Active energy ray-curable antifogging composition and resin molded article

Abstract

An active energy ray-curable antifogging composition which is solvent-free, comprising: a radically reactive material containing a hydrophilic group; a polyfunctional acrylate; and a compound represented by general formula (1), and having a viscosity of 10-50 mPa∙s. (In general formula (1), each A independently represents either a hydrogen atom or a methyl group, X represents an oxygen atom, and R1 represents either a hydroxy group or an amino group).

Description

Active energy ray-curable anti-fogging composition and resin molded body

[0001] The present invention relates to an active energy ray-curable anti-fogging composition and a resin molded article.

[0002] Transparent synthetic resins such as polycarbonate resin (PC) and polymethyl methacrylate resin (PMMA) have excellent transparency, moldability, and mechanical properties, and are therefore used in many fields, such as lamp covers for automobiles and motorcycles, eyeglass lenses, optical sensor covers, and various liquid crystal panels. However, there is a problem that scratches or dirt adhere to the surface of a molded product such as a synthetic resin, reducing light transmittance and causing poor visibility and malfunction of sensors, etc. To prevent such problems, transparency (scratch resistance, etc.) is ensured by applying a composition to the surface of the molded product such as a synthetic resin.

[0003] For example, Patent Document 1 discloses a curable composition containing a curable compound, 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane, a base, and a polymerization initiator.

[0004] Patent No. 6999862

[0005] However, when the surface temperature of a molded product such as a synthetic resin obtained by curing such a curable composition drops below the dew point, moisture in the air condenses into fine droplets, causing fogging, which reduces light transmittance and leads to poor visibility and malfunction of sensors, etc.

[0006] The present invention has been made in view of the above points, and an object of the present invention is to provide an active energy ray-curable anti-fogging composition and a resin molded article which are excellent in anti-fogging properties and durability.

[0007] The active energy ray-curable anti-fogging composition of the present invention is a solvent-free active energy ray-curable anti-fogging composition, which contains a radical-reactive material containing a hydrophilic group, a polyfunctional acrylate, and a compound represented by the following general formula (1), and has a viscosity of 10 to 50 mPa·s: (In general formula (1), each A independently represents either a hydrogen atom or a methyl group, X represents an oxygen atom, and R1 represents either a hydroxy group or an amino group).

[0008] 1 is a conceptual diagram showing a resin molded body of the present invention. 2 is a diagram showing a manufacturing process of a resin molded body of the present invention. 3 is a table summarizing the results of comparison between Examples and Comparative Examples of the active energy ray-curable anti-fogging composition of the present invention. 4 is a conceptual diagram showing a conventional resin molded body.

[0009] An embodiment of the present invention will be described below. The active energy ray-curable anti-fogging composition 10 of the present invention contains a radical-reactive material, a polyfunctional acrylate, compound A, and an initiator, and has a viscosity of 10 to 50 mPa·s.

[0010] The active energy ray-curable anti-fogging composition 10 is a solvent-free type. Here, "solvent-free type" means that the active energy ray-curable anti-fogging composition 10 does not contain a non-reactive volatile organic solvent or substantially does not contain a non-reactive volatile organic solvent. "Substantially does not contain a non-reactive volatile organic solvent" means that when the active energy ray-curable anti-fogging composition 10 is subjected to gas chromatography analysis at 200°C, the total amount of components detected that have a structure not containing a vinyl group or an acryloyl group is less than 1 mass%.

[0011] Because the active energy ray-curable anti-fogging composition 10 is solvent-free, when the active energy ray-curable anti-fogging composition 10 is cured, most of the active ingredient forms a cured film, which makes it possible to reduce the total amount of the active energy ray-curable anti-fogging composition 10 required for application to the surface of the substrate 20.

[0012] The radical-reactive material contains hydrophilic groups. As shown in Fig. 1, when an active energy ray-curable anti-fogging composition 10 is applied to the surface of a substrate 20 (e.g., a polycarbonate resin), at least a portion of the hydrophilic groups 11 are disposed in the surface layer of the active energy ray-curable anti-fogging composition 10. Then, by curing the active energy ray-curable anti-fogging composition 10 through a radical reaction, a cured film having hydrophilic groups can be formed on the surface of the substrate 20.

[0013] Since the hydrophilic groups are disposed on the surface of the active energy ray-curable anti-fogging composition 10, the surface of the active energy ray-curable anti-fogging composition 10 has a hydrophilic function. This reduces the contact angle between the surface of the active energy ray-curable anti-fogging composition 10 and water. As a result, moisture diffuses onto the surface of the active energy ray-curable anti-fogging composition 10 to form a water film, thereby ensuring the anti-fogging properties of the substrate 20.

