Molded bodies and lighting fixtures

Abstract

The objective is to provide a molded body and a lighting fixture that can maintain anti-fogging functionality even after being submerged in water. [Solution] A molded body having a base material and an active energy curable film 30 covering at least a portion of the surface of the base material, wherein the curable film 30 contains vinyl groups and at least one of hydroxyl groups and amide groups, with a total content of hydroxyl groups and amide groups of 4% by mass or more, and the contact angle Θ after 90 seconds of dropping 1 μL of pure water onto the surface of the cured film 30 after immersion of the molded body in water at 40 degrees Celsius for 1 hour and drying is 50° or less.

Description

Technical Field

[0001] The present invention relates to a molded body and a lighting fixture.

Background Art

[0002] Transparent synthetic resins such as polycarbonate resin (PC) and polymethyl methacrylate resin (PMMA) are excellent in transparency, moldability, and mechanical properties. Therefore, they are used in many fields such as outer lenses (light-transmitting covers) of lighting fixtures for automobiles and motorcycles, lenses of glasses, covers of optical sensors, and various liquid crystal panels. However, on the surface of a molded article such as a synthetic resin, when the surface temperature drops below the dew point temperature, moisture in the atmosphere condenses into fine water droplets, causing cloudiness. As a result, there is a problem of reducing the light transmittance, causing poor visibility, and malfunction of sensors and the like. In order to prevent such problems, a composition is applied to the surface of the molded article to form a cured film, thereby ensuring transparency.

[0003] For example, Patent Document 1 discloses an active energy ray-curable anti-fog coating composition containing a radically polymerizable compound (A) and a water-soluble surfactant (B), and further containing a polyfunctional (meth)acrylate (F) having a polyethylene glycol structure and a urethane structure, wherein the content of the polyfunctional (meth)acrylate (F) is 20 to 80% by mass based on the total amount of the radically polymerizable compounds contained in the composition. <0​​​​​​​​​​​​​​​​​​​​​However, there is a concern that when a cured film is obtained by curing a composition containing such surfactants, the surfactants that are oriented on the surface will wash away when it is submerged in water, causing it to lose its anti-fogging properties. Therefore, there was a problem in that the anti-fogging function could not be ensured after submersion in water.

[0006] This invention has been made in view of the above points, and aims to provide a molded body and a light fixture that can ensure anti-fogging function even after being submerged in water. [Means for solving the problem]

[0007] The molded article of the present invention is A molded body comprising a substrate and an active energy curable film covering at least a portion of the surface of the substrate, The cured film contains a vinyl group and at least one of a hydroxyl group and an amide group. The total content of the hydroxyl group and the amide group is 4% by mass or more. The molded body is immersed in water at 40 degrees Celsius for 1 hour, then dried, and the contact angle after 90 seconds of dropping 1 μL of pure water onto the surface of the cured film is 50° or less. [Brief explanation of the drawing]

[0008] [Figure 1] This is a conceptual diagram showing a molded article of the present invention. [Figure 2] This is a conceptual diagram illustrating the state when a water droplet is dropped onto the cured film of the molded article of the present invention. [Figure 3] This figure shows the manufacturing process of the molded article of the present invention. [Figure 4] This table summarizes the comparison results between the examples and comparative examples of the molded articles of the present invention. [Modes for carrying out the invention]

[0009] Embodiments of the present invention will now be described. As shown in Figure 1, the molded body 10 of the present invention has a base material 20 and an active energy curable film 30 that covers a portion of the surface of the base material 20.

[0010] The cured film 30 of the present invention is a cured film obtained by thin-film curing of an active energy curable composition containing a hydrophobic monomer 31, a hydrophilic monomer 32 having a hydrophilic functional group, and an initiator. The film thickness of the cured film 30 is 1 μm to 20 μm.

[0011] The hydrophobic monomer 31 is a highly reactive hydrophobic radical-reactive material. By including the hydrophobic monomer in the active energy ray-curable composition, the curing speed of the active energy ray-curable composition can be accelerated. Furthermore, the highly reactive hydrophobic monomer cures first, followed later by the hydrophilic monomer having hydrophilic functional groups. Therefore, the hydrophobic monomer 31, which is compatible with the hydrophobic substrate, adheres closely to the substrate 20, and the hydrophilic monomer 32, which cures later, is more likely to be positioned on the outermost surface. Thus, a thin film of hydrophilic monomer 32 can be applied to the surface of the cured film 30, improving its anti-fogging properties.

