Paints and Films

Abstract

The object is to provide a product, particularly a paint, that can prevent ice and / or snow from accumulating. The resin layer comprises a first oil component, a second oil component, and a first resin precursor, which is a precursor of a resin component. The first resin precursor containing the first and second oil components is cured to form an oil-containing resin layer containing the first and second oil components and a resin component. The second oil component constitutes a low-temperature phase-separable oil component that phase-separates from the first oil component and exudes from the oil-containing resin layer when the temperature drops below a predetermined value.

Description

[Technical Field]

[0001] The present invention relates to paints, and in particular to paints and films that can prevent ice and / or snow buildup. [Background technology]

[0002] Several products have been developed that can prevent ice and snow buildup on various structures, such as house roofs, power lines, mats, vehicles, and boats.

[0003] For example, Japanese Patent Laid-Open Publication No. 7-148879 (Patent Document 1) discloses an anti-icing and snow adhesion sheet that can prevent the adhesion of ice and snow to various structures in cold regions. This sheet consists of an insulating layer made of a sponge material and a surface layer laminated on the insulating layer, and the surface layer is made of rubber or resin in which an oil agent is dispersed so that it can bleed onto its surface. The oil agent is held in the surface layer and is designed to constantly bleed onto the surface of the surface layer. Meanwhile, in order to prevent significant bleeding of the oil agent, the viscosity of the oil agent is set to a predetermined value or higher, so that the anti-icing and snow adhesion effect can be maintained for as long as possible.

[0004] Japanese Patent Application Laid-Open Publication No. 2003-328308 (Patent Document 2) discloses a rubber mat that can prevent ice and snow from adhering. This rubber mat is made of synthetic rubber with a predetermined hardness, and is configured so that a liquid additive that has the effect of preventing ice and snow from adhering bleeds onto its surface when the temperature is below 5°C. In order to adjust the amount of the liquid additive that bleeds, the amount of liquid additive relative to the rubber of the rubber mat is adjusted within a predetermined range.

[0005] Japanese Patent No. 6245714 (Patent Document 3) discloses a wet gel that is difficult to adhere to ice and can spontaneously synerase due to temperature, chemical reaction, etc. This wet gel contains a crosslinked silicone resin formed by curing a silicone resin composition, a first liquid capable of dissolving the silicone resin composition, and a second liquid that is miscible with the first liquid (i.e., when the second liquid and the first liquid are mixed, a transparent mixed solution is formed without phase separation). However, it is stated that the first liquid may also serve as the second liquid. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 7-148879 [Patent Document 2] Japanese Patent Application Laid-Open No. 2003-328308 [Patent Document 3] Patent No. 6245714 Summary of the Invention [Problem to be solved by the invention]

[0007] However, with the configuration described in Patent Document 1, the oil continues to bleed regardless of temperature, making it difficult to achieve long-term effectiveness in preventing ice and snow adhesion. Also, there is a risk of excessive oil bleeding, and if the viscosity of the oil is set too high, bleeding may not occur smoothly. Furthermore, because all of the oil dispersed in the surface layer is bleedable, there is a risk of excessive oil bleeding. Furthermore, although the configuration described in Patent Document 2 makes it possible to control the amount of liquid additive that bleeds depending on the temperature conditions, all liquid additives added to the rubber of the rubber mat are capable of bleeding, so there is a risk that the liquid additive will bleed excessively. Furthermore, the configuration described in Patent Document 3 is a wet gel, and is not intended for use outdoors or the like where strength is required, and has the problem of insufficient strength. In addition, since the first liquid and the second liquid are miscible and the first liquid may also serve as the second liquid, there is a risk that the first liquid and the second liquid may syneresis simultaneously and excessively. The present invention has been made to solve these problems in the prior art, and aims to provide products, particularly paints and films, that have improved anti-icing and / or anti-snow properties. [Means for solving the problem]

[0008] In order to solve the above problems, one aspect of the present invention provides a paint comprising a first oil component, a second oil component, and a first resin precursor that is a precursor of a resin component, wherein the first resin precursor containing the first and second oil components is cured to form an oil-containing resin layer containing the first and second oil components and the resin component, and the second oil component constitutes a low-temperature phase-separable oil component that phase-separates from the first oil component and oozes out of the oil-containing resin layer when the temperature drops below a predetermined value. The predetermined value may be freezing point. This paint allows for flexible use. The oil component exuded from the oil-containing resin layer is a low-temperature exudation oil component that can exudate when the temperature drops below a predetermined value, preventing unnecessary bleeding and allowing it to bleed when necessary, thereby more reliably preventing, for example, the adhesion of ice and snow. Furthermore, since this oil component is only a portion of the oil component contained in the oil-containing resin layer, excessive bleeding of the oil component is also avoided.

[0009] In the paint of the above embodiment, it is preferable that the difference between the solubility parameter value (SP value) of the resin component of the oil-containing resin layer formed by curing the first resin precursor and the solubility parameter value of the first oil component is smaller than the difference between the solubility parameter value (SP value) of the resin component of the oil-containing resin layer and the solubility parameter value of the second oil component.

[0010] Furthermore, in the paint of the above aspect, the first resin precursor may be a moisture-curable type that is cured by moisture, an ultraviolet-curable type that is cured by ultraviolet irradiation, a thermosetting type that is cured by heating, or one that is cured by adding a curing agent that undergoes a crosslinking reaction with the first resin precursor, or a combination with a liquid curing agent that undergoes a crosslinking reaction with the first resin precursor of the paint to cure the first resin precursor.

[0011] Furthermore, in the paint of the above embodiment, it is preferable that the resin component of the oil-containing resin layer is contained in an amount of 25 wt % or more based on the weight of the entire oil-containing resin layer.

[0012] In the paint of the above embodiment, the second oil component is preferably contained in a proportion of 3 wt % or more based on the weight of the entire oil-containing resin layer.

[0013] Furthermore, the paint of the above aspect may further include a second resin precursor that forms a surface resin layer by being cured on the oil-containing resin layer formed by curing the first resin precursor, and the surface resin layer may have oil permeability that allows a low-temperature phase-separable oil component that has exuded from the oil-containing resin layer to permeate to the surface of the surface resin layer on the opposite side to the oil-containing resin layer.

[0014] In the paint of the above aspect, the surface resin layer preferably has higher abrasion resistance than the oil-containing resin layer. In addition, in the paint of the above embodiment, it is preferable that the amount of surface oil at -20°C is 40 μg / cm 2 or more. Furthermore, in the paint of the above aspect, the difference in solubility parameter between the first oil component and the resin component of the oil-containing resin layer is 0.6 (J / cm 3 ) 1 / 2 It is preferable that it is within .

[0015] In the paint of the above aspect, the wetting parameter, which is calculated as the absolute value of the difference between the solubility parameter value (SP value) of the oil-containing resin layer formed by curing the first resin precursor and the solubility parameter value (SP value) of the second oil component, is 1.5 (J / cm 3 ) 1 / 2 Preferably, it is: In the paint of the above aspect, it is preferable that the oil-containing resin layer formed by curing the first resin precursor has a solubility parameter contribution value of 0.1 or more.

[0016] In order to solve the above problems, a film according to one aspect of the present invention is a film having an oil-containing resin layer containing first and second oil components, and is characterized in that the second oil component constitutes a low-temperature phase-separable oil component that can phase-separate from the first oil component and exude from the oil-containing resin layer when the temperature drops below a predetermined value. [Effects of the Invention]

[0017] The present invention provides products that can prevent ice and / or snow buildup, particularly paints and films that can be used in a more flexible manner than sheets and the like that have a fixed physical shape from the start of use. [Brief explanation of the drawings]

[0018] [Figure 1] FIG. 2 is a diagram showing an oil-containing resin layer formed from a paint according to one embodiment of the present invention together with a structure. [Figure 2]FIG. 1 is a diagram showing a layer configuration including a surface resin layer formed from a paint according to an embodiment of the present invention, together with a structure. [Figure 3] 1 is an optical microscope image of the oil appearing on the surface of an oil-containing resin layer. [Figure 4] FIG. 1 is a schematic diagram of a testing machine used in a wear resistance test. DETAILED DESCRIPTION OF THE INVENTION

[0019] Preferred embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.

