Paints and Laminates

Abstract

The present invention pertains to a coating material containing a resin component and at least one oil component P, wherein below a predetermined temperature, the oil component P can be exuded from a coating layer cured and dried after the application of the coating material, the wetting parameter is 0.5 (J / cm3)1 / 2 or less, and the gel percentage in the coating layer is 30% or more.

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 investigations of the present inventors, conventional paints such as those disclosed in Patent Document 1 have the problem that the coating film layer obtained from the paint has low abrasion resistance.

[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 provide a coating layer that is highly abrasion resistant and has excellent anti-icing and / or anti-snowing properties. [Means for solving the problem]

[0008] As a result of extensive research into solving the above problems, the present inventors have focused on the wetting parameters and gel fraction of a coating film layer obtained from a coating material, and have completed the present invention.

[0009] That is, the present invention provides the following <1> ~ <7> It is related to. <1> A paint containing a resin component and at least one oil component P, The oil component P can ooze out from the coating film layer that has been cured or dried after application of the coating material when the temperature drops below a predetermined value, The wetting parameter calculated by the following formula (1) is 0.5 (J / cm 3 ) 1 / 2 is as follows: A coating material, wherein the coating layer has a gel fraction of 30% or more as determined by the following formula (2): Wetting parameter (J / cm 3 ) 1 / 2 ) = |Solubility parameter of coating layer − Solubility parameter of oil component P| (1) (In formula (1), the coating layer refers to a coating layer obtained by curing or drying the coating material.) 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. 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.) <2> The wetting parameter is 0.3 (J / cm 3 ) 1 / 2 Below is the <1> The paint according to claim 1. <3> The gel fraction is greater than 60%. <1> or <2> The paint according to claim 1. <4> Further containing oil component Q, <1> ~ <3> 1. A paint according to any one of the preceding items. <5> At least one of the oil component P and the oil component Q is a carbinol-modified silicone oil or an alkyl-modified silicone oil. <1> ~ <4> 1. A paint according to any one of the preceding items. <6> The solubility parameter contribution value calculated by the following formula (3) is 0.1 or more. <1> ~ <5> 1. A paint according to any one of the preceding items. 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).) 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). f dl =δ dl / (δdl +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 δ d2 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 hydrogen bond energy (J / cm) of immiscible molecular units 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 the oil component P. φ = (1 - gel fraction (%) / 100) × m (3b) (In formula (3b), the gel fraction (%) is a value calculated by formula (2) above, and m is a value calculated by formula (3b1) below.) 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.) <7> <1> ~ <6> 1. A laminate having a coating layer obtained by curing or drying 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 has high abrasion resistance and excellent anti-icing and / or anti-snowing properties. [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. [Figure 3] FIG. 3 is a schematic diagram of the Gakushin-type abrasion tester used in the examples. 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 and at least one oil component P.

[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-UK、KE-9710-UK、KE-742-UK、KE-752-UK、KE-762-UK、KE-772-UK、KE-782-U KE-850-UK, KE-870-UK, KE-880-UK, KE-890-UK, KE-9590-UK, KE-5590-UK, KE-5 52-UK、KE-582-UK、KE-552B-UK、KE-555-UK、KE-575-UK、KE-541-UK、KE-551-UK -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-38 01M-U、KE-5612G-U、KE-5620BL-U、KE-5620W-U、KE-5634-U、KE-7511-U、KE -7611-UK、KE-765-UK、KE-785-UK、KE-7008-UK、KE-7005-UK、KE-503-UK、KE-5042 -U, KE-505-U, KE-6801-U, KE-136Y-U) and the specifications of the LIMS (Linear Monitoring System). Picture of KEG-2000-40A / B KEG-2000-50A / B KEG-2000-60A / B KEG-2000-50A / B 2000-70A / B、KEG-2001-40A / B、KEG-2001-50A / B、KE-1950-10A / B、KE-195 0-20A / B、KE-1950-30A / B、KE-1950-35A / B、KE-1950-40A / B、KE-1950-50A / 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-2 017-40A / B、KE-2017-50A / B、KE-2090-40A / B、KE-2090-50A / B、KE-2090-60 A / 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., LR7665 series manufactured by Wacker Asahi Kasei Silicone Co., Ltd., LR3033 series manufactured by Wacker Asahi Kasei Silicone Co., Ltd., TSE3032 series manufactured by Momentive Corporation, and Sylgard 184 manufactured by Dow Corning Toray Co., Ltd.