[0012] Because the hydrophobic monomer 31 is hydrophobic, it can improve the adhesion between the active energy ray curable composition and the substrate when applied to a hydrophobic substrate 20. Therefore, it is possible to suppress the peeling of the cured film 30 from the substrate 20. In addition, because of the high adhesion between the cured film 30 and the substrate 20, it is also possible to suppress the occurrence of cracks in low-temperature environments. Thus, a highly durable cured film 30 can be formed on the substrate 20.

[0013] The content of hydrophobic monomer 31 is preferably 15% by mass or more and less than 80% by mass of the total amount of the active energy ray curable composition. If the content of hydrophobic monomer is less than 15% by mass, sufficient adhesion to the hydrophobic substrate cannot be ensured. On the other hand, if the content of hydrophobic monomer is 80% by mass or more, the proportion of hydrophilic groups decreases relatively, and therefore sufficient anti-fogging properties cannot be imparted to the substrate.

[0014] The hydrophobic monomer 31 has one or more vinyl groups. That is, the cured film 30 obtained by curing the active energy ray-curable composition containing the hydrophobic monomer contains one or more vinyl groups.

[0015] The vinyl groups contained in the cured film 30 can be determined under the following analysis conditions. (Qualitative analysis conditions) Using the following apparatus, check for the presence or absence of vinyl groups based on the presence or absence of the peak of the C=C stretching vibration at 1640 cm -1 against vibration. Apparatus: Fourier transform infrared spectrophotometer (Model: IRXross manufactured by Shimadzu Corporation) Prism: Diamond (Quantitative analysis conditions) Using the following apparatus, put a standard sample into the cured film solution stirred in deuterated chloroform for 48 hours and perform quantification by the absolute quantification method. Apparatus: NMR (Model: AVANCE NEO 400 Nanobay manufactured by Bruker Japan Co., Ltd.)

[0016] As the hydrophobic monomer 31, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, PEG200 diacrylate, pentaerythritol hexaacrylate, pentaerythritol triacrylate, pentaerythritol alkoxytetraacrylate, pentaerythritol ethoxytetraacrylate, PEG400 diacrylate, PEG600 diacrylate, isobornyl acrylate, 1,6-hexanediol diacrylate, etc. can be used.

[0017] The hydrophilic monomer 32 is a radical-reactive material. At least a part of the hydrophilic monomer is disposed on the surface layer of the active energy ray-curable composition when the active energy ray-curable composition is applied to the surface of the substrate 20 (for example, a polycarbonate resin). Then, by curing the active energy ray-curable composition by radical reaction, a cured film 30 having a hydrophilic function can be formed on the surface of the substrate.

[0018] Therefore, the contact angle of the surface of the molded body 10 having the cured film 30 formed on the surface of the base material 20 with water can be reduced. Thus, by diffusing moisture on the surface of the molded body (cured film), a water film can be formed, and the anti-fog property of the base material can be ensured.

[0019] The content of the hydrophilic monomer 32 is preferably 10% by mass or more and less than 50% by mass with respect to the total amount of the active energy ray-curable composition. When the content of the hydrophilic monomer is less than 10% by mass with respect to the total amount of the active energy ray-curable composition, a sufficient hydrophilic function cannot be ensured on the surface of the cured film, and fogging of the base material cannot be prevented. On the other hand, when the content of the hydrophilic monomer is 90% by mass or more, sufficient adhesion to the hydrophobic base material cannot be ensured.

[0020] The hydrophilic monomer 32 has at least one of a hydroxyl group and an amide group which are hydrophilic functional groups. That is, the cured film 30 obtained by curing the active energy ray-curable composition containing the hydrophilic monomer contains at least one of a hydroxyl group and an amide group which are hydrophilic functional groups, and the cured film 30 has an acrylamide structure and / or an alkylene glycol structure. The total content ratio of the hydroxyl group and the amide group contained in the cured film 30 is 4% by mass or more. Also, the total content ratio of the hydroxyl group and the amide group contained in the cured film 30 is 13% by mass or less.

[0021] The total content ratio of the hydroxyl group and the amide group contained in the cured film 30 can be determined by qualitative evaluation by thermal decomposition GC-MS under the following analysis conditions and then quantitative evaluation by GC-MS. For the quantitative evaluation, the coating film is thermally decomposed with 4-methyltetrahydrofuran / sodium hydroxide, separated into an aqueous layer and an organic layer by liquid separation operation, the hydroxyl group is extracted as alcohol into the organic layer, and the separated acrylamide is used as the amide group, and quantified by GC-MS. (Qualitative analysis conditions) Equipment: Pyrolysis GC-MS (Equipment name: Multi-shot Pyrolyzer, manufactured by Frontier Lab Co., Ltd.) Method: Double shot (First: 100 → 300℃ → Second: 650℃) Column: 123-7033UI (Manufactured by Agilent Technologies, Inc.) (Quantitative analysis conditions) Equipment: GC-MS (Model name: 8890A, manufactured by Agilent Technologies, Inc.) Column: 123-7033UI (Manufactured by Agilent Technologies, Inc.)

