Hard coating material, hard coating, and structure

Abstract

This functional coating material contains: a curable component; a polysiloxane compound having an amino group; and a sensitizer. The functional coating material may be a hard coating material. The hard coating comprises a cured product of the functional coating material. A structure according to the present invention includes a base material and the hard coating provided upon the base material.

Description

Hard coating material, hard coating and structure

[0001] The present invention relates to a hard coating material, a hard coating, and a structure. The present invention also relates to a functional coating material.

[0002]

[0003] For the purpose of imparting water repellency to substrates such as glass and plastics, a method of coating the surface of the substrate with a coating material containing a fluorine-containing resin such as polytetrafluoroethylene (PTFE) resin is known. Although fluorine-containing resin coatings have excellent water repellency, they have poor scratch resistance, making them difficult to use as hard coats. Therefore, acrylic compositions containing multifunctional acrylics have been proposed as water-repellent hard coat materials (see Patent Document 1 below).

[0003] JP 2015-34832 A

[0004] Examples of objects on which coatings such as hard coats are formed include display device components such as touch panels; indoor items in buildings such as kitchens, bathtubs, toilets, and washrooms; exterior parts of buildings, automobiles, trains, and the like; and solar panels for solar cells. It is desirable for coating materials to be transparent so as not to impair the appearance of the objects to which they are applied. However, when a coating material is cured by irradiating it with light using a high-pressure mercury lamp, the film formed by the coating material can become cloudy. Furthermore, when a coating material is cured by heating, the curing rate is slower than when it is cured by light irradiation, and the film tends to become more cloudy.

[0005] Therefore, an object of the present invention is to provide a functional coating material capable of forming a coating film (e.g., a hard coat) with suppressed cloudiness, and to provide a hard coat with suppressed cloudiness and a structure including the hard coat.

[0006] In order to solve the above problems, the present invention provides the following functional coating material, hard coat, and structure.

[0007] [1] A functional coating material comprising a curable component, a polysiloxane compound having an amino group, and a sensitizer. [2] The functional coating material according to [1], wherein the curable component is a photocurable resin composition. [3] The functional coating material according to [1] or [2], wherein the polysiloxane compound having an amino group has an amine equivalent of 500 to 5,000 g / mol. [4] The functional coating material according to any one of [1] to [3], wherein the sensitizer is an anthracene compound. [5] The functional coating material according to any one of [1] to [4], wherein the sensitizer is a benzophenone compound. [6] The functional coating material according to any one of [1] to [5], wherein the functional coating material is a hard coat material. [7] A hard coat comprising a cured product of the functional coating material according to any one of [1] to [6]. [8] The hard coat according to [7], wherein the haze is 2 or less. [9] A structure comprising a substrate and the hard coat according to [7] provided on the substrate.

[0008] According to the present invention, it is possible to provide a functional coating material capable of forming a coating film (e.g., a hard coat) in which clouding is suppressed. Furthermore, the present invention can provide a hard coat in which clouding is suppressed and a structure including the hard coat.

[0009] Hereinafter, a functional coating material, a hard coat, and a structure according to one embodiment of the present invention will be described.

[0010] In the present invention, when a numerical range is indicated using "to", the numerical values ​​before and after "to" are included as the minimum and maximum values, respectively. Furthermore, in the numerical ranges described in stages in the present invention, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another staged numerical range. Furthermore, in the numerical ranges described in the present invention, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. "A or B" may include either A or B, or may include both. Unless otherwise specified, the materials exemplified in the present invention can be used alone or in combination of two or more. In the present invention, when multiple substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of multiple substances present in the composition, unless otherwise specified.

[0011] <Functional Coating Material> The functional coating material of this embodiment includes a curable component, a polysiloxane compound having an amino group, and a sensitizer. The functional coating material refers to a coating material that can form a coating film having functions such as antifouling properties, transparency, water repellency, fingerprint resistance, and antifogging properties.

[0012] According to the functional coating material of one embodiment of the present invention, it is possible to form a coating (hard coat) in which clouding is suppressed. Furthermore, when the functional coating material of one embodiment of the present invention is a hard coat material, it is possible to form a hard coat in which clouding is suppressed. The reason why such an effect is achieved is not necessarily clear, but the inventor of the present invention speculates as follows.

[0013] That is, if the functional coating material is not cured sufficiently, unreacted materials remain in the functional coating material, and the unreacted materials aggregate, causing the coating (hard coat) to become cloudy. Furthermore, if the light irradiation dose is increased to reduce the unreacted materials in the functional coating material, the reaction tends to become uneven within the functional coating material, and in areas where the reaction progresses slowly, the unreacted materials aggregate, causing the coating (hard coat) to become cloudy. On the other hand, if the functional coating material contains a sensitizer, the curing rate of the functional coating material increases. This facilitates a uniform curing reaction throughout the functional coating material, reducing the amount of unreacted materials and preventing the coating (hard coat) from becoming cloudy. However, the mechanism of the present invention is not limited to the above reasons.

[0014] (Curable Component) The functional coating material contains a curable component. The curable component may be a photocurable resin composition or a thermosetting resin composition. From the viewpoint of increasing the degree of freedom in the substrate to which the functional coating material is applied (in other words, the substrate selectivity of the functional coating material), the curable component may be a photocurable resin composition or a UV-curable resin composition. The photocurable resin composition contains a polymerizable compound and a photopolymerization initiator, and may contain additives such as UV absorbers, silica particles, silane coupling agents, curing agents, curing accelerators, and catalysts as needed. From the viewpoint of improving heat resistance, the curable component may be a thermosetting resin composition. The thermosetting resin composition contains a polymerizable compound and a thermal polymerization initiator, and may contain additives such as UV absorbers, silica particles, silane coupling agents, curing agents, curing accelerators, and catalysts as needed.

[0015] The polymerizable compound may be a polyfunctional polymerizable compound having two or more polymerizable double bonds from the viewpoint of improving hardness. Examples of groups having a polymerizable double bond include a (meth)acryloyl group and a vinyl group. The polymerizable compound may be a (meth)acrylic acid compound from the viewpoint of easily forming a coating (hard coat) with reduced opacity.

