Paints and Laminates

Abstract

The present invention relates to a coating material comprising a resin component, a first oil component, and a second oil component. When the temperature drops to a predetermined value or lower, the second oil component has the ability to be exuded from a coated film layer obtained by coating and then curing or drying the coating material. The first oil component satisfies at least one condition among (1) having a kinematic viscosity of 300 cSt or higher at 25°C, and (2) having a viscosity of 0.1 Pa·s or higher at 20°C.

Description

[Technical Field]

[0001] The present invention relates to a paint, and more particularly to a paint used to prevent snow and ice from adhering to the surfaces of objects such as solar panels, aircraft, trains, automobiles, wind power generators, houses, traffic lights, signs, etc. The present invention also relates to a laminate formed using the paint. [Background technology]

[0002] The adhesion of ice to the surface of objects (icing) and the adhesion of snowflakes due to snowfall (snow accretion) are the cause of many damages and obstacles in various fields. For example, icing on aircraft wings, snow and ice on the underside of locomotives, snow on automobile headlights, icing on the blades of solar panels and wind turbines, and snow and ice on traffic lights can impede the operation, driving, and safety of these systems. Furthermore, snow and ice accumulation on residential roofs, signs, etc. can cause damage to these structures and injury to people due to falling snow.

[0003] Conventionally, in various industrial fields, various oil-containing paints have been developed as a measure to prevent snow and ice from adhering to the surfaces of objects.

[0004] For example, Patent Document 1 discloses a water-repellent coating paint that contains one or more mixed powders of fluororesin powder or inorganic fine powders whose surfaces have been subjected to hydrophobic treatment, a silicone resin binder, and one or more mixed oils selected from silicone oil and fluorosilicone oil. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2000-026844 Summary of the Invention [Problem to be solved by the invention]

[0006] However, according to the inventors' investigations, conventional paints such as those disclosed in Patent Document 1 have a problem in that a large amount of oil (hereinafter sometimes referred to as "initial bleed oil amount") bleeds from the coating layer obtained from the paint within a certain period of time (for example, within 20 hours), making it impossible to maintain the anti-icing and / or anti-snowing function of the coating layer for a long period of time.

[0007] The present invention has been made in consideration of the above-mentioned conventional situation, and aims to solve the problem of providing a paint that can suppress the amount of initial oil bleeding and can provide a coating layer that can maintain its anti-icing and / or anti-snowing function for a long period of time. [Means for solving the problem]

[0008] As a result of extensive research into solving the above problems, the present inventors focused on the kinematic viscosity of oil components and completed the present invention.

[0009] That is, the present invention provides the following <1> ~ <4> It is related to. <1> A paint containing a resin component, a first oil component and a second oil component, the second oil component is capable of seeping out from a coating film layer that has been cured or dried after application of the coating material when the temperature drops below a predetermined value; A paint, wherein the first oil component satisfies at least one of the following (1) and (2): (1) The kinematic viscosity at 25°C is 300 cSt or more. (2) The viscosity at 20°C is 0.1 Pa·s or more. <2> a difference between the solubility parameter value of the resin component and the solubility parameter value of the first oil component is smaller than a difference between the solubility parameter value of the resin component and the solubility parameter value of the second oil component; <1> The paint according to claim 1. <3> The viscosity of the first oil component at 20°C is 30 Pa·s or less. <1> or <2> The paint according to claim 1. <4> <1> ~ <3> 1. A laminate having a coating film layer obtained by curing the coating material according to any one of 1 to 8 above and an adhesive layer. [Effects of the Invention]

[0010] The coating film layer obtained from the coating material of the present invention can suppress the amount of oil that initially bleeds, and can maintain its anti-icing and / or anti-snowing function for a long period of time. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a cross-sectional view showing a coating layer formed from the coating material of the present invention together with a coated object. [Figure 2] FIG. 2 is a cross-sectional view showing an example of a layer structure including a coating layer formed from the coating material of the present invention, together with a coated object. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, the embodiments of the present invention will be described in more detail, but the present invention is not limited to the following embodiments.

[0013] [paint] The paint of the present invention contains a resin component, a first oil component, and a second oil component.