[0022] Examples of hydrophilic monomers 32 include N,N-diethylacrylamide, N,N-dimethylacrylamide, pentaerythritol triacrylate, glycerin 1,3-diglycerolate diacrylate, 2-hydroxyethyl acrylate, glycerol 1,2-diacrylate, 3-methylenehexane-1,6-diol, polyethylene glycol diacrylate, and polyethylene glycol triacrylate. These hydrophilic monomers may be used individually or in combination of two or more.

[0023] Based on the above, the cured film 30 contains vinyl groups and at least one of hydroxyl groups and amide groups, with a total content of hydroxyl groups and amide groups of 4% by mass or more. Therefore, as shown in Figure 2, after immersing the molded body 10 having the cured film 30 in water at 40 degrees Celsius for 1 hour, drying it, and dropping 1 μL of pure water (water droplet 40) onto the surface of the cured film 30, the contact angle Θ after 90 seconds can be made 50° or less. In other words, a molded body 10 is obtained that can ensure anti-fogging function even after immersion in water.

[0024] This effect cannot be achieved, for example, if the hydrophilic functional group contained in the cured film is a carboxyl group with high water retention capacity, or if the total content of hydroxyl groups and amide groups is less than 4% by mass.

[0025] Furthermore, the number of vinyl groups in the hydrophobic monomer 31 contained in the active energy ray curable composition that forms the cured film 30 is preferably two or more, and more preferably four or more. By using a hydrophobic monomer with two or more vinyl groups, a denser cured film can be formed, and the contact angle after 90 seconds of dropping 1 μL of pure water onto the surface of the cured film 30, after immersing the molded body 10 having the cured film 30 in water at 40 degrees Celsius for one hour and then drying it, can be reduced to 35° or less. Moreover, by using a hydrophobic monomer 31 with four or more vinyl groups, an even denser cured film can be formed, and the contact angle after 90 seconds of dropping 1 μL of pure water onto the surface of the cured film 30, after immersing the molded body 10 having the cured film 30 in water at 40 degrees Celsius for one hour and then drying it, can be reduced to 25° or less.

[0026] The initiator is a radical generator that produces highly active radicals upon irradiation with ultraviolet light. These radical species react with resin components such as hydrophobic monomers and hydrophilic monomers through decomposition and other processes. The reaction products then react with other resin components, causing a chain reaction. A crosslinking reaction then proceeds, increasing the molecular weight, curing the hydrophobic and hydrophilic monomers, and forming a cured film.

[0027] The initiator content is preferably 1% by mass or more and less than 15% by mass relative to the total amount of the active energy ray-curable composition. If the initiator content is less than 1% by mass, the curing of the active energy ray-curable composition will be insufficient, resulting in curing defects. On the other hand, if the initiator content is 15% by mass or more, the molecular weight will not increase, resulting in insufficient strength of the cured film.

[0028] Examples of initiators that can be used include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-(dimethylamino)-4'-morpholinobylophenone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropane-1-one. It is preferable to use two or more of these initiators in combination. By using two or more initiators in combination, the curing reaction rate of the active energy ray curable composition can be improved.

[0029] Furthermore, in addition to initiators, the active energy ray curable composition may contain various additives such as antibacterial agents, antifungal agents, defoaming agents, antioxidants, antistatic agents, dyes, polymerization inhibitors, ultraviolet absorbers, light stabilizers, and leveling agents.

[0030] Examples of antibacterial agents include captan, carbendazim, quinomethionate, chlorothalonil, clozolinate, cyprodinil, epoxyconazole, famoxadone, phenalimol, fenbuconazole, fenflam, fenpiclonil, azoxystrobin, venalaxyl, benomyl, vitertanol, fluazinam, fludioxonil, fluorimide, fluquinconazole, flusulfamide, flutolanil, and folpet. Hexachlorobenzene, hexaconazole, ipoconazole, iprodione, kresoximmethyl, mancozeb, maneb, mepanipyrim, mepronil, metconazole, methylam, phthalide, procymidone, propineb, quintozen, technazen, tifluzamide, thiophenate-methyl, thyram, tolclophosmethyl, tolfluanide, triadimephon, triadimenol, triazoxide, and triforine can be used. In addition, inorganic antimicrobial agents such as silver, copper, zinc, tin, lead, and gold can also be used. Furthermore, synthetic antimicrobial agents such as polyhexamethylene hyguanide, hydrochloride, benzethonium chloride, alkylpolyaminoethylglycine, and benzisothiazoline can be used.

