Active energy ray-curable antifogging composition and resin molded article

Abstract

A solvent-free active energy ray-curable antifogging composition which contains a radically reactive material containing a hydrophilic group, a polyfunctional acrylate, and a compound represented by general formula (1), and which has a viscosity of 10-50 mPa * s. (In general formula (1), A each independently represents a hydrogen atom or a methyl group, X represents an oxygen atom, and R1 represents a hydroxyl group or an amino group.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of active energy ray curing type anti-fog composition and resin molding body. BACKGROUND

[0002] Transparent synthetic resins such as polycarbonate resin (PC) and polymethyl methacrylate resin (PMMA) are used in various fields such as the outer cover of lamps for automobiles and motorcycles, eyeglass lenses, the outer cover of optical sensors, and various liquid crystal panels because of their excellent transparency, moldability, and mechanical properties. However, there is a problem in that the transmission of light is reduced, and the vision is poor, and the sensor and the like malfunction due to the attachment of damage or dirt on the surface of the molded article of the synthetic resin and the like. In order to prevent such a problem, the transparency (scratch resistance and the like) is ensured by applying a composition to the surface of the molded article of the synthetic resin and the like.

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

[0004] PRIOR ART DOCUMENTS

[0005] PATENT LITERATURE

[0006] Patent Literature 1: Japanese Patent No. 6999862 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] However, on the surface of the molded article of the synthetic resin and the like obtained by curing such a curable composition, when the temperature of the surface becomes the dew point temperature or less, the moisture in the atmosphere becomes a fine water droplet and dew condensation and fogging occur. Therefore, there is a problem in that the transmission of light is reduced, and the vision is poor, and the sensor and the like malfunction.

[0009] The present application was completed in view of the above-described problems, and an object thereof is to provide an active energy ray curing type anti-fog composition and a resin molding body which are excellent in anti-fog property and durability.

[0010] MEANS FOR SOLVING THE PROBLEMS

[0011] The active energy ray curing type anti-fog composition of the present application is a solvent-free active energy ray curing type anti-fog composition containing a radical-reactive material containing a hydrophilic group, a multifunctional acrylate, and a compound represented by the following general formula (1), and has a viscosity of 10 to 50 mPa-s.

[0012] (Chemical Formula 1)

[0013] (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). BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 is a conceptual diagram showing a resin molded body of the present application.

[0015] Figure 2 is a diagram showing a manufacturing process of a resin molded body of the present application.

[0016] Figure 3 is a table summarizing the results of comparison between Examples and Comparative Examples of the active energy ray-curable antifog composition of the present application.

[0017] Figure 4 is a conceptual diagram showing a conventional resin molded body. DETAILED DESCRIPTION

[0018] An embodiment of the present application will be described. The active energy ray-curable antifog composition 10 of the present application contains a radical-reactive material, a multifunctional acrylate, a compound A, and an initiator, and has a viscosity of 10 to 50 mPa-s.

[0019] The active energy ray-curable antifog composition 10 is of a solventless type. Here, the "solventless type" means that the active energy ray-curable antifog composition 10 contains no non-reactive volatile organic solvent or substantially no non-reactive volatile organic solvent. The "substantially no non-reactive volatile organic solvent" means that the total amount of components detected in a structure containing no vinyl group or acryloyl group is less than 1 mass% when the active energy ray-curable antifog composition 10 is subjected to gas chromatography analysis at 200°C.

[0020] The active energy ray-curable antifog composition 10 is of a solventless type, and therefore, when the active energy ray-curable antifog composition 10 is cured, most of it becomes a cured film as an effective component. Therefore, the total amount of the active energy ray-curable antifog composition 10 required when applied to the surface of the substrate 20 can be reduced.

[0021] The radical-reactive material contains a hydrophilic group. As shown in Figure 1 , when the active energy ray-curable antifog composition 10 is applied to the surface of the substrate 20 (e.g., a polycarbonate resin), at least a part of the hydrophilic group 11 is disposed in the surface layer of the active energy ray-curable antifog composition 10. Then, the active energy ray-curable antifog composition 10 is cured by radical reaction, and therefore, a cured film having a hydrophilic group can be formed on the surface of the substrate 20.

[0022] Hydrophilic groups are disposed on the surface of the active energy ray-cured antifog composition 10, thus giving the surface of the active energy ray-cured antifog composition 10 a hydrophilic function. Therefore, the contact angle between the surface of the active energy ray-cured antifog composition 10 and water can be reduced. Therefore, by the diffusion of water on the surface of the active energy ray-cured antifog composition 10 to form a water film, the antifog properties of the substrate 20 can be ensured.

[0023] Free radical reactive materials are resin components composed of monomers or oligomers. By including free radical reactive materials in the active energy ray-curable antifogging composition 10, the viscosity of the active energy ray-curable antifogging composition 10 can be reduced. Therefore, the active energy ray-curable antifogging composition 10 can be used for coating without dilution with organic solvents. Therefore, in the process of curing the active energy ray-curable antifogging composition 10 on the surface of the substrate 20, a heat drying process is not required, which can reduce power consumption during manufacturing.