[0016] Examples of polyfunctional polymerizable compounds include 2-hexamethylene acrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, (poly)tetramethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, ethoxylated bisphenol A diacrylate, (poly)ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 4,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, neopentyl glycol Bifunctional polymerizable compounds such as chol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dimethyloltricyclodecane diacrylate, and dicyclopentanyl diacrylate; trifunctional polymerizable compounds such as trimethylolpropane EO adduct triacrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, tris(2-acryloxyethyl)isocyanurate, ε-caprolactone-modified tris(2-acryloxyethyl)isocyanurate, ethoxylated glycerin triacrylate, and ditrimethylolpropane tetraacrylate;Examples of the polymerizable compound include polyfunctional polymerizable compounds having four or more polymerizable double bonds, such as trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, alkyl-modified dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and polypentaerythritol polyacrylate. The curable component (photocurable resin composition or thermosetting resin composition) may contain at least one of a bifunctional polymerizable compound and a trifunctional polymerizable compound, from the viewpoint of easily forming a coating (hard coat) with reduced cloudiness. When the curable component (photocurable resin composition or thermosetting resin composition) contains a bifunctional polymerizable compound, the curable component may contain at least one of 2-hexamethylene acrylate and 1,9-nonanediol diacrylate, from the viewpoint of easily forming a coating (hard coat) with more suppressed opacity. When the curable component (photocurable resin composition or thermosetting resin composition) contains a trifunctional polymerizable compound, the curable component may contain at least one selected from the group consisting of trimethylolpropane EO-adduct triacrylate and ethoxylated glycerin triacrylate, from the viewpoint of easily forming a coating (hard coat) with more suppressed opacity.

[0017] From the viewpoint of improving hardness, the curable component (photocurable resin composition or thermosetting resin composition) may contain a bifunctional polymerizable compound as a polymerizable compound, and the content of the bifunctional polymerizable compound may be 5 to 95 mass %, 15 to 85 mass %, 30 to 70 mass %, or 40 to 55 mass % based on the total amount of the polymerizable compounds.

[0018] From the viewpoint of improving hardness, the curable component (photocurable resin composition or thermosetting resin composition) may contain a trifunctional polymerizable compound as a polymerizable compound, and the content of the trifunctional polymerizable compound may be 5 to 95 mass %, 15 to 85 mass %, 30 to 70 mass %, or 45 to 60 mass % based on the total amount of the polymerizable compounds.

[0019] From the viewpoint of improving hardness and flexibility in a balanced manner, the polymerizable compound may contain a plurality of polymerizable compounds having different numbers of functional groups, for example, a bifunctional polymerizable compound and a tri- or higher functional polymerizable compound (a polymerizable compound having three or more functional groups), a bifunctional polymerizable compound and a trifunctional polymerizable compound, a bifunctional polymerizable compound and a tetrafunctional polymerizable compound, or a trifunctional polymerizable compound and a tetrafunctional polymerizable compound. From the viewpoint of improving hardness and flexibility in a balanced manner, the total content of these may be 5% by mass or more, 15% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, or 90% by mass or more based on the total amount of the polymerizable compound.

[0020] The ratio of the mass-based content of the tri- or higher functional polymerizable compound to the mass-based content of the bifunctional polymerizable compound (mass-based content of the tri- or higher functional polymerizable compound / mass-based content of the bifunctional polymerizable compound) may be 0.5 or more, 1 or more, 1.2 or more, or 1.4 or more from the viewpoint of improving hardness and flexibility in a balanced manner, and from the same viewpoint, may be 5 or less, 4 or less, 3 or less, 2 or less, or 1.5 or less. The ratio of the mass-based content of the trifunctional polymerizable compound to the mass-based content of the bifunctional polymerizable compound (mass-based content of the trifunctional polymerizable compound / mass-based content of the bifunctional polymerizable compound) may be 0.5 or more, 1 or more, 1.2 or more, or 1.4 or more from the viewpoint of improving hardness and flexibility in a balanced manner, and from the same viewpoint, may be 5 or less, 4 or less, 3 or less, 2 or less, or 1.5 or less. The ratio of the mass-based content of the tetrafunctional polymerizable compound to the mass-based content of the bifunctional polymerizable compound (mass-based content of the tetrafunctional polymerizable compound / mass-based content of the bifunctional polymerizable compound) may be 0.5 or more, 1 or more, 1.2 or more, or 1.4 or more from the viewpoint of improving hardness and flexibility in a balanced manner, and from the same viewpoint, may be 5 or less, 4 or less, 3 or less, 2 or less, or 1.5 or less. The ratio of the mass-based content of the tetrafunctional polymerizable compound to the mass-based content of the trifunctional polymerizable compound (mass-based content of the tetrafunctional polymerizable compound / mass-based content of the trifunctional polymerizable compound) may be 0.5 or more, 1 or more, 1.2 or more, or 1.4 or more from the viewpoint of improving hardness and flexibility in a balanced manner, and from the same viewpoint, may be 5 or less, 4 or less, 3 or less, 2 or less, or 1.5 or less.

[0021] The curable component (photocurable resin composition or thermosetting resin composition) may contain a monofunctional polymerizable compound as a polymerizable compound from the viewpoint of improving hardness and flexibility in a well-balanced manner. Examples of the monofunctional polymerizable compound include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, methoxypolyethylene glycol acrylate, phenoxydiethylene glycol acrylate, ethoxylated-o-phenylphenol acrylate, and 2-acryloyloxyethyl succinic acid.

[0022] (Photopolymerization initiator) The curable component (photocurable resin composition or thermosetting resin composition) may contain a photopolymerization initiator from the viewpoint of improving hardness. The photopolymerization initiator may be one that decomposes and / or reacts with light (including active energy rays such as ultraviolet rays and electron beams) to generate radicals. Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, Non, 4,4'-bis(diethylamino)benzophenone, 2,4-dihydroxybenzophenone, ethyl-4-(dimethylamino)-benzoate, [4-(methylphenylthio)phenyl]-phenylmethane, ethylhexyl-4-dimethylaminobenzoate, benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, methylbenzoyl formate, 2,2-dimethoxy-2-phenylacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropane, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane. These can be used in combination with at least one type to suit the optimal curing conditions.

[0023] The content of the photopolymerization initiator may be 0.1 to 30 parts by mass, or may be 0.5 to 20 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable compounds.

[0024] (Thermal Polymerization Initiator) The curable component (photocurable resin composition or thermosetting resin composition) may contain a thermal polymerization initiator from the viewpoint of improving heat resistance. The thermal polymerization initiator may be one that decomposes and / or reacts with heat to generate radicals. Examples of the thermal polymerization initiator include peroxydicarbonates such as di-2-ethylhexyl peroxydicarbonate; peroxyesters such as t-butyl peroxybenzoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate, and t-hexylperoxyisopropyl carbonate; peroxyketals such as di(t-butylperoxy)-2-methylcyclohexane, di(t-butylperoxy)3,3,5-trimethylcyclohexane, and di(t-butylperoxy)cyclohexane; dialkyl peroxides such as Niper BW (manufactured by NOF Corporation); and azo polymerization initiators such as VR-110 (NOF Corporation). These may be used in combination of at least one type in accordance with the optimum curing conditions.

[0025] The content of the thermal polymerization initiator may be 0.1 to 30 parts by mass, or may be 0.5 to 20 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable compounds.