[0031] Examples of fungicides that can be used include sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one, and their salts.

[0032] Examples of defoaming agents that can be used include fatty acid salts, liquid fatty oil sulfates, higher alcohol sulfates, aliphatic alcohol phosphates, fatty acid amide sulfonates, dibasic fatty acid ester sulfonates, alkylallyl sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, acrylic polymers, vinyl polymers, organopolysiloxanes, and the like.

[0033] Examples of antioxidants that can be used include phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of phenolic antioxidants that can be used include 2,6-di-tert-butyl-p-cresol, stearyl β-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4-hydroxybenzyl)benzene. Examples of phosphorus-based antioxidants that can be used include tris(2,4-di-tert-butylphenyl) phosphite, diphenyl mono(2-ethylhexyl) phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite, distearyl pentaerythritol diphosphite, and tri(mononylphenyl) phosphite. Examples of sulfur-based antioxidants that can be used include dilauryl-3,3'-thiodipropionate and pentaerythritol tetrakis(3-laurylthiopropionate).

[0034] Examples of antistatic agents that can be used include cationic antistatic agents having cationic groups such as primary to tertiary amino groups, quaternary ammonium salts, and pyridinium salts; anionic antistatic agents having anionic groups such as sulfonic acid bases, sulfate ester bases, phosphate ester bases, and phosphonic acid bases; amphoteric antistatic agents such as amino acid-based and aminosulfate ester-based agents; nonionic antistatic agents such as amino alcohol-based, glycerin-based, and polyethylene glycol-based agents; and polymeric antistatic agents that are high molecular weight versions of the aforementioned antistatic agents.

[0035] Examples of dyes that can be used include pyrazole azo compounds, anilino azo compounds, triarylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazoleazomethine compounds, xanthene compounds, phthalocyanine compounds, benzopyran compounds, indigo compounds, and pyromethene compounds.

[0036] Polymerization inhibitors may be added to prevent the double bond from reacting. Examples of polymerization inhibitors include hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), 2,6-di-t-butyl-4-methylphenol (BHT), t-butylcatechol (TBC), and phenol or naphthol derivatives such as 4-methoxy-1-naphthol, phenothiazine derivatives, and nitrosamine salts.

[0037] Examples of UV absorbers that can be used include octyl methoxycinnamate, octyl dimethoxybenzylidene dioxoimidazolidine propionate, diethylamino hydroxybenzoyl hexyl benzoate, t-butyl methoxydibenzoylmethane, octyl triazone, and 2-ethylhexyl paramethoxycinnamate.

[0038] Examples of light stabilizers that can be used include salicylate-based light stabilizers, benzophenone-based light stabilizers, benzotriazole-based light stabilizers, hindered amine-based light stabilizers, cyanoacrylate-based light stabilizers, oxalic acid anilide-based light stabilizers, and nickel-based quenchers.

[0039] Examples of leveling agents that can be used include silicon-based leveling agents, acrylic-based leveling agents, ester compounds, ketone compounds, and fluorine compounds.

[0040] Using Figure 3, we will explain how to manufacture a molded body 10 in which a cured film 30 formed by curing an active energy ray-curable composition is formed on the surface of a substrate 20. First, the active energy ray-curable composition was filled into a paint gun (S1). Then, the substrate 20 to be coated was fixed to a painting jig (S2). The active energy ray-curable composition was applied to the surface of the substrate 20 with the paint gun to a uniform film thickness of 10 μm (S3). Ultraviolet light was irradiated onto the active energy ray-curable composition (S4). The active energy ray-curable composition cured on the surface of the substrate 20 to form a cured film 30 (S5). As described above, a molded body 10 in which a cured film 30 formed by curing an active energy ray-curable composition is formed on the surface of a substrate 20 can be manufactured.

[0041] Furthermore, when applying the active energy ray curable composition to the surface of the substrate 20, it may be applied to a part of the surface of the substrate 20 or to the entire surface of the substrate 20. In other words, the cured film 30 may be formed on a part of the surface of the substrate 20 or to the entire surface of the substrate 20.

[0042] In this embodiment, a uniform cured film 30 of 10 μm thickness was formed on the surface of the substrate 20 by applying the active energy ray curable composition to a uniform thickness of 10 μm. However, the film thickness can be 1 μm to 20 μm, and preferably 10 μm to 18 μm. A film thickness of 10 μm or more can further improve the curing reaction rate of the active energy ray curable composition.

[0043] Furthermore, the method for applying the active energy ray-curable composition is not limited to a paint gun; other application methods such as inkjet or dispenser application methods can also be employed.

