from the base resin which is the same component as the coating composition of this invention, reinforcement particle | grains, a diluent, and a hardening | curing agent as shown in FIG. The ratio of the particles to the base resin is 5 to 8% by weight or 75 to 80% by weight, which is different from the ratio of the reinforcing particles of the coating composition of the present invention to the base resin (range of 10 to 70% by weight). .

  As shown in FIG. 9, “water drop sliding angle”, “water contact angle”, “icing adhesion force”, “icing” after the environmental test of the coating films formed from the coating compositions shown in Comparative Examples 1-7. Each of the evaluation criteria for the area ratio, the amount of icing, and the water repellency was 3 or 4. Therefore, the paint compositions of Comparative Examples 1 to 7 were comprehensively evaluated as Δ (low practicality) as a comprehensive evaluation standard. What was comprehensively evaluated as Δ was that the “hard icing property” and “easy icing removal property” of the coating film were low after the long-term durability test. Therefore, when the coating compositions shown in Comparative Examples 1 to 7 are used in cold regions, the “hard icing property” and “easy icing removal property” are expected to be low after long-term use.

  Next, with reference to FIGS. 7 to 9, “water drop sliding angle” and “water contact angle” after the environmental test of the coating films formed from the coating compositions shown in Examples 1 to 36 and Comparative Examples 1 to 7 are used. The measurement results of “Icing adhesion force”, “Icing area ratio”, “Icing amount”, and “Water repellency” are compared with the overall evaluation. From comparison between FIGS. 7 to 8 and FIG. 9, in the coating composition of the present invention, particularly when the proportion of reinforcing particles is 10 to 70 wt% with respect to the base resin, It became clear that the durability performance of “icing property” and “easy deicing property” was improved.

  Next, the evaluation result of the coating film after the environmental test of the coating compositions of Comparative Examples 8 to 12 will be described. As shown in FIG. 6, the coating compositions of Comparative Examples 8 to 12 have the same constituent components of the base resin, diluent, and curing agent of the coating compositions of Examples 1 to 36, and the base resin of reinforcing particles. Although the ratio with respect to is also included in the range of 35 to 70% by weight, the type of reinforcing particles is different. That is, in Examples 1-36, silicone rubber fine particles, silicone rubber surface-modified fine particles or a mixture thereof are used as reinforcing particles, whereas in Comparative Example 8, the fluorinated pitch is used, and in Comparative Example 9, the fluorinated graphite is used. However, in Comparative Examples 10 and 11, polytetrafluoroethylene is used, and in Comparative Example 12, water-repellent silica powder is used.

  As shown in FIG. 9, the water droplet sliding angle after the long-term durability test of the coating films formed from the coating compositions shown in Comparative Examples 8 to 12, “Water contact angle”, “Icing adhesion”, “Icing” Each of the evaluation criteria indicated an evaluation of 2 or 3 for “area ratio”, “icing amount”, and “water repellency”. Therefore, the paint compositions of Comparative Examples 8 to 12 were comprehensively evaluated as Δ (low practicality) or × (very low practicality) as a comprehensive evaluation. What was comprehensively evaluated as “Δ” or “x” indicates that the “hard icing property” and “easy icing removal property” of the coating film are low after the long-term durability test. Therefore, when the coating compositions shown in Comparative Examples 1 to 7 are used in cold regions, the “hard icing property” and “easy icing removal property” are expected to be low or extremely low after long-term use.

    Next, with reference to FIGS. 7 to 9, “water drop sliding angle” and “water contact angle” after an environmental test of the coating films formed from the coating compositions shown in Examples 1 to 36 and Comparative Examples 8 to 12 are used. The measurement results of “Icing adhesion force”, “Icing area ratio”, “Icing amount”, and “Water repellency” are compared with the overall evaluation. From comparison of FIGS. 7 to 8 and FIG. 9, in the coating composition of the present invention, silicone rubber fine particles or silicone rubber surface-modified fine particles are suitable as reinforcing particles for the base resin (fluororesin-siloxane graft polymer). It was shown that. Further, when the reinforcing particles are fluorinated pitch, graphite fluoride, polytetrafluoroethylene, or water-repellent silica powder, the environmental test is performed even if the reinforcing particles are contained in a proportion of 10 to 70% by weight with respect to the base resin. It was shown that the later coating film had low durability performance of “hard icing property” and “easy icing removal property”.

[Coating composition of the present invention]
The components of the coating composition of the present invention described above will be summarized. The coating composition of the present invention uses a fluororesin-siloxane graft type polymer as a base resin and silicone rubber fine particles, silicone rubber surface-modified fine particles, or a mixture thereof as reinforcing particles. In particular, when the reinforcing particles are contained in an amount of 10 to 70% by weight based on the base resin, the coating film formed by the coating composition has better “hard-to-freeze” and “easy-to-set” after the environmental test. "Ice removal".