[0014] The radical-reactive material is a radical-reactive material composed of a resin component such as a monomer or oligomer. By incorporating the radical-reactive material into the active energy ray-curable anti-fogging composition 10, the viscosity of the active energy ray-curable anti-fogging composition 10 can be reduced. Therefore, the active energy ray-curable anti-fogging composition 10 can be used for coating without being diluted with an organic solvent. Therefore, a thermal drying step is not required in the step of curing the active energy ray-curable anti-fogging composition 10 on the surface of the substrate 20, and power consumption during production can be reduced.

[0015] The content of the radical reactive material is preferably 70% by mass or more and less than 90% by mass, based on the total amount of the active energy ray-curable anti-fogging composition 10. By having the content be 70% by mass or more, based on the total amount of the active energy ray-curable anti-fogging composition 10, the viscosity of the active energy ray-curable anti-fogging composition 10 can be adjusted to a value suitable for spray coating without diluting it with an organic solvent. The viscosity suitable for spray coating is, for example, 10 to 50 mPa·s / 25°C.

[0016] Furthermore, if the content of the radical reactive material is less than 70% by mass, the surface of the cured film cannot be provided with sufficient hydrophilic function, and fogging of the substrate cannot be prevented, whereas if the content of the radical reactive material is 90% by mass or more, sufficient adhesion to the hydrophobic substrate 20 cannot be ensured.

[0017] Examples of radical reactive materials that can be used include polyethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, polytetramethylene glycol diacrylate, etc. These radical reactive materials may be used alone or in combination of two or more.

[0018] The polyfunctional acrylate is a highly reactive hydrophobic material. By including a polyfunctional acrylate in the active energy ray-curable anti-fogging composition, the curing rate of the active energy ray-curable anti-fogging composition 10 can be increased. Furthermore, the highly reactive polyfunctional acrylate cures, and the radical-reactive material having a hydrophilic group cures later. Therefore, the polyfunctional acrylate, which is compatible with hydrophobic substrates, adheres to the substrate, and the hydrophilic material that cures later is more likely to be positioned on the outermost surface. Therefore, a thin film of the hydrophilic material can be applied to the surface of the cured film, further improving the anti-fogging properties.

[0019] Because polyfunctional acrylates are hydrophobic, they can improve the adhesion between the active energy ray-curable anti-fogging composition 10 and the substrate 20 when applied to the hydrophobic substrate 20. This can prevent the cured film from peeling off from the substrate 20. Furthermore, the high adhesion between the cured film and the substrate 20 can also prevent cracks from occurring in low-temperature environments. This allows a cured film with excellent durability to be formed on the substrate 20.

[0020] The content of the polyfunctional monomer is preferably 1% by mass or more and less than 10% by mass with respect to the total amount of the active energy ray-curable anti-fog composition 10. If the content of the polyfunctional monomer is less than 1% by mass, sufficient adhesion to the hydrophobic substrate cannot be ensured. On the other hand, if the content of the polyfunctional monomer is 10% by mass or more, the proportion of hydrophilic groups decreases relatively, making it impossible to impart sufficient anti-fog properties to the substrate. Furthermore, if the content of the polyfunctional monomer is 10% by mass or more, the viscosity of the active energy ray-curable anti-fog composition increases, reducing the dischargeability during spray coating, making spray coating difficult.

[0021] As the polyfunctional monomer, dipentaerythritol hexaacrylate, trimethylolpropane ethoxy triacrylate, dipentaerythritol hexaacrylate, etc. can be used.

[0022] Compound A is represented by the following general formula (1). (In general formula (1), each A independently represents either a hydrogen atom or a methyl group, X represents an oxygen atom, and R1 represents either a hydroxy group or an amino group).

[0023] For example, when A in general formula (1) is a methyl group and R1 is a hydroxy group, compound A is 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane, and when A in general formula (1) is a hydrogen atom and R1 is a hydroxy group, compound A is 1,3-diallyloxy-2-propanol.

[0024] When an active energy ray-curable anti-fogging composition is cured into a thin film, the curing of the active energy ray-curable anti-fogging composition may be insufficient due to oxygen inhibition. However, because Compound A has an oxygen absorbing effect, the active energy ray-curable anti-fogging composition 10 containing Compound A can be prevented from being inhibited by oxygen curing. Therefore, the occurrence of water drip marks due to insufficient curing of the active energy ray-curable anti-fogging composition can be prevented.

[0025] The oxygen absorption mechanism of compound A is shown below. During the radical reaction, a radical is generated at the allylic position of compound A, which reacts with oxygen to generate a peroxide radical of compound A, capturing oxygen. The generated peroxide radical abstracts a hydrogen atom from another compound A, regenerating a radical and completing the oxygen absorption cycle of compound A.