[0024] The content of the free radical reactive material relative to the total amount of the active energy ray-curable antifogging composition 10 is preferably 70% by mass or more and less than 90% by mass. By ensuring that the content of the active energy ray-curable antifogging composition 10 is 70% by mass or more relative to the total amount of the active energy ray-curable antifogging composition 10, the viscosity of the active energy ray-curable antifogging composition 10 can be adjusted to a suitable viscosity for spraying, even without dilution with organic solvents. A suitable viscosity for spraying is, for example, 10~50 mPa·s / 25°C.

[0025] Furthermore, when the content of the free radical reactive material is less than 70% by mass, sufficient hydrophilicity cannot be ensured on the surface of the cured film, and substrate fogging cannot be prevented. On the other hand, when the content of the free radical reactive material is 90% by mass or more, sufficient adhesion to the hydrophobic substrate 20 cannot be ensured.

[0026] As free radical reactive materials, polyethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, polytetramethylene glycol diacrylate, etc., can be used. Furthermore, these free radical reactive materials can be used alone or in combination of two or more.

[0027] Multifunctional acrylates are highly reactive hydrophobic materials. By including multifunctional acrylates in the active energy ray-curable antifogging composition 10, the curing speed of the active energy ray-curable antifogging composition 10 can be accelerated. Furthermore, the highly reactive multifunctional acrylates cure, while the free radical reactive material with hydrophilic groups delays curing. Therefore, the multifunctional acrylates, which are well-compatible with the hydrophobic substrate, adhere tightly to the substrate, and the delayed-curing hydrophilic material is easily disposed on the outermost surface. Thus, the hydrophilic material, which can impart a thin film to the surface of the cured film, can further improve the antifogging properties.

[0028] The multifunctional acrylate is hydrophobic, thus improving the adhesion between the active energy ray-cured antifogging composition 10 and the substrate 20 when coated on the hydrophobic substrate 20. Therefore, peeling of the cured film from the substrate 20 can be suppressed. Furthermore, due to the high adhesion between the cured film and the substrate 20, cracking at low temperatures can also be suppressed. Therefore, a cured film with excellent durability can be formed on the substrate 20.

[0029] The content of the multifunctional monomer relative to the total amount of the active energy ray-cured antifogging composition 10 is preferably 1% by mass or more and less than 10% by mass. When the content of the multifunctional monomer is less than 1% by mass, sufficient adhesion to the hydrophobic substrate cannot be ensured. On the other hand, when the content of the multifunctional monomer is 10% by mass or more, the proportion of hydrophilic groups is relatively reduced, so sufficient antifogging properties cannot be imparted to the substrate. Furthermore, when the content of the multifunctional monomer is 10% by mass or more, the viscosity of the active energy ray-cured antifogging composition increases, and the sprayability during spraying decreases, thus making spraying difficult.

[0030] As a multifunctional monomer, dipentaerythritol hexaacrylate, trimethylolpropane ethoxytriacrylate, dipentaerythritol hexaacrylate, etc. can be used.

[0031] Compound A is represented by the following general formula (1).

[0032] (Chemical Formula 2)

[0033] (In general formula (1), A independently represents either a hydrogen atom or a methyl atom, X represents an oxygen atom, and R1 represents either a hydroxyl group or an amino group).

[0034] For example, when A in general formula (1) is methyl and R1 is hydroxyl, compound A is 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane, and when A in general formula (1) is hydrogen and R1 is hydroxyl, it is 1,3-diallyloxy-2-propanol.

[0035] When curing an active energy ray-curable antifog composition into a thin film, the curing process may become incomplete due to oxygen inhibition. However, compound A has an oxygen absorption effect, thus the active energy ray-curable antifog composition 10 containing compound A can suppress oxygen-induced curing hindrance. Therefore, it is possible to suppress the formation of water droplets due to insufficient curing of the active energy ray-curable antifog composition.

[0036] The oxygen absorption mechanism of compound A is illustrated below. During a radical reaction, a free radical is generated at the allylic position of compound A. This free radical reacts with oxygen, simultaneously generating a peroxide free radical of compound A and capturing oxygen. The generated peroxide free radical regenerates by abstracting hydrogen from other compounds of A, thus initiating the oxygen absorption cycle of compound A.

[0037] (Chemical Formula 3)

[0038] The content of compound A relative to the total amount of the active energy ray-cured antifog composition 10 is preferably 0.1% by mass or more and less than 5.0% by mass. When the content of compound A is less than 0.1% by mass, the oxygen absorption effect becomes insufficient, and the formation of water droplets cannot be adequately suppressed. On the other hand, when the content of compound A is 5.0% by mass or more, the reactivity of the active energy ray-cured antifog composition may become poor, resulting in water droplets.

