JP6876246B2 - Transparent coating, manufacturing method of transparent coating and antifouling parts for automobiles - Google Patents

Description

The present invention relates to a transparent coating, a method for producing a transparent coating, and an antifouling component for automobiles. More specifically, the present invention relates to a transparent coating, a method for producing a transparent coating, and an antifouling component for automobiles to which the transparent coating is applied.

Conventionally, there have been proposed articles that can repel foreign substances or reduce the adhesion of foreign substances to the water-repellent surface. This article is an article having a water repellent surface, a lubricating liquid that wets and adheres to the rough surface so as to form a substrate and a stabilizing liquid coating layer with a rough surface. The liquid comprises a lubricating liquid that covers the rough surface with a thickness sufficient to form a liquid upper surface above the rough surface, and the rough surface and the lubricating liquid are such that the lubricating liquid is the substrate. It has an affinity for each other so that it is substantially immobilized above to form a water repellent surface (see Patent Document 1).
Research has also been conducted on liquid-injected silicone as a medical material without biofouling (see Non-Patent Document 1).

Special Table 2014-509959

Noah MacCallum, Caitlin Howell, Philseok Kim, Derek Sun, Ronn Friedlander, Jonathan Ranisau, Oney・ Onye Ahanotu, Jennifer J. Lin, Alex Vena, Benjamin Hatton, Tak-Sing Wong, Joanna Eisen "Liquid-Infused Silicone As a Biofouling-Free Medical Material" by Joanna Aizenberg, Biomater. Sci. Eng .), American Chemical Society (ASC), January 2015, p43-51

However, the lubricating liquid holding layer made of polydimethylsiloxane (PDMS) injected with the oil described in Patent Document 1 and Non-Patent Document 1 has a problem that durability such as wear resistance is low.

The present invention has been made in view of the problems of the prior art. The present invention provides a transparent film having durability and optical properties such as excellent droplet sliding property, abrasion resistance, and heat resistance, a method for producing a transparent film, and an antifouling component for automobiles to which the transparent film is applied. The purpose is to provide.

The present inventors have made extensive studies to achieve the above object. As a result, a lubricating liquid holding layer arranged on the base material and a lubricating liquid film arranged on the lubricating liquid holding layer and containing the hydrophobic lubricating liquid are provided, and the lubricating liquid holding layer is provided with at least a cross-linking agent. A mixture of an elastomer material having a functional group A having the reactivity of the above, a resin material having a side chain having a functional group A, and a cross-linking agent having a functional group B that reacts with the functional group A is heated and subjected to a cross-linking reaction. The functional group A contained in the resin material and the elastomer material is obtained by retaining the hydrophobic lubricating liquid inside, the mixing ratio of the elastomer material to the resin material is 3 to 26 in terms of molar ratio. It has been found that the above object can be achieved by setting the ratio of the functional group B of the cross-linking agent to the cross-linking agent to 0.75 to 10 in terms of molar ratio, and the present invention has been completed.

According to the present invention, a transparent coating having excellent durability such as droplet sliding property, abrasion resistance, heat resistance, and optical characteristics, a method for producing a transparent coating, and an antifouling component for automobiles to which the transparent coating is applied. Can be provided.

FIG. 1 is an explanatory diagram schematically showing the structure of the transparent coating according to the second embodiment. FIG. 2 is an enlarged view of a portion of the transparent coating shown in FIG. 1 surrounded by the surrounding line II.

Hereinafter, the transparent film according to the embodiment of the present invention, the method for producing the transparent film, and the antifouling component for automobiles to which the transparent film is applied will be described in detail.

(First Embodiment)
First, the transparent coating according to the first embodiment of the present invention will be described in detail. The transparent coating of the present embodiment is arranged on a base material. The transparent coating includes a lubricating liquid holding layer arranged on the base material and a lubricating liquid film arranged on the lubricating liquid holding layer and containing a hydrophobic lubricating liquid. Here, the lubricating liquid film is not particularly limited, but it is preferable that the entire surface of the lubricating liquid holding layer is covered. Further, the lubricating liquid film containing the lubricating liquid includes a lubricating liquid film composed of only the lubricating liquid.

Further, the lubricant holding layer has at least an elastomer material having a functional group A having reactivity with a cross-linking agent, a resin material having a side chain having a functional group A, and a functional group B reacting with the functional group A. It is obtained by heating a mixture with a cross-linking agent and causing a cross-linking reaction, and holds a hydrophobic lubricating liquid inside.

Here, the lower limit of the reaction temperature at the time of carrying out the crosslinking reaction is not particularly limited, but is preferably 40 ° C. or higher, more preferably 80 ° C. or higher, further preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. The upper limit of the reaction temperature during the crosslinking reaction is not particularly limited, but is preferably 240 ° C. or lower, more preferably 200 ° C. or lower, and even more preferably 180 ° C. or lower.

The reaction time for the cross-linking reaction is not particularly limited, but is preferably 1 minute to 24 hours, and more preferably 1 minute to 2 hours. More specifically, when an elastomer material, a resin material and a cross-linking agent described later are used, for example, when the reaction temperature at the time of the cross-linking reaction is 80 to 180 ° C., the reaction time may be 1 minute to 2 hours.

The elastomer material of the lubricating liquid holding layer in the transparent film described above is reinforced with a resin material. That is, the elastomer portion derived from the elastomer material is reinforced by the resin portion derived from the resin material which is relatively excellent in wear resistance as compared with the elastomer portion. Therefore, the above-mentioned transparent coating has excellent durability such as abrasion resistance. Then, by improving the wear resistance, for example, it is possible to realize a long life of the antifouling performance.

The lubricating liquid holding layer in the transparent coating described above is obtained by heating a mixture of an elastomer material and a resin material and causing a cross-linking reaction. That is, the elastomer portion derived from the elastomer material and the resin portion derived from the resin material are contained in a dispersed state. Further, such an elastomer portion has pores at the molecular level. Then, by impregnating the pores with the lubricating liquid, the elastomer portion is in a swollen state, and the lubricating liquid can be held relatively firmly. That is, even in a high temperature environment, the outflow of the lubricating liquid from the elastomer portion derived from the elastomer material is suppressed. Therefore, the above-mentioned transparent coating has excellent durability such as heat resistance. Then, by improving the heat resistance, for example, it is possible to realize a long life of the antifouling performance.

Further, the lubricating liquid holding layer in the transparent coating described above can hold the lubricating liquid relatively firmly in a state where the elastomer portion derived from the elastomer material is swollen as described above. The lubricating liquid film arranged on such a lubricating liquid holding layer has self-repairing property. That is, even if the lubricating liquid film is removed, in other words, even if the lubricating liquid on the surface of the transparent film is wiped off, the lubricating liquid is removed from the elastomer part derived from the elastomer material of the lubricating liquid holding layer, for example, in about 2 to 3 hours. Exudes to restore the lubricating fluid film. Therefore, the above-mentioned transparent coating has excellent durability such as sliding property of droplets such as water droplets. Then, by improving the sliding property of water droplets, for example, it is possible to realize a long life of antifouling performance.