[0018] (oil ingredients) In the present invention, at least one oil component P is used.

[0019] The oil component P 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.

[0020] As the oil component P, for example, silicone oil, fluorine oil, hydrocarbon oil, polyether oil, ester oil, phosphorus compound oil, mineral oil, etc. can be used.

[0021] 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.

[0022] The paint of the present invention preferably further contains an oil component Q.

[0023] As the oil component Q, 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., 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.), silicone oils manufactured by Momentive Corporation (e.g., Element14*PDMS series, TSF404 series, TSF410 series, TSF4300 series, TSF431 series, TSF433 series, TS F437 series, TSF4420 series, TSF4421 series, etc.), silicone oils manufactured by Toray Dow Corning Co., Ltd. (e.g., BY16-846 series, SF8416 series, SF8427 series, SF-8428 series, SH200 series, SH203 series, SH230 series, SF8419 series, FS1265 series, SH510 series, SH550 series, SH710 series, FZ-2110 series, FZ-2203 series, BY16-201, etc.), silicone oils manufactured by Wacker Asahi Kasei Silicone Co., Ltd. (WACKER (registered trademark) SILICONE 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. can be used.

[0025] In the present invention, from the viewpoint of improving abrasion resistance and anti-icing and / or anti-snowing properties, it is preferable that at least one of oil component P and oil component Q is a carbinol-modified silicone oil or an alkyl-modified silicone oil.

[0026] (Characteristics of resin and oil components) The properties of the resin component and the oil component when two types of oil components (oil component P, oil component Q) are used will be described below.

[0027] As the oil component P, the oil component Q, and the resin component, it is preferable to select a combination that satisfies the following properties 1) and 2), for example.

[0028] 1) Resin component and / or oil component Q and oil component P are compatible and do not phase separate at temperatures that do not require bleeding of oil component P, 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, resin component and / or oil component Q and oil component P phase separate in a temperature environment that requires bleeding of oil component P, for example, a temperature below a predetermined value such as the freezing point.

[0029] 2) Oil component Q has affinity for the resin component both at temperatures that do not require bleeding of oil component P and at temperatures that require bleeding of oil component P. In contrast, in the presence of oil component Q, oil component P changes its behavior depending on whether the temperature is one that does not require bleeding of oil component P or one that requires bleeding of oil component P. In other words, oil component P functions as a low-temperature phase-separable oil component that phase-separates from the resin component and / or oil component Q.

[0030] 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 oil component Q, the oil component P, 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.

[0031] 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 oil component Q is set to be smaller than the difference between the solubility parameter of the resin component and the solubility parameter of the oil component P. In addition, the difference in solubility parameter between the oil component Q and the resin component is set to be 0.6 (J / cm 3) 1 / 2 It is preferable to set it within .

[0032] For example, when the above relationships 1) and 2) are satisfied, oil component P is compatible with resin component and / or oil component Q and does not bleed at temperatures that do not require bleeding of oil component P. On the other hand, when the temperature changes to a temperature that requires bleeding of oil component P, oil component P phase-separates from resin component and / or oil component Q and exudes from the resin component, and can function as a bleedable, low-temperature phase-separable oil component.

[0033] 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 oil components P and Q is set to a predetermined relationship, thereby causing a portion of the oil components in the coating layer, particularly oil component P, to bleed out (bleed), thereby preventing icing and / or snow accumulation, but the scope of the present invention is not limited to these embodiments.