[0014] (resin component) The resin component may be a moisture-curable resin that cures with moisture, an ultraviolet-curable resin that cures with ultraviolet light, or a thermosetting resin that cures with heat. The resin component may also be a resin that cures by adding a curing agent that crosslinks with the resin component, or a thermoplastic resin.

[0015] The resin component 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, EPDM (ethylene propylene diene rubber), SEBS (styrene-based thermoplastic elastomer), SBR (styrene butadiene rubber), etc.

[0016] 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).

[0017] 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, etc.). , KE-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-109 E-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-117603-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-5 -UK、KE-582-UK、KE-552B-U、KE-555-UK、KE-575-UK、KE-541-UK、KE-551-UK、KE-56 1-U, KE-571-U, KE-581-U, KE-520-U, KE-530B-2-U, KE-540B-2-U, KE-1551 -UK、KE-1571-UK、KE-152-UK、KE-174-UK、KE-3601SB-UK、KE-3711-UK、KE-3801M-U KE-5612G-U KE-5620BL-U KE-5620W-U KE-5634-U KE-7511-U KE-7 -UK KE-765-UK KE-785-UK KE-7008-UK KE-7005-UK KE-503-UK KE-5042-UK KE- 505-U, KE-6801-U, KE-136Y-U mount Recommendation of the LIMS(Liquid Measurement Monitoring System). )(From 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、K E-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-193185A / B、KE-1987A / B、KE-1988 A / 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-2090-6 0A / B, KE-2090-70A / B, KE-2096-40A / B, KE-2096-50A / B, KE-2096-6OA / B.Examples of usable products include dimethiconol (e.g., X-21-5847, X-21-5849) manufactured by Shin-Etsu Chemical Co., Ltd., 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.

[0018] (oil ingredients) In the present invention, a first oil component and a second oil component are used.

[0019] The first oil component satisfies at least one of the following (1) and (2): (1) The kinematic viscosity at 25°C is 300 cSt or more. (2) The viscosity at 20°C is 0.1 Pa·s or more.

[0020] The kinematic viscosity of the first oil component at 25°C is preferably 300 cSt or more, and from the viewpoint of suppressing the amount of initial oil bleeding, is more preferably 300 to 10,000 cSt, and even more preferably 300 to 5,000 cSt. The kinematic viscosity can be measured by the method described in the examples.

[0021] The viscosity of the first oil component at 20°C is preferably 0.1 Pa·s or more, and from the viewpoint of suppressing initial oil bleeding, more preferably 1 Pa·s or more, and even more preferably 5 Pa·s or more. There are no particular restrictions on the upper limit of the viscosity, but it can be, for example, 30 Pa·s or less. The viscosity can be measured by the method described in the examples.

[0022] It is presumed that when at least one of the above (1) and (2) is satisfied, the rate of mass transfer within the paint slows down, making it possible to suppress the amount of oil that initially bleeds.

[0023] 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.

[0024] Examples of silicone oils include silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., KF96 series, KF965 series, KF50 series, KF54 series, KF410 series, KF412 series, and FL series), silicone oils manufactured by Momentive Corporation (e.g., Element14*PDMS series, TSF433 series, TSF451 series, TSF456 series, THF450 series, TSF4420 series, and TSF4421 series), and silicone oils manufactured by Toray Industries, Inc. Silicone oils manufactured by Wacker Corning Corporation (e.g., SF8416 series, SF8422 series, SH200 series, SH203 series, FS1265 series, SH510 series, SH710 series, FZ-2164 series, FZ-2191 series, FZ-5609 series, L-7001 series, L-7002 series, L-7004 series, FZ-2203 series, etc.), and silicone oils manufactured by Wacker Asahi Kasei Silicones (WACKER (registered trademark) SILICONE FLUID AK series, WACKER (registered trademark) SILICONE FLUID AKF series, WACKER (registered trademark) SILICONE FLUID AP series, WACKER (registered trademark) SILICONE FLUID AR series, WACKER (registered trademark) TN series, WACKER (registered trademark) AF series, etc.) can be used.

[0025] The second oil component can ooze out from the coating film layer that has been cured or dried after application of the coating material of the present invention when the temperature drops below a predetermined value. The above-mentioned predetermined value or less means, for example, freezing point (0°C) or less.

[0026] 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.