[0039] Figure 4 This is a diagram showing a resin molded body 60 formed by curing an active energy ray-curable composition 40, which does not contain compound A, on a substrate 50. (See diagram) Figure 4 As shown, when the active energy ray curable composition 40 without compound A is cured on the surface of the substrate 50, some of the active energy ray curable composition 40 is poorly cured due to the effect of oxygen inhibition. Free radical reactive materials with hydrophilic groups leach out, resulting in water droplets 41 due to moisture, vapor, water droplets 70, etc. Because of the dissolution of the free radical reactive materials with hydrophilic groups, the surface of the cured product becomes a hydrophobic coating, reducing its anti-fogging function and causing fogging.

[0040] An initiator is a free radical generator that produces highly reactive free radicals upon exposure to ultraviolet light. These free radicals, after decomposition, react with resin components such as monomers and / or oligomers. The reaction products further react with other resin components in a chain reaction. Then, a cross-linking reaction occurs, increasing the molecular weight and curing the free radical reactive material and polyfunctional acrylate to form a cured film.

[0041] The content of the initiator relative to the total amount of the active energy ray-cured antifogging composition 10 is preferably 0.1% by mass or more and less than 5.0% by mass. When the content of the initiator is less than 0.1% by mass, the curing of the active energy ray-cured antifogging composition becomes insufficient, resulting in poor curing. On the other hand, when the content of the initiator is 5.0% by mass or more, the molecular weight does not increase, and the strength of the cured film is insufficient.

[0042] As initiators, known compounds such as benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, and 1-hydroxycyclohexylphenyl ketone, ketones, 2,2'-azobisisobutyronitrile, azobis-2-methylbutyronitrile, and azobispentanilonitrile, tert-butyl peroxide, tert-butyl peroxide-2-ethylhexanoate, tert-pentyl peroxide-3,5,5-trimethylhexanoate, tert-butyl peroxide-isopropyl carbonate, 2,2-di(4,4-di-tert-butylperoxycyclohexyl)propane, di-tert-butyl peroxide, and di-tert-pentyl peroxide, and acylphosphine compounds such as 2,6-dimethylbenzoyl diphenylphosphine oxide and 2,4,6-trimethylbenzoyl diphenylphosphine oxide are preferred. Among these, free radical cleavage initiators such as 1-hydroxycyclohexylphenyl ketone and 2,4,6-trimethylbenzoyl diphenylphosphine oxide are preferred. In addition, these initiators can be used alone or in combination of two or more.

[0043] In addition, the active energy ray curing type antifog composition 10 may contain various additives such as antibacterial agents, antifungal agents, defoamers, antioxidants, antistatic agents, and polymerization inhibitors, in addition to the initiator.

[0044] As antibacterial agents, examples include captan, carbendazim, fenvalerate, chlorothalonil, ethoxysulfuron, pyrimethanil, cyclophosphamide, cyclooxygen sulfadiazine, oxadixyl, chlorpyrifos, cyproconazole, methomyl, fipronil, amistar, benzalkonium chloride, benomyl, bifenthrin, fluazinam, fluflufenican, fluoxastrobin, fluazinam, fluquinazole, sulfadiazine, fluamide, captan, hexachlorobenzene, hexaconazole, isoconazole, iprodione, azoxystrobin, mancozeb, mancozeb, pyrimethanil, fenpyroxime, tebuconazole, fenpyroxime, phthalide, iprodione, propineb, pentachloronitrobenzene, tetrachloronitrobenzene, thifluzamide, thiophanate-methyl, thiram, methyl thiophanate, parathion, triadimefon, triadimefon, imidazopyr, and fenpyroximide. In addition, as inorganic antibacterial agents, silver, copper, zinc, tin, lead, and gold can also be used. In addition, antibacterial agents used as synthetic compounds include, for example, polyhexamethylene biguanide, hydrochloride, benzyl chloride, alkyl polyaminoethyl glycine, benzisothiazoline, etc.

[0045] As antifungal agents, sodium dehydroacetate, sodium benzoate, sodium pyrithione sodium-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and its salts can be used, for example.

[0046] As defoaming agents, for example, fatty acid salts, liquid fatty oil sulfates, higher alcohol sulfates, aliphatic alcohol phosphates, fatty acid amide sulfonates, sulfonates of dibasic fatty acid esters, alkyl aryl sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, acrylic polymers, vinyl polymers, and organopolysiloxanes can be used.

[0047] As antioxidants, phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants can be used, for example. Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, β-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate stearate, and 1,3,5-trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4-hydroxybenzyl)benzene. Examples of phosphorus antioxidants include tris(2,4-di-tert-butylphenyl) phosphite, diphenyl mono(2-ethylhexyl) phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite, distearate pentaerythritol diphosphite, and tris(mononophenyl) phosphite. Examples of sulfur antioxidants include dilauryl 3,3'-thiodipropionate and pentaerythritol tetra(3-lauryl thiopropionate).