[0026] (UV Absorber) The curable component (photocurable resin composition or thermosetting resin composition) may contain an UV absorber from the viewpoint of improving weather resistance. Known UV absorbers can be used, such as benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds. Examples of the UV absorber include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3- (2-ethylhexyloxy)propyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bisbutyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5 benzotriazole-based ultraviolet absorbers such as 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, and 2-[2-hydroxy-5-(2-(meth)acryloyloxyethyl)phenyl]-2H-benzotriazole; benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone; cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3-diphenylacrylate and octyl-2-cyano-3,3-diphenylacrylate; and inorganic particles that absorb ultraviolet light such as titanium oxide particles, zinc oxide particles, and tin oxide particles.

[0027] The content of the ultraviolet absorber may be 0.1 to 20 parts by mass, or may be 0.5 to 10 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable compounds.

[0028] (Silica Particles) The curable component (photocurable resin composition or thermosetting resin composition) may contain silica particles from the viewpoint of improving scratch resistance. The shape of the silica particles is not particularly limited. Examples of the shape of the silica particles include spherical, beaded, pearl necklace, chain, cocoon, association, and confetti-like shapes. The shape of the silica particles may be spherical. The silica particles may be colloidal silica or fumed silica.

[0029] The silica particles may have crosslinkable functional groups on a portion of their surfaces, such as amino groups, sulfo groups, epoxy groups, oxetanyl groups, acryloyl groups, methacryloyl groups, vinyl groups, methylol groups, and maleimide groups.

[0030] Silica particles are available as a dispersion of silica particles. Examples of the dispersion medium include water, isopropyl alcohol, 1-methoxy-2-propyl alcohol, ethyl alcohol, methyl alcohol, ethylene glycol, ethylene glycol-n-propyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dimethylacetamide, N-methylpyrrolidone, toluene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, and ethyl acetate. The dispersion medium may be a mixture of the above dispersion media. From the viewpoint of versatility, the dispersion medium for silica particles may be water.

[0031] The pH of the dispersion of silica particles may be 2 to 10, 4 to 9, 6 to 8, or 2 to 5. The pH of the dispersion of silica particles can be measured with a pH meter (for example, model number PHL-40, manufactured by Denki Kagaku Keiki Co., Ltd.). The measured pH is calibrated at three points using standard buffer solutions (phthalate pH buffer solution, pH: 4.01 (25°C), neutral phosphate pH buffer solution, pH: 6.86 (25°C), borate pH buffer solution, pH: 9.18 (25°C)), and then the electrode is placed in the dispersion solution, and the value obtained after 2 minutes or more has elapsed and the value has stabilized is used.

[0032] The zeta potential of the silica particles in the dispersion may be −50 to 40 mV, −50 to −11 mV, or 11 to 40 mV. When the zeta potential of the silica particles is −50 to −11 mV or 11 to 40 mV, the silica particles tend to repel each other in the dispersion, making it easier to suppress aggregation of the silica particles.

[0033] The zeta potential of silica particles can be measured using a zeta potential meter (e.g., Beckman Coulter, model number: Coulter Delsa 440). To measure the zeta potential, a dispersion medium is added to a dispersion of silica particles so that the silica particle concentration is 5 ppm based on the total amount of the test solution, and the silica particles are dispersed by ultrasonic treatment to prepare a test solution. The test solution is then placed in a measurement cell equipped with platinum electrodes on both sides, and a voltage of 10 V is applied to both electrodes. The charged silica particles migrate to the electrode with the opposite polarity to their charge. The zeta potential can be calculated from the migration speed of the charged silica particles.

