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 10-60 mPa * s. (In general formula (1), A each independently represents a hydrogen atom or a methyl group, and n represents 0 or 1).

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, lenses for glasses, 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 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 composition containing 3-methyl-1-methacryloyloxy-3-butene and a multifunctional compound, wherein the multifunctional compound (B) is a polyvalent (meth)acrylate having two or more (meth)acryloyloxy groups in the molecule, or a hydroxyl-containing polyvalent (meth)acrylate having two or more (meth)acryloyloxy groups in the molecule.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT LITERATURE

[0006] Patent Literature 1: Japanese Patent No. 7194176 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 in which such a composition is cured, 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 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, which contains 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 60 mPa-s.

[0012] (Chemical Formula 1)

[0013] (In General Formula (1), each A independently represents either a hydrogen atom or a methyl group, and n represents either 0 or 1.) BRIEF DESCRIPTION OF DRAWINGS

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

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

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

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

[0018] An embodiment of the present application will be described. The active energy ray-curable antifogging 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 60 mPa-s.

[0019] The active energy ray-curable antifogging composition 10 is of a solventless type. Here, the "solventless type" means that the active energy ray-curable antifogging 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 the structure containing no vinyl group or acryloyl group is less than 1 mass% when the active energy ray-curable antifogging composition 10 is subjected to gas chromatography analysis at 200°C.

[0020] The active energy ray-curable antifogging composition 10 is of a solventless type, and therefore, when the active energy ray-curable antifogging 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 antifogging composition 10 required when applied to the surface of the substrate 20 can be reduced.

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

[0022] The hydrophilic group is disposed on the surface of the active energy ray-curable antifog composition 10, so that the surface of the active energy ray-curable antifog composition 10 has a hydrophilic function. Therefore, the contact angle of the surface of the active energy ray-curable antifog composition 10 with water can be reduced. Therefore, by diffusing water on the surface of the active energy ray-curable antifog composition 10 to form a water film, the antifog property of the substrate 20 can be ensured.

[0023] The radical reaction material is a radical reaction material composed of a resin component such as a monomer or an oligomer. By containing the radical reaction material in the active energy ray-curable antifog composition 10, the viscosity of the active energy ray-curable antifog composition 10 can be reduced. Therefore, the active energy ray-curable antifog composition 10 can be used for coating without dilution with an organic solvent. Therefore, in the process of curing the active energy ray-curable antifog composition 10 on the surface of the substrate 20, a heat drying process is not required, and the power consumption at the time of production can be reduced.

[0024] The content of the radical reaction material is preferably 70% by mass or more and less than 90% by mass with respect to the total amount of the active energy ray-curable antifog composition 10. By being 70% by mass or more with respect to the total amount of the active energy ray-curable antifog composition 10, even if not diluted with an organic solvent, the active energy ray-curable antifog composition 10 can be adjusted to a viscosity suitable for spraying. The viscosity suitable for spraying is, for example, 10 to 50 mPa-s / 25°C.

[0025] Further, in the case where the content of the radical reaction material is less than 70% by mass, sufficient hydrophilic function cannot be ensured on the surface of the cured film, and the substrate cannot be prevented from fogging. On the other hand, in the case where the content of the radical reaction material is 90% by mass or more, sufficient adhesion to the hydrophobic substrate 20 cannot be ensured.

[0026] As the radical reaction material, polyethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, polytetramethylene glycol diacrylate, or the like can be used. Further, these radical reaction materials can be used alone or in combination with two or more kinds.

[0027] The multifunctional acrylate is a hydrophobic material with high reactivity. By including the multifunctional acrylate in the active energy ray-curable antifog composition, the curing speed of the active energy ray-curable antifog composition 10 can be accelerated. In addition, the multifunctional acrylate with high reactivity is cured, while the radical-reactive material having a hydrophilic group is delayed in curing. Therefore, the multifunctional acrylate which is compatible with a hydrophobic substrate well is adhered to the substrate, and the hydrophilic material which is delayed in curing is easily disposed on the surface. Thus, the hydrophilic material of the thin film can be imparted to the surface of the cured film, and the antifog property can be further improved.

[0028] The multifunctional acrylate is hydrophobic, and thus, when applied to a hydrophobic substrate 20, the adhesion of the active energy ray-curable antifog composition 10 to the substrate 20 can be improved. Thus, the cured film can be inhibited from peeling from the substrate 20. In addition, since the adhesion of the cured film to the substrate 20 is high, the generation of cracks in a low-temperature environment can also be inhibited. Thus, a cured film with excellent durability can be formed on the substrate 20.