[0026] The content of compound A is preferably 0.1% by mass or more and less than 5.0% by mass with respect to the total amount of the active energy ray-curable anti-fogging composition 10. If the content of compound A is less than 0.1% by mass, the oxygen absorption effect becomes insufficient and the occurrence of water drip marks cannot be sufficiently suppressed. On the other hand, if the content of compound A is 5.0% by mass or more, the reactivity of the active energy ray-curable anti-fogging composition may deteriorate, resulting in the occurrence of water drip marks.

[0027] 4 is a diagram showing a resin molded body 60 obtained by curing an active energy ray-curable composition 40 that does not contain compound A on a substrate 50. As shown in Fig. 4, when an active energy ray-curable composition 40 that does not contain compound A is cured on the surface of a substrate 50, a portion of the active energy ray-curable composition 40 is insufficiently cured due to the influence of oxygen inhibition, the radical-reactive material having a hydrophilic group bleeds out, and further, water droplets 41 are generated by moisture, steam, water droplets 70, etc. Because the radical-reactive material having a hydrophilic group elutes, the surface of the cured product becomes a hydrophobic coating, reducing the anti-fogging function and causing fogging.

[0028] The initiator is a radical generator that generates highly active radicals upon irradiation with ultraviolet light. These radical species undergo decomposition and react with resin components such as monomers and / or oligomers. This reaction product then reacts with other resin components, causing a chain reaction to proceed. The crosslinking reaction then proceeds, increasing the molecular weight and curing the radical-reactive material and polyfunctional acrylate to form a cured film.

[0029] The content of the initiator is preferably 0.1% by mass or more and less than 5.0% by mass, based on the total amount of the active energy ray-curable anti-fogging composition 10. If the content of the initiator is less than 0.1% by mass, the active energy ray-curable anti-fogging composition will not cure sufficiently, resulting in poor curing. On the other hand, if the content of the initiator is 5.0% by mass or more, the molecular weight will not increase, resulting in insufficient strength of the cured film.

[0030] Examples of the initiator include ketones such as benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, and 1-hydroxycyclohexyl phenyl ketone; azos such as 2,2'-azobisisobutylnitrile, azobis-2-methylbutyronitrile, and azobisdivaleronitrile; organic peroxides such as t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropyl carbonate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, di-t-butyl peroxide, and di-t-amyl peroxide; and acylphosphine compounds such as 2,6-dimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Known compounds can be used as the initiator. Among these, radical cleavage initiators such as 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. are preferred. These initiators may be used alone or in combination of two or more.

[0031] In addition to the initiator, the active energy ray-curable anti-fogging composition 10 may contain various additives such as an antibacterial agent, an antifungal agent, an antifoaming agent, an antioxidant, an antistatic agent, and a polymerization inhibitor.

[0032] Examples of antibacterial agents include captan, carbendazim, quinomethionate, chlorothalonil, clozolinate, cyprodinil, epoxiconazole, famoxadone, fenarimol, fenbuconazole, fenfuram, fenpiclonil, azoxystrobin, benalaxyl, benomyl, bitertanol, fluazinam, fludioxonil, fluorimide, fluquinconazole, flusulfamide, flutolanil, folpet, Hexachlorobenzene, hexaconazole, ipoconazole, iprodione, kresoxim methyl, manzeb, maneb, mepanipyrim, mepronil, metconazole, metiram, phthalide, procymidone, propineb, quintozene, tecnazene, thifluzamide, thiophenate methyl, thiram, tolclofos methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, triforine, etc. can be used. Inorganic antibacterial agents can also be used, for example, silver, copper, zinc, tin, lead, gold, etc. Furthermore, synthetic antibacterial agents can also be used, for example, polyhexamethylene hyguanide, hydrochloride, benzethonium chloride, alkylpolyaminoethylglycine, benzisothiazoline, etc.

[0033] Examples of the antifungal agent that can be used include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof.

[0034] Examples of the defoaming agent that can be used include fatty acid salts, liquid fatty oil sulfates, higher alcohol sulfates, fatty alcohol phosphates, fatty acid amide sulfonates, sulfonates of dibasic fatty acid esters, alkylarylsulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, acrylic polymers, vinyl polymers, and organopolysiloxanes.

[0035] Examples of the antioxidant that can be used include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of the phenol-based antioxidant 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 the phosphorus-based antioxidant include tris(2,4-di-tert-butylphenyl)phosphite, diphenylmono(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).