[0034] Commercially available colloidal silica dispersions may be used, for example, ST-PS-SO (manufactured by Nissan Chemical Industries, Ltd.), ST-PS-MO (manufactured by Nissan Chemical Industries, Ltd.), ST-PS-M (manufactured by Nissan Chemical Industries, Ltd.), ST-PS-S (manufactured by Nissan Chemical Industries, Ltd.), ST-UP (manufactured by Nissan Chemical Industries, Ltd.), ST-OUP (manufactured by Nissan Chemical Industries, Ltd.), IPA-ST-UP (manufactured by Nissan Chemical Industries, Ltd.), MA-ST-UP (manufactured by Nissan Chemical Industries, Ltd.), PGM-ST-UP (manufactured by Nissan Chemical Industries, Ltd.), MEK-ST-UP (manufactured by Nissan Chemical Industries, Ltd.), IPA-ST (manufactured by Nissan Chemical Industries, Ltd.), IPA -ST-L (manufactured by Nissan Chemical Industries, Ltd.), IPA-ST-ZL (manufactured by Nissan Chemical Industries, Ltd.), MA-ST-M (manufactured by Nissan Chemical Industries, Ltd.), MA-ST-L (manufactured by Nissan Chemical Industries, Ltd.), MA-ST-ZL (manufactured by Nissan Chemical Industries, Ltd.), EG-ST (manufactured by Nissan Chemical Industries, Ltd.), EG-ST-XL-30 (manufactured by Nissan Chemical Industries, Ltd.), NPC-ST-30 (manufactured by Nissan Chemical Industries, Ltd.), PGM-ST (manufactured by Nissan Chemical Industries, Ltd.), DMAC-ST (manufactured by Nissan Chemical Industries, Ltd.), DMAC-ST-ZL (manufactured by Nissan Chemical Industries, Ltd.), NMP-ST (manufactured by Nissan Chemical Industries, Ltd.), TOL-ST (manufactured by Nissan Chemical Industries, Ltd.) (Nissan Chemical Industries, Ltd.), MEK-ST-40 (Nissan Chemical Industries, Ltd.), MEK-ST-L (Nissan Chemical Industries, Ltd.), MEK-ST-ZL (Nissan Chemical Industries, Ltd.), MIBK-ST (Nissan Chemical Industries, Ltd.), MIBK-ST-L (Nissan Chemical Industries, Ltd.), CHO-ST-M (Nissan Chemical Industries, Ltd.), EAC-ST (Nissan Chemical Industries, Ltd.), PMA-ST (Nissan Chemical Industries, Ltd.), MEK-EC-2130Y (Nissan Chemical Industries, Ltd.), MEK-AC-2140Z (Nissan Chemical Industries, Ltd.), MEK-AC-4130Y (Nissan Chemical Industries, Ltd.), MEK-AC-514 0Z (manufactured by Nissan Chemical Industries, Ltd.), PGM-AC-2140Y (manufactured by Nissan Chemical Industries, Ltd.), PGM-AC-4130Y (manufactured by Nissan Chemical Industries, Ltd.), MIBK-AC-2140Z (manufactured by Nissan Chemical Industries, Ltd.), MIBK-SD-L (manufactured by Nissan Chemical Industries, Ltd.), ST-XS (manufactured by Nissan Chemical Industries, Ltd.), ST-OXS (manufactured by Nissan Chemical Industries, Ltd.), ST-NXS (manufactured by Nissan Chemical Industries, Ltd.), ST-CXS (manufactured by Nissan Chemical Industries, Ltd.), ST-S (manufactured by Nissan Chemical Industries, Ltd.), ST-OS (manufactured by Nissan Chemical Industries, Ltd.), ST-NS (manufactured by Nissan Chemical Industries, Ltd.), ST-30 (manufactured by Nissan Chemical Industries, Ltd.),ST-O (manufactured by Nissan Chemical Co., Ltd.), ST-N (manufactured by Nissan Chemical Co., Ltd.), ST-C (manufactured by Nissan Chemical Co., Ltd.), ST-AK (manufactured by Nissan Chemical Co., Ltd.), ST-50-T (manufactured by Nissan Chemical Co., Ltd.), ST-O-40 (manufactured by Nissan Chemical Co., Ltd.), ST-N-40 (manufactured by Nissan Chemical Co., Ltd.), ST-CM (manufactured by Nissan Chemical Co., Ltd.), ST-30L (manufactured by Nissan Chemical Co., Ltd.), ST-OL (manufactured by Nissan Chemical Co., Ltd.), ST-AK-L (manufactured by Nissan Chemical Co., Ltd.), ST-YL (manufactured by Nissan Chemical Co., Ltd.), S T-OYL (manufactured by Nissan Chemical Industries, Ltd.), ST-AK-YL (manufactured by Nissan Chemical Industries, Ltd.), ST-ZL (manufactured by Nissan Chemical Industries, Ltd.), MP-1040 (manufactured by Nissan Chemical Industries, Ltd.), MP-2040 (manufactured by Nissan Chemical Industries, Ltd.), MP-4540M (manufactured by Nissan Chemical Industries, Ltd.), PL-1-IPA (manufactured by Fuso Chemical Industries, Ltd.), PL-1-TOL (manufactured by Fuso Chemical Industries, Ltd.), PL-2L-PGME (manufactured by Fuso Chemical Industries, Ltd.), PL-2L-MEK (manufactured by Fuso Chemical Industries, Ltd.), PL-2L (manufactured by Fuso Chemical Industries, Ltd.), PL-3 (manufactured by Fuso Chemical Co., Ltd.), PL-4 (manufactured by Fuso Chemical Co., Ltd.), PL-5 (manufactured by Fuso Chemical Co., Ltd.), PL-1H (manufactured by Fuso Chemical Co., Ltd.), PL-3H (manufactured by Fuso Chemical Co., Ltd.), PL-5H (manufactured by Fuso Chemical Co., Ltd.), BS-2L (manufactured by Fuso Chemical Co., Ltd.) BS-3L (manufactured by Fuso Chemical Co., Ltd.), BS-5L (manufactured by Fuso Chemical Co., Ltd.), HL-2L (manufactured by Fuso Chemical Co., Ltd.), HL-3L (manufactured by Fuso Chemical Co., Ltd.), HL-4L (manufactured by Fuso Chemical Co., Ltd.), PL-3-C (manufactured by Fuso Chemical Co., Ltd.) Examples of suitable catalysts include SI-10 (manufactured by JGC Catalysts and Chemicals Co., Ltd.), PL-3-D (manufactured by Fuso Chemical Co., Ltd.), TCSOL800 (manufactured by Tama Chemicals Co., Ltd.), SI-40 (manufactured by JGC Catalysts and Chemicals Co., Ltd.), SI-50 (manufactured by JGC Catalysts and Chemicals Co., Ltd.), SI-45P (manufactured by JGC Catalysts and Chemicals Co., Ltd.), SI-80P (manufactured by JGC Catalysts and Chemicals Co., Ltd.), SIK-23 (manufactured by JGC Catalysts and Chemicals Co., Ltd.), S-30H (manufactured by JGC Catalysts and Chemicals Co., Ltd.), SIK-15 (manufactured by JGC Catalysts and Chemicals Co., Ltd.), and SI-550 (manufactured by JGC Catalysts and Chemicals Co., Ltd.).

[0035] The average particle size (average secondary particle size) of the silica particles may be 1 to 1,000 nm. The average particle size of the silica particles may be 3 nm or more, 5 nm or more, or 10 nm or more, or may be 700 nm or less, 500 nm or less, 300 nm or less, 200 nm or less, or 100 nm or less.

[0036] The average particle size of silica particles can be measured, for example, by the following procedure. That is, approximately 100 μL (L stands for liters; the same applies below) of a dispersion of silica particles is measured out and diluted with a dispersant to obtain a diluted solution so that the silica particle content is approximately 0.05% by mass (a content that results in a transmittance (H) of 60 to 70% during measurement). The diluted solution is then placed in the sample tank of a laser diffraction particle size distribution analyzer (manufactured by Horiba, Ltd., product name: LA-920, refractive index: 1.93, light source: He—Ne laser, absorption 0), and the average particle size of the silica particles can be measured.

[0037] The silica particles may be used alone or in combination of two or more different shapes depending on the packing rate and the structural thickness of the molded product. From the viewpoint of improving hardness and flexibility in a well-balanced manner, the total content of the silica particles may be 10 to 100 parts by mass or 25 to 60 parts by mass relative to 100 parts by mass of the total amount of the polymerizable compound.

[0038] (Silane Coupling Agent) The curable component (photocurable resin composition or thermosetting resin composition) may further contain a silane coupling agent from the viewpoint of improving crosslink density. Examples of the silane coupling agent include a silane coupling agent having an acryloyl group, a silane coupling agent having a methacryloyl group, a silane coupling agent having an alkyl group, a silane coupling agent having an alkenyl group, a silane coupling agent having an aryl group, a silane coupling agent having an epoxy group, and a silane coupling agent having an amino group.

[0039] Examples of silane coupling agents having an acryloyl group include 3-acryloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.), X-12-1048 (manufactured by Shin-Etsu Chemical Co., Ltd.), X-12-1050 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of silane coupling agents having a methacryloyl group include 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd., etc.), 8-methacryloxyoctyltrimethoxysilane (KBM-5803 manufactured by Shin-Etsu Chemical Co., Ltd., etc.), 3-methacryloxypropyltriethoxysilane (KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd., etc.), 3-methacryloxypropylmethyldimethoxysilane (KBM-502 manufactured by Shin-Etsu Chemical Co., Ltd., etc.), 3-methacryloxypropylmethyldiethoxysilane (KBE-502 manufactured by Shin-Etsu Chemical Co., Ltd., etc.), Z-6030 (manufactured by Toray Dow Co., Ltd.), Y9936 (manufactured by Momentive Performance Materials Co., Ltd.), and A-174 (manufactured by Momentive Performance Materials Co., Ltd.).