[0029] The content of the multifunctional 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 antifog composition 10. In the case where the content of the multifunctional monomer is less than 1% by mass, sufficient adhesion to a hydrophobic substrate cannot be ensured. On the other hand, in the case where the content of the multifunctional monomer is 10% by mass or more, the proportion of the hydrophilic group is relatively reduced, and thus, sufficient antifog property cannot be imparted to the substrate. In addition, in the case where the content of the multifunctional monomer is 10% by mass or more, the viscosity of the active energy ray-curable antifog composition is increased, and the discharge property at the time of spray coating is reduced, and thus, the spray coating becomes difficult.

[0030] As the multifunctional monomer, dipentaerythritol hexaacrylate, trimethylolpropane ethoxylate triacrylate, dipentaerythritol hexaacrylate, or the like can be used.

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

[0032] (Chemical Formula 2)

[0033] (In the general formula (1), each of A independently represents either a hydrogen atom or a methyl group, and n represents either 0 or 1).

[0034] For example, the compound A is isopentenyl methyl methacrylate (IPEMA) when A in the general formula (1) is a methyl group and n is 1. In addition, the compound A is allyl methyl methacrylate when one of A in the general formula (1) is a methyl group, the other is a hydrogen atom, and n is 1.

[0035] In the case of film curing of the active energy ray-curable antifog composition, the curing of the active energy ray-curable antifog composition can become insufficient due to oxygen inhibition. However, the active energy ray-curable antifog composition 10 containing the compound A is able to inhibit the inhibition of the curing by oxygen. Therefore, the occurrence of water droplet marks due to insufficient curing of the active energy ray-curable antifog composition can be inhibited.

[0036] The content of the 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 antifog composition 10. In the case where the content of the compound A is less than 0.1% by mass, the oxygen absorption effect becomes insufficient, and the occurrence of water droplet marks cannot be sufficiently inhibited. On the other hand, in the case where the content of the compound A is 5.0% by mass or more, the reactivity of the active energy ray-curable antifog composition can be deteriorated, and water droplet marks can occur.

[0037] Figure 4 is a view showing a resin molded body 60 in which the active energy ray-curable composition 40 not containing the compound A is cured on a substrate 50. As shown in Figure 4 In the case where the active energy ray-curable composition 40 not containing the compound A is cured on the surface of the substrate 50, a part of the active energy ray-curable composition 40 is cured poorly due to the influence of oxygen inhibition, and the radical-reactive material having a hydrophilic group with a low reactivity is formed in an uncured state and exudes to the surface of the substrate 50, and further, water droplet marks 41 occur due to moisture, vapor, water droplets 70, and the like. Since the radical-reactive material having a hydrophilic group is eluted, the surface of the cured product becomes a hydrophobic coating film, and the function of antifogging is reduced, and fogging occurs.

[0038] The initiator refers to a radical generator that generates a highly active radical by irradiation of ultraviolet rays. The radical species reacts with resin components such as monomers and / or oligomers, and the like, through decomposition or the like. The reaction product thereof further reacts with other resin components, and the reaction proceeds in a chain. Then, the crosslinking reaction proceeds, and the molecular weight increases, and the radical-reactive material and the multifunctional acrylate are cured, and a cured film is formed.

[0039] The content of the initiator 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 antifog composition 10. In the case where the content of the initiator is less than 0.1% by mass, the curing of the active energy ray-curable antifog composition becomes insufficient, and curing failure occurs. On the other hand, in the case where 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.

[0040] As the initiator, for example, known compounds such as ketone-based compounds such as benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, azo-based compounds such as 2,2'-azobisisobutylonitrile, azobis-2-methylbutylonitrile, azobis-2-pentylonitrile, organic peroxide-based compounds such as tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyisopropylcarbonate, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, di-tert-butyl peroxide, di-tert-amyl peroxide, acylphosphine-based compounds such as 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like can be used. Among them, radical cleavage type initiators such as 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like are preferred. In addition, these initiators can be used alone or in combination of two or more.

[0041] Note that in the active energy ray-curable antifog composition 10, various additives such as an antibacterial agent, a mildewcide, an antifoaming agent, an antioxidant, an antistatic agent, a polymerization inhibitor, and the like can be contained in addition to the initiator.