  For the reinforcing particles of the coating composition of the present invention, for example, silicone rubber-based, silicone rubber surface modified fine particles (KMP series) manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Further, the silicone rubber fine particles or the silicone rubber surface-modified fine particles which are reinforcing particles can be used alone or in combination with those having a predetermined average particle diameter (several to several tens of μm).

  The fluororesin-siloxane graft polymer of the present invention is composed of a radically polymerizable fluororesin, a radically polymerizable polysiloxane, an alkoxysilyl-containing monomer, and a hydroxyl group-containing monomer. For example, various hydrophobic properties manufactured by Fuji Kasei Kogyo Resin (ZX series) can be used. For example, a room temperature curing standard type (ZX-007C), a room temperature curing high weather resistance type (ZX-017), a room temperature curing highly crosslinked type (ZX-022), and a heat curing type (ZX-001) can be used. In the present invention, the room temperature curing standard type is mainly used, but it is not limited to this depending on the application field. For example, a room temperature curing type can be applied to large structures such as ships and steel structures, and a heat curing type can be applied to industrial products.

  In the coating composition of the present invention, if a fluororesin-siloxane graft type polymer is used alone as a base resin, the mechanical strength is insufficient, so it is necessary to use a polyisocyanate compound as a curing agent as a crosslinking agent. . Examples of the polyisocyanate compound include hexamethylene diisocyanate isocyanurate type trimer (Nihon Polyurethane Coronate HX), isophorone diisocyanate isocyanurate type trimer (Sumitomo Bayer Urethane Desmodur Z4370), and isocyanate groups. A blocked polyisocyanate compound blocked with a blocking agent can be used.

[Use of the coating composition of the present invention]
Finally, the use and method of use of the coating composition of the present invention described above will be described. The coating composition of the present invention suppresses icing on the object surface of various structures such as ships navigating in icing seas, telecommunication facilities in cold regions, road traffic signs, traffic lights, geothermal power generation facilities, automobiles, etc. Or can be used to facilitate deicing of ice that has landed on the object surface. When a coating film is formed using the coating composition of the present invention, it is possible to suppress icing on various structures such as ships, and even if icing is possible, deicing can be done with a simple operation. It becomes. Therefore, by using the coating composition of the present invention, it is possible to improve the safety of various structures including ships in cold regions and reduce economic loss due to their malfunction. it can.

[Method of using the coating composition of the present invention]
The coating composition of the present invention can be used in various coating methods. For example, the coating composition of the present invention can be dispersed in a solvent and applied by brushing in the form of a dispersion. Alternatively, the coating composition of the present invention can be stored in a can or the like and used for spray coating using a compressed gas.

  In the case where a coating film of the coating composition is formed on the object surface so as to suppress the icing on the object surface or to make it easy to deiculate the ice icing on the object surface. The paints may be overlaid. For example, in the case where a coating film is formed on the ship surface using the coating composition of the present invention so as to suppress the icing on the ship surface or to make it easy to deiculate the ice icing on the ship surface, For example, a modified epoxy resin paint is applied in an amount of 40 to 50 μm, then, as an intermediate coating, for example, a polyurethane-based paint is applied in an amount of 25 to 30 μm, and finally, a coating composition of the present invention is applied as an overcoat layer in an amount of 20 to 30 μm. It is formed by doing.

  In addition, said example is an example and can change the kind and number of layers of a coating material used for an undercoat layer and an intermediate coating layer according to the structure which requires a coating film. In addition, when it is desired to use the coating composition of the present invention after coloring, a pigment having a required color may be added.

It is a figure which shows a base-material resin selection test result. It is a figure which shows a reinforcement particle | grain selection test. It is a figure which shows an example of the mixing | blending of the structural component of the coating composition of this invention. It is a figure which shows an example of the mixing | blending of the structural component of the coating composition of this invention. It is a figure which shows an example of the mixing | blending of the structural component of the coating composition of this invention. It is a figure which shows an example of the mixing | blending of the structural component of the coating composition of a comparative example. It is a figure which shows the evaluation result of the long-term durability with respect to the coating film of the mixing | blending of an Example. It is a figure which shows the evaluation result of the long-term durability with respect to the coating film of the mixing | blending of an Example. It is a figure which shows the evaluation result of the long-term durability with respect to the coating film of the mixing | blending of a comparative example.