Further, as described above, the lubricating liquid holding layer in the transparent film described above is obtained by heating a mixture of the elastomer material and the resin material and causing a cross-linking reaction, so that the optical characteristics are deteriorated due to reflection, refraction, or the like. The resulting interface is difficult to form. Therefore, the transparent film described above has excellent optical characteristics.

The transparent coating is not particularly limited, but it is preferable that at least one of the resin material and the elastomer material forms a three-dimensional crosslinked structure, and more preferably at least the resin material forms a three-dimensional crosslinked structure. It is preferable that both the resin material and the elastomer material form a three-dimensional crosslinked structure. Further, it is particularly preferable that a part or all of the three-dimensional crosslinked structure is a three-dimensional network structure. This makes it possible to adjust the structure and arrangement of the elastomer part derived from the elastomer material and the resin part derived from the resin material by selecting the elastomer material, the resin material, and the cross-linking agent, and the abrasion resistance of the transparent film. It is possible to improve heat resistance, water droplet sliding property, optical characteristics, and the like.

The transparent film is not particularly limited, but it is preferable that one or both of the elastomer material and the resin material are bonded to the base material via a cross-linking agent. This makes it possible to improve the adhesion between one or both of the elastomer portion derived from the elastomer material and the resin portion derived from the resin material and the base material. As a result, it is possible to improve the adhesion between the base material and the transparent film.

The transparent film is not particularly limited, but the mixing ratio of the elastomer material to the resin material is 3 to 26 in terms of molar ratio, and the functionality of the cross-linking agent with respect to the functional group A of the resin material and the elastomer material. The ratio of the groups B is preferably 0.75 to 10 in terms of molar ratio. As a result, it is possible to more reliably improve the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, etc. of the transparent film.

The transparent film is not particularly limited, but the mixing ratio of the elastomer material to the resin material is 9 to 13 in terms of molar ratio, and the functionality of the cross-linking agent with respect to the functional group A of the resin material and the elastomer material. The ratio of the group B is preferably 0.75 to 3.5 in terms of molar ratio. As a result, not only the abrasion resistance, heat resistance, and optical characteristics of the transparent film can be improved, but also the water droplet sliding property of the transparent film can be further improved.

Further, the transparent film is not particularly limited, but it is preferable that the elastomer material is a silicone oil having functional groups A at both ends. This has the advantage that the elastomeric material can easily form a three-dimensional crosslinked structure, preferably a three-dimensional network structure. Further, the elastomer portion derived from such silicone oil tends to have a spiral structure exhibiting rubber elasticity, and has an advantage that the lubricating liquid can be easily held by the pores at the molecular level. As a result, the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, and the like of the transparent film can be improved.

The transparent coating is not particularly limited, but the resin material is preferably a silicone-modified acrylic resin oligomer having a side chain having a functional group A, and a side chain having a hydroxyl group as the functional group A is used. More preferably, it is a polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer having. Silicone oils having functional groups A at both ends have low polarity. Therefore, for example, by introducing a low-polarity polydimethylsiloxane (PDMS) into the side chain and further applying a polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer having a side chain having a hydroxyl group as the functional group A, the phase is introduced. It has the advantage that the solubility can be increased and a more uniform mixture can be obtained. As a result, the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, and the like of the transparent film can be improved.

The transparent film is not particularly limited, but is selected from the group consisting of a carbinol group, a hydroxyl group, an amino group, a carboxyl group and a phenolic hydroxyl group as a combination of the functional group A and the functional group B. It is preferable to apply a combination of at least one group and an isocyanate group. Thereby, one or both of the urethane bond and the urea bond can be formed. Such a bond can be formed by a conventionally known resin material, elastomer material and cross-linking agent. Further, since there are many choices of materials, it is possible to improve the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, etc. of the transparent film by appropriately selecting the material.

Further, the transparent film is not particularly limited, but the elastomer material is one of a silicone oil having a carbinol group as a functional group A at both ends and a silicone oil having a hydroxyl group as a functional group A at both ends. The resin material is a polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer having a side chain having a hydroxyl group as the functional group A, and the cross-linking agent is an isocyanate having an isocyanate group as the functional group B, preferably poly. Isocyanates and isocyanurate-type polyisocyanates are preferable. As a result, it is possible to improve the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, etc. of the transparent film.

As the silicone oil having a functional group A at both ends, when the functional group A is a carbinol group, a hydroxyl group, an amino group, a carboxyl group and a phenolic hydroxyl group, for example, KF manufactured by Shin-Etsu Chemical Industry Co., Ltd. -6000, X-21-5841, PAM-E, X-22-162C, KF-2201 can be mentioned.

Further, the polydimethylsiloxane (PDMS) -modified acrylic resin oligomer having a side chain having the functional group A can be prototyped by a resin manufacturer. Examples of the polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer having a side chain having a hydroxyl group as the functional group A include 8BS-9000 manufactured by Taisei Fine Chemicals Co., Ltd.

Further, as the cross-linking agent having an isocyanate group as the functional group B, for example, DN-980 manufactured by DIC Corporation can be mentioned.

Further, the transparent coating is not particularly limited, but it is preferable that the lubricating liquid contains one or both of dimethyl silicone oil and modified silicone oil. Thereby, excellent antifouling performance can be exhibited. In addition, the wear resistance, heat resistance, water droplet sliding property, optical characteristics, and the like of the transparent film are improved, and the life of the antifouling performance can be extended.

The dimethyl silicone oil is not particularly limited, and examples thereof include KF96-30cs manufactured by Shin-Etsu Chemical Co., Ltd.

The modified silicone oil is not particularly limited, but for example, a side chain type fluoroalkyl modified silicone oil such as FL-5 manufactured by Shin-Etsu Chemical Industry Co., Ltd. or a side chain type such as KF-4701. Long-chain alkyl-modified silicone oil, side-chain type polyether-modified silicone oil such as KF-354L, and the like can be mentioned.

Further, the base material on which the transparent film is arranged is not particularly limited, and examples thereof include glass, metal oxides, resins and metals, and any combination of two or more of these can be used. You can also. By applying these base materials, the transparent film is adhered to and held on the base material, and the excellent wear resistance, heat resistance, water droplet sliding property, optical characteristics, etc. of the transparent film are exhibited.

Although not particularly limited, the transparent film is particularly suitable for imparting antifouling property when the base material is a transparent optical component such as an optical display or an optical lens.

The glass is not particularly limited as long as it can adhere to the transparent film, and examples thereof include plate-shaped soda lime glass and quartz glass.

The metal oxide is not particularly limited as long as it can adhere to the transparent film, and examples thereof include plate-shaped silicon oxide, aluminum oxide, and zirconium oxide.

The resin is not particularly limited as long as it can adhere to the transparent film, and examples thereof include a plate-shaped acrylic resin, a urethane resin, a polypropylene resin, a polyvinyl chloride resin, and a polyethylene resin. be able to.

Further, the metal is not particularly limited as long as it can adhere to the transparent film, and examples thereof include plate-shaped steel (specifically, a steel plate for an automobile body) and aluminum. Can be done.