[0042] As the antibacterial agent, for example, captan, carbendazim, binamite, chlorothalonil, ethirim, cyprodinil, epoxyconazole, famoxadone, fenarimol, fenbuconazole, fenfuram, fipronil, amisoda, benalaxyl, benomyl, bitertanol, fluazinam, fludioxonil, fluazinam, fluoroimide, fluquinconazole, flusulfamide, flutolanil, folpet, hexachlorobenzene, hexaconazole, ipconazole, iprodione, kresoxim-methyl, mancozeb, maneb, mepanipyrim, mepronil, metconazole, metiram, phthalide, procymidone, propineb, quintozene, tecnazene, thifluzamide, thiophanate-methyl, thiram, toclofos-methyl, tolylfluanid, triticonazole, triflumizole, imazalil, oxpoconazole, and the like can be used. In addition, as the inorganic antibacterial agent, for example, silver, copper, zinc, tin, lead, gold, and the like can be used. Further, as the synthetic antibacterial agent, for example, polyhexamethylene biguanide, hydrochloride, benzalkonium chloride, alkyl polyaminoethyl glycine, benzisothiazolin, and the like can be used.

[0043] As the mildewcide, for example, sodium dehydroacetate, sodium benzoate, sodium pyrithione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one, and salts thereof, and the like can be used.

[0044] As the defoaming agent, for example, fatty acid salts, liquid fatty oil sulfuric acid esters, higher alcohol sulfuric acid salts, fatty alcohol phosphoric acid esters, fatty acid amide sulfonic acid salts, sulfonic acid salts of dibasic fatty acid esters, alkyl aryl sulfonic acid salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, acrylic polymer, vinyl polymer, organopolysiloxane, and the like can be used.

[0045] As the antioxidant, for example, phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like can be used. As the phenol-based antioxidant, for example, 2,6-di-tert-butyl-p-cresol, stearyl β-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4-hydroxybenzyl)benzene, and the like can be used. As the phosphorus-based antioxidant, for example, tris(2,4-di-tert-butylphenyl) phosphite, diphenyl mon(2-ethylhexyl) phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite, distearyl pentaerythritol diphosphite, tris(monononylphenyl) phosphite, and the like can be used. As the sulfur-based antioxidant, for example, dilauryl 3,3'-thiodipropionate, pentaerythritol tetra(3-laurylthiopropionate), and the like can be used.

[0046] As the antistatic agent, for example, various cationic antistatic agents having a cationic group such as primary amino group to tertiary amino group, quaternary ammonium salt, pyridinium salt, and the like; anionic antistatic agents having an anionic group such as sulfonic acid salt group, sulfuric acid ester salt group, phosphoric acid ester salt group, phosphonic acid salt group, and the like; amphoteric antistatic agents such as amino acid-based, amino sulfate-based, and the like; nonionic antistatic agents such as amino alcohol-based, glycerol-based, polyethylene glycol-based, and the like; high molecular antistatic agents obtained by high-molecular-weighting the above-described antistatic agents; and the like can be used.

[0047] A polymerization inhibitor can also be added so that the double bond does not react. As the polymerization inhibitor, for example, hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), 2,6-di-tert-butyl-4-methylphenol (BHT), p-tert-butylcatechol (TBC), 4-methoxy-1-naphthol, or a phenol or naphthol derivative, phenothiazine derivative, nitrosamine salt, and the like can be used.

[0048] Using Figure 2A method for producing the resin molded body 30 in which the active energy ray-curable antifog composition 10 is cured on the surface of the substrate 20 will be described. First, the active energy ray-curable antifog composition 10 is filled into a coating gun (S1). Then, the substrate 20 to be coated is fixed to a coating jig (S2). The active energy ray-curable antifog composition 10 is applied on the surface of the substrate 20 in a film thickness of less than 10 μm and uniform (S3). The active energy ray-curable antifog composition 10 is irradiated with ultraviolet rays (S4). The active energy ray-curable antifog composition 10 is cured on the surface of the substrate 20 to form a cured film (S5). As described above, the resin molded body 30 in which the active energy ray-curable antifog composition 10 is cured on the surface of the substrate 20 can be produced.

[0049] Note that, when the active energy ray-curable antifog composition 10 is applied to the surface of the substrate 20, it can be applied to a part of the surface of the substrate 20 or to the entire surface of the substrate 20. Further, the method for applying the active energy ray-curable antifog composition 10 is not limited to the coating gun, and inkjet or a method using a dispenser, or the like can be used.

[0050] As the substrate 20, in addition to the polycarbonate resin (PC), a hydrophobic synthetic resin such as polymethyl methacrylate resin (PMMA), a hydrophobic material such as glass, or the like can be used.