Claims (15)

A coating composition for forming a coating film on the surface of the object so as to suppress icing on the surface of the object or to easily deice the ice icing on the surface of the object,
A fluororesin-siloxane graft polymer;
At least one fine particle among silicone rubber fine particles and silicone rubber surface-modified fine particles obtained by coating the surface of the silicone rubber fine particles with a silicone resin;
A coating composition comprising:   The fluororesin-siloxane graft type polymer is formed using a radical polymerizable fluororesin, a radical polymerizable polysiloxane, an alkoxysilyl-containing monomer, a hydroxyl group-containing monomer, and an isocyanate compound that is a crosslinking agent. The coating composition according to claim 1, wherein   The at least one fine particle is a silicone rubber fine particle, and the silicone rubber fine particle is contained in the coating composition in a proportion of 10 to 70% by weight based on the solid content of the fluororesin-siloxane graft polymer. The coating composition according to claim 1 or 2, wherein   4. The coating composition according to claim 3, wherein the silicone rubber fine particles are silicone rubber fine particles having a predetermined average particle diameter or a mixture of two or more kinds of silicone rubber fine particles having different average particle diameters.   The at least one fine particle is a silicone rubber surface-modified fine particle, and the silicone rubber surface-modified fine particle is in a ratio of 10 to 70% by weight based on the solid content of the fluororesin-siloxane graft polymer in the coating composition. The coating composition according to claim 1, wherein the coating composition is contained.   6. The silicone rubber surface modified fine particles are silicone rubber fine particles having a predetermined average particle diameter or a mixture of two or more types of silicone rubber surface modified fine particles having different average particle diameters. Paint composition.   The at least one fine particle is a mixture of silicone rubber fine particles and silicone rubber surface-modified fine particles, and the mixture is 10 to 70% by weight based on the solid content of the fluororesin-siloxane graft polymer in the coating composition. The coating composition according to claim 1, wherein the coating composition is contained at a ratio of   The silicone rubber fine particles are silicone rubber fine particles having a predetermined average particle diameter, or a mixture of two or more types of silicone rubber fine particles having different average particle diameters, and the silicone rubber surface-modified fine particles have a predetermined average particle diameter. The coating composition according to claim 7, wherein the coating composition is a mixture of two or more types of silicone rubber surface-modified fine particles having different average particle diameters. A method for evaluating a coating composition that forms a coating film on the surface of an object so as to suppress icing on the surface of the object or to easily deice ice that has been iced on the surface of the object,
Exposing the coating film to an environmental test simulating the environment in which the coating film is used;
For the coating film after being exposed to the environmental test, a plurality of measurements for evaluating the difficult icing property to suppress icing of the coating film and the easy icing removal property to easily deicing even when icing. Carrying out the test;
Depending on whether or not the comprehensive evaluation determined based on each measurement value obtained by the plurality of measurement tests satisfies a predetermined evaluation criterion, the hard-to-freeze property of the coating film after being exposed to the environmental test And an evaluation process for comprehensively evaluating the easy icing removal property,
The evaluation method of the coating composition characterized by having.   The environmental test includes a water immersion test in which the coating film is immersed in water for a predetermined period of time, and an outdoor exposure test in which the coating film after the water immersion test is exposed to an outdoor natural environment for a predetermined period of time. The evaluation method of the coating composition of Claim 9.   11. The method for evaluating a coating composition according to claim 10, wherein in the environmental test, a cycle in which the water immersion test and the outdoor exposure test are made one cycle is repeated a predetermined number of cycles.   The plurality of measurement tests include measurement of a water drop sliding angle, a water contact angle, an icing adhesion force, an icing area ratio, an icing amount, and a water repellency of the coating film after the environmental test. The evaluation method of the coating composition of Claim 11.   13. The method for evaluating a coating composition according to claim 12, wherein in the evaluation step, for each measurement test, the measured value is classified according to a predetermined evaluation standard to calculate a grade value. .   In the evaluation step, the grade value calculated for each of the measurement tests is based on which of the comprehensive evaluation criteria for comprehensively evaluating the difficult ice formation property and the easy ice removal property of the coating film after the environmental test. 14. The method for evaluating a coating composition according to claim 13, wherein the coating film after being subjected to the environmental test is comprehensively evaluated by determining whether or not the condition is satisfied. A coating method for forming a coating film of a coating composition on the surface of an object so as to suppress icing on the surface of the object or to make it easy to deiculate the ice icing on the surface of the object,
Forming an undercoat layer by applying an undercoat on the object surface;
Applying an intermediate coating on the undercoat layer to form an intermediate coating layer;
A coating method comprising: forming a topcoat layer on the intermediate coat layer using the coating composition according to any one of claims 1 to 8.

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