[0048] As antistatic agents, for example, various cationic antistatic agents with cationic groups such as primary to tertiary amino groups, quaternary ammonium salts, and pyridinium salts can be used; anionic antistatic agents with anionic groups such as sulfonate groups, sulfate groups, phosphate groups, and phosphonate groups can be used; amphoteric antistatic agents such as amino acid-based and aminosulfate-based agents; nonionic antistatic agents such as amino alcohol-based, glycerol-based, and polyethylene glycol-based agents; and polymeric antistatic agents obtained by increasing the molecular weight of the above antistatic agents, etc.

[0049] Polymerization inhibitors can also be added to prevent the double bonds from reacting. Examples of polymerization inhibitors include hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), 2,6-di-tert-butyl-4-methylphenol (BHT), p-tert-butylcatechol (TBC), 4-methoxy-1-naphthol and other phenols or naphthol derivatives, phenothiazine derivatives, nitrosamine salts, etc.

[0050] use Figure 2The manufacturing method of a resin molded body 30 formed by curing an active energy ray-curable anti-fogging composition 10 on the surface of a substrate 20 will be described. First, the active energy ray-curable anti-fogging composition 10 is filled into a coating gun (S1). Then, the substrate 20, which is to be coated, is fixed to a coating fixture (S2). The active energy ray-curable anti-fogging composition 10 is applied to the surface of the substrate 20 with a uniform film thickness of less than 10 μm using the coating gun (S3). The active energy ray-curable anti-fogging composition 10 is irradiated with ultraviolet light (S4). The active energy ray-curable anti-fogging composition 10 is cured on the surface of the substrate 20 to form a cured film (S5). As described above, a resin molded body 30 formed by curing an active energy ray-curable anti-fogging composition 10 on the surface of a substrate 20 can be manufactured.

[0051] Furthermore, when applying the active energy ray-curable antifog composition 10 to the surface of the substrate 20, it can be applied to a portion of the surface of the substrate 20 or to the entire surface of the substrate 20. Moreover, the method of applying the active energy ray-curable antifog composition 10 is not limited to a coating gun; inkjet printing or a dispensing method can also be used.

[0052] In addition to polycarbonate resin (PC), hydrophobic synthetic resins such as polymethyl methacrylate resin (PMMA) and hydrophobic materials such as glass can also be used as the base material 20.

[0053] As an application of the active energy ray-curable antifog composition 10, it can be used as an antifog coating. In addition, as an application of the resin molded body 30 formed by curing the active energy ray-curable antifog composition on the surface of a substrate, it can be used for outer lenses (transparent covers) of vehicle lamps, window glass, eyeglass lenses, covers of optical sensor surfaces, etc.

[0054] (Variation Example 1)

[0055] A modified example 1 of the active energy ray-cured antifogging composition of this embodiment will be described. Modified example 1 of the active energy ray-cured antifogging composition is a solvent-free active energy ray-cured antifogging composition containing a free radical reactive material, a polyfunctional acrylate, compound A, an initiator, and a thiol material, with a viscosity of 10~50 mPa·s.

[0056] Thiol materials refer to compounds containing polyfunctional thiol groups. By including thiol materials in the active energy ray-cured antifog composition 10, oxygen inhibition polymerization can be suppressed through the thiol ene reaction.

[0057] The reaction mechanism of the thiol ene reaction is illustrated below. First, irradiation with ultraviolet light causes the initiator to break down or transfer energy (initiation reaction). Then, the initiator abstracts electrons from the thiol material and generates sulfur radicals. These sulfur radicals attack the double bonds of monomers in either the hydrophobic or hydrophilic material, forming a hydrophobic or hydrophilic material with thioether crosslinks and radicals. This further abstracts hydrogen from the thiol material and generates sulfur radicals. The generated sulfur radicals then attack the double bonds of monomers in other hydrophobic or hydrophilic materials (growth reaction). In this way, the reaction proceeds in a chain reaction, enabling the efficient curing of the active energy ray-cured antifog composition 10.

[0058] (Chemical Formula 4)

[0059] Start of reaction

[0060] Growth response

[0061] By including a thiol material in the active energy ray-curable antifogging composition 10, curing can be promoted via a dark reaction even under atmospheric conditions (oxygen atmosphere). The reaction mechanism under an oxygen atmosphere is shown below. First, oxygen reacts with the monomer to generate peroxide radicals. Then, the peroxide radicals abstract hydrogen from the thiol, thereby generating sulfur radicals. The aforementioned growth reaction then proceeds via the sulfur radicals. Therefore, the active energy ray-curable antifogging composition can be cured even under an oxygen atmosphere.

[0062] (Chemical Formula 5)

[0063] By including a thiol material in the active energy ray-cured antifog composition 10, a thioether cross-linked structure can be formed, improving the flexibility of the cured film. Therefore, cracking under low-temperature conditions can be suppressed, further improving durability. The reason for this improved flexibility is that sulfur atoms can undergo rotation and other movements within the thioether cross-linked structure.