[0051] As the use of the active energy ray-curable antifog composition 10, it can be used as an antifog coating. Further, as the use of the resin molded body 30 in which the active energy ray-curable antifog composition is cured on the surface of the substrate, it can be used for an outer lens (light-transmissive cover) of a vehicle lamp, window glass, a spectacle lens, a cover for an optical sensor surface, or the like.

[0052] (Variation 1)

[0053] A variation 1 of the active energy ray-curable antifog composition of the present embodiment will be described. The variation 1 of the active energy ray-curable antifog composition is a solvent-free active energy ray-curable antifog composition, and contains a radical-reactive material, a multifunctional acrylate, the compound A, an initiator, and a thiol material, and has a viscosity of 10 to 60 mPa-s.

[0054] The thiol material refers to a compound containing a multifunctional thiol group. By containing the thiol material in the active energy ray-curable antifog composition 10, oxygen inhibition can be suppressed by thiol-ene reaction.

[0055] The reaction mechanism of the thiol-ene reaction is shown below. First, ultraviolet rays are irradiated, an initiator is cleaved or energy is transferred (initiation reaction). Then, the initiator abstracts an electron from the thiol material and generates a sulfur radical. The sulfur radical attacks the double bond of the monomer of the hydrophobic material or the hydrophilic material to form the hydrophobic material or the hydrophilic material having a thiol crosslink and a radical. This further abstracts hydrogen from the thiol material and generates a sulfur radical. Then, the generated sulfur radical attacks the double bond of the monomer of the other hydrophobic material or the hydrophilic material (propagation reaction). In this way, the reaction proceeds in a chain, and the active energy ray-curable antifog composition 10 can be efficiently cured.

[0056] (Chemical Formula 3)

[0057] Initiation reaction

[0058] Propagation reaction

[0059] By containing the thiol material in the active energy ray-curable antifog composition 10, the curing can be promoted by a dark reaction even under the atmosphere (under an oxygen atmosphere). The reaction mechanism under an oxygen atmosphere is shown below. First, oxygen reacts with the monomer to generate a peroxide radical. Then, the peroxide radical abstracts hydrogen from the thiol to generate a sulfur radical. Then, the above-described propagation reaction proceeds by the sulfur radical. Thus, the active energy ray-curable antifog composition can be cured even under an oxygen atmosphere.

[0060] (Chemical Formula 4)

[0061] By containing the thiol material in the active energy ray-curable antifog composition 10, a sulfide crosslink structure can be formed, and the flexibility of the cured film can be improved. Thus, the generation of cracking under a low-temperature environment can be suppressed, and the durability can be further improved. The reason why the flexibility of the cured film can be improved is that, in the sulfide crosslink structure, the sulfur atom can perform a motion such as rotation.

[0062] By containing the thiol material in the active energy ray-curable antifog composition 10, the curing shrinkage can be suppressed. The reason why the curing shrinkage occurs is that the double bond of the radical-reactive material is polymerized by radical polymerization, changes to a high-molecular-weight product connected by a single bond, and the molecular bonding distance becomes short. However, by containing the thiol material, the double bond of the radical-reactive material and the sulfide crosslink are formed, and thus the shortening of the molecular bonding distance can be suppressed. Thus, the curing shrinkage is suppressed, and the generation of defects such as cracking and warping of the cured film can be suppressed.

[0063] The content of the thiol material is preferably 1% by mass or more and less than 5% by mass relative to the total amount of the active energy ray-curable antifog composition 10.

[0064] Examples

[0065] Hereinafter, the present application will be further described in detail by way of examples and comparative examples. In addition, the present application is not limited to these examples.

[0066] (Example 1)

[0067] In a 300 mL separable flask equipped with a stirrer blade, 90 parts by mass of PEG200 diacrylate (product name: PEG200DA manufactured by Daicel-Allnex Corporation) was added as a radical reactive material, 5 parts by mass of dipentaerythritol hexaacrylate (product name: Light Acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.) was added as a multifunctional acrylate, and 2 parts by mass of isopentenyl methacrylate (product code: M3509 manufactured by Tokyo Chemical Industry Co., Ltd.) was added as Compound A. Then, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184 manufactured by Sanyo Trading Co., Ltd.) was added as an initiator. This was stirred at room temperature for 30 minutes, thereby obtaining 100 parts by mass of the active energy ray-curable antifog composition of Example 1.