[0044] As the base material 20, in addition to polycarbonate resin (PC), transparent materials such as hydrophobic synthetic resins like polymethyl methacrylate resin (PMMA) and glass can be used.

[0045] The molded body 10 can be used as an outer lens (translucent cover) for vehicle lighting fixtures, window glass, eyeglass lenses, and a cover for the surface of an optical sensor. [Examples]

[0046] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples.

[0047] [Example 1] In a 300 mL separable flask equipped with a stirring blade, isobornyl acrylate (product code: I0638, manufactured by Tokyo Chemical Industry Co., Ltd.), which has one vinyl group as a hydrophobic monomer, and N,N-diethylacrylamide (product code: D3737, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 7.86 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 60% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and cured with UV light to obtain a molded article of Example 1 having a cured film with a total content of hydroxyl groups and amide groups of 4% by mass and an acrylamide structure.

[0048] [Example 2] In a 300 mL separable flask equipped with a stirring blade, isobornyl acrylate (product code: IBOA-B, manufactured by Daicel Ornex Co., Ltd.), which has one vinyl group as a hydrophobic monomer, pentaerythritol triacrylate (product code: P2084, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 2.83 hydrophilic groups per molecular size, and N,N-diethylacrylamide (product code: D3737, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 7.86 hydrophilic groups per molecular size, were added. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 60% was obtained. This was applied to the surface of a polymethyl methacrylate resin (PMMA) substrate and UV cured to obtain the molded article of Example 2, which has the substrate and a cured film having a total content of hydroxyl groups and amide groups of 4% by mass, and having polyalkylene glycol structure and acrylamide structure.

[0049] [Example 3] In a 300 mL separable flask equipped with a stirring blade, isobornyl acrylate (product code: IBOA-B, manufactured by Daicel Ornex Co., Ltd.), which has one vinyl group as a hydrophobic monomer, and glycerin 1,3-diglycerolate diacrylate (product code: 475807, manufactured by Merck), which has 8.61 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 60% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and cured with UV light to obtain the molded article of Example 3, which has a cured film with a total content of hydroxyl groups and amide groups of 6% by mass and has polyalkylene glycol and acrylamide structures.

[0050] [Example 4] In a 300 mL separable flask equipped with a stirring blade, isobornyl acrylate (product code: IBOA-B, manufactured by Daicel Ornex Co., Ltd.), which has one vinyl group as a hydrophobic monomer, and 2-hydroxyethyl acrylate (product code: A0743, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 8.61 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 60% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and UV cured to obtain the molded article of Example 4, which has a cured film having a polyalkylene glycol structure and a total content of 6% by mass of hydroxyl and amide groups.

[0051] [Example 5] In a 300 mL separable flask equipped with a stirring blade, 1,6-hexanediol diacrylate (product code: B2936, manufactured by Tokyo Chemical Industry Co., Ltd.), which has two vinyl groups as a hydrophobic monomer, and N,N-diethylacrylamide (product code: D3737, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 7.86 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 60% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and cured with UV light to obtain the molded article of Example 5, which has a cured film with an acrylamide structure and a total content of hydroxyl groups and amide groups of 4% by mass.

[0052] [Example 6] In a 300 mL separable flask equipped with a stirring blade, 1,6-hexanediol diacrylate (product code: B2936, manufactured by Tokyo Chemical Industry Co., Ltd.), which has two vinyl groups as a hydrophobic monomer, and glycerin 1,3-diglycerolate diacrylate (product code: 475807, manufactured by Merck), which has 8.61 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 60% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and cured with UV light to obtain the molded article of Example 6, which has a cured film with a polyalkylene glycol structure and a total content of 6% by mass of hydroxyl groups and amide groups.

[0053] [Example 7] In a 300 mL separable flask equipped with a stirring blade, 1,6-hexanediol diacrylate (product code: B2936, manufactured by Tokyo Chemical Industry Co., Ltd.), which has two vinyl groups as a hydrophobic monomer, and 2-hydroxyethyl acrylate (product code: A0743, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 8.61 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 60% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and UV cured to obtain the molded article of Example 7, which has a cured film having a polyalkylene glycol structure and a total content of 6% by mass of hydroxyl groups and amide groups.

[0054] [Example 8] In a 300 mL separable flask equipped with a stirring blade, 1,6-hexanediol diacrylate (product code: B2936, manufactured by Tokyo Chemical Industry Co., Ltd.), which has two vinyl groups as a hydrophobic monomer, and N,N-diethylacrylamide (product code: D3737, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 7.86 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 60% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and cured with UV light to obtain the molded article of Example 8, which has a cured film with a polyalkylene glycol structure and a total content of 4% by mass of hydroxyl groups and amide groups.