[0020] 1. Types of paint (1) First Paint The first paint contains a first resin precursor, which is a precursor of a resin component, and two types of oil components, i.e., a first oil component and a second oil component. The first resin precursor containing the first oil component and the second oil component is cured to form an oil-containing resin layer 11. The oil-containing resin layer 11 is a solid resin layer that contains the first oil component, the second oil component, and a resin component, and is capable of bleeding a portion of the contained oil, particularly the second oil component, from the resin component, and the exuded second oil component prevents ice and / or snow from adhering.

[0021] 1 shows an oil-containing resin layer 11 formed by applying and curing a first coating material together with a structure 10. The thickness of the oil-containing resin layer 11 is roughly determined by the thickness of the applied first coating material. Although not particularly limited, it is preferably 10,000 μm or less to allow the oil to properly exude, and is preferably 10 μm or more from the viewpoint of strength.

[0022] <First resin precursor> The first resin precursor is a precursor that constitutes the resin component of the oil-containing resin layer 11, and may be any of a moisture-curing type that cures with moisture, an ultraviolet-curing type that cures with ultraviolet light, or a thermosetting type that cures with heat. It may also be one that cures by adding a curing agent that undergoes a crosslinking reaction with the first resin precursor. Furthermore, it may be a combination of a paint that cures by adding a curing agent that undergoes a crosslinking reaction with the first resin precursor, and a liquid curing agent that cures the first resin precursor by crosslinking with the first resin precursor of the paint.

[0023] The first resin precursor is not particularly limited, but examples thereof include silicone resin, polyurethane resin, polyurethane acrylic resin, vinyl chloride resin, polyester resin, elastomers, fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.), acrylic resin, etc., and among these, silicone resin is preferred from the viewpoint of excellent bleeding effect of oil components and durability against outdoor exposure.

[0024] As the silicone resin, any appropriate silicone resin can be adopted as long as it does not impair the effects of the present invention. The silicone resin may be one type only, or two or more types. Such a silicone resin may be a condensation type silicone resin or an addition type silicone resin. Furthermore, such a silicone resin may be a one-component silicone resin that dries alone (for example, a one-component room temperature vulcanizable (RTV) resin), or a two-component silicone resin (for example, a two-component room temperature vulcanizable (RTV) resin).

[0025] Examples of silicone resins include one-component RTV rubbers manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., KE-3423, KE-347, KE-3475, KE-3495, KE-4895, KE-4896, KE-1830, KE-1884, KE-3479, KE-348, KE-4897, KE-4898, KE-1820, KE-1825, KE-1831, KE-1833, KE-1885, KE-1056, KE-1151, KE-1842, KE-1886, KE-3424G, KE-3494, KE-3490, KE-40RTV, KE-4890 ...1833, KE-1885, KE-1056, KE-1151, KE-1842, KE-1886, KE-3424G, KE-3494, KE-3490, KE-40RT E-3497, KE-3498, KE-3493, KE-3466, KE-3467, KE-1862, KE-1867, KE-3491, KE-3492, KE-3417, KE-3418, KE-3427, KE-3428, KE-41, KE-42, KE-44, KE-45, KE-441, KE-445, KE-45S, etc.), two-component RTV rubber manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., KE-1800T-A / B, KE-66, KE-1031-A / B, KE-200, KE-118, KE-103, KE-108, KE-119, KE-109E-A / B, KE-1051J-A / B, KE-1012-A / B, KE-106, KE-1282-A / B, KE-1283-A / B, KE-1800-A / B / C, KE-1801-A / B / C, KE-1802-A / B / C, KE-1281-A / B, KE-1204-A / B, KE-1204-AL / BL, KE-1280-A / B, KE-513-A / B, KE-521-A / B, KE-1285-A / B, KE-1861-A / B, KE-12, KE-14, KE-17, KE-113, KE-24, KE-26, KE-1414, KE-1415, KE-1416, KE-1417, KE-1300T, KE-1310ST, KE-1314-2, KE-1316, KE-1600, KE-1603-A / B, KE-1606, KE-1222-A / B, KE-1241, etc.), silicone sealants manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., KE-42AS, KE-420, KE-450, etc.), rubber compounds manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., KE-655-U, KE-675-U, KE-931-U, KE-941-U, KE-951-U, KE-961-U, KE-971-U, KE-981-U,KE-961T-U, KE-971T-U, KE-871C-U, KE-9410-U, KE-9510-U, KE-9610-U, KE-9710-U, KE-742-U, KE-752-U, KE-762-U, KE-772-U, KE-782-U, KE-850-U, KE-870-U, KE-880-U, KE-890-U, KE-9590-U, KE-5590-U, KE-552-U, KE-582-U, KE-552B-U, KE-555-U, KE-575-U, KE-541-U, KE-551-U, KE-561-U, KE-571-U, KE-581-U, KE-520-U, KE-530B-2-U, KE-540B-2-U, KE-1551-U, KE-1571-U, KE-152-U, KE-174-U, KE-3601SB-U, KE-3711-U, KE-3801M-U, KE-5612G-U, KE-5620BL-U, KE-5620W-U, KE-5634-U, KE-7511-U, KE-7611-U, KE-765-U, KE-785-U, KE-7008-U, KE-7005-U, KE-503-U, KE-5042-U, KE-505-U, KE-6801-U, KE-136Y-U, etc.), LIMS (Liquid Silicone Rubber Injection Molding System) manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., KEG-2000-40A / B, KEG-2000-50A / B, KEG-2000-60A / B, KEG-2000-70A / B, KEG-2001-40A / B, KEG-2001-50A / B, KE-1950-10A / B, KE-1950-20A / B, KE-1950-30A / B, KE-1950-35A / B, KE-1950-40A / B, KE-1950-50A / B, KE-1950-60A / B, KE-1950-70A / B, KE-1935A / B, KE-1987A / B, KE-1988A / B, KE-2019-40A / B, KE-2019-50A / B, KE-2019-60A / B, KE-2017-30A / B, KE-2017-40A / B, KE-2017-50A / B, KE-2090-40A / B, KE-2090-50A / B, KE-2090-60A / B, KE-2090-70A / B, KE-2096-40A / B, KE-2096-50A / B, KE-2096-60A / B, etc.),Examples include the LR7665 series manufactured by Wacker Asahi Kasei Silicone Co., Ltd., the LR3033 series manufactured by Wacker Asahi Kasei Silicone Co., Ltd., the TSE3032 series manufactured by Momentive Corporation, and Sylgard 184 manufactured by Dow Corning Toray Co., Ltd.

[0026] <Oil ingredients> As the first oil component, for example, silicone oil, fluorine oil, hydrocarbon oil, polyether oil, ester oil, phosphorus compound oil, mineral oil, etc. can be used. Examples of silicone oils include silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, KF414 series, FL series, KF-6000, KF-6001, KF-6002, KF-6003, etc.), Momentive Silicone oils manufactured by Dow Corning Toray Co., Ltd. (for example, Element14*PDMS series, TSF404 series, TSF410 series, TSF4300 series, TSF431 series, TSF433 series, TSF437 series, TSF4420 series, TSF4421 series, etc.), silicone oils manufactured by Dow Corning Toray Co., Ltd. (for example, BY16-846 series, SF8416 series, SH200 series, SH203 series, SH230 series, SF8419 series, FS1265 series, SH510 series, SH550 series, SH710 series, FZ-2110 series, FZ-2203 series, etc.), silicone oils manufactured by Wacker Asahi Kasei Silicone Co., Ltd. (WACKER® SILICONE FLUID AK series, WACKER® SILICONE FLUID AP series, WACKER® SILICONE FLUID AR series, WACKER® SILICONE FLUID AS series, WACKER (registered trademark) TN series, WACKER (registered trademark) L series, WACKER (registered trademark) AF series, etc.