(Second Embodiment)
Next, the transparent coating according to the second embodiment of the present invention will be described in detail with reference to the drawings. FIG. 1 is an explanatory diagram schematically showing the structure of the transparent coating according to the second embodiment. Further, FIG. 2 is an enlarged view of a portion of the transparent coating shown in FIG. 1 surrounded by the surrounding line II.

As shown in FIGS. 1 and 2, the transparent coating film 10 of the present embodiment is arranged on the base material 20. The transparent coating 10 is arranged on the base material 20 and is arranged on the lubricating liquid holding layer 11 and the lubricating liquid holding layer 11 which holds the hydrophobic lubricating liquid 30 inside 11a, and contains the lubricating liquid 30. It includes a lubricating liquid film 13. Here, the lubricating liquid film 13 is not particularly limited, but as shown, it is preferable that the entire surface of the lubricating liquid holding layer 11 is covered. Further, the lubricating liquid film 13 containing the lubricating liquid 30 includes a lubricating liquid film 13 composed of only the lubricating liquid 30.

Further, the lubricating liquid holding layer 11 includes a resin skeleton portion 111 having a three-dimensional crosslinked structure such as a three-dimensional network structure, and a lubricating liquid holding portion 113 arranged in a dispersed state on the surface 111a of the resin skeleton portion 111. And have. Here, in the present specification, "the lubricating liquid holding portions are arranged in a dispersed state" means the abundance ratio of the lubricating liquid holding portions throughout the in-plane direction and the thickness direction of the lubricating liquid holding layer. It means that there is no or little bias in the lubricating fluid, and the portion formed only by the lubricating liquid holding portion is hardly observed. As a typical example of the portion formed only by the lubricating liquid holding portion, a portion formed only by the elastomer material which is crosslinked between the elastomer materials and is not crosslinked with the resin material at all can be mentioned.

_{Further, the resin skeleton portion 111 is a crosslinked portion 111B (111B 1} ) derived from a plurality of resin portions 111A derived from a resin material and interposed between the resin portions 111A to bond the resin portion 111A. And is included.

Further, the lubricating liquid holding portion 113 has an elastomer portion 113A derived from the elastomer material and an elastomer portion 113A and a resin portion 111A derived from the cross-linking agent and interposed between the elastomer portion 113A and the resin portion 111A. It includes a bonded cross-linked portion 111B (111B ₂ ).

In the lubricant holding layer in the transparent film described above, the resin portion constituting the resin skeleton portion having a three-dimensional crosslinked structure, preferably a three-dimensional network structure is relatively excellent in abrasion resistance as compared with the elastomer portion. An elastomer portion is bonded to such a resin portion. Therefore, the above-mentioned transparent coating has excellent durability such as abrasion resistance. Then, by improving the wear resistance, for example, it is possible to realize a long life of the antifouling performance.

The lubricating liquid holding layer in the transparent coating described above is arranged in a state where the lubricating liquid holding portions are dispersed on the surface of the resin skeleton portion having a three-dimensional crosslinked structure, preferably a three-dimensional network structure. The elastomer portion constituting the lubricating liquid holding portion has pores at the molecular level. Then, by impregnating the pores with the lubricating liquid, the elastomer portion is in a swollen state, and the lubricating liquid can be held relatively firmly. That is, even in a high temperature environment, the outflow of the lubricating liquid from the lubricating liquid holding portion is suppressed. Therefore, the above-mentioned transparent coating has excellent durability such as heat resistance. Then, by improving the heat resistance, for example, it is possible to realize a long life of the antifouling performance.

Further, the lubricating liquid holding layer in the transparent coating described above can hold the lubricating liquid relatively firmly in a state where the elastomer portion constituting the lubricating liquid holding portion is swollen as described above. The lubricating liquid film arranged on such a lubricating liquid holding layer has self-repairing property. That is, even if the lubricating liquid film is removed, in other words, even if the lubricating liquid on the surface of the transparent film is wiped off, the lubricating liquid seeps out from the lubricating liquid holding portion of the lubricating liquid holding layer, for example, in about 2 to 3 hours. This restores the lubricating fluid film. Therefore, the above-mentioned transparent coating has excellent durability such as sliding property of droplets such as water droplets. Then, by improving the sliding property of water droplets, for example, it is possible to realize a long life of antifouling performance.

Further, as described above, the lubricating liquid holding layer in the transparent coating described above is arranged in a state where the lubricating liquid holding portions are dispersed on the surface of the resin skeleton portion having a three-dimensional crosslinked structure, preferably a three-dimensional network structure. Therefore, it is difficult to form an interface whose optical characteristics can be deteriorated by reflection or refraction. Therefore, the transparent film described above has excellent optical characteristics.

The transparent coating is not particularly limited, but as shown in the drawing, at the lubricating liquid holding portion 113, the crosslinked portion 111B (111B ₃ ) is interposed between the elastomer portions 113A to form the elastomer portion 113A. It is preferably bonded. This makes it possible to adjust the structure and arrangement of the lubricating liquid holding portion formed by the elastomer portion by selecting an elastomer material or a cross-linking agent. Optical characteristics and the like can be improved.

The transparent coating is not particularly limited, but the lubricating liquid holding portion 113 itself preferably has a three-dimensional crosslinked structure, and more preferably has a three-dimensional network structure. As a result, it is possible to improve the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, etc. of the transparent film.

Further, the transparent film is not particularly limited, but as shown in the figure, in the resin skeleton portion 111, the crosslinked portion 111B (111B ₄ ) is interposed between the base material 20 and the resin portion 111A. It is preferable that the base material 20 and the resin portion 111A are bonded to each other. This makes it possible to improve the adhesion between the resin portion and the base material, and as a result, it is possible to improve the adhesion between the base material and the transparent film.

Furthermore, although the transparent coating is not particularly limited, as shown in the figure, in the resin skeleton portion 113, the crosslinked portion 111B (111B ₅ ) is interposed between the base material 20 and the elastomer portion 113A. It is preferable that the base material 20 and the elastomer portion 113A are bonded to each other. This makes it possible to improve the adhesion between the elastomer portion and the base material, and as a result, it is possible to improve the adhesion between the base material and the transparent film.

The transparent film is not particularly limited, but it is preferable that the elastomer portion is derived from silicone oil, which is an elastomer material. The elastomer portion derived from silicone oil tends to have a spiral structure exhibiting rubber elasticity, and has an advantage that the lubricating liquid can be easily held by the pores at the molecular level. As a result, it is possible to improve the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, etc. of the transparent film.

The transparent film is not particularly limited, but the resin portion is preferably derived from a silicone-modified acrylic resin oligomer which is a resin material, and may be derived from a polydimethylsiloxane (PDMS) -modified acrylic resin oligomer. More preferred. Silicone-modified acrylic resin oligomers, especially resin materials such as polydimethylsiloxane (PDMS) -modified acrylic resin oligomers, are highly compatible with silicone oil, which is an elastomer material. As a result, the resin portion and the elastomer portion are easily arranged in a dispersed state, and the lubricating liquid holding portion is easily arranged in a dispersed state on the surface of the resin skeleton portion having a three-dimensional crosslinked structure, preferably a three-dimensional network structure. There is an advantage. As a result, the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, and the like of the transparent film can be improved.