[0027] Examples of silicone oils include silicone oils manufactured by Toray Dow Corning Co., Ltd. (e.g., BY16-201, etc.), silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., KF-6000, KF-6001, KF-6002, KF-6003, KF-6011, KF-6011P, KF-6043, PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, X-22-9409, X-22-4952, X-22-4272, KF-6123, X-22-16 2C, X-21-5841, KF-9701, KF-864, KF-865, KF-868, KF-859, KF-393, KF-860, KF-880, KF-8004, KF-8002, KF-8005, KF-867, KF-8021, KF-869, KF-861, X-22-3939A, X-22-4039, X-22-4015, X-22-3701E, X-22-173BX, X-22-173DX, X-22-176F, X-22-176DX, X-22-176GX-A, X-22-3710, etc.) can be used.

[0028] (Characteristics of resin and oil components) The properties of the resin component and the oil component when two types of oil components (first oil component, second oil component) are used will be described below.

[0029] As the first oil component, the second oil component, and the resin component, it is preferable to select a combination that satisfies the following properties 1) and 2), for example.

[0030] 1) The resin component and / or the first oil component and the second oil component are compatible and do not phase separate at temperatures that do not require bleeding of the second oil component, for example, room temperature of about 20°C to 80°C, which is significantly higher than a predetermined value such as the freezing point. On the other hand, the resin component and / or the first oil component and the second oil component phase separate in a temperature environment that requires bleeding of the second oil component, for example, a temperature below a predetermined value such as the freezing point.

[0031] 2) The first oil component has affinity for the resin component both at temperatures that do not require bleeding of the second oil component and at temperatures that require bleeding of the second oil component. In contrast, the second oil component, in the presence of the first oil component, changes its behavior depending on whether the temperature is that does not require bleeding of the second oil component or that requires bleeding of the second oil component. In other words, the second oil component functions as a low-temperature phase-separable oil component that phase-separates from the resin component and / or the first oil component.

[0032] It is also empirically known that the solubility parameter (SP value) is a guide to 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 described above can also be explained based on the relationship between their solubility parameters. The solubility parameter can be measured by the method described in the Examples.

[0033] In order to satisfy the above relationships 1) and 2), it is preferable that the difference between the solubility parameter of the resin component and the solubility parameter of the first oil component is set to be smaller than the difference between the solubility parameter of the resin component and the solubility parameter of the second oil component. In addition, the difference in solubility parameter between the first oil component and the resin component is set to be 0.6 (J / cm 3 ) 1 / 2 It is preferable to set it within

[0034] For example, when the above relationships 1) and 2) are satisfied, the second oil component is compatible with the resin component and / or the first oil component and does not bleed at temperatures that do not require bleeding of the second oil component. On the other hand, when the temperature changes to a temperature that requires bleeding of the second oil component, the second oil component phase-separates from the resin component and / or the first oil component, exudes from the resin component, and can function as a bleedable, low-temperature phase-separable oil component.

[0035] Here, an embodiment has been described as an example in which the difference between the solubility parameter value of the resin component 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 components in the coating layer, particularly the second oil component, to bleed out (bleed), thereby preventing ice and / or snow from adhering; however, the scope of the present invention is not limited to these embodiments.

[0036] 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 resin component and / or the first oil component and exuded from the coating layer when the temperature drops below a predetermined value.

[0037] In the present invention, the wettability parameter calculated by the following formula (1) is 1.5 (J / cm 3 ) 1 / 2 It is preferably 0.8 (J / cm or less, more preferably 0.8 (J / cm 3 ) 1 / 2 and more preferably 0.5 (J / cm 3 ) 1 / 2 It is particularly preferable that the 3 ) 1 / 2 The following is the result.

[0038] Wetting parameter (J / cm 3 ) 1 / 2 ) = |Solubility parameter of coating layer − Solubility parameter of second oil component| (1) (In formula (1), the coating layer refers to a coating layer obtained by curing or drying the coating material.)

[0039] As shown in the above formula (1), the wetting parameter is calculated as the absolute value of the difference between the solubility parameter value SP1 of the coating film layer obtained by curing or drying the coating material of the present invention and the solubility parameter value SP2 of the second oil component. The solubility parameter value can be measured by the method described in the Examples.