[0036] Examples of the antistatic agent that can be used include various cationic antistatic agents having a cationic group such as a primary to tertiary amino group, a quaternary ammonium salt, or a pyridinium salt; anionic antistatic agents having an anionic group such as a sulfonate group, a sulfate group, a phosphate group, or a phosphonate group; amphoteric antistatic agents such as amino acid-based or amino sulfate-based; nonionic antistatic agents such as amino alcohol-based, glycerin-based, or polyethylene glycol-based; and polymeric antistatic agents obtained by increasing the molecular weight of the above-mentioned antistatic agents.

[0037] A polymerization inhibitor may be added to prevent the double bond from reacting. Examples of the polymerization inhibitor 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.

[0038] 2, a method for producing a resin molded article 30 in which an active energy ray-curable anti-fog composition 10 is cured on the surface of a substrate 20 will be described. First, the active energy ray-curable anti-fog composition 10 was loaded into a paint gun (S1). Then, the substrate 20 to be coated was fixed to a painting jig (S2). The active energy ray-curable anti-fog composition 10 was applied to the surface of the substrate 20 with the paint gun to a uniform film thickness of less than 10 μm (S3). The active energy ray-curable anti-fog composition 10 was irradiated with ultraviolet light (S4). The active energy ray-curable anti-fog composition 10 was cured on the surface of the substrate 20 to form a cured film (S5). As described above, a resin molded article 30 in which the active energy ray-curable anti-fog composition 10 is cured on the surface of the substrate 20 can be produced.

[0039] When applying the active energy ray-curable anti-fogging composition 10 to the surface of the substrate 20, the composition may be applied to a part of the surface of the substrate 20 or to the entire surface of the substrate 20. The method for applying the active energy ray-curable anti-fogging composition 10 is not limited to a paint gun, and application methods using an inkjet or a dispenser may also be used.

[0040] As the substrate 20, in addition to polycarbonate resin (PC), hydrophobic synthetic resin such as polymethyl methacrylate resin (PMMA), hydrophobic materials such as glass, and the like can be used.

[0041] The active energy ray-curable anti-fog composition 10 can be used as an anti-fog coating. Furthermore, the resin molded article 30 obtained by curing the active energy ray-curable anti-fog composition on the surface of a substrate can be used as an outer lens (translucent cover) for a vehicle lamp, a window glass, a lens for eyeglasses, a cover for the surface of an optical sensor, and the like.

[0042] [Variation 1] Variation 1 of the active energy ray-curable anti-fogging composition of the present embodiment will be described. Variation 1 of the active energy ray-curable anti-fogging composition is a solvent-free active energy ray-curable anti-fogging composition that contains a radical-reactive material, a polyfunctional acrylate, compound A, an initiator, and a thiol material, and has a viscosity of 10 to 50 mPa·s.

[0043] The thiol material is a compound containing a polyfunctional thiol group. By including a thiol material in the active energy ray-curable anti-fogging composition 10, oxygen inhibition due to a thiol-ene reaction can be suppressed.

[0044] The reaction mechanism of the thiol-ene reaction is shown below. First, ultraviolet light is irradiated, causing the initiator to cleave or undergo energy transfer (initiation reaction). The initiator then abstracts an electron from the thiol material, generating a thiyl radical. The thiyl radical attacks the double bond of a monomer of a hydrophobic or hydrophilic material to form a hydrophobic or hydrophilic material having a thioether crosslink and a radical. This further abstracts a hydrogen atom from the thiol material, generating a thiyl radical. The generated thiyl radical then attacks the double bond of a monomer of another hydrophobic or hydrophilic material (propagation reaction). This chain reaction proceeds in this manner, allowing the active energy ray-curable anti-fogging composition 10 to be efficiently cured.

[0045] By including a thiol material in the active energy ray-curable anti-fogging composition 10, curing can be promoted by a dark reaction even in the atmosphere (oxygen atmosphere). The reaction mechanism under an oxygen atmosphere is shown below. First, oxygen reacts with a monomer to generate a peroxy radical. Then, the peroxy radical abstracts hydrogen from the thiol to generate a thiyl radical. The thiyl radical then undergoes the above-mentioned propagation reaction. Therefore, the active energy ray-curable anti-fogging composition can be cured even in an oxygen atmosphere.

[0046] By including a thiol material in the active energy ray-curable anti-fogging composition 10, a thioether crosslinked structure is formed, thereby increasing the flexibility of the cured film. This can suppress the occurrence of cracks in low-temperature environments and further improve durability. Here, the flexibility of the cured film can be increased because the sulfur atoms in the thioether crosslinked structure can move, such as rotate.

[0047] By including a thiol material in the active energy ray-curable anti-fogging composition 10, cure shrinkage can be suppressed. Cure shrinkage occurs when the double bonds of the radical-reactive material are polymerized by radical polymerization, converting them into a high-molecular-weight compound connected by single bonds, thereby shortening the molecular bond distance. However, by including a thiol material, shortening of the molecular bond distance can be suppressed by forming a thioether crosslink with the double bonds of the radical-reactive material. Therefore, cure shrinkage is suppressed, and defects such as cracks and warpage of the cured film can be suppressed.