[0027] On the other hand, as the second oil component, for example, silicone oil, fluorine oil, hydrocarbon-based oil, polyether-based oil, ester-based oil, phosphorus compound-based oil, mineral oil, etc. can be used. Examples of silicone oils include silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, KF414 series, FL series, KF-6000, KF-6001, KF-6002, KF-6003, etc.), and silicone oils manufactured by Momentive Performance Materials Japan, LLC (e.g., Element14*PDMS series, TSF404 series, TSF410 series, TSF4300 series, etc.). , TSF431 series, TSF433 series, TSF437 series, TSF4420 series, TSF4421 series, etc.), silicone oils manufactured by Dow Corning Toray Co., Ltd. (for example, BY16-846 series, SF8416 series, SH200 series, SH203 series, SH230 series, SF8419 series, FS1265 series, SH510 series, SH550 series, SH710 series, FZ-2110 series, FZ-2203 series, etc.), silicone oils manufactured by Wacker Asahi Kasei Silicone Co., Ltd. (WACKER (registered trademark) SILICONE FLUID AK series, WACKER (registered trademark) SILICONE FLUID AP series, WACKER (registered trademark) SILICONE FLUID AR series, WACKER (registered trademark) SILICONE FLUID AS series, WACKER (registered trademark) TN series, WACKER (registered trademark) L series, WACKER (registered trademark) AF series, etc.).

[0028] For the first oil component, the second oil component, and the resin component (first resin precursor) of the oil-containing resin layer 11, a combination that satisfies the following properties 1) and 2) is selected, for example.

[0029] 1) The first oil component and the second oil component are compatible and do not phase separate at temperatures that do not require the second oil component to seep into the oil-containing resin layer 11, for example, at room temperature of about 20°C to 80°C, which is significantly higher than a predetermined value such as the freezing point. However, they phase separate in a temperature environment that requires the second oil component to seep into the oil-containing resin layer 11, for example, below a predetermined value such as the freezing point. 2) The first oil component has affinity for the resin component of the oil-containing resin layer 11 at both temperatures at which it is not necessary to exude the second oil component into the oil-containing resin layer 11 and temperatures at which it is necessary to exude the second oil component into the oil-containing resin layer 11. In contrast, the second oil component, in the presence of the first oil component, changes its behavior depending on whether the temperature is at which it is not necessary to exude the second oil component into the oil-containing resin layer 11 or at which it is necessary to exude the second oil component into the oil-containing resin layer 11. More specifically, in the absence of the first oil component, the second oil component does not have affinity for the resin component of the oil-containing resin layer 11, in other words, it exudes from the resin component of the oil-containing resin layer 11, both at temperatures that do not require the second oil component to exude into the oil-containing resin layer 11 and at temperatures that require the second oil component to exude into the oil-containing resin layer 11. On the other hand, in the presence of the first oil component, the second oil component is compatible with the first oil component at temperatures that do not require the second oil component to exude into the oil-containing resin layer 11, and therefore has affinity for the resin component of the oil-containing resin layer 11, in other words, it does not exude from there. However, at temperatures that require the second oil component to exude into the oil-containing resin layer 11, it phase-separates from the first oil component and has no affinity for the resin component of the oil-containing resin layer 11, in other words, it functions as a low-temperature phase-separable oil component that phase-separates from the first oil component.

[0030] It is empirically known that the value of the solubility parameter serves as a guide for determining the ease of mixing between a solvent and a solute. The relationship between the first oil component, the second oil component, and the resin component of the oil-containing resin layer 11 (first resin precursor) described above can also be explained based on the relationship between their solubility parameter values ​​(SP values). In this specification, the Hansen solubility parameter is used. This value can be determined by performing Fourier transform nuclear magnetic resonance spectroscopy analysis on the first oil component, the second oil component, and the resin component of the oil-containing resin layer 11 to determine the types and molar ratios of the molecular units constituting the molecular structure of each component, and then calculating the weighted average of the Hansen solubility parameters of each molecular unit type based on the molar ratio. The Hansen solubility parameter of each molecular unit type can be determined using the molecular group contribution method using the software "HSPiP, Hansen Solubility Parameters in Practice ver. 4," available from the link (https: / / hansen-solubility.com / ). Specifically, each constituent unit of the target substance is entered in SMILES notation, and the HSP value (δ) for each unit is calculated. d, δ p , δ h ) can be calculated.

[0031] In order to maintain the relationship between 1) and 2) above, it is preferable that the difference between the solubility parameter value of the resin component of the oil-containing resin layer 11 and the solubility parameter value of the first oil component is set to be smaller than the difference between the solubility parameter value of the resin component of the oil-containing resin layer 11 and the solubility parameter value of the second oil component. Also, in order to maintain the relationship between 1) and 2) above, the blending ratios are, for example, based on the weight of the entire oil-containing resin layer to be finally formed, such that the resin component is at least 25 wt% or more, the first oil component is at least 5 wt% or more, and the second oil component is at least 3 wt% or more. Furthermore, the difference in solubility parameter between the first oil component and the resin component of the oil-containing resin layer 11 is 0.6 (J / cm 3 ) 1 / 2 It is preferable to set it within . More specifically, the resin component of the oil-containing resin layer 11 is preferably 30 wt% or more, more preferably 35 wt% or more, and even more preferably 40 wt% or more, based on the weight of the entire oil-containing resin layer to be finally formed. The upper limit is not particularly limited and is set appropriately in relation to the oil component, but can be, for example, 70 wt% or less. The first oil component can be set to, for example, 10 wt% or more, 15 wt% or more, or 20 wt% or more based on the weight of the entire oil-containing resin layer that is finally formed. The upper limit is not particularly limited, but it can be set to preferably 65 wt% or less, for example, 50 wt% or less, 40 wt% or less, 30 wt% or less, or 20 wt% or less. The second oil component is preferably 5 wt% or more, more preferably 10 wt% or more, and even more preferably 15 wt% or more, based on the total weight of the oil-containing resin layer to be finally formed. The upper limit is not particularly limited, but can be set to preferably 62 wt% or less, for example, 60 wt% or less, 50 wt% or less, 40 wt% or less, or 30 wt% or less.

[0032] For example, when the above relationships 1) and 2) are satisfied, the second oil component is compatible with the first oil component at temperatures that do not require the second oil component to exude into the oil-containing resin layer 11, and therefore will not exude from the surface of the oil-containing resin layer 11.On the other hand, when the temperature changes to a temperature that requires the second oil component to exude into the oil-containing resin layer 11, the second oil component can function as a low-temperature exudation oil component that can phase-separate from the first oil component and exude (bleed) from the surface of the oil-containing resin layer 11.