[0040] From the viewpoint of improving the crosslink density, the content of the silane coupling agent may be 0.001 to 5.0 parts by mass, or may be 0.01 to 1.0 part by mass, relative to 100 parts by mass of the total amount of the polymerizable compounds.

[0041] (Polysiloxane Compound Having Amino Group) The functional coating material contains a polysiloxane compound having an amino group (hereinafter also simply referred to as "polysiloxane compound"). The polysiloxane compound has a siloxane chain and an amino group. The polysiloxane compound may have an amino group at the end of the siloxane chain, or may have an amino group at a side chain of the siloxane chain. From the viewpoint of compatibility with the curable component, the polysiloxane compound may have an amino group at the side chain or end of the siloxane compound. The functional coating material may contain a reaction product of the curable component and the polysiloxane compound having an amino group.

[0042] The polysiloxane compound can also be said to be a compound in which some of the structural units constituting the siloxane chain are substituted with structural units having an amino group.

[0043] The siloxane chain of the polysiloxane compound may be composed of, for example, a structural unit represented by the following formula (1-1).

[0044]

[0045] In the formula, R １ represents an alkyl group or a phenyl group. １ may be the same or different.

[0046] R １ may be an alkyl group having 1 to 6 carbon atoms, or a phenyl group, or may be a methyl group, or an ethyl group, or may be a methyl group.

[0047] The terminal of the structural unit contained in the polysiloxane compound may be, for example, a structural unit represented by the following formula (1-X), (1-Y), or (1-Z).

[0048]

[0049] Rx in the formulas (1-X) and (1-Z) may be an alkyl group having 1 to 10 carbon atoms, a phenyl group, a methyl group, an ethyl group, or a methyl group. １ may be an alkyl group having 1 to 6 carbon atoms, a phenyl group, a methyl group, an ethyl group, or a methyl group. １ may be the same or different.

[0050] The siloxane chain of the polysiloxane compound may have a structural unit represented by the following formula (2-1) as a structural unit having an amino group.

[0051]

[0052] In the formula, R ２ represents an alkyl group, and L １ represents a divalent group.

[0053] R ２ may be an alkyl group having 1 to 6 carbon atoms, a methyl group or an ethyl group, or may be a methyl group.

[0054] L １ Examples of the alkanediyl group include an alkanediyl group and —CH ２ At least one of the -s is substituted with -NH- or -O-. The alkanediyl group may have 2 to 12 carbon atoms, or 4 to 8 carbon atoms, for example.

[0055] L １ For example, -R ２１ -NH-R ２２ - is an example of a group represented by R ２１ and R ２２ Each independently represents an alkanediyl group. ２１ is a group bonded to Si, and R ２２ is NH ２ is a group that bonds to

[0056] R ２１ and R ２２ The alkanediyl group may have, for example, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.

[0057] The polysiloxane compound may have a 2-[(2-aminoethyl)amino]propyl group in the side chain from the viewpoint of improving water repellency and antifouling properties.

[0058] The average number of amino groups contained in one molecule of the polysiloxane compound may be, for example, 1 to 10, and from the viewpoint of water repellency, may be 1 to 7 or 1 to 4.

[0059] The content C of the structural unit represented by formula (1-1) in the siloxane chain of the polysiloxane compound １ The content C of the structural unit represented by formula (2-1) ２ The molar ratio (C ２ / C １ The average value of ) may be, for example, 0.01 to 100, 0.01 to 10, or 0.01 to 1.

[0060] The average number of silicon atoms contained in one molecule of the polysiloxane compound may be, for example, at least 10, at least 50, at least 100, at least 200, or at least 300. When the number of silicon atoms in the polysiloxane compound is large, that is, when the degree of polymerization of the polysiloxane compound is high, the water repellency of the formed coating (hard coat) tends to be further improved.

[0061] The average number of silicon atoms contained in one molecule of the polysiloxane compound may be, for example, 500 or less, 400 or less, or 360 or less, from the viewpoint of compatibility with the curable component.

[0062] From the viewpoint of water repellency and viscosity, the polysiloxane compound may have an alkyl group having 12 to 50 carbon atoms (hereinafter referred to as a long-chain alkyl group). The number of carbon atoms in the long-chain alkyl group may be 12 to 30, or 15 to 17. The long-chain alkyl group may be linear or branched, with linear being more preferred.

[0063] The polysiloxane compound may have a long-chain alkyl group at the terminal of the siloxane chain, or may have a long-chain alkyl group on a side chain of the siloxane chain. From the viewpoint of water repellency, the polysiloxane compound may have a long-chain alkyl group at the terminal of the siloxane chain.

[0064] The terminal of the siloxane chain of the polysiloxane compound may be, for example, a structural unit represented by the following formula (3-1) or a structural unit represented by the following formula (3-2): These structural units may be bonded directly to the oxygen atom terminal of the siloxane chain, or may be bonded to the silicon atom terminal via an oxygen atom.

[0065]

[0066]

[0067] In the formula, R ３１ , R ３２ and R ３３ Each of R independently represents an alkyl group. ３１ may be the same or different.

[0068] R ３１is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0069] R ３２ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0070] R ３３ may be an aralkyl group, a long-chain alkyl group having 12 to 50 carbon atoms, a long-chain alkyl group having 15 to 17 carbon atoms (for example, a cetearyl group [CH ３ (CH ２ ) １５～１７ -]). ３３ is an aralkyl group, R ３３ may be (iii) below:

[0071] From the viewpoint of water repellency, the terminal of the siloxane chain of the polysiloxane compound may be a structural unit represented by formula (3-2).

[0072] The weight average molecular weight of the polysiloxane compound may be, for example, 950 or more, 2500 or more, 8000 or more, or 20000 or more. When the weight average molecular weight of the polysiloxane compound is large, the water repellency of the formed coating (hard coat) tends to be further improved.

[0073] From the viewpoint of compatibility with the curable component, the weight average molecular weight of the polysiloxane compound may be, for example, 40,000 or less, preferably 35,000 or less, and more preferably 25,000 or less, which tends to further improve dispersibility in the curable component.