Further, the transparent film is not particularly limited, but it is preferable that the crosslinked portion has one or both of a urethane bond and a urea bond. Such a cross-linked portion can be formed by a conventionally known resin material, elastomer material and cross-linking agent. Further, since there are many choices of materials, it is possible to improve the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, etc. of the transparent film by appropriately selecting the material.

The transparent film is not particularly limited, but the elastomer part is derived from silicone oil which is an elastomer material, and the resin part is a silicone-modified acrylic resin oligomer which is a resin material, particularly polydimethylsiloxane (PDMS). It is preferably derived from the modified acrylic resin oligomer and the crosslinked portion has a urethane bond. As a result, it is possible to improve the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, etc. of the transparent film.

The transparent coating is not particularly limited, but it is preferable that the lubricating liquid contains one or both of dimethyl silicone oil and modified silicone oil. Thereby, excellent antifouling performance can be exhibited. In addition, the wear resistance, heat resistance, water droplet sliding property, optical characteristics, and the like of the transparent film are improved, and the life of the antifouling performance can be extended.

The dimethyl silicone oil is not particularly limited, and examples thereof include KF96-30cs manufactured by Shin-Etsu Chemical Co., Ltd.

The modified silicone oil is not particularly limited, but for example, a side chain type fluoroalkyl modified silicone oil such as FL-5 manufactured by Shin-Etsu Chemical Industry Co., Ltd. or a side chain type such as KF-4701. Long-chain alkyl-modified silicone oil, side-chain type polyether-modified silicone oil such as KF-354L, and the like can be mentioned.

Further, the base material on which the transparent film is arranged is not particularly limited, and examples thereof include glass, metal oxides, resins and metals, and any combination of two or more of these can be used. You can also. By applying these base materials, the transparent film is adhered to and held on the base material, and the excellent wear resistance, heat resistance, water droplet sliding property, optical characteristics, etc. of the transparent film are exhibited.

Although not particularly limited, the transparent film is particularly suitable for imparting antifouling property when the base material is a transparent optical component such as an optical display or an optical lens.

The glass is not particularly limited as long as it can adhere to the transparent film, and examples thereof include plate-shaped soda lime glass and quartz glass.

The metal oxide is not particularly limited as long as it can adhere to the transparent film, and examples thereof include plate-shaped silicon oxide, aluminum oxide, and zirconium oxide.

The resin is not particularly limited as long as it can adhere to the transparent film, and examples thereof include a plate-shaped acrylic resin, a urethane resin, a polypropylene resin, a polyvinyl chloride resin, and a polyethylene resin. be able to.

Further, the metal is not particularly limited as long as it can adhere to the transparent film, and examples thereof include plate-shaped steel (specifically, a steel plate for an automobile body) and aluminum. Can be done.

Here, the transparent coating film of the present invention may be obtained by adding a part or all of the configurations of the transparent coating film of the second embodiment to the transparent coating film of the first embodiment described above. A part or all of the constitution of the transparent film of the first embodiment may be added to the transparent film of the second embodiment.

With such a configuration, durability and optical characteristics such as excellent water droplet sliding resistance, abrasion resistance, and heat resistance can be obtained.

(Third Embodiment)
Next, a method for producing a transparent coating according to a third embodiment of the present invention will be described in detail. The method for producing a transparent film of the present embodiment is an embodiment of the above-described method for producing a transparent film of the present invention. Therefore, the transparent film of the present invention is not limited to that obtained by the method for producing a transparent film of the present embodiment.

The method for producing a transparent film of the present embodiment includes the following steps (1) to (3).

In step (1), a mixture containing an elastomer material having a functional group A, a resin material having a side chain having a functional group A, and a cross-linking agent having a functional group B that reacts with the functional group A is used as a base material. This is the process of applying on top.

The step (2) is executed after the step (1) and is a step of heating the mixture to form the above-mentioned predetermined lubricating liquid holding layer.

The step (3) is carried out after the step (2), and a hydrophobic lubricating liquid is applied to the lubricating liquid holding layer to form a lubricating liquid holding layer that holds the lubricating liquid inside the lubricating liquid holding layer. This is a step of forming a lubricating liquid film containing a lubricating liquid on the lubricating liquid holding layer.

By going through the above-mentioned steps, it is possible to obtain a transparent film having the desired durability such as water droplet sliding property, abrasion resistance, heat resistance, and optical properties.

In the method for producing the transparent film, the mixing ratio of the elastomer material to the resin material in the step (1) is set to 3 to 26 in terms of molar ratio, and the functional group contained in the cross-linking agent with respect to the functional group A possessed by the resin material and the elastomer material. The ratio of B is preferably 0.75 to 10 in terms of molar ratio. This makes it possible to more reliably obtain a transparent film having durability and optical characteristics such as excellent water droplet sliding resistance, abrasion resistance, and heat resistance.

Further, in the method for producing a transparent film, the mixing ratio of the elastomer material to the resin material in the step (1) is set to 9 to 13 in terms of molar ratio, and the functional group contained in the cross-linking agent with respect to the functional group A possessed by the resin material and the elastomer material. The ratio of B is preferably 0.75 to 3.5 in terms of molar ratio. As a result, it is possible to more reliably obtain a transparent film having durability and optical characteristics such as excellent water droplet sliding property, excellent wear resistance, and heat resistance.

Further, in the method for producing a transparent film, it is preferable to use a silicone oil having a functional group A at both ends as an elastomer material. This has the advantage that a three-dimensional crosslinked structure, preferably a three-dimensional network structure, can be easily formed between the elastomer portion and the crosslinked portion constituting the lubricating liquid holding portion. As a result, the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, and the like of the transparent film can be improved.

In the method for producing a transparent film, it is preferable to use a silicone-modified acrylic resin oligomer having a side chain having a functional group A as the resin material, and polydimethylsiloxane having a side chain having a hydroxyl group as the functional group A ( It is more preferable to use a PDMS) modified acrylic polyol oligomer. Silicone oils having functional groups A at both ends have low polarity. Therefore, for example, by introducing low-polarity polydimethylsiloxane (PDMS) into the side chain and using a polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer having a side chain having a hydroxyl group as the functional group A, compatibility is achieved. There is an advantage that a more uniform mixture can be obtained. As a result, the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, and the like of the transparent film can be improved.

Further, in the method for producing a transparent film, at least one selected from the group consisting of a carbinol group, a hydroxyl group, an amino group, a carboxyl group and a phenolic hydroxyl group as a combination of the functional group A and the functional group B. It is preferable to apply a combination of a group and an isocyanate group. As a result, the crosslinked portion has one or both of the urethane bond and the urea bond. Such a cross-linked portion can be formed by a conventionally known resin material, elastomer material and cross-linking agent. Further, since there are many choices of materials, it is possible to improve the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, etc. of the transparent film by appropriately selecting the material.