[0064] By including a thiol material in the active energy ray-cured antifogging composition 10, curing shrinkage can be suppressed. Curing shrinkage occurs because the double bonds of free radical reactive materials polymerize through free radical polymerization, transforming into high molecular weight products linked by single bonds, thus shortening the molecular bond distance. However, by including the thiol material, the double bonds of the free radical reactive materials and thioether crosslinks are formed, thereby suppressing the shortening of the molecular bond distance. Therefore, curing shrinkage is suppressed, and the generation of defects such as cracking and warping of the cured film can be prevented.

[0065] The content of thiol material relative to the total amount of the active energy ray curing antifog composition 10 is preferably 1% by mass or more and less than 5% by mass.

[0066] Example

[0067] The present invention will be further described in detail below through embodiments and comparative examples. However, the present invention is not limited to these embodiments.

[0068] (Example 1)

[0069] In a 300 mL separable flask equipped with a stirrer, 90 parts by weight of PEG200 diacrylate (product name: PEG200DA, manufactured by Daicel-Allnex Co., Ltd.) was added as a free radical reactive material, 5 parts by weight of dipentaerythritol hexaacrylate (product name: Light Acrylate DPE-6A, manufactured by Kyoei Chemical Co., Ltd.) was added as a polyfunctional acrylate, and 2 parts by weight of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as compound A. Next, 3 parts by weight of 1-hydroxycyclohexylphenyl 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 to obtain 100 parts by weight of the active energy ray-cured antifogging composition of Example 1.

[0070] (Example 2)

[0071] In a 300 mL separable flask equipped with a stirrer, 85 parts by weight of PEG200 diacrylate (product name: PEG200DA, manufactured by Daicel-Allnex Co., Ltd.) were added as a free radical reactive material, 5 parts by weight of dipentaerythritol hexaacrylate (product name: Light Acrylate DPE-6A, manufactured by Kyoei Chemical Co., Ltd.) as a polyfunctional acrylate, 1 part by weight 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 weight of pentaerythritol tetra(3-mercaptobutyrate) (product name: Karenz MT(R) PE1, manufactured by Resonac Co., Ltd.) as a thiol material. Next, 4 parts by weight of 1-hydroxycyclohexylphenyl ketone (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) were added as an initiator. Stir it at room temperature for 30 minutes to obtain 100 parts by weight of the active energy ray curable antifog composition of Example 2.

[0072] (Example 3)

[0073] In a 300mL separable flask equipped with a stirrer, 90 parts by weight of PEG600 diacrylate (product name: EBECRYL 11 Daicel-Allnex Co., Ltd.) were added as a free radical reactive material, 5 parts by weight of trimethylolpropane ethoxytriacrylate (product code: T0949 Tokyo Chemical Industry Co., Ltd.) as a polyfunctional acrylate, 1 part by weight of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420 Tokyo Chemical Industry Co., Ltd.) as compound A, and 1 part by weight of pentaerythritol tetra(3-mercaptobutyrate) (product name: Karenz MT(R) PE1 Resonac Co., Ltd.) as a thiol material. Next, 3 parts by weight of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropane (product name: Omnirad 2959, manufactured by Sanyo Trading Co., Ltd.) were added as an initiator. The mixture was stirred at room temperature for 30 minutes to obtain 100 parts by weight of the active energy ray-cured antifog composition of Example 3.

[0074] (Example 4)

[0075] In a 300 mL separable flask equipped with a stirrer, 90 parts by weight of triethylene glycol diacrylate (product name: Light Acrylate 3EG-A, manufactured by Kyoei Chemical Co., Ltd.) were added as a free radical reactive material, 3 parts by weight of trimethylolpropane ethoxytriacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polyfunctional acrylate, 3 parts by weight 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 weight of pentaerythritol tetra(3-mercaptobutyrate) (product name: Karenz MT(R) PE1, manufactured by Resonac Co., Ltd.) as a thiol material. Next, 3 parts by weight of 1-hydroxycyclohexylphenyl ketone (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) were added as an initiator. Stir it at room temperature for 30 minutes to obtain 100 parts by weight of the active energy ray curable antifog composition of Example 4.

[0076] (Example 5)

[0077] In a 300 mL separable flask equipped with a stirrer, 80 parts by weight of triethylene glycol diacrylate (product name: Light Acrylate 3EG-A, manufactured by Kyoei Chemical Co., Ltd.) were added as a free radical reactive material, 15 parts by weight of trimethylolpropane ethoxytriacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polyfunctional acrylate, 1 part by weight 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 weight of trimethylolpropane tris(3-mercaptobutyrate) (product name: Karenz MT(R) TPMB, manufactured by Resonac Co., Ltd.) as a thiol material. Next, 3 parts by weight of 1-hydroxycyclohexylphenyl ketone (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) were added as an initiator. Stir it at room temperature for 30 minutes to obtain 100 parts by weight of the active energy ray curable antifog composition of Example 5.