[0033] Furthermore, the wetting parameter "Z" is calculated as the absolute value of the difference between the solubility parameter value (SP value) SP1 of the oil-containing resin layer formed by curing the first resin precursor and the solubility parameter value (SP value) SP2 of the second oil component, and is 1.5 (J / cm 3 ) 1 / 2 It is preferable that: The wetting parameter "Z" is preferably 0.8 (J / cm3 ) 1 / 2 and more preferably 0.5 (J / cm 3 ) 1 / 2 It is particularly preferable that the 3 ) 1 / 2 The lower limit of Z is 0 (J / cm 3 ) 1 / 2 There is no particular limitation as long as the value is higher, but for example, 0.001 (J / cm 3 ) 1 / 2 More preferably, 0.01 (J / cm 3 ) 1 / 2 If Z is within this range, the second oil component that bleeds out into the oil-containing resin layer formed will have high wettability, and even a small amount of oil will bleed out and spread efficiently over the surface of the oil-containing resin layer. This allows the anti-icing effect to be achieved with a smaller amount of oil. The solubility parameter value of the oil-containing resin layer and the solubility parameter value of the second oil component can be calculated by the method described above.

[0034] Furthermore, the solubility parameter contribution value "F" of the oil-containing resin layer formed by curing the first resin precursor is preferably 0.1 or more. It is more preferably 0.2 or more, even more preferably 0.3 or more, and particularly preferably 0.4 or more. The upper limit can be, for example, 3.0 or less, preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.5 or less. The solubility parameter contribution value "F" can be calculated by the method described below. F represents the degree of compatibility of the oil-containing resin layer; the larger the value, the more likely it is to become incompatible. If F is within the above-mentioned range, the contained oil component will easily bleed, thereby achieving a high anti-icing effect.

[0035] Here, an embodiment has been described as an example in which the difference between the solubility parameter value of the resin component of the oil-containing resin layer 11 and the solubility parameter values ​​of the first oil component and the second oil component is set to a predetermined relationship, thereby causing a portion of the oil contained in the oil-containing resin layer 11, particularly the second oil component, to bleed out (bleed), thereby preventing ice and / or snow accumulation, but the scope of the present invention is not limited to these embodiments. For example, compatibility can be similarly controlled by utilizing differences in molecular weight or molecular structure between the first oil component and the second oil component, and the second oil component can be phase-separated from the first oil component and bleed out of the oil-containing resin layer when the temperature drops below a predetermined value.

[0036] As is clear from the above explanation, the first oil component and the second oil component do not need to be physically distinct, but only need to be distinguished from each other in terms of the functions and actions described above. Therefore, the first oil component and the second oil component do not both need to be composed of a single oil component, and as long as the above conditions are met, each of the first oil component and the second oil component may contain multiple oil components.

[0037] (2) Second paint The second coating material contains at least a second resin precursor, which is a precursor of the resin component. Furthermore, like the first coating material, it may contain two types of oil components, i.e., a third oil component and a fourth oil component. After forming an oil-containing resin layer using the first coating material, the second coating material is applied onto the oil-containing resin layer and the second resin precursor is cured. Alternatively, the second resin precursor containing the third and fourth oil components is cured. This allows the formation of a surface resin layer 12 containing at least the resin component and further containing the third and fourth oil components. Here, the third and fourth oil components do not necessarily need to be included in the second coating material; they may be included in the first coating material. Therefore, the use of the third and fourth oil components in the second coating material is optional.

[0038] The surface resin layer 12 that can be formed using the second paint is a solid resin layer that can be provided in a laminated state on one side of the oil-containing resin layer 11 for the purpose of protecting the surface of the oil-containing resin layer 11. The surface resin layer 12 is optionally provided to protect the surface of the oil-containing resin layer 11, and therefore the use of the second paint is optional. Because the surface resin layer 12 is disposed on the surface of the oil-containing resin layer 11, the surface resin layer 12 has oil permeability that allows the second oil component that has exuded from the oil-containing resin layer 11 to permeate to the surface of the surface resin layer 12 on the opposite side from the oil-containing resin layer 11, even when covering the oil-containing resin layer 11, so that the anti-icing and / or anti-snowing function of the second oil component accumulated in the oil-containing resin layer 11 is not hindered.

[0039] 2 shows a layer configuration including a surface resin layer 12 formed by applying and curing a second coating material on the oil-containing resin layer 11, together with a structure 10. The structure 10 is placed on the other side of the oil-containing resin layer 11, opposite to the side on which the surface resin layer 12 is laminated.

[0040] Although not particularly limited, the second resin precursor can be made of the same material as the first resin precursor of the first paint, the third oil component can be made of the same material as the first oil component of the first paint, and the fourth oil component can be made of the same material as the second oil component of the first paint.

[0041] The third oil component, the fourth oil component, and the resin component (second resin precursor) of the surface resin layer 12, like the first oil component, the second oil component, and the resin component (first resin precursor) of the oil-containing resin layer 11 of the first coating material, have the properties 1) and 2) above. Therefore, like the first coating material, the blending ratios, based on the total weight of the surface resin layer to be finally formed, are at least 25 wt% of the resin component, at least 5 wt% of the third oil component, and at least 3 wt% of the fourth oil component. Other preferred values ​​are also the same as those for the first oil component of the first coating material. However, since the surface resin layer 12 is provided for the purpose of protecting the surface of the oil-containing resin layer 11, it is preferable that it have higher abrasion resistance than the oil-containing resin layer 11. In this case, in order to improve abrasion resistance compared to the oil-containing resin layer 11, the proportion of the second resin precursor in the second coating material is set to a value significantly greater than the proportion of the first resin precursor in the first coating material. For example, it is preferable that the resin component is 30 wt% or more, the third oil component is 20 wt%, and the fourth oil component is 10 wt%, based on the weight of the entire surface resin layer that is finally formed.

[0042] (3) Film The first paint, or the first paint and the second paint, may be cured in advance in a state where a thin film of, for example, 10 to 1000 μm is formed, to form a film. In this case, the film can be attached to various structures, etc., instead of applying a paint. The film, like the paint, has an oil-containing resin layer containing first and second oil components. The second oil component functions as a low-temperature phase-separable oil component that phase-separates from the first oil component and exudes from the oil-containing resin layer when the temperature drops below a predetermined value. As the resin component constituting the oil-containing resin layer, for example, a resin obtained by crosslinking the first resin precursor described in "<First Resin Precursor>" can be suitably used, and a crosslinked silicone resin is preferred. The first and second oil components can be the "<Oil Component>" described above. The blending ratio of each component is also designed in the same manner as above. In this way, a film can be provided using the first paint and the second paint.

[0043] 2. Examples Hereinafter, the present invention will be explained in more detail with reference to examples of the first coating material for forming the oil-containing resin layer, but the present invention is not limited to the following examples in any way.

[0044] [Example 1] The first paint was prepared in the following manner. 1) First resin precursor The first resin precursor was dimethylpolysiloxane rubber (Sylgard 184 manufactured by Dow Corning Toray Co., Ltd.), which hardens when heated (see Table 3 below).

[0045] 2) Oil ingredients Dimethylsiloxane oil (product number KF-96-100CS manufactured by Shin-Etsu Silicones Co., Ltd.) was used as the first oil component, and methylphenylsiloxane oil (TSF437 manufactured by Momentive Corporation) was used as the second oil component (see also Table 3 below).

[0046] 3) Mixing The first resin precursor (1) and the first and second oil components (2) were mixed at 25°C and 101 kPa, and the mixture was stirred with a spatula at approximately 120 rpm for 60 seconds. It was then stirred for an additional 60 seconds and degassed for 60 seconds using a planetary centrifugal mixer (Thinky Corporation, Conditioning Mixer AR-250), yielding a first coating material. The blending ratios, based on the total weight of the oil-containing resin layer that would ultimately be formed, were 60 wt% resin component, 23 wt% first oil component, and 17 wt% second oil component.