[0048] The content of the thiol material is preferably 1% by mass or more and less than 5% by mass with respect to the total amount of the active energy ray-curable anti-fogging composition 10 .

[0049] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0050] Example 1 A 300 mL separable flask equipped with a stirring blade was charged with 90 parts by mass of PEG200 diacrylate (product name: PEG200DA, manufactured by Daicel-Allnex Corporation) as a radical-reactive material, 5 parts by mass of dipentaerythritol hexaacrylate (product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) as a polyfunctional acrylate, and 2 parts by mass of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) as Compound A. Next, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) as an initiator was added. The mixture was stirred at room temperature for 30 minutes to obtain 100 parts by mass of the active energy ray-curable anti-fogging composition of Example 1.

[0051] Example 2 A 300 mL separable flask equipped with a stirring blade was charged with 85 parts by mass of PEG200 diacrylate (product name: PEG200DA, manufactured by Daicel-Allnex Corporation) as a radical-reactive material, 5 parts by mass of dipentaerythritol hexaacrylate (product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) as a multifunctional acrylate, 1 part by mass of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) as compound A, and 5 parts by mass of pentaerythritol tetrakis(3-mercaptobutyrate) (product name: KarenzMT® PE1, manufactured by Resonac Corporation) as a thiol material. Next, 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) was added as an initiator. This was stirred at room temperature for 30 minutes, yielding 100 parts by mass of the active energy ray-curable anti-fogging composition of Example 2.

[0052] Example 3 A 300 mL separable flask equipped with a stirring blade was charged with 90 parts by mass of PEG600 diacrylate (product name: EBECRYL 11, manufactured by Daicel-Allnex Corporation) as a radical-reactive material, 5 parts by mass of trimethylolpropane ethoxy triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polyfunctional acrylate, 1 part by mass of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) as compound A, and 1 part by mass of pentaerythritol tetrakis(3-mercaptobutyrate) (product name: KarenzMT(R) PE1, manufactured by Resonac Corporation) as a thiol material. Next, 3 parts by mass of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropane (product name: Omnirad2959, manufactured by Sanyo Trading Co., Ltd.) was added as an initiator, and the mixture was stirred at room temperature for 30 minutes, yielding 100 parts by mass of the active energy ray-curable anti-fogging composition of Example 3.

[0053] Example 4 A 300 mL separable flask equipped with a stirring blade was charged with 90 parts by mass of triethylene glycol diacrylate (product name: Light Acrylate 3EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) as a radical-reactive material, 3 parts by mass of trimethylolpropane ethoxy triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polyfunctional acrylate, 3 parts by mass of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) as compound A, and 1 part by mass of pentaerythritol tetrakis(3-mercaptobutyrate) (product name: KarenzMT(R) PE1, manufactured by Resonac Co., Ltd.) as a thiol material. Next, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) as an initiator was added. This was stirred at room temperature for 30 minutes, yielding 100 parts by mass of the active energy ray-curable anti-fogging composition of Example 4.

[0054] Example 5 A 300 mL separable flask equipped with a stirring blade was charged with 80 parts by mass of triethylene glycol diacrylate (product name: Light Acrylate 3EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) as a radical-reactive material, 15 parts by mass of trimethylolpropane ethoxy triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polyfunctional acrylate, 1 part by mass of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) as compound A, and 1 part by mass of trimethylolpropane tris(3-mercaptobutyrate) (product name: KarenzMT® TPMB, manufactured by Resonac Corporation) as a thiol material. Next, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) as an initiator was added. This was stirred at room temperature for 30 minutes, yielding 100 parts by mass of the active energy ray-curable anti-fogging composition of Example 5.

[0055] Example 6 To a 300 mL separable flask equipped with a stirring blade were added 10 parts by mass of pentaerythritol triacrylate (product name: Light Acrylate PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) and 70 parts by mass of triethylene glycol diacrylate (product name: Light Acrylate 3EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) as radical-reactive materials, 5 parts by mass of dipentaerythritol hexaacrylate (product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) as a polyfunctional acrylate, 1 part by mass of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) as compound A, and 1 part by mass of pentaerythritol tetrakis(3-mercaptobutyrate) (product name: KarenzMT(R) PE1, manufactured by Resonac Corporation) as a thiol material. Next, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) was added as an initiator, and the mixture was stirred at room temperature for 30 minutes to obtain 100 parts by mass of the active energy ray-curable anti-fogging composition of Example 6.