[0078] (Example 6)

[0079] In a 300mL separable flask equipped with a stirrer, 10 parts by weight of pentaerythritol triacrylate (product name: Light Acrylate PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) and 70 parts by weight of triethylene glycol diacrylate (product name: Light Acrylate 3EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) were added as free radical reactive materials, 5 parts by weight of dipentaerythritol hexaacrylate (product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) were added as polyfunctional acrylates, 1 part by weight of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) were added as compound A, and 1 part by weight of pentaerythritol tetra(3-mercaptobutyrate) (product name: Karenz MT (R) PE1, manufactured by Resonac Co., Ltd.) were added as thiol materials. Next, 3 parts by weight of 1-hydroxycyclohexylphenyl ketone (product name: Omnirad 184, manufactured by Sanyo Trading Co., Ltd.) were added as an initiator. The mixture was stirred at room temperature for 30 minutes to obtain 100 parts by weight of the active energy ray-cured antifog composition of Example 6.

[0080] (Example 7)

[0081] In a 300 mL separable flask equipped with a stirrer, 90 parts by weight of 2-hydroxy-3-acryloyloxypropyl acrylate (product name: Light Ester G-201P, manufactured by Kyoei Chemical Co., Ltd.) were added as a free radical reactive material, 5 parts by weight of trimethylolpropane ethoxytriacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polyfunctional acrylate, 1 part by weight 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 weight of 1,4-bis(3-mercaptobutyryloxy)butane (product name: Karenz MT(R)BD1, manufactured by Resonac Co., Ltd.) as a thiol material. Next, 3 parts by weight of 2-methyl-4′-(methylthio)-2-morpholinophenylacetone (product name: Omnirad907, manufactured by Sanyo Trading Co., Ltd.) were added as an initiator. The mixture was stirred at room temperature for 30 minutes to obtain 100 parts by weight of the active energy ray-cured antifog composition of Example 7.

[0082] (Example 8)

[0083] In a 300 mL separable flask equipped with a stirrer, 60 parts by weight of 2-hydroxy-3-acryloyloxypropyl acrylate (product name: Light Ester G-201P, manufactured by Kyoeisha Chemical Co., Ltd.) and 30 parts by weight of polytetramethylene glycol diacrylate (product name: Light Acrylate PTMGA-250, manufactured by Kyoeisha Chemical Co., Ltd.) were added as free radical reactive materials; 5 parts by weight of trimethylolpropane ethoxytriacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) were added as polyfunctional acrylates; 1 part by weight of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as compound A; and 2 parts by weight of 1,4-bis(3-mercaptobutyryloxy)butane (product name: Karenz MT(R) BD1) were added. The thiol material was prepared by adding 2 parts by weight of 1-hydroxycyclohexylphenyl ketone (product name: Omnirad 184, manufactured by Sanyo Trading Co., Ltd.) as an initiator. The mixture was stirred at room temperature for 30 minutes to obtain 100 parts by weight of the active energy ray-cured antifog composition of Example 8.

[0084] (Example 9)

[0085] In a 300mL separable flask equipped with a stirrer, 90 parts by weight of polytetramethylene glycol diacrylate (product name: Light Acrylate PTMGA-250, manufactured by Kyoei Chemical Co., Ltd.) were added as a free radical reactive material, 5 parts by weight of trimethylolpropane ethoxytriacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polyfunctional acrylate, 1 part by weight 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 weight of pentaerythritol tetra(3-mercaptobutyrate) (product name: Karenz MT(R) PE1, manufactured by Resonac Co., Ltd.) as a thiol material. Next, 3 parts by weight of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropane (product name: Omnirad 2959, manufactured by Sanyo Trading Co., Ltd.) were added as an initiator. The mixture was stirred at room temperature for 30 minutes to obtain 100 parts by weight of the active energy ray-cured antifog composition of Example 9.

[0086] (Example 10)

[0087] In a 300 mL separable flask equipped with a stirrer, 70 parts by weight of PEG600 diacrylate (product name: EBECRYL 11 Daicel-Allnex Co., Ltd.) and 20 parts by weight of polytetramethylene glycol diacrylate (product name: Light Acrylate PTMGA-250 Kyoei Chemical Co., Ltd.) were added as free radical reactive materials, 5 parts by weight of trimethylolpropane ethoxytriacrylate (product code: T0949 Tokyo Chemical Industry Co., Ltd.) were added as polyfunctional acrylate, 1 part by weight of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420 Tokyo Chemical Industry Co., Ltd.) were added as compound A, and 1 part by weight of pentaerythritol tetra(3-mercaptobutyrate) (product name: Karenz MT(R) PE1 Resonac Co., Ltd.) were added as thiol materials. Next, 3 parts by weight of 1-hydroxycyclohexylphenyl ketone (product name: Omnirad 184, manufactured by Sanyo Trading Co., Ltd.) were added as an initiator. The mixture was stirred at room temperature for 30 minutes to obtain 100 parts by weight of the active energy ray-cured antifog composition of Example 10.