[0074] The weight average molecular weight is calculated by gel permeation chromatography (GPC) from a calibration curve using standard polystyrene. The calibration curve is approximated by a cubic equation using a set of five standard polystyrene samples (PStQuick MP-H, PStQuick B [product name, Tosoh Corporation]). The GPC conditions are, for example, as follows. The injection amount is adjusted according to the peak height and peak resolution. Apparatus: High-speed GPC apparatus "HLC-8320GPC" (Tosoh Corporation, trade name) Detector: Ultraviolet absorption detector "UV-8320" (Tosoh Corporation, trade name) Columns: Guard column; TSKgel guard column Super (HZ)-M+, column; TSKgel SuperMultipore HZ-M (2 columns), reference column; TSKgel Super H-RC (2 columns) (all Tosoh Corporation, trade names) Column size: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column), 6.0 x 150 mm (reference column) Eluent: Tetrahydrofuran Sample concentration: 10 mg / 1 mL Injection volume: 20 μL or 2 μL Flow rate: 0.35 mL / min Measurement temperature: 40°C

[0075] The amine equivalent of the polysiloxane compound may be 500 to 5000 g / mol or 1000 to 3000 g / mol from the viewpoint of improving water repellency and antifouling properties, and may be 1000 to 1500 g / mol from the viewpoint of further improving the transparency, scratch resistance, and antifouling properties of the coating (hard coat).

[0076] The blending ratio of the curable component and the polysiloxane compound having an amino group in the functional coating material of this embodiment may be 0.01 to 10 parts by mass, 0.1 to 5 parts by mass, or 0.3 to 1.0 parts by mass per 100 parts by mass of the curable component, from the viewpoints of abrasion resistance and water repellency. Furthermore, when the functional coating material contains a polymerizable compound as the curable component, the blending ratio of the polysiloxane compound having an amino group may be 0.01 to 10 parts by mass, 0.1 to 5 parts by mass, or 0.1 to 1.0 part by mass per 100 parts by mass of the polymerizable compound, from the viewpoints of abrasion resistance and water repellency.

[0077] (Sensitizer) The functional coating material contains a sensitizer. When the functional coating material contains a sensitizer, a coating (hard coat) in which cloudiness is suppressed can be formed.

[0078] Examples of sensitizers include anthracene compounds, benzophenone compounds, pyrazoline compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. From the viewpoint of easily forming a coating (hard coat) with reduced opacity, the sensitizer may contain at least one selected from the group consisting of anthracene compounds, benzophenone compounds, and pyrazoline compounds. From the viewpoint of being particularly useful with high-pressure mercury lamps with a narrow irradiation wavelength range, the sensitizer preferably has an absorption wavelength of 350 to 450 nm.

[0079] Examples of anthracene compounds include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene. From the viewpoint of easily forming a coating (hard coat) with reduced cloudiness, the sensitizer may contain at least one selected from the group consisting of 9,10-dibutoxyanthracene and 9,10-diethoxyanthracene.

[0080] Examples of benzophenone compounds include benzophenone; dialkylaminobenzophenones such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone; N,N,N',N'-tetraalkyl-4,4'-diaminobenzophenones such as N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (also known as Michler's ketone) and N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone; and 4-benzoyl-4'-methyldiphenyl sulfide. From the viewpoint of facilitating the formation of a coating (hard coat) with reduced opacity, the sensitizer may contain at least one selected from the group consisting of dialkylaminobenzophenones, 4,4'-bis(diethylamino)benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

[0081] Examples of the pyrazoline compound include 1-(4-methoxyphenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1,5-bis-(4-methoxyphenyl)-3-(4-methoxystyryl)-pyrazoline, 1-(4-isopropylphenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1,5-bis-(4-isopropylphenyl)-3-(4- isopropylstyryl)-pyrazoline, 1-(4-methoxyphenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(4-isopropyl-styryl)-5-(4-isopropyl 1-(4-methoxyphenyl)-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5 -(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2,4-dimethoxystyryl)-5-(2 ,4-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(2,5-dimethoxystyryl)-5 -(2,5-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(3,4-dimethoxystyryl)-5- (3,4-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, and 1-(4-isopropyl-phenyl)-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline.

[0082] From the viewpoint of reducing the amount of unreacted material remaining during UV curing, the maximum absorption wavelength of the sensitizer may be 330 nm or more, 340 nm or more, 350 nm or more, or 360 nm or more, or may be 400 nm or less, 390 nm or less, 380 nm or less, or 370 nm or less.

[0083] From the viewpoint of easily forming a coating (hard coat) in which cloudiness is further suppressed, the molecular weight of the sensitizer may be 100 or more, 150 or more, 200 or more, 250 or more, or 300 or more, or may be 500 or less, 450 or less, 400 or less, or 350 or less.

[0084] The content of the sensitizer may be 0.1 parts by mass, 0.5 parts by mass or more, 1 part by mass or more, 1.2 parts by mass or more, 1.5 parts by mass or more, or 1.7 parts by mass or more relative to 100 parts by mass of the curable component, from the viewpoint of easily forming a coating (hard coat) with more suppressed cloudiness. The content of the sensitizer may be 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, or 2 parts by mass or less relative to 100 parts by mass of the curable component, from the viewpoint of easily adjusting the curing rate of the functional coating material.

[0085] The content of the sensitizer may be 100 parts by mass or more, 150 parts by mass or more, 200 parts by mass or more, 250 parts by mass or more, 300 parts by mass or more, 350 parts by mass or more, or 400 parts by mass or more relative to 100 parts by mass of the polysiloxane compound having an amino group, from the viewpoint of easily forming a coating (hard coat) with more suppressed cloudiness. The content of the sensitizer may be 1000 parts by mass or less, 800 parts by mass or less, 700 parts by mass or less, 600 parts by mass or less, 500 parts by mass or less, or 450 parts by mass or less relative to 100 parts by mass of the polysiloxane compound having an amino group, from the viewpoint of easily adjusting the curing rate of the functional coating material.

[0086] The content of the sensitizer may be 0.1 parts by mass, 0.5 parts by mass or more, 1 part by mass or more, 1.2 parts by mass or more, 1.5 parts by mass or more, or 1.7 parts by mass or more, relative to 100 parts by mass of the total of the curable component and the polysiloxane compound having an amino group, from the viewpoint of easily forming a coating (hard coat) with more suppressed cloudiness. The content of the sensitizer may be 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, or 2 parts by mass or less, relative to 100 parts by mass of the total of the curable component and the polysiloxane compound having an amino group, from the viewpoint of easily adjusting the curing rate of the functional coating material. The functional coating material may contain a single sensitizer or multiple sensitizers.

[0087] The functional coating material of this embodiment may contain a liquid medium.

[0088] Examples of the liquid medium that can be used include water, organic solvents, and mixtures thereof. Examples of organic solvents include alcohols such as methyl alcohol, ethyl alcohol, 1-propanol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, diacetone alcohol, 1-butoxy-2-propanol, 1-hexanol, 1-octanol, 2-octanol, and 3-methoxy-3-methyl-1-butanol; glycols such as polyethylene glycol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol n-propyl ether, and propylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; cyclic hydrocarbons such as cyclohexane; and acetonitrile. These organic solvents may be used alone or in combination.

[0089] The content of the liquid medium may be 100 to 1000 parts by mass, or may be 250 to 750 parts by mass, relative to 100 parts by mass of the total of the curable component and the polysiloxane compound having an amino group.