[0056] Example 7 A 300 mL separable flask equipped with a stirring blade was charged with 90 parts by mass of 2-hydroxy-3-acryloyloxypropyl acrylate as a radical-reactive material (product name: Light Ester G-201P, manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of trimethylolpropane ethoxy triacrylate as a polyfunctional acrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.), 1 part by mass of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) as compound A (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.), and 1 part by mass of 1,4-bis(3-mercaptobutyryloxy)butane as a thiol material (product name: KarenzMT(R) BD1, manufactured by Resonac Inc.). Next, 3 parts by mass of 2-methyl-4'-(methylthio)-2-morpholinopropiophenone (product name: Omnirad907, manufactured by Sanyo Trading Co., Ltd.) was added as an initiator, and the mixture was stirred at room temperature for 30 minutes to obtain 100 parts by mass of the active energy ray-curable anti-fogging composition of Example 7.

[0057] Example 8 A 300 mL separable flask equipped with a stirring blade was charged with 60 parts by mass of 2-hydroxy-3-acryloyloxypropyl acrylate (product name: Light Ester G-201P, manufactured by Kyoeisha Chemical Co., Ltd.) and 30 parts by mass of polytetramethylene glycol diacrylate (product name: Light Acrylate PTMGA-250, manufactured by Kyoeisha Chemical Co., Ltd.) as radical-reactive materials, 5 parts by mass of trimethylolpropane ethoxy triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polyfunctional acrylate, 1 part by mass of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) as compound A, and 2 parts by mass of 1,4-bis(3-mercaptobutyryloxy)butane (product name: KarenzMT(R) BD1) as a thiol material. Next, 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) was added as an initiator. The mixture was stirred at room temperature for 30 minutes, yielding 100 parts by mass of the active energy ray-curable anti-fogging composition of Example 8.

[0058] Example 9 To a 300 mL separable flask equipped with a stirring blade were added 90 parts by mass of polytetramethylene glycol diacrylate (product name: Light Acrylate PTMGA-250, manufactured by Kyoeisha Chemical Co., Ltd.) as a radical-reactive material, 5 parts by mass of trimethylolpropane ethoxy triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polyfunctional acrylate, 1 part by mass of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) as compound A, and 1 part by mass of pentaerythritol tetrakis(3-mercaptobutyrate) (product name: KarenzMT(R) PE1, manufactured by Resonac Corporation) as a thiol material. Next, 3 parts by mass of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropane (product name: Omnirad2959, manufactured by Sanyo Trading Co., Ltd.) was added as an initiator, and the mixture was stirred at room temperature for 30 minutes to obtain 100 parts by mass of the active energy ray-curable anti-fogging composition of Example 9.

[0059] Example 10 To a 300 mL separable flask equipped with a stirring blade were added 70 parts by mass of PEG600 diacrylate (product name: EBECRYL 11, manufactured by Daicel-Allnex Corporation) and 20 parts by mass of polytetramethylene glycol diacrylate (product name: Light Acrylate PTMGA-250, manufactured by Kyoeisha Chemical Co., Ltd.) as radical-reactive materials, 5 parts by mass of trimethylolpropane ethoxy triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polyfunctional acrylate, 1 part by mass of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) as compound A, and 1 part by mass of pentaerythritol tetrakis(3-mercaptobutyrate) (product name: KarenzMT(R) PE1, manufactured by Resonac Corporation) as a thiol material. Next, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) was added as an initiator, and the mixture was stirred at room temperature for 30 minutes to obtain 100 parts by mass of the active energy ray-curable anti-fogging composition of Example 10.

[0060] Example 11 To a 300 mL separable flask equipped with a stirring blade were added 10 parts by mass of pentaerythritol triacrylate (product name: Light Acrylate PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) and 70 parts by mass of triethylene glycol diacrylate (product name: Light Acrylate 3EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) as radical-reactive materials, 5 parts by mass of dipentaerythritol hexaacrylate (product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) as a polyfunctional acrylate, 1 part by mass of 1,3-diallyloxy-2-propanol (GDAE) (product code: D2146, manufactured by Tokyo Chemical Industry Co., Ltd.) as compound A, and 1 part by mass of pentaerythritol tetrakis(3-mercaptobutyrate) (product name: KarenzMT(R) PE1, manufactured by Resonac Corporation) as a thiol material. Next, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) was added as an initiator, and the mixture was stirred at room temperature for 30 minutes to obtain 100 parts by mass of an active energy ray-curable anti-fogging composition of Example 11.