Further, in the method for producing a transparent film, one or both of a silicone oil having a carbinol group as a functional group A at both ends and a silicone oil having a hydroxyl group as a functional group A at both ends are used as an elastomer material, and a resin is used. As a material, a polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer having a side chain having a hydroxyl group as the functional group A is used, and as a cross-linking agent, an isocyanate having an isocyanate group as the functional group B, preferably a polyisocyanate or an isocyanurate type. It is preferable to use polyisocyanate. As a result, it is possible to improve the abrasion resistance, heat resistance, water droplet sliding property, optical characteristics, etc. of the transparent film.

As the silicone oil having a functional group A at both ends, when the functional group A is a carbinol group, a hydroxyl group, an amino group, a carboxyl group and a phenolic hydroxyl group, for example, KF manufactured by Shin-Etsu Chemical Industry Co., Ltd. -6000, X-21-5841, PAM-E, X-22-162C, KF-2201 can be mentioned.

Further, the polydimethylsiloxane (PDMS) -modified acrylic resin oligomer having a side chain having the functional group A can be prototyped by a resin manufacturer. Examples of the polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer having a side chain having a hydroxyl group as the functional group A include 8BS-9000 manufactured by Taisei Fine Chemicals Co., Ltd.

Further, as the cross-linking agent having an isocyanate group as the functional group B, for example, DN-980 manufactured by DIC Corporation can be mentioned.

Further, in the method for producing a transparent coating film, one or both of dimethyl silicone oil and modified silicone oil can be used as the lubricating liquid because of the advantages described in the first or second embodiment.

In the method for producing a transparent film, as the base material, glass, metal oxide, resin or metal, or any combination of two or more of them can be arbitrarily combined from the advantages described in the first or second embodiment. Can be used.

Here, the details of each of the above steps (1) to (3) will be described.

The step (1) is not particularly limited, but it is preferable to premix the elastomer material and the resin material when preparing a mixture containing the elastomer material, the resin material, and the cross-linking agent. .. This has the advantage that it is easy to obtain a transparent film having the desired durability such as water droplet sliding property, abrasion resistance, heat resistance, and optical properties.

The step (1) is not particularly limited, but it is preferable that the mixture contains a solvent for adjusting the viscosity and dispersibility. This has the advantage that it is easy to obtain a transparent film having the desired durability such as water droplet sliding property, abrasion resistance, heat resistance, and optical properties. The solvent does not have to dissolve all of the elastomer material, the resin material and the cross-linking agent.

Further, in the above step (1), although not particularly limited, when the mixture is applied onto the substrate, brush coating, roller coating, spin coating, spray coating, roll coating, flow coating, and dip coating are performed. For example, a conventionally known method can be adopted. Of course, hand-painting using cotton or the like can also be adopted.

Further, in the above step (2), although not particularly limited, the lower limit of the reaction temperature at the time of carrying out the crosslinking reaction when heating the mixture is preferably 40 ° C. or higher, preferably 80 ° C. or higher. The temperature is more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. Further, the upper limit of the reaction temperature at the time of the cross-linking reaction is preferably 240 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 180 ° C. or lower.

Further, in the above step (2), although not particularly limited, the reaction time for the cross-linking reaction when heating the mixture is preferably 1 minute to 24 hours, and 1 minute to 2 hours. It is more preferable to set the time. When the above-mentioned elastomer material, resin material and cross-linking agent are used, for example, when the reaction temperature at the time of the cross-linking reaction is 80 to 180 ° C., the reaction time may be 1 minute to 2 hours. It is also necessary to consider the heat resistance of the base material.

Further, in the above step (3), if a lubricating liquid holding layer holding the lubricating liquid can be formed inside the lubricating liquid holding layer and a lubricating liquid film containing the lubricating liquid can be formed on the lubricating liquid holding layer. , Not particularly limited. For example, when the hydrophobic lubricating liquid is applied to the lubricating liquid holding layer, a conventionally known method described as a method of applying the mixture on the substrate can be applied.

In addition, various surface modification treatments may be performed as the pretreatment of the above step (1). Examples thereof include surface cleaning and hydroxyl group exposure by atmospheric pressure plasma treatment, improvement of wettability and compatibility with a silane coupling agent, and formation of chemical bonds and hydrogen bonds.

(Fourth Embodiment)
Next, the antifouling parts for automobiles according to the fourth embodiment of the present invention will be described in detail with reference to the drawings. As shown in FIGS. 1 and 2, the automobile antifouling component 1 of the present embodiment includes a base material 20 and a transparent coating film 10 of the present invention arranged on the base material 20. The base material 20 is an automobile part.

With such a configuration, the inner layer parts and exterior parts for automobiles can be made into antifouling parts having excellent antifouling performance due to the effect of the transparent film of the present invention described above.

For example, an antifouling body can be realized by applying it to a coating film or the like in a body for an automobile.

Further, for example, by applying it to the fins of an air conditioner evaporator, dew condensation and freezing can be prevented, so that the heat exchange efficiency of the air conditioner can be improved.

Further, for example, by applying it to a camera lens, it is possible to prevent droplet adhesion, so that it is possible to improve the visibility of the camera. Thereby, for example, the reliability of the sensor camera for automatic driving can be improved.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to such Examples.

(Example 1)
<Preparation of main agent A>
Polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer (manufactured by Taisei Fine Chemical Co., Ltd., 8BS-9000), which is a resin material, and 100.0 parts by mass, and both-terminal carbinol-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.), which is an elastomer material. , KF-6000) 5.2 parts by mass was mixed until it became colorless and transparent, and then allowed to stand for 18 hours to obtain a mixture. This is called the main agent A.

<Preparation of cross-linking agent B>
4.4 parts by mass of isocyanate (manufactured by DIC Corporation, DN-980) as a cross-linking agent and 70.0 parts by mass of ethyl acetate as a solvent were mixed until they became colorless and transparent, and then allowed to stand for 18 hours. To obtain the mixture. This is called a cross-linking agent B.

<Preparation of modifier A>
A 1% by mass aqueous solution of 3-aminopropyltriethoxysilane was prepared. This is called modifier A.

<Surface modification treatment of the glass plate that is the base material>
A glass plate (length: 5 cm, width: 5 cm, thickness: 1.8 mm) is placed at a speed of ^{1 cm 2} / s on a glass plate (length: 5 cm, width: 5 cm, thickness: 1.8 mm) for surface cleaning and hydroxyl group exposure. ) Was surface-modified to obtain a modified glass plate. This is called a modified glass plate A.

The modifier A was applied to the modified glass plate A with a spin coater, and then dried at 90 ° C. for 30 minutes to obtain a modified glass plate. This is called a modified glass plate B. Here, the operating conditions of the spin coater were as follows: 1 mL of the modifier A was dropped onto the modified glass plate A, and then the modifier A was rotated at a rotation speed of 500 rpm for 10 seconds, and then rotated at a rotation speed of 1000 rpm for 20 seconds.

<Formation of lubricating liquid holding layer>
The main agent A and the cross-linking agent B were mixed to obtain a mixed solution. This is called a mixed solution A. Next, 1.64 parts by mass of the mixed solution A was added dropwise to the modified glass plate B in a horizontal state, then allowed to stand for 3 hours, and then dried at 150 ° C. for 1 hour to cure. To form a lubricating liquid holding layer. This is called a film-forming glass plate C.