[0040] Wetting parameter is 1.5 (J / cm 3 ) 1 / 2 If the second oil component is below this level, the coating layer formed will have high wettability, and even a small amount of oil will spread efficiently over the surface of the coating layer, thereby achieving the desired anti-icing and / or anti-snow effect with a smaller amount of oil component.

[0041] The wetting parameter 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 It can be more than that.

[0042] In the present invention, the solubility parameter contribution value calculated by the following formula (3) is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, and particularly preferably 0.4 or more.

[0043] Solubility parameter contribution value = f × φ × l00 (3) (In formula (3), f is a value calculated by the following formula (3a), and φ is a value calculated by the following formula (3b).)

[0044] f=((f dl -f d2 ) 2 +(f p1 -f p2 ) 2 +(f hl -f h2 ) 2 )0.5 (3a) (In formula (3a), f dl is the value calculated by the following formula (3a1), and f d2 is the value calculated by the following formula (3a2), and f p1 is the value calculated by the following formula (3a3), and f p2 is the value calculated by the following formula (3a4), and f hl is the value calculated by the following formula (3a5), and f h2 is the value calculated by the following formula (3a6).

[0045] f dl =δ dl / (δ dl +δ pl +δ hl )···(3a1) f d2 =δ d2 / (δ d2 +δ p2 +δ h2 )···(3a2) f p1 =δ p1 / (δ dl +δ pl +δ hl )···(3a3) f p2 =δ p2 / (δ d2 +δ p2 +δ h2 )···(3a4) f hl =δ hl / (δ dl +δ pl +δ hl )···(3a5) f h2 =δ h2 / (δ d2 +δ p2 +δ h2 )···(3a6) (In formulas (3a1) to (3a6), δ dl is the energy due to the dispersion force of the miscible molecular units (J / cm 3 ) 1 / 2 and δd2 is the energy due to the dispersion forces of immiscible molecular units (J / cm 3 ) 1 / 2 and δ pl is the energy due to the dipole-dipole interaction of the miscible molecular units (J / cm 3 ) 1 / 2 and δ p2 is the energy due to the dipole-dipole interaction of immiscible molecular units (J / cm 3 ) 1 / 2 and δ hl is the hydrogen bond energy of the miscible molecular units (J / cm 3 ) 1 / 2 and δ h2 is the energy due to hydrogen bonding of immiscible molecular units (J / cm 3 ) 1 / 2 is. The compatible molecular unit is a molecular unit that is most abundant in a coating film layer obtained by curing or drying the coating material, The difference in solubility parameter between the immiscible molecular unit and the compatible molecular unit is 0.01 (J / cm 3 ) 1 / 2 The above is the molecular unit of oil component P.

[0046] φ = (1 - gel fraction (%) / 100) × m (3b) (In formula (3b), the gel fraction (%) is a value calculated by the following formula (2), and m is a value calculated by the following formula (3b1).)

[0047] Gel fraction (%) = {mass of coating layer after heat drying (g) / mass of coating layer (g)} × 100 (2) (In formula (2), the coating layer refers to a coating layer obtained by curing or drying the coating material of the present invention. The coating layer after heat drying refers to a coating layer obtained by immersing the coating layer in toluene for 24 hours and then heat drying it in an environment of 150°C for 2 hours.)

[0048] m = {mass of incompatible molecular units contained in all oil components in the coating layer (g) / mass of all oil components in the coating layer (g)} (3b1) (In formula (3b1), "the mass of the immiscible molecular units contained in all the oil components in the coating layer" can be calculated by NMR measurement of all the oil components contained in the coating layer after curing or drying the paint. "All the oil components" refers to the residue obtained by immersing the coating layer in toluene for 24 hours and drying it in an environment of 150°C for 2 hours.)

[0049] The upper limit of the solubility parameter contribution value can be set to, 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.

[0050] The solubility parameter contribution value indicates the degree of compatibility of the coating layers, and the higher the value, the more likely the coating layers are to be incompatible. If the solubility parameter contribution value is within the above-mentioned range, the contained oil components will easily bleed, thereby achieving a high anti-icing and / or anti-snowing effect.

[0051] 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.

[0052] (Other ingredients) The coating material of the present invention may further contain an inorganic filler such as silica, a crosslinking agent, and a curing catalyst.