[0034] For example, compatibility can be similarly controlled by utilizing the difference in molecular weight or molecular structure between oil component Q and oil component P, and oil component P can be phase-separated from the resin component and / or oil component Q and exuded from the coating layer when the temperature drops below a predetermined value.

[0035] In the present invention, the wettability parameter calculated by the following formula (1) is 0.5 (J / cm 3 ) 1 / 2 The following is the result. Wetting parameter (J / cm 3 ) 1 / 2 ) = |Solubility parameter of coating layer − Solubility parameter of oil component P| (1) (In formula (1), the coating layer refers to a coating layer obtained by curing or drying the coating material.)

[0036] 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 oil component P. The solubility parameter value can be measured by the method described in the Examples.

[0037] Wetting parameter is 0.5 (J / cm 3 ) 1 / 2 If the oil component P is below this level, the oil component P that bleeds out of the coating layer will have high wettability, and even a small amount of oil will spread efficiently over the surface of the coating layer, thereby achieving the anti-icing and / or anti-snowing effect with a smaller amount of oil component.

[0038] The wetting parameter is 0.3 (J / cm 3 ) 1 / 2 It is preferably 0.25 (J / cm or less, more preferably 0.25 (J / cm 3 ) 1 / 2 and more preferably 0.2 (J / cm 3 ) 1 / 2 The wettability parameter is 0.01 (J / cm 3 ) 1 / 2 It is preferable that the concentration is equal to or higher than 0.03 (J / cm 3 ) 1 / 2 More preferably, it is 0.05 (J / cm 3 ) 1 / 2 That's all.

[0039] In the present invention, the gel fraction of the coating layer calculated by the following formula (2) is 30% or more. 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.)

[0040] When the gel fraction is 30% or more, the coating material of the present invention can contain a sufficient amount of resin components, and a coating layer with high abrasion resistance can be obtained.

[0041] The gel fraction is preferably more than 60%, more preferably 65% ​​or more, and even more preferably 70% or more, and is preferably 95% or less, more preferably 90% or less, and even more preferably 85% or less.

[0042] In the present invention, the solubility parameter contribution value calculated by the following formula (3) is preferably 0.1 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) fd2 =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 δ d2 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 hydrogen bond energy (J / cm) of immiscible molecular units 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 the oil component P.

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

[0047] 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.)

[0048] The solubility parameter contribution value is more preferably 0.2 or more, even more preferably 0.3 or more, and particularly preferably 0.4 or more.

[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, oil component P and oil component Q 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, oil component P and oil component Q do not both need to be composed of a single oil component, and as long as the above conditions are met, oil component P and oil component Q may each 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 the curing catalyst 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 can be set to preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, based on the total mass of the finally formed coating layer. The content of the resin component can be set to preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, based on the total mass of the finally formed coating layer.

[0058] The content of oil component P 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 content of oil component P can be set to preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less, based on the total mass of the finally formed coating layer.

[0059] The content of oil component Q 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 content of oil component Q can be set to preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% 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. The substrate 10 may also be in the form of a film or sheet.

[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.) Oil component P: Carbinol-modified oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-6003) was prepared.

[0077] The above resin components [KE-1935A (25% by mass), KE-1935B (25% by mass)] and oil component P (50% 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 coating material was applied to a PET (polyethylene terephthalate) film (Lumirror (registered trademark) 75-S10, manufactured by Toray Industries, Inc.) 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 14, Comparative Example 1] A coating layer having a thickness of 250 μm was formed in the same manner as in Example 1, except that the coating components and the content of each component were as shown in Table 1.

[0080] The details of each component listed in Table 1 are as follows: KF-6002: Carbinol-modified oil, manufactured by Shin-Etsu Chemical Co., Ltd. BY 16-201: Carbinol-modified oil, manufactured by Dow Corning Toray Co., Ltd. TSF-437: Methylphenylsiloxane oil, manufactured by Momentive KF-96-50: Dimethylsiloxane oil, manufactured by Shin-Etsu Chemical Co., Ltd.