[0090] The functional coating material of this embodiment may have a solids concentration of 50 to 100% by mass, 75 to 100% by mass, or 90 to 100% by mass.

[0091] The functional coating material of this embodiment may contain various additives such as a polymerization inhibitor, a silane coupling agent, an antioxidant, a light stabilizer, a thickener, an anti-condensation agent, and an anti-snow agent, as needed, within the range in which the desired effect is obtained.

[0092] The functional coating material may be used for forming a hard coat. That is, the functional coating material may be a hard coat material. The hard coat material may be a functional hard coat material. The functional hard coat material means a hard coat material capable of forming a hard coat having functions such as antifouling properties, transparency, water repellency, fingerprint resistance, and antifogging properties. The hard coat material may be capable of forming a hard coat having both water repellency and / or antifouling properties. That is, the hard coat material may be a water-repellent hard coat material, an antifouling hard coat material, or a water-repellent and antifouling hard coat material.

[0093] <Hard Coat> The hard coat of this embodiment is made of a cured product of the functional coating material of this embodiment described above.

[0094] The hard coat can be formed by applying the functional coating material of this embodiment to a desired substrate and curing it.

[0095] The substrate may be a glass substrate, a plastic substrate such as a polycarbonate substrate or an acrylic substrate, or a metal substrate such as aluminum or stainless steel (SUS).Examples of the substrate include automobile components such as body exteriors, glass exteriors, headlamps, sensor lenses, and window glass, image display devices such as liquid crystal displays, CRT displays, plasma displays, EL (electroluminescence) displays, and touch panels, buildings such as exterior walls, roofs, and window glass, building interiors such as kitchens, bathtubs, toilets, and washrooms, solar panels for solar cells, electric wires for power grids, and fibers for clothing and tents.

[0096] Examples of the coating method include spin coating, dip coating, spray coating, flow coating, bar coating, gravure coating, bar coating, and wiping. These methods may be used alone or in combination of two or more.

[0097] The method for curing the coating film can be appropriately selected depending on the curable component, and includes heating, irradiation with active energy rays, natural drying, etc. A combination of these methods may also be used. When the functional coating material contains a polymerizable compound and a photopolymerization initiator as curable components, it can be cured, for example, by irradiation with active energy rays (such as ultraviolet rays). In this case, the coating film may be further heated after irradiation with active energy rays.

[0098] The ultraviolet irradiation may be carried out using a halogen lamp or a high-pressure mercury lamp. The amount of ultraviolet irradiation is, for example, 1000 mJ / cm from the viewpoint of increasing the curing speed of the functional coating material. ２ Above, 3000mJ / cm ２ or more, or 5000 mJ / cm ２ From the viewpoint of easily forming a coating (hard coat) in which cloudiness is further suppressed, for example, 5000 mJ / cm ２ Below, 3000mJ / cm ２ or less, or 1000 mJ / cm ２ It may be the following:

[0099] The hard coat may have both water repellency and antifouling properties, that is, the hard coat may be a water repellent and antifouling hard coat.

[0100] The haze of the hard coat may be 2 or less, 1.8 or less, 1.6 or less, 1.4 or less, or 1.2 or less. The smaller the haze of the hard coat, the more the cloudiness of the hard coat is suppressed. The haze of the hard coat may be 0.1 or more. The haze of the hard coat can be measured by the method described in the examples below.

[0101] The transmittance of the hard coat may be 80% or more, 82% or more, 84% or more, 86% or more, or 88% or more. The higher the transmittance of the hard coat, the more the cloudiness of the hard coat is suppressed. The transmittance of the hard coat can be measured by the method described in the examples below.

[0102] The difference in haze of the hard coat before and after the scratch resistance test may be 2.0 or less, 1.5 or less, or 1.0 or less. The difference in haze can be measured by the method described in the examples below.

[0103] The pencil hardness of the hard coat is, for example, 3B or more. The pencil hardness of the hard coat may be 2B or more, B or more, or HB or more. The pencil hardness can be measured in accordance with JIS-K5600-5-4.

[0104] The thickness of the hard coat may be 0.1 μm or more, 1 μm or more, or 10 μm or more from the viewpoint of scratch resistance, water repellency, and stain resistance, and may be 1000 μm or less, 500 μm or less, or 100 μm or less from the viewpoint of transparency.

[0105] <Structure> The structure of this embodiment includes a substrate and the hard coat of this embodiment provided on the substrate. When the hard coat has both water repellency and antifouling properties, the structure can be said to be a water-repellent and antifouling structure.

[0106] Examples of the substrate include those described above.

[0107] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to these examples.

[0108] <Preparation of Curable Component A1> 230 g of IPA-dispersed spherical nanosilica (manufactured by Nissan Chemical Industries, Ltd., product name: IPA-ST, average particle size 12 nm, solid content of spherical nanosilica 70 g), 70 g of trimethylolpropane EO-adduct triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: AT-20E), 50 g of hexamethylene 2-acrylate, and 14 g of 2-hydroxy-2-methylpropiophenone (photopolymerization initiator, rich 4 g of 2,4-dihydroxybenzophenone (photopolymerization initiator, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 4 g of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (ultraviolet absorber, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and 0.1 g of X-12-1050 (acrylic silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed. The resulting mixture was then distilled with stirring at 80°C for 2 hours to remove the IPA, yielding curable component A1.

[0109] <Preparation of Curable Component A2> 200 g of IPA-dispersed spherical nanosilica (manufactured by Nissan Chemical Industries, Ltd., product name: IPA-ST, average particle size 12 nm, solid content of spherical nanosilica 60 g), 60 g of ethoxylated glycerin triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-GLY-9E), 50 g of 1,9-nonanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-NOD-N), and 17 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methyl-2-propanol. 4 g of 2,4-dihydroxybenzophenone (photopolymerization initiator, manufactured by FUJIFILM Wako Pure Chemical Industries), 4 g of 2,4-dihydroxybenzophenone (photopolymerization initiator, manufactured by FUJIFILM Wako Pure Chemical Industries), 8 g of 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (ultraviolet absorber, manufactured by FUJIFILM Wako Pure Chemical Industries), and 0.1 g of X-12-1050 (acrylic silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed. The resulting mixture was then distilled with stirring at 80°C for 2 hours to remove the IPA, yielding curable component A2.

[0110] <Preparation of Curable Component A3> 200 g of MEK-dispersed spherical nanosilica (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-AC-2140Z, average particle size 12 nm, solid content of spherical nanosilica 80 g), 60 g of ethoxylated glycerin triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-GLY-9E), 50 g of 1,9-nonanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-NOD-N), 17 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone (photopolymerization initiator, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 4 g of 2,4-dihydroxybenzophenone (photopolymerization initiator, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and 8 g of 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (ultraviolet absorber, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were mixed together. The resulting mixture was then distilled at 60°C for 1 hour with stirring to remove the MEK, yielding Curable Component A3.