[0053] Examples of silica that can be used include silica manufactured by Nippon Aerosil Co., Ltd. (e.g., AEROSIL50, 130, 200, 300, R972, R974, R976, RX50, RX200, RX300, RY50, RY300, R7200, R8200, and R9200).

[0054] Examples of crosslinking agents that can be used include those manufactured by Colcoat Co., Ltd. (e.g., Ethyl Silicate 40, Ethyl Silicate 48, Methyl Silicate 51, Methyl Silicate 53A, EMS-485, Ethyl Silicate 28, Ethyl Silicate 28P, N-Propyl Silicate, N-Butyl Silicate, HAS-1, HAS-6, and HAS-10), those manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., Methyl Trimethoxysilane, Dimethyl Dimethoxysilane, Tetraethoxysilane, Methyl Triethoxysilane, Dimethyl Diethoxysilane, N-Propyl Trimethoxysilane, N-Propyl Triethoxysilane, Hexyl Trimethoxysilane, Hexyl Triethoxysilane, and Octyl Triethoxysilane), and those manufactured by Evonik Japan Co., Ltd. (e.g., Dynasylan Silbond 40).

[0055] Examples of curing catalysts that can be used include curing catalysts manufactured by Nippon Chemical Industry Co., Ltd. (e.g., Pucat 25, etc.), curing catalysts manufactured by Tokyo Chemical Industry Co., Ltd. (e.g., dibutyltin dilaurate, etc.), and curing catalysts manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., CAT-PL-50T).

[0056] (Paint manufacturing method) The paint of the present invention can be obtained by mixing and / or stirring the above-mentioned components by a known method. The content of each component in the paint is as follows.

[0057] The content of the resin component is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more, based on the mass of the entire coating layer to be finally formed. The upper limit of the content of the resin component is not particularly limited and is set appropriately in relation to the oil component, but can be, for example, 70% by mass or less, based on the mass of the entire coating layer to be finally formed.

[0058] The content of the first oil component can be set to preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on the mass of the entire coating layer to be finally formed. There is no particular upper limit to the content of the first oil component, but it can be set to preferably 65% ​​by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, particularly preferably 30% by mass or less, and most preferably 20% by mass or less, based on the mass of the entire coating layer to be finally formed.

[0059] The content of the second oil component is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the total mass of the finally formed coating layer. There are no particular restrictions on the upper limit of the content of the second oil component, but it can be set to preferably 62% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, particularly preferably 40% by mass or less, and most preferably 30% by mass or less, based on the total mass of the finally formed coating layer.

[0060] The silica content can be set to preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total mass of the finally formed coating layer. The silica content can be set to preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on the total mass of the finally formed coating layer.

[0061] The content of the crosslinking agent can be set to preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on the total mass of the finally formed coating layer. The content of the crosslinking agent can be set to preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 15% by mass or less, based on the total mass of the finally formed coating layer.

[0062] The content of the curing catalyst can be set to preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, based on the total mass of the finally formed coating layer. The content of the curing catalyst can be set to preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on the total mass of the finally formed coating layer.

[0063] (coating layer) For example, as shown in FIG. 1, a first coating layer 11 can be obtained by applying the coating material of the present invention to an object 10 to be coated. The coating material of the present invention can be applied by common methods such as brush application, spray application, various coater application, etc. Application is usually carried out once or twice.

[0064] The thickness of the first coating layer 11 is not particularly limited, but is preferably 1000 μm or less so that oil components can easily penetrate to the surface of the coating layer, in other words, to ensure oil permeability to the first coating layer 11, and is preferably 50 μm or more from the standpoint of strength.

[0065] The substrate 10 used in the present invention may be, for example, polyurethane resin, polyurethane acrylic resin, rubber resin, vinyl chloride resin, polyester resin, silicone resin, elastomers, fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.), metal plate or metal foil (aluminum, copper, silver, iron, nickel, tin, stainless steel, etc.), concrete, ceramics, etc.

[0066] After the coating material of the present invention has been applied to the substrate 10, the coating material can be cured or dried by leaving it to stand for, for example, 3 minutes to 3 hours in an environment of 20 to 180°C, preferably 80 to 150°C, and most preferably by leaving it to stand for 3 minutes in an environment of 150°C.