[0081] KE-1935 is a mixed liquid of KE-1935A and KE-1935B in a 1:1 (mass ratio).

[0082] [Example 15] As a paint ingredient, Resin component: KE-1935A (Shin-Etsu Chemical Co., Ltd.), KE-1935B (Shin-Etsu Chemical Co., Ltd.) Oil component P: Carbinol-modified oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-6003) and carbinol-modified oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-6002) were prepared.

[0083] The above resin components [KE-1935A (28.75% by mass), KE-1935B (28.75% by mass)] and oil component P, KF-6003 (25% by mass) and KF-6002 (17.5% 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 paint.

[0084] The resulting coating material was applied to a PET (polyethylene terephthalate) film (Lumirror (registered trademark) 75-S10, manufactured by Toray Industries, Inc.) and cured by heating in an environment of 150°C for 3 minutes to form a coating layer with a thickness of 250 μm.

[0085] Comparative Example 2 As a paint ingredient, Resin components: Sylgard 184 base resin (manufactured by Dow Corning Toray Co., Ltd.), Sylgard 184 hardener (manufactured by Dow Corning Toray Co., Ltd.) Oil component P: Methylphenylsiloxane oil (manufactured by Asahi Kasei Wacker Silicone Co., Ltd., product number: AR-20) was prepared.

[0086] The above resin components [main agent (24.4% by mass), curing agent (2.6% by mass)] and oil component P (73% by mass) were mixed under conditions of 25°C and 101 kPa. The resulting mixture was stirred in the same manner as in Example 1 to obtain a coating material.

[0087] The resulting coating material was heat-cured in the same manner as in Example 1 to form a coating layer with a thickness of 250 μm.

[0088] Comparative Example 3 As a paint ingredient, Resin components: Sylgard 184 base resin (manufactured by Dow Corning Toray Co., Ltd.), Sylgard 184 hardener (manufactured by Dow Corning Toray Co., Ltd.) Oil component P: Phenylsiloxane oil (Momentive, product number: TSF-437) Oil component Q: Dimethylsiloxane oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-96-100) was prepared.

[0089] The above resin components [main agent (72.7% by mass), curing agent (7.3% by mass)], oil component P (8% by mass), and oil component Q (12% by mass) were mixed under conditions of 25°C and 101 kPa. The resulting mixture was stirred in the same manner as in Example 1 to obtain a coating material.

[0090] The resulting coating material was heat-cured in the same manner as in Example 1 to form a coating layer with a thickness of 250 μm.

[0091] Comparative Example 4 A coating layer having a thickness of 250 μm was formed in the same manner as in Comparative Example 3, except that the content of each component was changed to resin component [main agent (63.6 mass%), curing agent (6.4 mass%)], oil component P (12 mass%), and oil component Q (18 mass%).

[0092] <Evaluation> The resulting coating layer was subjected to the following evaluations, and the results are shown in Table 1.

[0093] [Wetting parameters] First, the solubility parameter values ​​of the coating layer and the oil component P were determined by the following method.

[0094] (solubility parameter) 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 the coating layer and oil component P. The solubility parameter (Hansen solubility parameter) of each molecular unit was determined by calculating a weighted average based on the molar ratio.

[0095] The Hansen solubility parameters of each molecular unit can be determined by the group contribution method using the software "HSPiP, Hansen Solubility Parameters in Practice ver4" available from the link (https: / / hansen - solubility.com / ). Specifically, each constituent unit in the target substance is input in SMILES notation, and the HSP values (δ d , δ p , δ h ) for each unit can be calculated.

[0096] And the wetting parameter [(J / cm 3 ) 1 / 2 was determined by the above formula (1).

[0097] 〔Gel fraction〕 The coating film layer was cut into 3.0 cm × 3.0 cm, and the mass (g) of the coating film layer was measured. The cut coating film layer was placed in a vial filled with 20 g of toluene and immersed in toluene at 20°C for 24 hours. Then, the coating film layer was taken out of the vial and dried by heating in a forced - air dryer at 150°C for 2 hours, and the mass (g) of the coating film layer after heat drying was measured.