[0088] (Example 11)

[0089] In a 300 mL separable flask equipped with a stirrer, 10 parts by weight of pentaerythritol triacrylate (product name: Light Acrylate PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) and 70 parts by weight of triethylene glycol diacrylate (product name: Light Acrylate 3EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) were added as free radical reactive materials, 5 parts by weight of dipentaerythritol hexaacrylate (product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) were added as polyfunctional acrylates, 1 part by weight of 1,3-diallyloxy-2-propanol (GDAE) (product code: D2146, manufactured by Tokyo Chemical Industry Co., Ltd.) were added as compound A, and 1 part by weight of pentaerythritol tetra(3-mercaptobutyrate) (product name: Karenz MT(R) PE1, manufactured by Resonac Co., Ltd.) were added as thiol materials. Next, 3 parts by weight of 1-hydroxycyclohexylphenyl ketone (product name: Omnirad 184, manufactured by Sanyo Trading Co., Ltd.) were added as an initiator. The mixture was stirred at room temperature for 30 minutes to obtain 100 parts by weight of the active energy ray-cured antifog composition of Example 11.

[0090] (Comparative Example 1)

[0091] In a 300 mL separable flask equipped with a stirrer, 90 parts by weight of pentaerythritol (tri / tetra) acrylate (product names: Light Acrylate PE-3A, Light Acrylate PE-4A, manufactured by Kyoei Chemical Co., Ltd.) as a multifunctional acrylate and 5 parts by weight of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane (DPNG) (product code: B6420, manufactured by Tokyo Chemical Industry Co., Ltd.) as compound A were added. Next, 5 parts by weight of 1-hydroxycyclohexylphenyl ketone (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) were added as an initiator. The mixture was stirred at room temperature for 30 minutes to obtain 100 parts by weight of the active energy ray-curable composition of Comparative Example 1.

[0092] (Evaluation of dissolution)

[0093] Test pieces with the active energy ray-cured antifogging compositions of Examples 1-11 or the active energy ray-cured composition of Comparative Example 1 cured on their surfaces were placed on a heating plate heated to 90°C, and 20 μL of pure water heated to 50°C was dropped onto the test pieces. The drip marks observed after the pure water evaporated were then visually confirmed, and the solubility was evaluated using five levels: A to E. A was rated when no trace of the dissolved components was visible; B was rated when traces of the dissolved components were partially visible; C was rated when traces of the dissolved components were thinly diffused; D was rated when traces of the dissolved components were clearly visible; and E was rated when light could not pass through due to the dissolved components. Figure 3 The evaluation results of the dissolution of Examples 1-11 and Comparative Example 1 are summarized in the table.

[0094] (Evaluation of anti-fog performance)

[0095] Each test piece with the active energy ray-cured antifogging composition of Examples 1-11 or the active energy ray-cured composition of Comparative Example 1 cured on its surface was immersed in warm water at 40°C for 240 hours. Then, it was dried at room temperature, and breath was blown onto the test pieces at room temperature. The surface area of ​​the test pieces that fogged was visually confirmed, and the antifogging performance was evaluated on a scale of A to E. A was rated A if no fogging occurred on the test piece; B if fogging occurred on approximately 10% of the test piece's surface area; C if fogging occurred on approximately 50% of the test piece's surface area; D if fogging occurred on approximately 80% of the test piece's surface area; and E if fogging occurred on the entire surface area of ​​the test piece. Figure 3 The evaluation results of the anti-fogging properties of Examples 1-11 and Comparative Example 1 are summarized and shown in the table.

[0096] (Status evaluation under low temperature environment)

[0097] Test pieces with the active energy ray-cured antifogging compositions of Examples 1-11 or the active energy ray-cured composition of Comparative Example 1 cured on their surfaces were placed in a freezer at -40°C for 240 hours. Then, they were brought back to room temperature, and the state of the cured film was visually confirmed, evaluated on a scale of A to E. An A grade was given for the cured film having neither cracks nor fissures; a B grade was given for the cured film having no cracks but observing slight fissures; a C grade was given for the cured film having no cracks but observing fissures; a D grade was given for the cured film having cracks and fissures observed in a portion of it; and an E grade was given for the cured film having large fissures observed. Figure 3 The evaluation results of the conditions of Examples 1-11 and Comparative Example 1 under low temperature conditions are summarized and shown in the table.

[0098] (Evaluation of the content of non-reactive volatile organic solvents)

[0099] The active energy ray-curable antifogging compositions of Examples 1-11 and the active energy ray-curable composition of Comparative Example 1 were subjected to gas chromatography analysis at 200°C to determine the total value of the components detected in the structure without vinyl or acryloyl groups. A total value less than 1% by mass was rated A; a total value of 1% or more but less than 10% by mass was rated B; a total value of 10% or more but less than 30% by mass was rated C; a total value of 30% or more but less than 50% by mass was rated D; and a total value of 50% or more by mass was rated E. Figure 3 The evaluation results of the content of non-reactive volatile organic solvents in Examples 1-11 and Comparative Example 1 are summarized in the table.