[0061] Comparative Example 1 A 300 mL separable flask equipped with a stirring blade was charged with 90 parts by mass of pentaerythritol (tri / tetra)acrylate as a polyfunctional acrylate (product name: Light Acrylate PE-3A, Light Acrylate PE-4A, manufactured by Kyoeisha Chemical Co., Ltd.) and 5 parts by mass of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) as compound A (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.). Next, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone as an initiator (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) was added. The mixture was stirred at room temperature for 30 minutes, yielding 100 parts by mass of the active energy ray-curable composition of Comparative Example 1.

[0062] (Evaluation of Dissolution Properties) Each test piece, the surface of which was cured with the active energy ray-curable anti-fogging composition of Examples 1 to 11 or the active energy ray-curable composition of Comparative Example 1, was placed on a hot plate heated to 90°C, and 20 μL of pure water heated to 50°C was dropped onto the test piece. The traces of the drop visible after the pure water was evaporated were then visually observed to evaluate the dissolution properties on a 5-point scale of A to E. The evaluation was based on the following criteria: A indicates that no trace of the eluted components was visible; B indicates that a partial trace of the eluted components was visible; C indicates that a thin, spreading trace of the eluted components was visible; D indicates that a trace of the eluted components was clearly visible; and E indicates that light was not transmitted due to the eluted components. The evaluation results of dissolution properties for Examples 1 to 11 and Comparative Example 1 are summarized in FIG. 3 .

[0063] (Evaluation of Anti-Fog Properties) Each test piece, the surface of which was cured with the active energy ray-curable anti-fogging composition of Examples 1 to 11 or the active energy ray-curable composition of Comparative Example 1, was immersed in warm water at 40°C for 240 hours. The test piece was then dried at room temperature, and breath was blown onto the test piece at room temperature. The surface area of ​​the test piece where fogging occurred was visually confirmed to evaluate the anti-fogging properties on a 5-point scale of A to E. The evaluation was based on the following criteria: A: no fogging occurred on the test piece; B: fogging occurred over about 10% of the surface area of ​​the test piece; C: fogging occurred over about 50% of the surface area of ​​the test piece; D: fogging occurred over about 80% of the surface area of ​​the test piece; and E: fogging occurred over the entire surface area of ​​the test piece. The evaluation results of the anti-fogging properties of Examples 1 to 11 and Comparative Example 1 are summarized in FIG. 3 .

[0064] (Evaluation of Condition in a Low-Temperature Environment) Each test piece, on the surface of which the active energy ray-curable anti-fogging composition of Examples 1 to 11 or the active energy ray-curable composition of Comparative Example 1 was cured, was left in a −40° C. freezer for 240 hours. The test piece was then returned to room temperature, and the condition of the cured film was visually inspected to evaluate the condition in a low-temperature environment on a 5-point scale of A to E. The evaluation was based on the following criteria: A indicates that the cured film was free of cracks and fractures; B indicates that the cured film was free of cracks but had minor cracks; C indicates that the cured film was free of cracks but had some cracks; D indicates that the cured film had some cracks and fractures; and E indicates that the cured film had large cracks. FIG. 3 shows a summary of the evaluation results of the condition in a low-temperature environment for Examples 1 to 11 and Comparative Example 1.

[0065] (Evaluation of Non-reactive Volatile Organic Solvent Content) The active energy ray-curable anti-fogging compositions of Examples 1 to 11 and the active energy ray-curable composition of Comparative Example 1 were each subjected to gas chromatography analysis at 200°C, and the total value of components detected with a structure not containing a vinyl group or an acryloyl group was determined. The evaluation was performed as follows: A when the total value was less than 1 mass%, B when the total value was 1 mass% or more but less than 10 mass%, C when the total value was 10 mass% or more but less than 30 mass%, D when the total value was 30 mass% or more but less than 50 mass%, and E when the total value was 50 mass% or more. Figure 3 shows a summary of the evaluation results for the non-reactive volatile organic solvent content of Examples 1 to 11 and Comparative Example 1.

[0066] (Evaluation of Dischargeability) The viscosity of each of the active energy ray-curable anti-fogging compositions of Examples 1 to 11 and the active energy ray-curable composition of Comparative Example 1 was measured and evaluated. The viscosity was measured using an E-type viscometer (product name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K2283. The evaluation was performed as follows: A: viscosity of 3 mPa·s or more but less than 30 mPa·s; B: viscosity of 30 mPa·s or more but less than 40 mPa·s; C: viscosity of 40 mPa·s or more but less than 50 mPa·s; D: viscosity of 50 mPa·s or more but less than 80 mPa·s; and E: viscosity of 80 mPa·s or more. FIG. 3 shows a summary of the evaluation results of dischargeability for Examples 1 to 11 and Comparative Example 1.