<Formation of lubricating liquid film>
The film-formed glass plate C is immersed in dimethyl silicone oil (KF96-30cs, manufactured by Shin-Etsu Chemical Co., Ltd.) for 18 hours, then tilted at 80 to 90 ° and left at room temperature (20 ° C ± 15 ° C) for 10 minutes. After that, the excess oil adhering to the film-formed glass plate C was wiped back and forth 20 times with cotton gauze to obtain the transparent film of this example. Here, when wiping, a new surface of cotton gauze was used for each round trip. A part of the specifications is shown in Table 1.

(Example 2)
Instead of the cross-linking agent B, 5.9 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 75.5 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 1.66 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 3)
Instead of the cross-linking agent B, 7.4 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 81.0 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 1.68 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 4)
Instead of the cross-linking agent B, 8.8 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 86.6 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 1.71 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 5)
Instead of the cross-linking agent B, 10.3 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 92.1 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 1.73 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 6)
Instead of the cross-linking agent B, 11.8 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 95.8 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 1.74 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 7)
Instead of the cross-linking agent B, 14.7 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 108.7 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 1.79 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 8)
Instead of the cross-linking agent B, 17.7 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 119.7 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 1.83 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 9)
Instead of the cross-linking agent B, 20.6 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 128.9 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 1.85 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 10)
Instead of the cross-linking agent B, 23.6 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 141.8 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 1.89 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 11)
Instead of the cross-linking agent B, 29.5 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 162.1 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 1.94 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 12)
Instead of the cross-linking agent B, 44.2 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 217.3 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 2.05 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 13)
Instead of the cross-linking agent B, 58.9 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 268.9 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 2.12 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 14)
Instead of the main agent A, 100.0 parts by mass of polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer (8BS-9000 manufactured by Taisei Fine Chemical Co., Ltd.), which is a resin material, and carbinol-modified silicone oil at both ends (Shinetsu Chemical Industry Co., Ltd.) 1.8 parts by mass of KF-6000) manufactured by the company was mixed until it became colorless and transparent, and then allowed to stand for 18 hours, and the obtained mixture was used instead of the cross-linking agent B as a cross-linking agent. 3.9 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) and 57.1 parts by mass of ethyl acetate as a solvent were mixed until they became colorless and transparent, and then allowed to stand for 18 hours to obtain the obtained substance. The same operation as in Example 1 was repeated except that the amount of dropping application in the mixed solution A was changed from 1.64 parts by mass to 1.63 parts by mass, and a transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 15)
Instead of the main agent A, 100.0 parts by mass of polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer (8BS-9000 manufactured by Taisei Fine Chemical Co., Ltd.), which is a resin material, and carbinol-modified silicone oil at both ends (Shinetsu Chemical Industry Co., Ltd.) 7.7 parts by mass of KF-6000) manufactured by the company was mixed until it became colorless and transparent, and then allowed to stand for 18 hours, and the obtained mixture was used instead of the cross-linking agent B as a cross-linking agent. 7.4 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) and 88.4 parts by mass of ethyl acetate as a solvent were mixed until they became colorless and transparent, and then allowed to stand for 18 hours to obtain the obtained substance. The same operation as in Example 1 was repeated except that the amount of dropping application in the mixed solution A was changed from 1.64 parts by mass to 1.67 parts by mass, and a transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Example 16)
Instead of the main agent A, 100.0 parts by mass of polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer (8BS-9000 manufactured by Taisei Fine Chemical Co., Ltd.), which is a resin material, and carbinol-modified silicone oil at both ends (Shinetsu Chemical Industry Co., Ltd.) 15.3 parts by mass of KF-6000) manufactured by the company was mixed until it became colorless and transparent, and then allowed to stand for 18 hours, and the obtained mixture was used instead of the cross-linking agent B as a cross-linking agent. 11.8 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) and 128.9 parts by mass of ethyl acetate as a solvent were mixed until they became colorless and transparent, and then allowed to stand for 18 hours to obtain the obtained substance. The same operation as in Example 1 was repeated except that the amount of dropping application in the mixed solution A was changed from 1.64 parts by mass to 1.70 parts by mass, and a transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Comparative Example 1)
Instead of the cross-linking agent B, 2.9 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 64.5 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 1.61 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Comparative Example 2)
Instead of the cross-linking agent B, 117.9 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 488.0 parts by mass of ethyl acetate as a solvent are mixed until they become colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the same operation as in Example 1 was repeated except that 1.64 parts by mass of the dropping coating amount in the mixed solution A was changed to 2.33 parts by mass using the obtained mixture. , The transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Comparative Example 3)
Instead of the main agent A, 100.0 parts by mass of polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer (8BS-9000 manufactured by Taisei Fine Chemical Co., Ltd.), which is a resin material, and carbinol-modified silicone oil at both ends (Shinetsu Chemical Industry Co., Ltd.) 45.9 parts by mass of KF-6000) manufactured by the company was mixed until it became colorless and transparent, and then allowed to stand for 18 hours, and the obtained mixture was used instead of the cross-linking agent B as a cross-linking agent. 29.5 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) and 291.0 parts by mass of ethyl acetate as a solvent were mixed until they became colorless and transparent, and then allowed to stand for 18 hours to obtain the obtained substance. The same operation as in Example 1 was repeated except that the amount of dropping application in the mixed solution A was changed from 1.64 parts by mass to 1.76 parts by mass, and a transparent film of this example was obtained. A part of the specifications is shown in Table 1.

(Comparative Example 4)
Instead of the main agent A, 100.0 parts by mass of a polydimethylsiloxane (PDMS) -modified acrylic polyol oligomer (8BS-9000 manufactured by Taisei Fine Chemical Co., Ltd.), which is a resin material, was stirred, and then allowed to stand for 18 hours. Using the obtained product, instead of the cross-linking agent B, 2.9 parts by mass of isocyanate (manufactured by DIC Co., Ltd., DN-980) as a cross-linking agent and 36.8 parts by mass of ethyl acetate as a solvent are colorless and transparent. After that, the mixture was allowed to stand for 18 hours, and the obtained mixture was used, except that the amount of dropping application in the mixed solution A was changed from 1.64 parts by mass to 1.50 parts by mass. The same operation as in 1 was repeated to obtain the transparent film of this example. A part of the specifications is shown in Table 1.

(Comparative Example 5)
KE109A manufactured by Shin-Etsu Chemical Co., Ltd. as the main agent A and KE109B manufactured by Shin-Etsu Chemical Co., Ltd. as the curing agent B were mixed with the main agent A: curing agent B = 1: 1 (mass ratio) to obtain a mixed solution. Next, 0.40 parts by mass of the obtained mixed solution was added dropwise to a horizontal glass plate (length: 5 cm, width: 5 cm, thickness: 1.8 mm), and then dried at 100 ° C. for 1 hour. As a result, it was cured to form a lubricating liquid holding layer.