[0111] <Preparation of Curable Component A4> 200 g of MEK-dispersed spherical nanosilica (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-AC-2140Z, average particle size 12 nm, solid content of spherical nanosilica 80 g), 60 g of ethoxylated glycerin triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-GLY-9E), 50 g of 1,9-nonanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-NOD-N), 7 g of t-butylperoxy-2-ethylhexanate (manufactured by NOF Corporation, trade name: Perocta-O), and 8 g of 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (ultraviolet absorber, manufactured by Fujifilm Wako Pure Chemical Industries) were mixed. The resulting mixture was then distilled with stirring at 60°C for 1 hour to remove the MEK, yielding Curable Component A4.

[0112] <Preparation of Curable Component A5> 100 g of PGM-dispersed spherical nanosilica (manufactured by Nissan Chemical Industries, Ltd., trade name: PGM-AC-4130Y, average particle size 45 nm, solid content of spherical nanosilica 30 g), 120 g of trimethylolpropane EO adduct triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-TMPT-9EO), and 100 g of 1,9-nonanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-NOD -N), 17 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone (photopolymerization initiator, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 4 g of 2,4-dihydroxybenzophenone (photopolymerization initiator, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and 8 g of 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (ultraviolet absorber, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). Next, the resulting mixture was distilled at 60°C for 1 hour with stirring to remove the PGM, and curable component A5 was obtained.

[0113] <Preparation of Polysiloxane Compound B> 100 parts by mass of styrene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 parts by mass of a 1% chloroplatinic acid isopropanol solution were heated to 70°C while stirring. Next, 74 parts by mass of a polyorganosiloxane represented by the following formula (i) (manufactured by Momentive Performance Materials Japan LLC, product name "XF40-C2195") was added dropwise. After completion of the dropwise addition, the temperature was raised to 80°C and stirring was continued for 1 hour to obtain an alkyl-modified polyorganosiloxane represented by the following formula (ii). In formula (ii), R Ｂ represents an aralkyl group shown in (iii). H(CH ３ ) ２ -SiO-((CH ３ ) ２ SiO) １８ -Si(CH ３ ) ２ H ... (i) R Ｂ (CH ３ ) ２ -SiO-((CH ３ ) ２ SiO) １８ -Si(CH ３ ) ２ R Ｂ ... (ii)

[0114] Next, 186 parts of the obtained alkyl-modified polyorganosiloxane, 651 parts of octamethylcyclotetrasiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 25 parts of N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and heated to 90 ° C. while stirring. Next, 90 ppm of a 10% aqueous tetramethylammonium hydroxide solution (manufactured by Nacalai Tesque, Inc.) was added as an active ingredient, and the mixture was stirred at 90 ° C. for 3 hours. Next, the low molecular weight siloxane was distilled off under reduced pressure to obtain a both-terminal aralkyl-side chain amino-modified organopolysiloxane (polysiloxane compound B). The average amine equivalent of polysiloxane compound B was 1,400, the weight average molecular weight was 23,000, the average number of silicon atoms in one molecule was 305, and the content C of the structural unit represented by the formula (1-1) in the siloxane chain １ The content C of the structural unit represented by formula (2-1) ２ The molar ratio (C ２ / C １ ) was 0.06.

[0115] <Sensitizer> The following compounds were used as sensitizers: 9,10-dibutoxyanthracene (manufactured by Air Water Performance Chemicals, Inc., trade name: Anthracure UVS1331, maximum absorption wavelength: 368 nm, 388 nm, 410 nm) 4,4'-bis(diethylamino)benzophenone (manufactured by Kanto Chemical Co., Inc., maximum absorption wavelength: 360 nm) 9,10-diethoxyanthracene (Fujifilm Wako Pure Chemical Industries, Ltd.) 4-benzoyl-4'-methyldiphenyl sulfide (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0116] <Preparation of Functional Coating Materials> (Examples 1 to 5 and Comparative Example 1) Each component was mixed at 40°C in the composition (parts by mass) shown in Table 1 to obtain each functional coating material.

[0117] <Evaluation of Hard Coat> A functional coating material was applied to a polycarbonate substrate using a bar coater (No. 8, manufactured by Daiichi Rika Co., Ltd.) to form a coating film. The coating film was then exposed to ultraviolet light (exposure amount: in the atmosphere as shown in Table 1) using a high-pressure mercury lamp (manufactured by Ushio Inc., product name: UVC-8kW2-500HCC-1). Subsequently, a hard-coated substrate was obtained in which a hard coat (thickness: 20 to 30 μm) was formed on the polycarbonate substrate. The following evaluations were carried out on the obtained hard-coated substrate. The results are shown in Table 1.

[0118] (Appearance) The appearance of the center of the hard-coated substrate was visually observed to check for the presence or absence of cloudiness.

[0119] (Haze) The haze at the center of the hard-coated substrate was measured using a spectroscopic haze meter SH7000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

[0120] (Transmittance) The transmittance at the center of the hard-coated substrate was measured using a spectroscopic haze meter SH7000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

[0121] (Scratch Resistance) A scratch resistance test was carried out on a hard-coated substrate. The hard-coated substrate was placed on the stage of a surface measuring instrument TYPE: 14FW (manufactured by Shinto Scientific Co., Ltd.), steel wool (#0000) was set on a circular probe with a diameter of 2 cm, and a 500 g weight was placed on it. The hard coating was scratched under the following conditions: abrasion distance: 50 mm one way, abrasion speed: 6000 mm / min, and 10 reciprocating strokes. The haze before and after scratching was measured using a spectroscopic haze meter SH7000, and the difference in haze was calculated.

[0122]

[0123] As shown in Table 1, it can be seen that the functional coating materials of Examples 1 to 5 can form coatings (hard coats) with sufficiently low haze and sufficiently suppressed cloudiness.

Claims

1. A functional coating material comprising a curable component, a polysiloxane compound having an amino group, and a sensitizer.

2. The functional coating material according to claim 1, wherein the curable component is a photocurable resin composition.

3. The functional coating material according to claim 1, wherein the amine equivalent of the polysiloxane compound having an amino group is 500 to 5000 g / mol.

4. The functional coating material according to claim 1, wherein the sensitizer is an anthracene compound.

5. The functional coating material according to claim 1, wherein the sensitizer is a benzophenone compound.

6. The functional coating material according to claim 1, which is a hard coat material.

7. A hard coat comprising a cured product of the functional coating material according to any one of claims 1 to 6.

8. The hard coat according to claim 7, having a haze of 2 or less.

9. A structure comprising a substrate and the hard coat according to claim 7 provided on the substrate.

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