[0047] The first coating material obtained by the above method was applied to a PET film (Lumirror S10#125 manufactured by Toray Industries, Inc.) and cured by heating in a 100°C environment for 3 hours to form an oil-containing resin layer with a thickness of approximately 140 μm. The oil-containing resin layer was evaluated as follows. The solubility parameter of the first oil component, dimethylsiloxane oil, was 11.7 (J / cm 3 ) 1 / 2 The solubility parameter of the second oil component, methylphenylsiloxane oil, was 13.9 (J / cm 3 ) 1 / 2 Furthermore, the solubility parameter of the dimethylpolysiloxane rubber used as the resin component formed by curing the first resin precursor was 11.9 (J / cm 3 ) 1 / 2 is.

[0048] 5) Evaluation <Layer thickness> The layer thickness was measured using a film thickness meter MFC-101 (manufactured by Nikon). Although not particularly limited, when a surface resin layer is provided, the thickness of the surface resin layer is preferably 75% or less of the oil-containing resin layer, more preferably 50% or less, and even more preferably 35% or less, so that oil can easily penetrate to the surface of the surface resin layer, in other words, to ensure oil permeability to the surface resin layer. Furthermore, although it depends on the resin component of the surface resin layer, from the viewpoint of strength, the thickness is preferably 5% or more of the oil-containing resin layer, more preferably 20% or more, and even more preferably 30% or more.

[0049] <Phase separation and compatibility, etc.> The following were evaluated: a) phase separation and compatibility between the "first oil component" and the "second oil component" in response to temperature changes, b) affinity between the "first oil component" and the "resin component of the oil-containing resin layer" in response to temperature changes, and c) affinity between the "second oil component" and the "resin component of the oil-containing resin layer" in response to temperature changes. However, the direct objects of analysis were the mixture of the "first oil component" and the "second oil component" extracted from the oil-containing resin layer, and the oil component that bled from the surface of the oil-containing resin layer. To evaluate the above item a), the oil-containing resin layer was first immersed in toluene (Fujifilm Wako Pure Chemical Industries, Ltd.) at 20°C for 24 hours to extract the first and second oil components as a mixture. The first and second oil components were separated from the mixture using liquid chromatography. The extracted mixture of the first and second oil components was measured for transmittance at 20°C and 500 nm and transmittance at 3°C ​​and 500 nm, respectively, and the difference between these transmittances was used to determine whether the mixture was "phase-separated (not miscible)" or "miscible (not phase-separated)" based on the percentage of the transmittance at 20°C and 500 nm. More specifically, a difference of 10% or more was evaluated as "phase-separated (not miscible) in response to temperature change," and a difference of less than 10% was evaluated as "miscible (not phase-separated) in response to temperature change." The transmittance was measured using an ultraviolet-visible spectrophotometer (JASCO Corporation, V-750) with a measurement wavelength of 500 nm, a scan speed of 1000 nm / min, and a stirring speed of 400 rpm. The sample was set to 20°C or 3°C, and then allowed to stand for 10 minutes before measurement. Air was used as the reference. The evaluation criteria are as follows: ○ 10% or more × Less than 10% Regarding the above b) and c), the oil-containing resin layer was prepared by adding only each oil component to the oil-containing resin layer from which the oil component had been extracted. The oil-containing resin layer was then placed in an environment of 20°C and an environment of 3°C, and the evaluation was carried out based on whether or not the first oil component or the second oil component bleeds from the surface of the oil-containing resin layer. The evaluation criteria are as follows: ○ Bleeding was performed at both 20℃ and 3℃. × No bleeding occurred at either 20°C or 3°C

[0050] <Surface oil amount> The amount of oil bled onto the surface of the oil-containing resin layer was measured at 20°C, the freezing point (0°C), and -20°C. During the measurement, it was confirmed that the bled oil was mainly the second oil component. Figure 3 shows an example of an optical microscope image of the oil bled onto the surface of the oil-containing resin layer. The amount of surface oil is measured by the following method. The oil-containing resin layer was cut near the center to a size of 10 cm x 2 cm and left for 16 hours at temperatures of 20°C, 0°C, and -20°C. The oil that bled onto the surface of the oil-containing resin layer was then collected using a cell scraper (Kenis, CSS-10) at temperatures of 20°C, 0°C, and -20°C, and the oil was then absorbed until no change in the weight (oil absorption) of the oil blotting paper was observed. The oil collection with the cell scraper and blotting with the oil blotting paper were repeated seven times per minute. The difference in weight of the oil blotting paper before and after blotting was taken as the surface oil amount. The test was performed three times, and the average value was calculated. The evaluation criteria are as follows: ◎ 300μg / cm 2 End ○ 40μg / cm 2 More than 300μg / cm 2 less than × 40μg / cm 2 less than To prevent unnecessary bleeding, the surface oil amount is 40 μg / cm at 20°C. 2It is preferable that the concentration is less than 40 μg / cm at 0°C and -20°C to prevent snow and ice buildup. 2 It is preferably 300 μg / cm or more. 2 However, it is more preferable that the concentration is 40 μg / cm at 20°C or more. 2 Even if it is more than 40 μg / cm at 0 °C and -20 °C 2 The following may still be usable:

[0051] <Wear resistance> The abrasion resistance of the oil-containing resin layer was evaluated. A Gakushin-type abrasion tester (model number: RT-300S, Daiei Scientific Instruments Manufacturing Co., Ltd.) was used as the measuring device. Figure 4 shows a schematic diagram of the tester. The tester 2 comprises a test stand 21, a support plate 22 fixed to the test stand 21 by screws 22a or the like, and a friction element 25 (size: 2 cm x 2 cm) located above the support plate 22 and below a cantilever-shaped load arm 24 to which a weight 23 is applied. Using this tester 2, a test piece 32 was attached to the support plate 22 via an adhesive 31 (manufactured by Nitto Denko Corporation, No. 5000NS). The oil-containing resin layer of the test piece 32, particularly a 20 mm x 120 mm area thereof, was subjected to abrasion with a water-resistant abrasive 34 with a grit size of #120 attached via the adhesive 31 to the underside of the friction element 25. The abrasion was applied to the oil-containing resin layer of the test piece 32 via the adhesive 31. The abrasion was applied to the oil-containing resin layer of the test piece 32 via the adhesive 31 to a 20 mm x 120 mm area of ​​the oil-containing resin layer. The abrasion was applied to the oil-containing resin layer of the test piece 32 via the adhesive 31. The abrasion was applied to the oil-containing resin layer of the test piece 32 at a pressure of 125 g / cm2 adjusted by the weight 23 and the load arm 24. 2 The reduction rate of the oil-containing resin layer was determined when the sample was reciprocated 30 times under a pressing force of 100 mm / s at a speed of 100 mm / s. The room temperature was set at 20°C. The evaluation criteria are as follows: ◎ Less than 50% ○ 50% or more but less than 80% × 80% or more The abrasion resistance is preferably less than 80%, more preferably less than 50%, and even more preferably less than 35%, although there are cases where it is usable even if it is 80% or more.

[0052] <Icing power> The object of measurement is the force required to move ice blocks that have adhered to an oil-containing resin layer in an environment of -20°C, and for convenience, the magnitude of this force is defined in this specification as the "icing force." The ice adhesion force is measured by the following method. 1. First, a cylindrical ice block is created by placing a stainless steel ring (inner diameter 25 mm) on the bottom of a 16-inch square polystyrene case (manufactured by AS ONE), pouring 6 g of pure water into it, and freezing it at -20°C for at least 16 hours. After freezing, the stainless steel ring is removed. 2. Next, the film was left to stand in a -20°C environment for 16 hours, and then attached to a stainless steel plate placed parallel to the floor, with the oil-containing resin layer facing outwards. 2 The cylindrical ice block was frozen. 3. The ambient temperature was set to -20°C, and after 3 hours of freezing the cylindrical ice block, the ice block was pressed parallel to the floor surface with a load cell (IMADA Corporation DPU-50, attachment jig A-4) at a speed of 0.1 mm / s in a -20°C environment. The load applied over a 40-second period was measured with a force gauge (IMADA Corporation ZTS-50N). The maximum load measured was measured at an adhesion area of ​​4.9 cm. 2 The value obtained by dividing by this was recorded as the ice adhesion force. The test was performed three times and the average value was calculated. This measurement method was determined with reference to "Research on Snow and Ice Accretion Prevention Technology (First Report), Hokkaido Prefectural Industrial Research Institute Report No. 292 (1993)." At least at -20°C, the ice adhesion force increases approximately proportionally in response to an increase in the amount of surface oil. The evaluation criteria are as follows: ◎ 0.1N / cm 2 less than ○ 0.1N / cm 2 More than 1.0N / cm 2 less than × 1.0N / cm 2 End The smaller the value of the ice adhesion force, the better, but 1.0N / cm 2 If it is less than 1.0N / cm, it is considered sufficient for practical use.2 Even if it is more than this, it may still be usable.