[0098] And the gel fraction (%) of the coating film layer was determined by the above formula (2).

[0099] 〔Dissolution parameter contribution value〕 <Value of f δ dl : Energy due to the dispersion force of compatible molecular units, δ d2 : Energy due to the dispersion force of incompatible molecular units, δ pl : Energy due to the dipole - dipole interaction of compatible molecular units, δ p2 : Energy due to the dipole - dipole interaction of incompatible molecular units, δ hl : Energy due to the hydrogen bond of compatible molecular units, δ h2 : Energy due to the hydrogen bond of incompatible molecular units were determined by the group contribution method using the above - mentioned software.

[0100] Next, f is calculated using the above formulas (3a1) to (3a6). dl , f d2 , f p1 , f p2 , f hl , f h2 The value of was then calculated using (3a) above.

[0101] <value of φ> The gel fraction (%) of the coating layer was determined by the method described above.

[0102] The total oil content in the coating layer was obtained by the following procedure. The coating layer was cut into a piece of 2.0 x 4.5 cm, placed in a vial filled with 20 g of toluene, and immersed in toluene at room temperature for 24 hours. The coating layer was removed from the vial and dried in a fan dryer at 150°C for 2 hours to obtain a residue, which contains all of the oil components in the paint.

[0103] The "mass of the immiscible molecular units contained in all the oil components in the coating layer" was calculated by NMR measurement of all the oil components contained in the coating layer, and the value of m was determined by (3b1) above.

[0104] The value of φ was calculated using the gel fraction (%) and the value of m according to (3b) above.

[0105] Then, the solubility parameter contribution value was calculated using the values ​​of f and φ according to the above formula (3).

[0106] [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."

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] [Wear resistance] The abrasion resistance of the coating layer was evaluated. The measurement device used was a Gakushin-type abrasion tester (model number: RT-300S, manufactured by Daiei Scientific Instruments Manufacturing Co., Ltd.). A schematic diagram of the Gakushin-type abrasion tester is shown in Figure 3. The Gakushin-type abrasion tester 20 includes a test stand 21, a support plate 22 fixed to the test stand 21 with 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.

[0112] Using this Gakushin-type abrasion tester 20, a coating layer of a test piece 32 was attached to a support plate 22 via an adhesive 31 (manufactured by Nitto Denko Corporation, No. 5000NS), particularly in a 20 mm x 120 mm area thereof. A water-resistant abrasive 33 with a grit size of #120 was attached to the underside of the friction element 25 via the adhesive 31, and the abrasive was applied with a pressure of 125 g / cm2 adjusted by the weight 23 and the load arm 24. 2 The reduction rate of the coating film layer was determined when the sample was reciprocated 100 times under a pressing force of 100 mm / s at a speed of 100 mm / s. The room temperature was set at 20°C.

[0113] The evaluation criteria are as follows: ◯: The reduction rate was less than 80% by mass. ×: The reduction rate was 80% by mass or more.

[0114] [Table 1]

[0115] The results in Table 1 show that the paint of the present invention provides a coating layer that is highly abrasion resistant and has excellent anti-icing and / or anti-snowing properties.

[0116] 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. 2020-082732) filed on May 8, 2020, the contents of which are incorporated herein by reference. [Explanation of symbols]

[0117] 10 Object to be coated 11 First coating layer 12 Second coating layer 20 Gakushin-type abrasion tester 21 Test stand 22 Support plate 22a screw 23 Weight 24 Load arm 25 Friction element 31 Adhesive 32 test specimens 33 Water-resistant polishing pad