[0067] As shown in FIG. 2, for example, a second coating layer 12 can be formed by applying a topcoat paint as needed on the first coating layer 11 obtained from the coating material of the present invention. There are no particular limitations on the top coat paint, and for example, the same paint as the paint of the present invention can be used, but the top coat paint does not have to contain an oil component.

[0068] The topcoat can be applied by any common method, such as brush painting, spray painting, or various coater painting. Painting is usually done once or twice.

[0069] The thickness of the second coating layer 12 is not particularly limited, but is preferably 500 μm or less so that oil components can easily penetrate to the surface of the coating layer, in other words, to ensure oil permeability to the second coating layer 12, and is preferably 50 μm or more from the standpoint of strength.

[0070] The curing or drying temperature and curing or drying time when applying the topcoat paint to the first coating layer 11 are the same as the curing or drying temperature and curing or drying time when applying the paint of the present invention to the substrate 10. The curing or drying of the coating material of the present invention and the curing or drying of the topcoat coating material may be carried out simultaneously or separately.

[0071] [Laminate] The laminate of the present invention has a coating layer formed by curing or drying the coating material of the present invention and an adhesive layer. The laminate of the present invention can be obtained by forming a thin film of the coating material of the present invention, for example, 10 to 1000 μm, and curing or drying it in advance to form a coating film layer, and then providing a pressure-sensitive adhesive layer on the coating film layer using a conventionally known process.

[0072] The adhesive layer can be used to adhere the coating film layer obtained by curing or drying the coating material of the present invention to the surface of various objects. The adhesive layer is not particularly limited, but examples thereof include acrylic resin adhesives, epoxy resin adhesives, amino resin adhesives, vinyl resin (such as vinyl acetate polymers) adhesives, curable acrylic resin adhesives, and silicone resin adhesives.

[0073] The adhesive layer may be an oil-impermeable adhesive layer to prevent outflow of oil components from the coating layer.

[0074] The oil-impermeable adhesive layer is not particularly limited, but examples thereof include acrylic resin adhesives, epoxy resin adhesives, amino resin adhesives, vinyl resin (such as vinyl acetate polymers) adhesives, curable acrylic resin adhesives, and silicone resin adhesives. [Example]

[0075] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to the following examples in any way.

[0076] <Preparation of coating layer> [Example 1] As a paint ingredient, Resin component: KE-1935A (Shin-Etsu Chemical Co., Ltd.), KE-1935B (Shin-Etsu Chemical Co., Ltd.) First oil component: Dimethylsiloxane oil (Shin-Etsu Chemical Co., Ltd., product number: KF-96-300) Second oil component: Carbinol-modified oil (BY16-201, manufactured by Toray Dow Corning Co., Ltd.) was prepared.

[0077] The above resin components [KE-1935A (20% by mass), KE-1935B (20% by mass)], first oil component (48% by mass), and second oil component (12% by mass) were mixed at 25°C and 101 kPa. The resulting mixture was stirred with a spatula at approximately 120 rpm for 60 seconds, and then stirred with a Disper (Primix Corporation, Labo-Lution) at 2000 rpm for 5 minutes to obtain a coating material.

[0078] The resulting mixture was applied to a PET (polyethylene terephthalate) sheet (Lumirror S10#75, manufactured by Toray Industries, Inc.) using an applicator and cured by heating in an environment of 150°C for 3 minutes to form a coating layer with a thickness of 250 μm.

[0079] [Examples 2 to 7, Comparative Examples 1 to 3] A coating layer was formed in the same manner as in Example 1, except that the product number of the first oil component: dimethylsiloxane oil (manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to that shown in Table 1.

[0080] [Examples 8 to 10, Comparative Examples 4 and 5] A coating layer was formed in the same manner as in Example 1, except that the second oil component was changed to a carbinol-modified oil (KF-6002, manufactured by Shin-Etsu Chemical Co., Ltd.) and the product number of the first oil component: dimethylsiloxane oil (manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to that shown in Table 2.

[0081] <Evaluation> The following evaluations were carried out using each paint component and the resulting coating layer, and the results are shown in Tables 1 and 2.

[0082] [First oil component] (Kinematic viscosity at 25°C) The kinematic viscosity of the first oil component at 25°C was measured using an Ubbelohde viscometer based on JIS Z 8803:2011 (https: / / kikakurui.com / z8 / Z8803-2011-01.html).