[0067] As is clear from Figure 3, Examples 1 to 11, which are active energy ray-curable anti-fogging compositions containing a radical-reactive material having a hydrophilic group and Compound A, clearly ensure excellent elution properties and anti-fogging properties, and also suppress the occurrence of cracks in the cured film in a low-temperature environment. Therefore, a cured film with excellent anti-fogging properties and durability can be formed. In this specification, "excellent elution properties" means that the components contained in the active energy ray-curable anti-fogging composition are unlikely to be eluted.

[0068] Furthermore, it is clear that Examples 1 to 11, which are active energy ray-curable anti-fogging compositions containing a radical-reactive material having a hydrophilic group and Compound A, can reduce the content of non-reactive volatile organic solvents and ensure excellent dischargeability. Therefore, the proportion of the active ingredient that forms the cured film is large, allowing for a reduction in the total amount of materials, and also eliminating the need for dilution with an organic solvent when spray coating, thereby reducing power consumption during production.

[0069] From the results of Examples 2 to 11, it is clear that when a thiol material was contained, the cured film was free of cracks in the state evaluation under low temperature conditions, or even if any, the cracks were minor, and therefore the occurrence of cracks under low temperature conditions could be further suppressed.

[0070] From the results of Examples 2 to 4, 6, and 9 to 11, it is clear that when pentaerythritol tetrakis(3-mercaptobutyrate) was contained as the thiol material, the cured film was free of cracks in the state evaluation under low temperature conditions, and therefore the occurrence of cracks under low temperature conditions could be further suppressed.

[0071] From the results of Examples 1, 2, 6, and 11, it is clear that when dipentaerythritol hexaacrylate was contained as the polyfunctional acrylate, even if fogging occurred in the evaluation of anti-fogging property, it was only about 10% of the surface area of ​​the test piece, and in the evaluation of ejection property, the viscosity was less than 40 mPa s, so that the anti-fogging property and ejection property were excellent.

[0072] From the results of Examples 4 to 6 and 11, it is clear that when triethylene glycol diacrylate or pentaerythritol triacrylate was contained as the radical-reactive material, no traces of eluted components were visible in the evaluation of elution property, or even if they were visible, they were only partial, and therefore excellent elution property was achieved.

[0073] From the results of Example 11, when 1,3-diallyloxy-2-propanol was contained as compound A, no trace of eluted components was observed in the evaluation of elution property, and no fogging occurred on the test piece in the evaluation of anti-fogging property, so it is clear that the composition has excellent elution property and anti-fogging property.

[0074] In contrast, in Comparative Example 1, which is an active energy ray-curable composition that does not contain a radical-reactive material having a hydrophilic group, light is not transmitted due to the eluted components in the elution evaluation. Furthermore, in the anti-fogging evaluation, the entire surface of the test piece was fogged, meaning that sufficient anti-fogging properties were not ensured. Furthermore, in the condition evaluation under low-temperature conditions, large cracks were found, indicating that low-temperature cracking is likely to occur, and the viscosity is 80 mPa s or more, indicating that spray coating is not possible unless the composition is diluted with an organic solvent.

[0075] As described above, the active energy ray-curable anti-fogging composition and resin molded article of the present invention can ensure excellent anti-fogging properties and durability.

[0076] REFERENCE SIGNS LIST 10 Active energy ray-curable anti-fogging composition 11 Hydrophilic group 20 Substrate 30 Resin molded body 40 Active energy ray-curable composition 41 Water drop mark 50 Substrate 60 Resin molded body 70 Water drop

Claims

1. A solvent-free active energy ray-curable anti-fogging composition, comprising a radical-reactive material having a hydrophilic group, a polyfunctional acrylate, and a compound represented by the following general formula (1), and having a viscosity of 10 to 50 mPa·s: (In general formula (1), each A independently represents either a hydrogen atom or a methyl group, X represents an oxygen atom, and R1 represents either a hydroxyl group or an amino group).

2. The active energy ray-curable anti-fogging composition according to claim 1, wherein the active energy ray-curable anti-fogging composition contains a thiol material.

3. The active energy ray-curable anti-fogging composition according to claim 2, wherein the thiol material is pentaerythritol tetrakis(3-mercaptobutyrate).

4. The active energy ray-curable anti-fogging composition according to claim 1, wherein the compound represented by the general formula (1) is 1,3-diallyloxy-2-propanol.

5. A resin molded article comprising a cured film obtained by curing the active energy ray-curable anti-fogging composition according to any one of claims 1 to 4, and a substrate having the cured film on at least a portion of its surface.

6. The resin molded article according to claim 5, wherein the substrate is hydrophobic.

7. The resin molded article according to claim 6, wherein the substrate is made of a polymethyl methacrylate resin or a polycarbonate resin.

8. The resin molding according to claim 5, which is an outer lens of a vehicle lamp.

Images