[0053] [Examples 2 to 6 and Reference Examples 1 to 6] The procedure was the same as in Example 1, except that the blending ratio of the resin component, the first oil component, and the second oil component was changed when preparing the first paint.

[0054] [Example 7] The procedure was the same as in Example 1, except that the first paint was prepared in the following manner. 1) First resin precursor The same first resin precursor as in Example 1 was used.

[0055] 2) Oil ingredients Dimethylsiloxane oil (product number KF-96-50CS manufactured by Shin-Etsu Silicones Co., Ltd.) was used as the first oil component, and carbinol silicone oil (product number KF-6001 manufactured by Shin-Etsu Silicones Co., Ltd.) was used as the second oil component.

[0056] 3) Mixing The first coating material was obtained by mixing the first resin precursor (1) with the first and second oil components (2). The blending ratios, based on the total weight of the oil-containing resin layer to be finally formed, were 60 wt% for the resin component, 28 wt% for the first oil component, and 12 wt% for the second oil component. Here, the solubility parameter value of the dimethylsiloxane oil, which is the first oil component, is 11.7, the solubility parameter value of the carbinol-modified silicone oil, which is the second oil component, is 12.2, and furthermore, the solubility parameter value of the dimethylpolysiloxane rubber, which is the resin component formed by curing the above-mentioned first resin precursor, is 11.9 (J / cm 3 ) 1 / 2 is.

[0057] [Comparative Example 1] The first coating material was the same as in Example 1, except that it contained only the first resin precursor and did not contain any oil component.

[0058] Comparative Example 2 The procedure was the same as in Example 1, except that the first paint was prepared in the following manner. 1) First resin precursor The same first resin precursor as in Example 1 was used.

[0059] 2) Oil ingredients As the first oil component, methylphenylsiloxane oil (product number AR-20 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) was used, and as the second oil component, methylphenylsiloxane oil (TSF437 manufactured by Momentive Corporation) with an SP value different from that of the first oil component was used.

[0060] 3) Mixing A first coating material was obtained by mixing the first resin precursor (1) and the first and second oil components (2) in the same manner as in Example 1. The blending ratios, based on the total weight of the oil-containing resin layer to be finally formed, were 25 wt% resin component, 56 wt% first oil component, and 19 wt% second oil component. The first coating material obtained by the above method was cured in the same manner as in Example 1 to form an oil-containing resin layer with a thickness of approximately 140 μm, and the oil-containing resin layer was evaluated as follows. Here, the solubility parameter value of the first oil component, methylphenylsiloxane oil, was 12.7 (J / cm 3 ) 1 / 2 The solubility parameter of the second oil component, methylphenylsiloxane oil, was 13.9 (J / cm 3 ) 1 / 2 Furthermore, the solubility parameter of the dimethylpolysiloxane rubber used as the resin component formed by curing the first resin precursor described above is 11.9 (J / cm 3 ) 1 / 2 is.

[0061] The evaluation results are shown in Table 1 below. Regarding the evaluation of "phase separation and compatibility (change in transmittance, etc.)" in the table, the notation "first oil / second oil" indicates the evaluation results of the phase separation and compatibility between the "first oil component" and the "second oil component," corresponding to the above-mentioned a), the notation "first oil / resin" indicates the evaluation results of the affinity between the "first oil component" and the "resin component of the oil-containing resin layer," corresponding to the above-mentioned b), and the notation "second oil / resin" indicates the evaluation results of the affinity between the "second oil component" and the "resin component of the oil-containing resin layer," corresponding to the above-mentioned c).

[0062] [Table 1]

[0063] Regarding the solubility parameter, which is a measure of the ease of mixing of a solvent and a solute, in Examples 1 to 6 and Reference Examples 1 to 6, the difference between the solubility parameter value of the resin component of the oil-containing resin layer and the solubility parameter value of the first oil component, i.e., |11.9-11.7|=0.2 (J / cm 3 ) 1 / 2 is the difference between the solubility parameter of the resin component of the oil-containing resin layer and the solubility parameter of the second oil component, i.e., |11.9-13.9| = 2.0 (J / cm 3 ) 1 / 2 The difference in solubility parameter between the first oil component and the resin component of the oil-containing resin layer 11, i.e., |11.7-11.9|=0.2 (J / cm 3 ) 1 / 2 is 0.6(J / cm 3 ) 1 / 2 It is set within. Similarly, in Example 7, the difference between the solubility parameter value of the resin component of the oil-containing resin layer and the solubility parameter value of the first oil component, i.e., |11.9-11.7|=0.2 (J / cm 3 ) 1 / 2 is the difference between the solubility parameter of the resin component of the oil-containing resin layer and the solubility parameter of the second oil component, i.e., |11.9-12.2| = 0.3 (J / cm 3 ) 1 / 2The difference in solubility parameter between the first oil component and the resin component of the oil-containing resin layer 11, i.e., |11.7-11.9|=0.2 (J / cm 3 ) 1 / 2 is 0.6 (J / cm 3 ) 1 / 2 It is set within. On the other hand, in Comparative Example 2, the difference between the solubility parameter value of the resin component of the oil-containing resin layer and the solubility parameter value of the first oil component, i.e., |11.9-12.7|=0.8 (J / cm 3 ) 1 / 2 is the difference between the solubility parameter of the resin component of the oil-containing resin layer and the solubility parameter of the second oil component, i.e., |11.9-13.9| = 2.0 (J / cm 3 ) 1 / 2 The difference in solubility parameter between the first oil component and the resin component of the oil-containing resin layer 11, i.e., |12.7-11.9|=0.8 (J / cm 3 ) 1 / 2 is 0.6 (J / cm 3 ) 1 / 2 It has a larger value.

[0064] Regarding phase separation and compatibility, the transmittance of the mixture of the first oil component and the second oil component changed significantly when the temperature was changed from 20°C to 3°C, which clearly indicates that the first oil component and the second oil component were phase separated. Since the first oil component did not substantially bleed onto the surface of the oil-containing resin layer at both 20°C and 3°C, it can be said that it has affinity for the resin component of the oil-containing resin layer. On the other hand, the second oil component bled from the surface of the oil-containing resin layer when the oil-containing resin layer was placed in a 20°C environment, but did not substantially bleed when placed in a 3°C environment. This behavior corresponds to the phase separation between the first oil component and the second oil component, and it can be seen that the behavior of the second oil component changed in response to temperature changes in the presence of the first oil component. Furthermore, the second oil component has affinity for the resin component of the surface resin layer at a 20°C environment, but does not have affinity for the resin component of the surface resin layer at a 3°C environment. This behavior is also evident from the results of the surface oil amount.