[0068] (Example 2)

[0069] In a 300 mL separable flask equipped with a stirrer blade, 85 parts by mass of PEG200 diacrylate (product name: PEG200DA manufactured by Daicel-Allnex Corporation) was added as a radical reactive material, 5 parts by mass of dipentaerythritol hexaacrylate (product name: Light Acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.) was added as a multifunctional acrylate, 1 part by mass of isopentenyl methacrylate (product code: M3509 manufactured by Tokyo Chemical Industry Co., Ltd.) was added as Compound A, and 5 parts by mass of pentaerythritol tetra(3-mercapto butyrate) (product name: Karenz MT(R) PE1 manufactured by Resonac Corporation) was added as a thiol material. Then, 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184 manufactured by Sanyo Trading Co., Ltd.) was added as an initiator. This was stirred at room temperature for 30 minutes, thereby obtaining 100 parts by mass of the active energy ray-curable antifog composition of Example 2.

[0070] (Example 3)

[0071] In a 300 mL separable flask equipped with a stirring blade, 90 parts by mass of PEG600 diacrylate (product name: EBECRYL 11, manufactured by Daicel-Allnex) was added as the radical-reactive material, 5 parts by mass of trimethylolpropane ethoxylate triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as the multifunctional acrylate, 1 part by mass of allyl methacrylate (product code: M0075, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as the compound A, and 1 part by mass of pentaerythritol tetra(3-mercapto butyrate) (product name: Karenz MT(R) PE1, manufactured by Resonac Corporation) was added as the thiol material. Subsequently, 3 parts by mass of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropane (product name: Omnirad 2959, manufactured by Sanko Trading Co., Ltd.) was added as the initiator. This was stirred at room temperature for 30 minutes, thereby obtaining 100 parts by mass of the active energy ray-curable antifog composition of Example 3.

[0072] (Example 4)

[0073] In a 300 mL separable flask equipped with a stirring blade, 90 parts by mass of triethylene glycol diacrylate (product name: Light Acrylate 3EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) was added as the radical-reactive material, 3 parts by mass of trimethylolpropane ethoxylate triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as the multifunctional acrylate, 3 parts by mass of isopentenyl methacrylate (product code: M3509, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as the compound A, and 1 part by mass of pentaerythritol tetra(3-mercapto butyrate) (product name: Karenz MT(R) PE1, manufactured by Resonac Corporation) was added as the thiol material. Subsequently, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by Sanko Trading Co., Ltd.) was added as the initiator. This was stirred at room temperature for 30 minutes, thereby obtaining 100 parts by mass of the active energy ray-curable antifog composition of Example 4.

[0074] (Example 5)

[0075] In a 300 mL separable flask equipped with a stirring blade, 80 parts by mass of triethylene glycol diacrylate (product name: Light Acrylate 3EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) was added as a radical reactive material, 15 parts by mass of trimethylolpropane ethoxylate triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a multifunctional acrylate, 1 part by mass of isopentenyl methacrylate (product code: M3509, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as Compound A, and 1 part by mass of trimethylolpropane tris(3-mercaptopropionate) (product name: Karenz MT(R) TPMB, manufactured by Resonac Corporation) was added as a thiol material. Subsequently, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by Sankyo Trading Co., Ltd.) was added as an initiator. This was stirred at room temperature for 30 minutes, thereby obtaining 100 parts by mass of the active energy ray-curable antifog composition of Example 5.

[0076] (Example 6)

[0077] In a 300 mL separable flask equipped with a stirring blade, 80 parts by mass of triethylene glycol diacrylate (product name: Light Acrylate 3EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) was added as a radical reactive material, 15 parts by mass of trimethylolpropane ethoxylate triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a multifunctional acrylate, 1 part by mass of isopentenyl methacrylate (product code: M3509, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as Compound A, and 1 part by mass of trimethylolpropane tris(3-mercaptopropionate) (product name: Karenz MT(R) TPMB, manufactured by Resonac Corporation) was added as a thiol material. Subsequently, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by Sankyo Trading Co., Ltd.) was added as an initiator. This was stirred at room temperature for 30 minutes, thereby obtaining 100 parts by mass of the active energy ray-curable antifog composition of Example 5.

[0078] (Example 7)

[0079] In a 300 mL separable flask equipped with a stirrer, 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.) were added as the radical-reactive material, 5 parts by mass of trimethylolpropane ethoxylate triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as the multifunctional acrylate, 1 part by mass of isopentenyl methacrylate (product code: M3509, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as the compound A, and 2 parts by mass of 1,4-bis(3-mercaptobutyryloxy)butane (product name: Karenz MT(R) BD1, manufactured by Resonac Corporation) was added as the thiol material. Then, 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by Sankyo Co., Ltd.) was added as the initiator. This was stirred at room temperature for 30 minutes, thereby obtaining 100 parts by mass of the active energy ray-curable antifog composition of Example 8.