[0055] [Example 9] In a 300 mL separable flask equipped with a stirring blade, 1,6-hexanediol diacrylate (product code: B2936, manufactured by Tokyo Chemical Industry Co., Ltd.), which has two vinyl groups as a hydrophobic monomer, and pentaerythritol triacrylate (product code: P2084, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 2.83 hydrophilic groups per molecular size, and N,N-diethylacrylamide (product code: D3737, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 7.86 hydrophilic groups per molecular size, were added. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 60% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and UV cured to obtain the molded article of Example 9, which has a total content of hydroxyl groups and amide groups of 4% by mass and a cured film having a polyalkylene glycol structure and an acrylamide structure.

[0056] [Example 10] In a 300 mL separable flask equipped with a stirring blade, pentaerythritol tetraacrylate (product code: P2084, manufactured by Tokyo Chemical Industry Co., Ltd.), which has four vinyl groups as a hydrophobic monomer, and glycerol 1,2-diacrylate (product code: B2938, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 8.76 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 50% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and UV cured to obtain a molded article of Example 10 having a cured film with a polyalkylene glycol structure and a total content of 7% by mass of hydroxyl groups and amide groups.

[0057] [Example 11] In a 300 mL separable flask equipped with a stirring blade, pentaerythritol tetraacrylate (product code: P2084, manufactured by Tokyo Chemical Industry Co., Ltd.), which has four vinyl groups as a hydrophobic monomer, and 2-hydroxyethyl acrylate (product code: A0743, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 8.61 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this mixture at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 60% was obtained. This was applied to the surface of a polymethyl methacrylate resin (PMMA) substrate and cured with UV light to obtain the molded article of Example 11, which has a cured film with a polyalkylene glycol structure and a total content of 6% by mass of hydroxyl and amide groups.

[0058] [Example 12] In a 300 mL separable flask equipped with a stirring blade, pentaerythritol tetraacrylate (product code: P2084, manufactured by Tokyo Chemical Industry Co., Ltd.), which has four vinyl groups as a hydrophobic monomer, and 3-methylenehexane-1,6-diol (product name: MPD, manufactured by Kuraray Co., Ltd.), which has 17.2 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 65% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and UV cured to obtain a molded article of Example 12 having a cured film with a polyalkylene glycol structure and a total content of 10% by mass of hydroxyl groups and amide groups.

[0059] [Example 13] In a 300 mL separable flask equipped with a stirring blade, pentaerythritol tetraacrylate (product code: P2084, manufactured by Tokyo Chemical Industry Co., Ltd.), which has four vinyl groups as a hydrophobic monomer, and 3-methylenehexane-1,6-diol (product name: MPD, manufactured by Kuraray Co., Ltd.), which has 17.2 hydrophilic groups per molecular size, and N,N-diethylacrylamide (product code: D3737, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 7.86 hydrophilic groups per molecular size, were added. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 50% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and UV cured to obtain the molded article of Example 13, which has a cured film having a polyalkylene glycol structure and a total content of 13% by mass of hydroxyl groups and amide groups.

[0060] [Comparative Example 1] In a 300 mL separable flask equipped with a stirring blade, isobornyl acrylate (product code: IBOA-B, manufactured by Daicel Ornex Co., Ltd.), which has one vinyl group as a hydrophobic monomer, and N,N-diethylacrylamide (product code: D3737, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 7.86 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 50% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and UV cured to obtain a molded article of Comparative Example 1 having a cured film with an acrylamide structure and a total content of hydroxyl groups and amide groups of 1% by mass.

[0061] [Comparative Example 2] In a 300 mL separable flask equipped with a stirring blade, isobornyl acrylate (product code: IBOA-B, manufactured by Daicel Ornex Co., Ltd.), which has one vinyl group as a hydrophobic monomer, and pentaerythritol triacrylate (product code: P2084, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 2.83 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 50% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and UV cured to obtain a molded article of Comparative Example 2 having a cured film with a polyalkylene glycol structure and a total content of hydroxyl groups and amide groups of 1% by mass.

[0062] [Comparative Example 3] In a 300 mL separable flask equipped with a stirring blade, isobornyl acrylate (product code: IBOA-B, manufactured by Daicel Ornex Co., Ltd.), which has one vinyl group as a hydrophobic monomer, and N,N-diethylacrylamide (product code: D3737, manufactured by Tokyo Chemical Industry Co., Ltd.), which has 7.86 hydrophilic groups per molecular size, were added as a hydrophilic monomer. Next, an initiator was added. By stirring this at room temperature for 30 minutes, an active energy ray curable composition with a hydrophobic monomer content of 50% was obtained. This was applied to the surface of a polycarbonate resin (PC) substrate and UV cured to obtain a molded article of Comparative Example 3 having a cured film with an acrylamide structure and a total content of hydroxyl groups and amide groups of 3% by mass.