[0065] In the example, the surface oil amount and ice adhesion force do not reach significant values ​​at room temperature, for example, 20°C, and only when the temperature drops below a predetermined value, for example, the surface oil amount at -20°C is 40 μg / cm 2 As a result, the ice adhesion force was less than 1.0. Furthermore, since the oil component that bled from the oil-containing resin layer 11 was mainly the second oil component among the oil components contained in the oil-containing resin layer, this configuration prevents excessive bleeding of the oil component as in the past, and allows the second oil component to be used to prevent adhesion of ice and snow, for example. From the above, it can be seen that the second oil component functions as a low-temperature exudation oil component that can bleed (exude) from the surface of the oil-containing resin layer on the surface resin layer side in a temperature environment below a predetermined value.

[0066] In Comparative Example 2, in which the first oil component and the second oil component do not phase separate even at low temperatures, the oil component can bleed (exude) from the surface of the oil-containing resin layer on the surface resin layer side under temperature environments below a predetermined value. However, because the first oil component and the second oil component do not phase separate even at low temperatures, a large amount of oil component must be added to cause bleeding. As a result, the abrasion resistance is 100%, and the strength of the oil-containing resin layer cannot be increased. On the other hand, in the oil-containing resin layer produced from the paint of this example, the first oil component and the second oil component phase separate at low temperatures, so even a relatively small amount of oil component can bleed from the surface of the oil-containing resin layer. This allows the resin component content to be increased, resulting in a strong oil-containing resin layer.

[0067] As shown in Example 7, when carbinol-modified silicone oil was used as the second oil component, the ice adhesion force was significantly reduced, which is presumably due to improved wettability to the oil-containing resin layer compared to when phenyl-modified silicone oil was used as the second oil component.

[0068] Furthermore, the temperature at which the second oil component phase separates from the first oil component, in other words, the temperature at which it bleeds from the surface resin layer, can be adjusted by appropriately selecting the first oil component and the second oil component, so the second oil component can function as a low-temperature exudation oil component at various temperatures, for example, at or below freezing point or above freezing point.

[0069] [Examples 8 to 20, Comparative Example 3] The first paint was prepared in the same manner as in Example 1, except that the types and blending ratios of the resin component, the first oil component, and the second oil component were changed as shown in Table 2. Specifically, in all of Examples 8 to 20 and Comparative Example 3, the resin component used was "dimethylpolysiloxane rubber KE-1935" (product name "KE-1935" manufactured by Shin-Etsu Silicones Co., Ltd.), and the first oil component used was "dimethylsiloxane KF-96 50CS" (product name "KF-96 50CS" manufactured by Shin-Etsu Silicones Co., Ltd.). Regarding the second oil component, In Examples 8 to 11, "long-chain alkyl-modified siloxane oil KF-4917" (trade name "KF-4917" manufactured by Shin-Etsu Silicone Co., Ltd.) was used. In Examples 12, 13, and 17, "epoxy-modified siloxane oil X-22-163" (product name "X-22-163" manufactured by Shin-Etsu Silicone Co., Ltd.) was used. In Examples 14, 15, 19, and 20, "Carbinol-modified oil KF-6001" (trade name "KF-6001" manufactured by Shin-Etsu Silicone Co., Ltd.) was used. In Examples 16 and 18 and Comparative Example 3, "methylphenylsiloxane oil TSF437" (trade name "TSF437" manufactured by Momentive Corporation) was used. Each was used. The evaluation results are shown in Table 2 below.

[0070] [Table 2]

[0071] The examples were further evaluated for the following items. <Solubility parameter contribution value> The solubility parameter contribution value "F" was calculated by the following formula: F=f×φ×100 Here, f is the "solubility parameter contribution value" (f d1 , f p1 , f h1 ) and "the difference between the solubility parameter of the compatible molecular unit is 0.01 (J / cm 3 ) 1 / 2The "solubility parameter contribution value" (f d2 , f p2 , f h2 ) can be calculated using the following formula: f= ((f d1 -f d2 ) 2 +(f p1 -f p2 ) 2 +(f h1 -f h2 ) 2 ) 0.5 In addition, when there are multiple immiscible molecular units, the contribution values ​​of each are averaged to determine the above f. Also, the contribution value f of the solubility parameter d , f p , f h can be calculated using the following formulas: f d =δ d / (δ d +δ p +δ h ) f p =δ p / (δ d +δ p +δ h ) f h =δ h / (δ h +δ p +δ h ) Furthermore, φ means the weight fraction of the incompatible component, and can be calculated by the following formula. φ = (1 - gel fraction) × weight ratio of immiscible molecular units contained in the oil component The gel fraction can be determined by the following procedure. 1. Cut the oil-containing resin layer into a 2.0 cm x 4.5 cm piece and measure its weight. 2. The oil-containing resin layer is placed in a vial filled with 20 g of toluene and immersed in the toluene at room temperature for 24 hours. 3. The oil-containing resin layer is removed and heated and dried in a blower dryer at 150°C for 2 hours, after which the weight of the residue is measured. 4. Calculate the gel fraction using the formula below. Gel fraction = weight of residue after heat drying (g) / weight of oil-containing resin layer before heat drying (g) The "weight ratio of the immiscible molecular units contained in the oil component" can be calculated by NMR measurement of all oil components, including both the first oil component and the second oil component, contained in the oil-containing resin layer. All oil components, including both the first oil component and the second oil component, can be obtained by the following procedure. 1. Cut the oil-containing resin layer into a piece of 2.0 x 4.5 cm, place it in a vial filled with 20 g of toluene, and immerse it in toluene at room temperature for 24 hours. 2. The oil-containing resin layer is removed from the vial and dried in a fan dryer at 150°C for 12 hours to obtain a residue, which contains all of the oil components, including both the first oil component and the second oil component.

[0072] <Wetting parameters> The wetting parameter "Z" can be determined by the absolute value of the difference between the solubility parameter of the oil-containing resin layer formed by curing the first resin precursor and the solubility parameter of the second oil component. The solubility parameter of the oil-containing resin layer is calculated as a weighted average based on the weight fractions of the solubility parameters of the resin component, the first oil component, and the second oil component.

[0073] <UV resistance> The UV resistance of the oil-containing resin layer was evaluated as follows. The test equipment used was a Super Xenon Weather Meter (Model: SX75, Suga Test Instruments Co., Ltd.). A test piece film (size: 55mm x 130mm) cut to the size of the sample holder was placed in the tester and irradiated with ultraviolet light (wavelength: 300nm - 400nm). The test method was based on JIS D0205 Weather Resistance Test Method for Automotive Parts, and the annual average radiation exposure of ultraviolet light (wavelength: 300nm - 400nm) was set at 306kW / m 2The test specimen film was irradiated with this amount of radiation exposure. The test environment temperature was set to simulate summer, with the tester's internal temperature at 30°C, the test specimen back temperature at 55°C, humidity at 55% RH, and a rotation speed of 1 rotation / min. The first and second oil components remaining in the test piece film after UV irradiation were extracted, and the reduction rate of the second oil component before and after UV irradiation was calculated from the change in the ratio of the first and second oil components. It has been confirmed that the first oil component does not decrease due to UV irradiation. The method for extracting the first oil and the second oil in the film and the method for calculating the reduction rate of the second oil are as follows. 1. Cut the film into 20mm x 40mm pieces and place them in a screw cap vial. 2. Place approximately 30 g of chloroform in a screw cap vial and seal it. 3. Vibrate the film at 100 rpm for 15 hours using a shaker (Double Action Lab Shaker SRR-2, AS ONE Corporation) to extract any remaining oil from the film. 4. Remove any solids remaining in the screw cap bottle. 5. The chloroform containing the extracted oil is dried in a dryer at 100°C for 2 hours to obtain a mixture of the first and second oils. 6. Approximately 3 mg of the resulting mixture of the first oil and second oil and approximately 700 mg of deuterated chloroform are placed in a vial to create a mixed solution. 7. Transfer the mixture to an NMR sample tube. 8. 1H NMR was measured using an NMR (model number: ULTRASHIELD 300, manufactured by BRUKER) and assigned based on the molecular structure of each second component oil. 9. The reduction rate of the second component oil caused by UV irradiation is calculated from the change in the number of H atoms in Si-CH3 before and after UV irradiation. The evaluation criteria are as follows: 1. Second component oil reduction rate: Less than 10% 2. Second component oil reduction rate: 10-30% or less 3. Second component oil reduction rate: 30-50% or less