[0080] (Example 8)

[0081] In a 300 mL separable flask equipped with a stirrer, 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.) were added as the radical-reactive material, 5 parts by mass of trimethylolpropane ethoxylate triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as the multifunctional acrylate, 1 part by mass of isopentenyl methacrylate (product code: M3509, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as the compound A, and 2 parts by mass of 1,4-bis(3-mercaptobutyryloxy)butane (product name: Karenz MT(R) BD1, manufactured by Resonac Corporation) was added as the thiol material. Then, 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by Sankyo Co., Ltd.) was added as the initiator. This was stirred at room temperature for 30 minutes, thereby obtaining 100 parts by mass of the active energy ray-curable antifog composition of Example 8.

[0082] (Example 9)

[0083] In a 300 mL separable flask equipped with a stirring blade, 90 parts by mass of polytetramethylene glycol diacrylate (product name: Light Acrylate PTMGA-250, manufactured by Kyoeisha Chemical Co., Ltd.) was added as a radical reactive material, 5 parts by mass of trimethylolpropane ethoxylate triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a multifunctional acrylate, 1 part by mass of isopentenyl methacrylate (product code: M3509, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as Compound A, and 1 part by mass of pentaerythritol tetra(3-mercaptobutyrate) (product name: Karenz MT(R) PE1, manufactured by Resonac Corporation) was added as a thiol material. Subsequently, 3 parts by mass of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropane (product name: Omnirad 2959, manufactured by Sanko Trading Co., Ltd.) was added as an initiator. This was stirred at room temperature for 30 minutes, thereby obtaining 100 parts by mass of the active energy ray-curable antifog composition of Example 9.

[0084] (Example 10)

[0085] In a 300 mL separable flask equipped with a stirring blade, 70 parts by mass of PEG600 diacrylate (product name: EBECRYL 11, manufactured by Daicel-Allnex Co., Ltd.) and 20 parts by mass of polytetramethylene glycol diacrylate (product name: Light Acrylate PTMGA-250, manufactured by Kyoeisha Chemical Co., Ltd.) were added as radical reactive materials, 5 parts by mass of trimethylolpropane ethoxylate triacrylate (product code: T0949, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a multifunctional acrylate, 1 part by mass of isopentenyl methacrylate (product code: M3509, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as Compound A, and 1 part by mass of pentaerythritol tetra(3-mercaptobutyrate) (product name: Karenz MT(R) PE1, manufactured by Resonac Corporation) was added as a thiol material. Subsequently, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by Sanko Trading Co., Ltd.) was added as an initiator. This was stirred at room temperature for 30 minutes, thereby obtaining 100 parts by mass of the active energy ray-curable antifog composition of Example 10.

[0086] (Comparative Example 1)

[0087] In a 300 mL separable flask equipped with a stirring blade, 90 parts by mass of pentaerythritol (tri- / tetra-) acrylate (product name: Light Acrylate PE-3A, Light Acrylate PE-4A, manufactured by Kyoeisha Chemical Co., Ltd.) was added as a multifunctional acrylate, and 5 parts by mass of isopentenyl methacrylate (product code: M3509, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as the compound A. Subsequently, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by Sankyo Trading Co., Ltd.) was added as an initiator. This was stirred at room temperature for 30 minutes, thereby obtaining 100 parts by mass of the active energy ray-curable composition of Comparative Example 1.

[0088] (Evaluation of the dissolubility)

[0089] Each test piece on which the active energy ray-curable antifogging composition of Examples 1 to 10 or the active energy ray-curable composition of Comparative Example 1 was cured on the surface was placed on a hot plate heated to 90°C, and 20 μL of pure water heated to 50°C was added dropwise to the test piece. Then, the droplet mark seen after the evaporation of the pure water was confirmed visually, and the dissolubility was evaluated in five grades of A to E. In the case where no trace of the dissolubility component was seen, A was evaluated, in the case where a trace of the dissolubility component was partially seen, B was evaluated, in the case where the trace of the dissolubility component was thinly spread, C was evaluated, in the case where the trace of the dissolubility component was clearly seen, D was evaluated, and in the case where light was unable to pass through due to the dissolubility component, E was evaluated. Figure 3 The evaluation results of the dissolubility of Examples 1 to 10 and Comparative Example 1 are shown in Table 2.