The glass plate on which the lubricating liquid holding layer is formed is immersed in dimethyl silicone oil (KF96-30cs, manufactured by Shin-Etsu Chemical Co., Ltd.) for 18 hours, then tilted at 80 to 90 ° and at room temperature (20 ° C ± 15 ° C). After leaving it for 10 minutes, the excess oil adhering to the glass plate on which the lubricating liquid holding layer was formed was wiped off with cotton gauze 20 times to obtain the transparent film of this example. Here, when wiping, a new surface of cotton gauze was used for each round trip. A part of the specifications is shown in Table 1.

Here, the “NCO group / OH group (molar ratio) (−)” in Table 1 was calculated from the amounts of the cross-linking agent, the resin material, and the elastomer material used.

^{The "NCO density (mmol / cm 3} ) in the lubricating liquid holding layer" in Table 1 was calculated from the amount of isocyanate used as a cross-linking agent and the volume of the formed lubricating liquid holding layer.

[Performance evaluation]
The following performance was evaluated for the transparent coatings of each of the above examples.

(Water droplet slipperiness)
After removing the lubricating liquid by wiping it back and forth 20 times with cotton gauze, 5 μL of water droplets were dropped onto the transparent film when 24 hours had passed, and the fall angle was measured. A contact angle meter (Drop Master manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the fall angle. The results obtained are shown in Table 2. In Table 2, "◎" in "water droplet sliding property" indicates that the falling angle is 10 ° or less, "○" indicates that the falling angle is more than 10 ° and 25 ° or less, and "△". Indicates that the fall angle is more than 25 ° and 30 ° or less, and “x” indicates that the fall angle is more than 30 °.

(Abrasion resistance)
The state of the film when it was worn back and forth 5000 times with a canvas cloth was visually observed. The results obtained are shown in Table 2. “◎” in “Abrasion resistance” in Table 2 indicates that the film did not peel off until 5000 reciprocating wear, and “○” indicates that the film did not peel off until 1000 reciprocating wear. , And “x” indicates that the film had peeled off by the time of 500 reciprocating wears.

(optical properties)
The haze value was measured using a haze meter (manufactured by Murakami Color Technology Laboratory Co., Ltd.). The results obtained are shown in Table 2. In "optical characteristics" in Table 2, "◎" indicates that the haze value is 1% or less, "○" indicates that the haze value is more than 1% and 3% or less, and "△" indicates that the haze value is more than 1% and 3% or less. , Indicates that the haze value is more than 3% and 5% or less, and “x” indicates that the haze value is more than 5%.

(Heat-resistant)
After performing the test of holding the atmosphere temperature at 90 ° C. for 4 hours four times, 5 μL of water droplets were dropped onto the transparent film, and the falling angle was measured. A contact angle meter (Drop Master manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the fall angle. The results obtained are shown in Table 2. In "heat resistance" in Table 2, "◎" indicates that the fall angle is 10 ° or less, "○" indicates that the fall angle is more than 10 ° and 25 ° or less, and "△" indicates that the fall angle is more than 10 ° and 25 ° or less. , Indicates that the fall angle is more than 25 ° and 30 ° or less, and “x” indicates that the fall angle is more than 30 °.

The following can be said from Table 2.

In Example 1, immediately after wiping the lubricating liquid 20 times back and forth with cotton gauze, the falling angle measured by dropping 5 μL of water droplets on the transparent film was 30 ° or more, but 24 hours passed after wiping. The falling angle of the 5 μL water droplet is 10 ° or less. Therefore, the water droplet sliding property is excellent with "◎". This is because the lubricating liquid held by the silicone elastomer reinforced with the polydimethylsiloxane (PDMS) -modified acrylic resin oligomer exudes to the surface of the elastomer due to the elastic force of the elastomer, and the lubricating liquid film self-repairs. Conceivable.

Then, in the first embodiment, the wear resistance is excellent with "⊚". It is considered that this is because the silicone elastomer cross-linked with the carbinol-modified silicone oils at both ends was reinforced with a polydimethylsiloxane (PDMS) -modified acrylic resin oligomer having excellent wear resistance to form a strong three-dimensional network structure. ..

Further, in the first embodiment, the optical characteristic is excellent with "⊚".

Further, in Example 1, the heat resistance is excellent with "⊚". This is because the elastomer having a three-dimensional network structure swells and the lubricating liquid is firmly held in the molecular level pores of the elastomer, and the outflow of the lubricating liquid from the elastomer is suppressed even in a high temperature environment. It is thought that this is because it is done.

Further, also in Examples 2 to 9, the water droplet sliding property is "⊚", which is very excellent. Further, also in Examples 2 to 9, the wear resistance is "⊚", which is very excellent. Further, also in Examples 2 to 9, the optical characteristics are "⊚", which is very excellent. Furthermore, also in Examples 2 to 9, the heat resistance is "⊚", which is very excellent.

Further, in Examples 10 to 14, the water droplet sliding property is excellent with "◯". Further, in Examples 10 to 14, the wear resistance is "⊚", which is very excellent. Further, in Examples 10 to 14, the optical characteristics are "⊚", which is very excellent. Furthermore, in Examples 10 to 14, the heat resistance is excellent with "◯".

Further, in Example 15, the water droplet sliding property is "⊚", which is very excellent. Further, in Example 15, the wear resistance is "⊚", which is very excellent. Further, in Example 15, the optical characteristic is "⊚", which is very excellent. Furthermore, in Example 15, the heat resistance is "⊚", which is very excellent.

Then, in Example 16, the water droplet sliding property is "⊚", which is very excellent. Further, in Example 16, the wear resistance is excellent with "◯". Further, in Example 16, the optical characteristic is "⊚", which is very excellent. Furthermore, in Example 16, the heat resistance is "⊚", which is very excellent.

Further, in Comparative Example 1, the water droplet sliding property was "⊚", which was very excellent. Further, in Comparative Example 1, the wear resistance is “x”. After 500 reciprocating wear, the lubricating liquid holding layer was peeled off. It is considered that this is because the addition amount of isocyanate as a cross-linking agent was too small and the cross-linking reaction did not proceed sufficiently. Further, in Comparative Example 1, the optical characteristic is "⊚", which is very excellent. Furthermore, in Comparative Example 1, the heat resistance is "⊚", which is very excellent.

Further, in Comparative Example 2, the water droplet sliding property is “x”. It is considered that this is because the addition amount of isocyanate as a cross-linking agent was too large, so that the cross-linking reaction proceeded excessively and the dimethyl silicone oil as the lubricating liquid could not be sufficiently impregnated. Further, in Comparative Example 2, the wear resistance is "⊚", which is very excellent. Further, in Comparative Example 2, the optical characteristic is "⊚", which is very excellent. Furthermore, in Comparative Example 2, the heat resistance is "x".

Then, in Comparative Example 3, as shown in Table 2, the lubricating liquid holding layer became cloudy without being thermoset. It is considered that this is because the amount of polydimethylsiloxane (PDMS) -modified acrylic resin oligomer, which is a resin material, was too small.

Further, in Comparative Example 4, the water droplet sliding property is “x”. It is considered that this is because the lubricating liquid holding layer is composed only of the polydimethylsiloxane (PDMS) -modified acrylic resin oligomer which is a resin material, and the dimethylsilicone oil of the lubricating liquid could not be sufficiently impregnated. Further, in Comparative Example 4, the wear resistance is "⊚", which is very excellent. Further, in Comparative Example 4, the optical characteristic is "⊚", which is very excellent. Furthermore, in Comparative Example 2, the heat resistance is "x".