[0083] (Viscosity at 20°C) The viscosity as a function of shear rate was measured using a rotational viscometer (Thermo Fisher Scientific, HAAKE). The shear rate was increased from 0.1 to 1,000 [1 / s] over 30 seconds, and the viscosity value at a shear rate of 1.0 [1 / s] was used. Parallel plates (35 mm diameter) were used as the measurement jig, with a gap between the plates of 0.024 mm, and the measurement temperature was set to 20°C using a temperature control unit.

[0084] [Solubility parameters] Fourier transform nuclear magnetic resonance spectroscopy was performed to examine the types and molar ratios of the molecular units that make up the molecular structure of each paint component. The solubility parameters (Hansen solubility parameters) of each molecular unit were calculated by weighting the molar ratio.

[0085] The Hansen solubility parameters of each molecular unit can be calculated 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 d ,δ p ,δ h ) can be calculated.

[0086] [Coating layer] (Icing power) The object of measurement is the force required to move an ice block attached to a coating layer in an environment of -20°C, and for convenience, the magnitude of this force is defined in this specification as the "icing force."

[0087] The ice adhesion force was measured in the following manner. First, a cylindrical ice block was 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 Corporation), 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 was removed.

[0088] Next, the PET film and coating layer were left to stand in a -20°C environment for 16 hours, and then attached to a stainless steel plate placed parallel to the floor surface with the coating layer facing outward. 2 The cylindrical ice block was attached to the surface.

[0089] The ambient temperature was set to -20°C. Three hours after the ice block was attached, 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 0.1 mm / s for an attachment 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.

[0090] 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 decreases approximately proportionally in response to an increase in the amount of surface oil.

[0091] (Initial oil bleed amount) The measurement was made on the amount of oil that bled onto the surface of the coating layer at -20° C. During the measurement, it was confirmed that the bled oil was mainly the second oil component.

[0092] The amount of oil initially bled was measured by the following method. A 10cm x 2cm piece was cut near the center of the coating layer and left at -20°C for 20 hours. The oil that had bled onto the surface of the coating layer was collected using a cell scraper (Kenis Co., Ltd., CSS-2510), and the oil was then absorbed using oil blotting paper until no change in the mass (oil absorption) of the oil blotting paper was observed. The process of collecting oil using the cell scraper and absorbing it with the oil blotting paper was repeated seven times per minute. The difference in mass of the oil blotting paper before and after absorbing the oil was taken as the initial amount of bleed oil. The test was performed three times, and the average value was calculated.

[0093] [Table 1]

[0094] [Table 2]

[0095] The results in Tables 1 and 2 show that the paint of the present invention can suppress the amount of oil that initially bleeds and can provide a coating layer that can maintain its anti-icing and / or anti-snowing function for a long period of time.

[0096] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2020-082731) filed on May 8, 2020, the contents of which are incorporated herein by reference. [Explanation of symbols]

[0097] 10 Object to be coated 11 First coating layer 12 Second coating layer

Claims

1. A paint containing a resin component, a first oil component, and a second oil component, The second oil component is capable of seeping out from a coating layer that has hardened or dried after application of the coating material when the temperature drops below freezing point, The first oil component satisfies at least one of the following (1) and (2): a difference between the solubility parameter value of the resin component and the solubility parameter value of the first oil component is smaller than a difference between the solubility parameter value of the resin component and the solubility parameter value of the second oil component; the difference in solubility parameter between the first oil component and the resin component is within 0.6 (J / cm 3 ) 1 / 2 ; the resin component is a silicone resin, the first oil component is a silicone oil; The paint, wherein the second oil component is a silicone oil. (1) The kinematic viscosity at 25°C is 300 cSt or more. (2) The viscosity at 20°C is 0.1 Pa·s or more.

2. The paint according to claim 1, wherein the difference between the solubility parameter value of the resin component and the solubility parameter value of the first oil component is smaller than the difference between the solubility parameter value of the resin component and the solubility parameter value of the second oil component.

3. The paint according to claim 1 or 2, wherein the viscosity of the first oil component at 20°C is 30 Pa·s or less.

4. A laminate comprising a coating layer obtained by curing the coating material according to any one of claims 1 to 3 and an adhesive layer.

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