[0074] <Water resistance> The water resistance of the oil-containing resin layer was evaluated as follows. A rainfall tester (manufactured by Nishiyama Manufacturing Co., Ltd.) was used as the test equipment. A test film (size: 150mm x 150mm) was placed inside, and an amount of rain equivalent to the annual amount of precipitation was allowed to fall from above the film. The annual amount of precipitation was set to 1600mm based on data from the Japan Meteorological Agency. The test environment temperature was set to 5°C inside the tester, simulating a rainy winter day, with the precipitation temperature at 5°C and the rainfall rate at approximately 500mm / h. The first and second oil components remaining in the test piece film after the water resistance test were extracted, and the reduction rate of the second oil component before and after the water resistance test was calculated from the change in the ratio of the first and second oil components. It has been confirmed that the first oil component does not decrease during the water resistance test. The method for extracting the first oil and the second oil from the film, the method for calculating the reduction rate of the second oil, and the evaluation criteria were the same as those in the previous section, <UV resistance>. The evaluation results are shown in the following Table 3. For convenience, Table 3 also lists the composition of the oil-containing resin layer, that is, the resin component, the first oil component, and the second oil component.

[0075] [Table 3] TIFF0007733867000004.tif239145 TIFF0007733867000005.tif155161

[0076] <Icing force 0.15N / cm 2 The amount of oil required is By changing the ratio of the first oil component to the second oil component while maintaining the resin component at a predetermined blend ratio (wt%), the ice adhesion force can be increased to 0.15 N / cm. 2 The results are shown in Table 4 below. As with Table 3, Table 4 also lists the composition of the oil-containing resin layer, i.e., the resin component, the first oil component, and the second oil component.

[0077] [Table 4]

[0078] As is clear from the above results, when long-chain alkyl-modified siloxane oil or carbinol-modified silicone oil was used as the second oil component, the 2 It was found that even a small amount of oil exhibited low ice adhesion, i.e., high snow and ice prevention.

[0079] As described above, the present invention provides products that can prevent ice and / or snow accumulation, particularly paints and films that can be used in a more flexible manner than sheets and the like that have a fixed shape from the beginning of use.

[0080] It should be understood that the foregoing description is of preferred embodiments and is merely representative of the article. It can be appreciated that variations and modifications of different embodiments will be readily apparent to those skilled in the art in light of the above teachings. Accordingly, exemplary embodiments, as well as alternative embodiments, can be made without departing from the spirit of the article as set forth in the appended claims. [Explanation of symbols]

[0081] 10 Structures 11 Oil-containing resin layer 12 Surface resin layer

Claims

1. A first oil component; A second oil component; a first resin precursor that is a precursor of a resin component; Including, the first oil component is a silicone oil, the second oil component is a long-chain alkyl-modified silicone oil, an epoxy-modified siloxane oil, or a carbinol-modified silicone oil, the first resin precursor is a silicone resin, A coating material that forms an oil-containing resin layer containing the first and second oil components and the resin component by curing the first resin precursor containing the first and second oil components, The second oil component constitutes a low-temperature phase-separable oil component that can phase-separate from the first oil component and exude from the oil-containing resin layer when the temperature drops below a predetermined value. A paint characterized by:

2. 2. The paint according to claim 1, wherein the first resin precursor is a moisture-curing type that is cured by moisture.

3. 2. The paint according to claim 1, wherein the first resin precursor is an ultraviolet curable type that is cured by irradiation with ultraviolet light.

4. 2. The paint according to claim 1, wherein the first resin precursor is a thermosetting type that is cured by heating.

5. 2. The paint according to claim 1, wherein the first resin precursor is cured by adding a curing agent that undergoes a crosslinking reaction with the first resin precursor.

6. A combination of the coating material according to claim 5 and a liquid curing agent that undergoes a crosslinking reaction with the first resin precursor of the coating material, thereby curing the first resin precursor.

7. The paint according to any one of claims 1 to 5, A paint characterized in that the resin component of the oil-containing resin layer is contained in an amount of 25 wt % or more based on the weight of the entire oil-containing resin layer.

8. The paint according to claim 7, A paint comprising the second oil component in a proportion of 3 wt % or more based on the weight of the entire oil-containing resin layer.

9. The paint according to any one of claims 1 to 5, 7 and 8, wherein the amount of surface oil at -20°C is 40 μg / cm 2 A paint characterized by the above.

10. 10. The paint according to any one of claims 1 to 5 and claims 7 to 9, wherein the difference in solubility parameter between the first oil component and the resin component of the oil-containing resin layer is 0.6 (J / cm 3 ) within 1 / 2.

11. 11. The paint according to claim 1, wherein the predetermined value is a freezing point.

12. The paint according to any one of claims 1 to 5 and claims 7 to 9, A wetting parameter of 1.5 (J / cm), which is calculated as the absolute value of the difference between the solubility parameter value (SP value) of the oil-containing resin layer formed by curing the first resin precursor and the solubility parameter value (SP value) of the second oil component, is obtained. 3 ) 1 / 2 or less.

13. The paint according to any one of claims 1 to 5 and claims 7 to 9, A coating material, characterized in that the oil-containing resin layer formed by curing the first resin precursor has a solubility parameter contribution value of 0.1 or more.

14. A film having an oil-containing resin layer containing first and second oil components, the first oil component is a silicone oil, the second oil component is a long-chain alkyl-modified silicone oil, an epoxy-modified siloxane oil, or a carbinol-modified silicone oil, the resin component of the oil-containing resin layer is a silicone resin, The second oil component constitutes a low-temperature phase-separable oil component that can phase-separate from the first oil component and exude from the oil-containing resin layer when the temperature drops below a predetermined value. A film characterized by:

15. 15. The film of claim 14, A film characterized in that the resin component of the oil-containing resin layer is contained in an amount of 25 wt % or more based on the weight of the entire oil-containing resin layer.

16. The paint according to claim 15, A film comprising the second oil component in an amount of 3 wt % or more based on the total weight of the oil-containing resin layer.

17. 17. A film according to any one of claims 14 to 16, A surface resin layer is further provided on the oil-containing resin layer, The surface resin layer has oil permeability that allows a low-temperature phase-separable oil component that has seeped out from the oil-containing resin layer to penetrate to the surface of the surface resin layer on the opposite side from the oil-containing resin layer.

18. 18. The film according to claim 17, wherein the surface resin layer has higher abrasion resistance than the oil-containing resin layer.

19. The paint according to any one of claims 14 to 18, wherein the amount of surface oil at -20°C is 40 μg / cm 2 A film characterized by the above.

20. 20. The film according to claim 14, wherein the difference in solubility parameter between the first oil component and the resin component of the oil-containing resin layer is 0.6 (J / cm 3 ) 1 / 2 or less.

21. 21. The film of any one of claims 14 to 20, wherein the predetermined value is a freezing point.

22. 22. The film of any one of claims 14 to 21, The wetting parameter, which is calculated as the absolute value of the difference between the solubility parameter value (SP value) of the oil-containing resin layer and the solubility parameter value (SP value) of the second oil component, is 1.5 (J / cm 3 ) 1 / 2 or less.

23. 23. The film of any one of claims 14 to 22, A film characterized in that the solubility parameter contribution value of the oil-containing resin layer is 0.1 or more.

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