[0100] (Ejaculatory evaluation)

[0101] The viscosities of the active energy ray-cured antifogging compositions of Examples 1-11 and the active energy ray-cured composition of Comparative Example 1 were measured respectively. Viscosities were measured using an E-type viscometer (product name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.) according to JIS K2283. A viscosity of 3 mPa·s or more and less than 30 mPa·s was rated A; 30 mPa·s or more and less than 40 mPa·s was rated B; 40 mPa·s or more and less than 50 mPa·s was rated C; 50 mPa·s or more and less than 80 mPa·s was rated D; and 80 mPa·s or more was rated E. Figure 3 The evaluation results of the ejection properties of Examples 1-11 and Comparative Example 1 are summarized in the table.

[0102] Depend on Figure 3 As can be seen, according to Examples 1 to 11 of the active energy ray-cured antifogging composition containing a free radical reactive material with hydrophilic groups and compound A, excellent dissolution and antifogging properties can be ensured, and the cracking of the cured film under low-temperature conditions can be suppressed. Therefore, a cured film with excellent antifogging properties and durability can be formed. Furthermore, in this specification, "excellent dissolution" means that the components contained in the active energy ray-cured antifogging composition are not easily dissolved.

[0103] Furthermore, according to Examples 1 to 11 of the active energy ray-curable antifogging composition comprising a free radical reactive material containing hydrophilic groups and compound A, it is possible to ensure a reduction in the content of non-reactive volatile organic solvents and excellent sprayability. Therefore, a high proportion of the effective component that forms the cured film reduces the total amount of material, and since dilution with organic solvents is not required during spraying, power consumption during manufacturing can be reduced.

[0104] According to the results of Examples 2 to 11, in the case of thiol materials, in the condition evaluation under low temperature environment, there are no cracks on the cured film, or even if there are, they are slight cracks, so the cracking under low temperature environment can be further suppressed.

[0105] According to the results of Examples 2-4, 6, 9-11, when pentaerythritol tetra(3-mercaptobutyrate) is used as a thiol material, no cracks were found on the cured film in the low-temperature environment condition evaluation, thus further suppressing the occurrence of cracking in the low-temperature environment.

[0106] According to the results of Examples 1, 2, 6, and 11, when dipentaerythritol hexaacrylate is used as a polyfunctional acrylate, the anti-fogging performance is excellent. Even if fogging occurs, it is only about 10% of the surface area of ​​the test piece. The viscosity is less than 40 mPa·s in the spray performance evaluation. Therefore, the anti-fogging performance and spray performance are excellent.

[0107] According to the results of Examples 4-6 and 11, when triethylene glycol diacrylate or pentaerythritol triacrylate is used as a free radical reactive material, no trace of the dissolved components can be seen in the evaluation of solubility, or even if they are seen, only a portion of them are visible. Therefore, the solubility is excellent.

[0108] According to the results of Example 11, when 1,3-diallyloxy-2-propanol is contained as compound A, no trace of the dissolved component is visible in the evaluation of dissolution, and no fogging occurs on the test piece in the evaluation of anti-fogging properties. Therefore, the dissolution and anti-fogging properties are excellent.

[0109] In contrast, according to Comparative Example 1, which does not contain free radical reactive materials with hydrophilic groups, light could not pass through due to the dissolved components in the evaluation of dissolution. Furthermore, in the anti-fogging evaluation, fogging occurred on the entire surface of the test piece, failing to ensure adequate anti-fogging performance. Moreover, it was found that in the low-temperature environment condition evaluation, large cracks were generated, making low-temperature cracking likely; and because the viscosity was above 80 mPa·s, spraying was impossible without dilution with an organic solvent.

[0110] The active energy ray-cured antifog composition and resin molded body according to the present invention can ensure excellent antifog properties and durability.

[0111] Symbol Explanation

[0112] 10: Active energy ray-cured antifog composition; 11: Hydrophilic group; 20: Substrate; 30: Resin molded body; 40: Active energy radiation-cured composition; 41: Water droplets; 50: Substrate; 60: Resin molded body; 70: Water droplet.

Claims

1. A solvent-free active energy ray-curable antifog composition characterized by comprising a radical-reactive material containing a hydrophilic group, a multifunctional acrylate, and a compound represented by the following general formula (1) having a viscosity of 10 to 50 mPa-s, (Chemical Formula 1) In the general formula (1), each of 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. comprising a thiol material.

2. The active energy ray-curable antifogging composition according to claim 1, characterized by The thiol material is pentaerythritol tetra(3-mercapto butyrate).

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

4. The active energy ray-curable antifogging composition according to claim 1, characterized by comprising: a cured film obtained by curing the active energy ray-curable antifog composition according to any one of claims 1 to 4; and a substrate having the cured film on at least a part of a surface thereof.

5. A resin-molded body characterized by comprising a resin composition according to any one of claims 1 to 4. The substrate is hydrophobic.

6. The resin-molded body according to claim 5, characterized by The substrate is a polymethyl methacrylate resin or a polycarbonate resin.

7. The resin-molded body according to claim 6, wherein It is an outer lens of a vehicle lamp.

8. The resin-molded body according to claim 5, wherein ​

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