[0063] [Comparative Example 4] In a 300 mL separable flask equipped with a stirring blade, 16 wt% of dimethylacrylamide (product code: D1091, manufactured by Tokyo Chemical Industry Co., Ltd.) and hexamethylene diisocyanate (product code: H0324, manufactured by Tokyo Chemical Industry Co., Ltd.) were added as the main components. By stirring this mixture at room temperature for 30 minutes, a thermosetting composition was obtained. This was applied to the surface of a substrate and heated at 80 degrees Celsius for 40 minutes to cure, resulting in a molded article of Comparative Example 4 having a thermosetting cured film.

[0064] [Comparative Example 5] In a 300 mL separable flask equipped with a stirring blade, 20 wt% methyl methacrylate (product code: M0087, manufactured by Tokyo Chemical Industry Co., Ltd.) and sodium alkylbenzene sulfonylate (product name: D0900, manufactured by Tokyo Chemical Industry Co., Ltd.) were added as the main components. By stirring this mixture at room temperature for 30 minutes, a thermosetting composition was obtained. This was applied to the surface of a substrate and heated at 80 degrees Celsius for 40 minutes to cure, resulting in a molded article of Comparative Example 5 having a thermosetting cured film.

[0065] (Evaluation of initial contact angle) The initial contact angle was evaluated in five stages, A to E, by dropping 1 μL of pure water onto the surface of the cured film on each molded body of Examples 1 to 13 or Comparative Examples 1 to 5, and measuring the contact angle of the pure water 90 seconds later. The evaluation was as follows: A for a contact angle of 0° to 10°, B for a contact angle of 11° to 20°, C for a contact angle of 21° to 30°, D for a contact angle of 31° to 50°, and E for a contact angle of 51° or more. Figure 4 summarizes the evaluation results of the initial contact angles for Examples 1 to 13 and Comparative Examples 1 to 5.

[0066] (Evaluation of contact angle after immersion) The molded bodies of Examples 1-13 or Comparative Examples 1-5 were immersed in water at 40 degrees Celsius for 1 hour and then dried. Next, 1 μL of pure water was dropped onto the surface of the cured film on each molded body, and the contact angle of the pure water was measured 90 seconds later to evaluate the post-immersion contact angle on a 5-point scale from A to E (in accordance with JIS D 0203 Test Methods for Humidity and Water Resistance of Automotive Parts). The evaluation was categorized as follows: A for a contact angle of 0° to 25°, B for a contact angle of 26° to 35°, C for a contact angle of 36° to 45°, D for a contact angle of 46° to 55°, and E for a contact angle of 56° or more. Figure 4 summarizes the evaluation results of the initial contact angles for Examples 1-13 and Comparative Examples 1-5.

[0067] (Evaluation of adhesion) Under the analytical conditions described below, the adhesion between the substrate and the cured film was evaluated on a five-point scale from A to E by measuring the peel strength of the substrate and the cured film of the molded articles of Examples 1 to 13 or Comparative Examples 1 to 5 using the surface-interface cutting method (SAICAS method). The evaluation was as follows: A was given when the peel strength was 1.5 kN / m or more; B was given when the peel strength was 1.0 kN / m or more and less than 1.5 kN / m; C was given when the peel strength was 0.5 kN / m or more and less than 1.0 kN / m; D was given when the peel strength was 0.1 kN / m or more and less than 0.5 kN / m; and E was given when the peel strength was less than 0.1 kN / m. Figure 4 summarizes the evaluation results of the adhesion between the substrate and the cured film of Examples 1 to 13 and Comparative Examples 1 to 5. (Analysis conditions) Equipment name: Surface and interface property analysis system (Model: saicas EN type, manufactured by Daipla Wintes Co., Ltd.) Cutting blade: CBN Cutting edge width: 1.0 mm Load cell: Horizontal / Vertical 20N