Further, in Comparative Example 5, the water droplet sliding property was "⊚", which was very excellent. It is considered that this is because the lubricating liquid held by the silicone elastomer exudes to the surface of the elastomer due to the elastic force of the elastomer, and the lubricating liquid film is self-repaired. Further, in Comparative Example 5, the wear resistance is “x”. It is considered that this is because the silicone elastomer is not reinforced with a resin material such as a polydimethylsiloxane (PDMS) -modified acrylic resin oligomer. Further, in Comparative Example 5, the optical characteristic is "⊚", which is very excellent. Furthermore, in Comparative Example 5, the heat resistance is "⊚", which is very excellent.

Although the present invention has been described above with reference to some embodiments and examples, the present invention is not limited thereto, and various modifications can be made within the scope of the gist of the present invention.

For example, the configurations described in the above-described embodiments and examples are not limited to the respective embodiments and examples, and the configurations of the respective embodiments may be changed or the configurations of the respective embodiments may be changed in the above-described embodiments. It can be a combination other than the form.

1 automotive antifouling component 10 transparent film 11 lubricant holding layer 11a inside 111 resin skeleton portion 111A resin portion 111B _(111B 1 ~111B ₅₎ the bridge portion 111a surface 113 lubricating liquid holding portion 113A elastomer section 13 lubricant film 20 groups Material 30 Lubricating fluid

Claims (17)

A transparent coating placed on a substrate,
A lubricating liquid holding layer arranged on the base material and a lubricating liquid film arranged on the lubricating liquid holding layer are provided.
The lubricant holding layer has at least an elastomer material having a functional group A having reactivity with a cross-linking agent, a resin material having a side chain having a functional group A, and a cross-linking having a functional group B that reacts with the functional group A. It was obtained by heating the mixture with the agent and causing a cross-linking reaction.
The lubricating liquid holding layer holds a hydrophobic lubricating liquid inside.
The lubricating liquid film is, only contains the above-mentioned lubricating fluid,
The mixing ratio of the elastomer material to the resin material is 3 to 26 in terms of molar ratio.
A transparent coating having a molar ratio of the functional group B of the cross-linking agent to the functional group A of the resin material and the elastomer material of 0.75-10. The mixing ratio of the elastomer material to the resin material is 9 to 13 in terms of molar ratio.
The first aspect of claim 1 , wherein the ratio of the functional group B of the cross-linking agent to the functional group A of the resin material and the elastomer material is 0.75 to 3.5 in terms of molar ratio. Transparent coating. The transparent coating according to claim 1 or 2 , wherein the elastomer material is a silicone oil having the functional groups A at both ends. The transparent coating according to any one of claims 1 to 3, wherein the resin material is a silicone-modified acrylic resin oligomer having a side chain having a functional group A. The combination of the functional group A and the functional group B is a combination of an isocyanate group and at least one group selected from the group consisting of a carbinol group, a hydroxyl group, an amino group, a carboxyl group and a phenolic hydroxyl group. The transparent coating according to any one of claims 1 to 4, wherein the transparent coating is provided. The transparent coating according to any one of claims 1 to 5, wherein the lubricating liquid contains at least one of a dimethyl silicone oil and a modified silicone oil. The elastomer material is at least one of a silicone oil having a carbinol group as the functional group A at both ends and a silicone oil having a hydroxyl group as the functional group A at both ends.
The resin material is a polydimethylsiloxane-modified acrylic polyol oligomer having a side chain having a hydroxyl group as the functional group A.
The transparent coating according to any one of claims 1 to 6, wherein the cross-linking agent is an isocyanate having an isocyanate group as the functional group B. The transparent coating according to any one of claims 1 to 7, wherein the base material is at least one selected from the group consisting of glass, metal oxide, resin and metal. With the base material
An automobile antifouling component comprising the transparent coating according to any one of claims 1 to 8. A method for producing a transparent film, which is the following steps (1) to (3).
A mixture containing an elastomer material having a functional group A, a resin material having a side chain having the functional group A, and a cross-linking agent having a functional group B that reacts with the functional group A is applied onto the substrate. Step (1) and
It is executed after the step (1), and the mixture is heated to have a resin skeleton portion having a three-dimensional crosslinked structure and a lubricant holding portion arranged in a dispersed state on the surface of the resin skeleton portion. However, the resin skeleton portion includes a plurality of resin portions derived from the resin material, and a cross-linked portion derived from the cross-linking agent and intervening between the resin portions to bond the resin portions. The lubricant holding portion is a cross-linked portion derived from an elastomer material and a cross-linking agent, which is interposed between the elastomer portion and the resin portion and bonds the elastomer portion and the resin portion. And the step (2) of forming the lubricating liquid holding layer including
It is executed after the step (2), and a hydrophobic lubricating liquid is applied to the lubricating liquid holding layer to form a lubricating liquid holding layer holding the lubricating liquid inside the lubricating liquid holding layer, and the lubricating liquid holding layer is formed. forming a lubricant film containing the lubricating liquid on the lubricating liquid holding layer (3), only it contains,
The mixing ratio of the elastomer material to the resin material is 3 to 26 in terms of molar ratio.
Production of a transparent coating characterized in that the ratio of the functional group B of the cross-linking agent to the functional group A of the resin material and the elastomer material is 0.75 to 10 in terms of molar ratio. Method. The mixing ratio of the elastomer material to the resin material is 9 to 13 in terms of molar ratio.
The tenth aspect of claim 10 , wherein the ratio of the functional group B of the cross-linking agent to the functional group A of the resin material and the elastomer material is 0.75 to 3.5 in terms of molar ratio. A method for producing a transparent coating. The method for producing a transparent coating according to claim 10 or 11 , wherein the elastomer material is a silicone oil having the functional groups A at both ends. The method for producing a transparent coating according to any one of claims 10 to 12, wherein the resin material is a silicone-modified acrylic resin oligomer having a side chain having a functional group A. The combination of the functional group A and the functional group B is a combination of an isocyanate group and at least one group selected from the group consisting of a carbinol group, a hydroxyl group, an amino group, a carboxyl group and a phenolic hydroxyl group. The method for producing a transparent coating according to any one of claims 10 to 13, wherein the transparent coating is produced. The method for producing a transparent coating according to any one of claims 10 to 14, wherein the lubricating liquid contains at least one of a dimethyl silicone oil and a modified silicone oil. The elastomer material is at least one of a silicone oil having a carbinol group as the functional group A at both ends and a silicone oil having a hydroxyl group as the functional group A at both ends.
The resin material is a polydimethylsiloxane-modified acrylic polyol oligomer having a side chain having a hydroxyl group as the functional group A.
The method for producing a transparent film according to any one of claims 10 to 15, wherein the cross-linking agent is an isocyanate having an isocyanate group as the functional group B. The method for producing a transparent coating according to any one of claims 10 to 16, wherein the base material is at least one selected from the group consisting of glass, metal oxide, resin and metal. ..

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