[0090] (Evaluation of the antifogging property)

[0091] Each test piece on which the active energy ray-curable antifogging composition of Examples 1 to 10 or the active energy ray-curable composition of Comparative Example 1 was cured on the surface was immersed in warm water at 40°C for 240 hours, respectively. Then, it was dried at room temperature, and the test piece was blown with breath at ordinary temperature, and the surface area of the test piece on which fogging occurred was confirmed visually, and the antifogging property was evaluated in five grades of A to E. In the case where no fogging occurred on the test piece, A was evaluated, in the case where fogging occurred on about 1% of the surface area of the test piece, B was evaluated, in the case where fogging occurred on about 5% of the surface area of the test piece, C was evaluated, in the case where fogging occurred on about 8% of the surface area of the test piece, D was evaluated, and in the case where fogging occurred on the entire surface area of the test piece, E was evaluated. Figure 3 The evaluation results of the antifogging property of Examples 1 to 10 and Comparative Example 1 are shown in Table 3.

[0092] (Evaluation of the state in a low-temperature environment)

[0093] Each test piece on which the active energy ray-curable antifog composition of Examples 1 to 10 or the active energy ray-curable composition of Comparative Example 1 was cured on the surface was left in a freezer at -40°C for 240 hours. Then, it was returned to room temperature, and the state of the cured film was confirmed by visual observation to evaluate the state in a low-temperature environment in five grades of A to E. A was evaluated in the case where there was neither a crack nor a fissure in the cured film, B was evaluated in the case where there was no crack in the cured film but a slight fissure was observed, C was evaluated in the case where there was no crack in the cured film but a fissure was observed, D was evaluated in the case where a crack and a fissure were observed on a part of the cured film, and E was evaluated in the case where a large crack was observed on the cured film. Figure 3 The evaluation results of the state in a low-temperature environment of Examples 1 to 10 and Comparative Example 1 are shown in Table 2.

[0094] (Evaluation of content of non-reactive volatile organic solvent)

[0095] Gas chromatographic analysis at 200°C was performed on the active energy ray-curable antifog composition of Examples 1 to 10 or the active energy ray-curable composition of Comparative Example 1, respectively, and the total value of components detected in the structure not containing a vinyl group or an acryloyl group was calculated. A was evaluated in the case where the total value was less than 1 mass%, B was evaluated in the case where the total value was 1 mass% or more and less than 10 mass%, C was evaluated in the case where the total value was 10 mass% or more and less than 30 mass%, D was evaluated in the case where the total value was 30 mass% or more and less than 50 mass%, and E was evaluated in the case where the total value was 50 mass% or more. Figure 3 The evaluation results of the content of non-reactive volatile organic solvent of Examples 1 to 11 and Comparative Example 1 are shown in Table 4.

[0096] (Evaluation of discharge property)

[0097] Evaluation was performed by measuring the viscosity of the active energy ray-curable antifog composition of Examples 1 to 10 or the active energy ray-curable composition of Comparative Example 1, respectively. The measurement of the viscosity was performed using an E-type viscometer (product name: TVE-22L, manufactured by Tokimec, Inc.) in accordance with JIS K2283. A was evaluated in the case where the viscosity was 3 mPa-s or more and less than 30 mPa-s, B was evaluated in the case where the viscosity was 30 mPa-s or more and less than 40 mPa-s, C was evaluated in the case where the viscosity was 40 mPa-s or more and less than 50 mPa-s, D was evaluated in the case where the viscosity was 50 mPa-s or more and less than 80 mPa-s, and E was evaluated in the case where the viscosity was 80 mPa-s or more. Figure 3 The evaluation results of the discharge property of Examples 1 to 10 and Comparative Example 1 are shown in Table 5.

[0098] From the above results, it was found that the active energy ray-curable antifog compositions of Examples 1 to 10 had a high content of non-reactive volatile organic solvent, a high discharge property, and a high state in a low-temperature environment, and were excellent in the antifog property.Figure 3 As is apparent from Examples 1 to 10 of the active energy ray-curable antifog composition containing the radical-reactive material containing a hydrophilic group and Compound A, it is possible to ensure excellent elution property and antifog property, and to inhibit the generation of cracking of the cured film in a low-temperature environment. Thus, it is possible to form a cured film excellent in antifog property and durability. In addition, in the present specification, "excellent elution property" means that the components contained in the active energy ray-curable antifog composition are not easily eluted.