[0068] (Evaluation of appearance after thermal cycling test) Each of the molded bodies from Examples 1 to 13 or Comparative Examples 1 to 5 was subjected to a temperature increase from room temperature to 80 degrees Celsius at a rate of 2 degrees Celsius per minute, and maintained at 80 degrees Celsius for 120 minutes. Subsequently, each molded body was lowered to -40 degrees Celsius at a rate of 2 degrees Celsius per minute, and maintained at -40 degrees Celsius for 120 minutes. This heating and cooling cycle was repeated 10 times. After that, the molded bodies were raised to 20 degrees Celsius at a rate of 2 degrees Celsius per minute, and the appearance of the cured film on the molded bodies was examined to evaluate the appearance after the heating and cooling cycle test on a 5-point scale from A to E. The evaluation criteria were as follows: A if no change was observed in the cured film after the cold cycle compared to the cured film before the test; B if a change of less than 1% of the surface area of ​​the cured film after the cold cycle was observed; C if a change of 1% or more but less than 5% of the surface area of ​​the cured film after the cold cycle was observed; D if a change of 5% or more but less than 20% of the surface area of ​​the cured film after the cold cycle was observed; and E if a change of 20% or more of the surface area of ​​the cured film after the cold cycle was observed. Changes observed in the cured film after the cold cycle are, for example, changes similar to efflorescence, where solid matter (white crystals) appears on the surface. Figure 4 summarizes the evaluation results of the appearance after the cold cycle test for Examples 1 to 13 and Comparative Examples 1 to 5.

[0069] Figure 4 shows that the cured films of the molded bodies in Examples 1 to 14 have an initial contact angle of less than 50°, indicating that a sufficient initial contact angle is ensured. Furthermore, the cured films of the molded bodies in Examples 1 to 14 have a contact angle of 45° or less after immersion in water, indicating that a sufficient contact angle is ensured even after immersion. In addition, the cured films of the molded bodies in Examples 1 to 14 have a peel strength of 0.5 kN / m or more in the adhesion evaluation, indicating that sufficient adhesion is ensured between the substrate and the cured film. Moreover, in the appearance evaluation after the thermal cycling test, the cured films of the molded bodies in Examples 1 to 14 showed a change of less than 5% in the surface area of ​​the cured film after the thermal cycling test compared to the cured film before the test, indicating that they can withstand temperature changes.

[0070] The results from Examples 5 to 13 show that when the number of vinyl groups contained in the cured film is two or more, the contact angle after immersion is 35° or less, indicating that a superior contact angle can be secured even after immersion.

[0071] The results from Examples 10-13 show that when the number of vinyl groups contained in the cured film is four or more, the contact angle after immersion is 35° or less, indicating that a superior contact angle can be secured even after immersion.

[0072] In contrast, Comparative Examples 1 and 2, in which the total content of hydroxyl groups and amide groups in the cured film was 1% by mass, showed a contact angle of 56° or more after immersion, indicating that a sufficient contact angle could not be secured after immersion. Furthermore, in the evaluation of adhesion, the peel strength was less than 0.5 kN / m, indicating that adhesion between the substrate and the cured film could not be ensured. Moreover, in the evaluation of appearance after the thermal cycling test, comparing the cured film after the thermal cycling with the cured film before the test, the change in the surface area of ​​the cured film after the thermal cycling was 5% or more, indicating that it could not withstand temperature changes.

[0073] Furthermore, in Comparative Example 3, where the total content of hydroxyl groups and amide groups in the cured film is 3% by mass, the contact angle after immersion is 46° or higher, indicating that a sufficient contact angle cannot be secured after immersion. In addition, in the adhesion evaluation, the peel strength is less than 0.5 kN / m, indicating that adhesion between the substrate and the cured film cannot be secured. Moreover, in the appearance evaluation after the thermal cycling test, comparing the cured film after thermal cycling with the cured film before the test, the change in the surface area of ​​the cured film after thermal cycling was 5% or more, indicating that it cannot withstand temperature changes.

[0074] Furthermore, in Comparative Examples 4 and 5, which are thermosetting compositions, the contact angle after immersion is 46° or higher, indicating that a sufficient contact angle cannot be secured after immersion.

[0075] As described above, the molded article of the present invention can ensure anti-fogging functionality even after submersion in water. [Explanation of symbols]

[0076] 10 Molded body 20 Base material 30 Cured film 31 Hydrophobic monomers 32 Hydrophilic monomers 40 water drops

Claims

1. A molded body comprising a substrate and an active energy curable film covering at least a portion of the surface of the substrate, The cured film contains a vinyl group and at least one of a hydroxyl group and an amide group. The total content of the hydroxyl group and the amide group is 4% by mass or more. The molded body is immersed in water at 40 degrees Celsius for one hour, then dried, and the contact angle after 90 seconds of dropping 1 μL of pure water onto the surface of the cured film is 50° or less.

2. A molded article according to claim 1, A molded article having at least one of an acrylamide structure and an alkylene glycol structure in the cured film.

3. A molded article according to claim 1, The molded body is immersed in water at 40 degrees Celsius for one hour, then dried, and the contact angle after 90 seconds of dropping 1 μL of pure water onto the surface of the cured film is 40° or less.

4. A molded article according to claim 1, A molded article in which the base material is polycarbonate resin or polymethyl methacrylate resin.

5. A vehicle light fixture having the molded body described in claim 1.

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