Claims

1. A paint containing a resin component, at least one oil component P and an oil component Q, The oil component P can ooze out from the coating film layer that has been hardened or dried after application of the coating material when the temperature drops below freezing point, The wetting parameter calculated by the following formula (1) is 0.5 (J / cm ３ ) １／２ is as follows: the coating layer has a gel fraction of 30% or more as calculated by the following formula (2), the difference between the solubility parameter value of the resin component and the solubility parameter value of the oil component Q is smaller than the difference between the solubility parameter value of the resin component and the solubility parameter value of the oil component P, the difference in solubility parameter between the oil component Q and the resin component is within 0.6 (J / cm 3 ) 1 / 2 ; the resin component is a silicone resin, The oil component P is a silicone oil, The paint, wherein the oil component Q is a silicone oil. Wetting parameter [(J / cm ３ ) １／２ ) = |Solubility parameter of coating layer−Solubility parameter of oil component P| (1) (In formula (1), the coating layer is a coating layer obtained by curing or drying the coating material.) Gel fraction (%) = {mass (g) of coating layer after heat drying / mass (g) of coating layer} × 100 (2) (In formula (2), the coating film layer refers to a coating film layer obtained by curing or drying the coating material. The coating film layer after heat drying refers to a coating film layer obtained by immersing the coating film layer in toluene for 24 hours and then heat-drying it in an environment of 150°C for 2 hours.)

2. The wetting parameter is 0.3 (J / cm ３ ) １／２ 2. The paint of claim 1, wherein:

3. 3. The paint of claim 1, wherein the gel fraction is greater than 60%.

4. 4. The paint according to claim 1, wherein at least one of the oil component P and the oil component Q is a carbinol-modified silicone oil or an alkyl-modified silicone oil.

5. The paint according to any one of claims 1 to 4, wherein the solubility parameter contribution value calculated by the following formula (3) is 0.1 or more: 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).) 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 a value calculated by the following formula (3a1), and f ｄ２ is a value calculated by the following formula (3a2), and f ｐ１ is a value calculated by the following formula (3a3), and f ｐ２ is a value calculated by the following formula (3a4), and f ｈｌ is a value calculated by the following formula (3a5), and f ｈ２ is a value calculated by the following formula (3a6): f ｄｌ =d ｄｌ / (d) ｄｌ +d ｐｌ +d ｈｌ )・・・(3a1) f ｄ２ =d ｄ２ / (d) ｄ２ +d ｐ２ +d ｈ２ )・・・(3a2) f ｐ１ =d ｐ１ / (d) ｄｌ +d ｐｌ +d ｈｌ )・・・(3a3) f ｐ２ =d ｐ２ / (d) ｄ２ +d ｐ２ +d ｈ２ )・・・(304) f ｈｌ =d ｈｌ / (d) ｄｌ +d ｐｌ +d ｈｌ )・・・(3a5) f ｈ２ =d ｈ２ / (d) ｄ２ +d ｐ２ +d ｈ２ )・・・(3A6) (In formulas (3a1) to (3a6), δ ｄｌ is the energy due to the dispersion force of the compatible molecular units (J / cm ３ ) １／２ and δ ｄ２ is the energy due to the dispersion force of the immiscible molecular units (J / cm ３ ) １／２ and δ ｐｌ is the energy due to the dipole interaction of the compatible molecular units (J / cm ３ ) １／２ and δ ｐ２ is the energy due to the dipole interaction of the immiscible molecular units (J / cm ３ ) １／２ and δ ｈｌ is the hydrogen bond energy of the compatible molecular units (J / cm ３ ) １／２ and δ ｈ２ is the hydrogen bond energy of the 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 incompatible molecular unit and the compatible molecular unit is 0.01 (J / cm ３ ) １／２ The above is the molecular unit in the oil component P. φ=(1−gel fraction (%) / 100)×m (3b) (In formula (3b), the gel fraction (%) is a value calculated by formula (2) above, and m is a value calculated by formula (3b1) below.) m = {mass (g) of the immiscible molecular units contained in all oil components in the coating layer / mass (g) of all oil components in the coating layer} (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 obtained by curing or drying the coating material. "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.)

6. A laminate having a coating layer formed by curing or drying the paint described in any one of claims 1 to 5 and an adhesive layer.

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