[0099] In addition, as is apparent from Examples 1 to 10 of the active energy ray-curable antifog composition containing the radical-reactive material containing a hydrophilic group and Compound A, it is possible to ensure a decrease in the content of non-reactive volatile organic solvent and excellent discharge property. Thus, the proportion of the effective components of the cured film is large, it is possible to decrease the total amount of the material, and it is not necessary to dilute with an organic solvent at the time of spray coating, and it is possible to decrease the power consumption at the time of production.

[0100] As is apparent from the results of Examples 2 to 10, in the case where the thiol material is contained, there is no cracking on the cured film, or even if there is cracking, it is slight cracking in the state evaluation in a low-temperature environment, and thus it is possible to further inhibit the generation of cracking in a low-temperature environment.

[0101] As is apparent from the results of Examples 2 to 4, 6, 9 to 10, in the case where pentaerythritol tetra(3-mercapto butyrate) is contained as the thiol material, there is no cracking on the cured film in the state evaluation in a low-temperature environment, and thus it is possible to further inhibit the generation of cracking in a low-temperature environment.

[0102] As is apparent from the results of Examples 1, 2, 6, in the case where dipentaerythritol hexaacrylate is contained as the multifunctional acrylate, even if fogging occurs, it is about 1% or less of the surface area of the test piece in the evaluation of antifog property, and the viscosity is less than 40 mPa s in the evaluation of discharge property, and thus the antifog property and the discharge property are more excellent.

[0103] As is apparent from the results of Examples 4 to 6, in the case where triethylene glycol diacrylate or pentaerythritol triacrylate is contained as the radical-reactive material, no trace of the eluted components is observed, or even if a trace is observed, it is only a part thereof in the evaluation of elution property, and thus the elution property is more excellent.

[0104] As is apparent from the results of Example 6, in the case where pentaerythritol triacrylate or triethylene glycol diacrylate is contained as the radical-reactive material, no trace of the eluted components is observed in the evaluation of elution property, and no fogging occurs on the test piece in the evaluation of antifog property, and thus the elution property and the antifog property are more excellent.

[0105] On the other hand, according to Comparative Example 1 which does not include the radical-reactive material containing the hydrophilic group in the active energy ray-curable composition, in the evaluation of the dissolubility, the dissolving component was clearly confirmed by visual observation, and the LED light could not be transmitted due to the dissolving component. In addition, in the antifogging evaluation, fogging occurred on the entire surface of the test piece, and sufficient antifogging properties could not be ensured. Further, in the evaluation of the state in a low temperature environment, since a large crack was generated, low temperature cracking was easily generated, and since the viscosity was 80 mPa-s or more, if the organic solvent was not diluted, the spray coating could not be performed.

[0106] According to the active energy ray-curable antifogging composition and the resin molded body according to the present application, excellent antifogging properties and durability can be ensured.

[0107] (Symbol explanation)

[0108] 10: Active energy ray-curable antifogging composition; 11: Hydrophilic group; 20: Base material; 30: Resin molded body; 40: Active energy ray-curable composition; 41: Water droplet trace; 50: Base material; 60: Resin molded body; 70: Water droplet.

Claims

1. A solvent-free, active energy radiation-cured antifog composition, characterized in that, The active energy ray-cured antifog composition comprises a free radical reactive material containing hydrophilic groups, a polyfunctional acrylate, and a compound represented by the following general formula (1), with a viscosity of 10~60 mPa·s. (Chemical Formula 1) In general formula (1), A independently represents either a hydrogen atom or a methyl group, and n represents 0 or 1.

2. The active energy ray-cured antifog composition according to claim 1, characterized in that, The active energy ray-cured antifog composition contains thiol materials.

3. The active energy ray-cured anti-fog composition according to claim 2, characterized in that, The thiol material is pentaerythritol tetra(3-mercaptobutyrate).

4. The active energy ray-cured antifog composition according to claim 1, characterized in that, The free radical reactive material contains pentaerythritol triacrylate and triethylene glycol diacrylate.

5. A resin molded article, characterized in that, Include: A cured film obtained by curing the active energy ray-cured antifog composition according to any one of claims 1 to 4; as well as The substrate has the cured film on at least a portion of its surface.

6. The resin molded article according to claim 5, characterized in that, The substrate is hydrophobic.

7. The resin molded article according to claim 6, characterized in that, The substrate is polymethyl methacrylate resin or polycarbonate resin.

8. The resin molded article according to claim 5, characterized in that, It is the outer lens of vehicle lights.

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