WO2025150226A1 - Hard coating material, hard coating, and structure - Google Patents

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 coat material, hard coat and structure

The present invention relates to a hard coat material, a hard coat, and a structure. The present invention also relates to a functional coating material.

In order to impart water repellency to substrates such as glass and plastics, a method is known in which the surface of the substrate is coated with a coating material containing a fluorine-containing resin such as polytetrafluoroethylene (PTFE) resin. 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 hard coat materials with water repellency (see Patent Document 1 below).

JP 2015-34832 A

　Examples of objects on which films such as hard coats can be formed include display device parts such as touch panels; indoor objects in buildings such as kitchens, bathtubs, toilets and washrooms; exterior parts of buildings, automobiles and trains; solar panels for solar cells, etc. It is desirable for coating materials to be transparent so as not to mar the appearance of the objects to which they are applied, but when the 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. In addition, when the coating material is cured by heating, the curing speed is slower than when it is cured by irradiating it with light, so the film tends to become more cloudy.

The present invention therefore aims to provide a functional coating material capable of forming a coating (e.g., a hard coat) with suppressed clouding. It also aims to provide a hard coat with suppressed clouding, and a structure including the hard coat.

To solve the above problems, the present invention provides the following functional coating material, hard coat, and structure.

[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 amine equivalent of the polysiloxane compound having an amino group is 500 to 5000 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], which 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], having a haze of 2 or less.
[9] A structure comprising a substrate and the hard coat according to [7] provided on the substrate.

The present invention can provide a functional coating material capable of forming a coating (e.g., a hard coat) with suppressed clouding. The present invention can also provide a hard coat with suppressed clouding, and a structure including the hard coat.

The following describes the functional coating material, hard coat, and structure according to one embodiment of the present invention.

In the present invention, the numerical ranges indicated using "~" include the numerical values before and after "~" as the minimum and maximum values, respectively. In addition, 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 numerical range described in stages. In addition, in the numerical ranges described in the present invention, the upper or lower limit value of the 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 may be used alone or in combination of two or more types. In the present invention, the content of each component in the composition means the total amount of multiple substances present in the composition when multiple substances corresponding to each component are present in the composition, unless otherwise specified.

<Functional coating materials>
The functional coating material of the present embodiment includes a curable component, a polysiloxane compound having an amino group, and a sensitizer. The functional coating material means a coating material capable of forming a coating film having functions such as antifouling properties, transparency, water repellency, fingerprint resistance, and antifogging properties.

The functional coating material according to one embodiment of the present invention can form a coating (hard coat) in which clouding is suppressed. Furthermore, when the functional coating material according to one embodiment of the present invention is a hard coat material, a hard coat in which clouding is suppressed can be formed. The reason why such an effect is achieved is not entirely clear, but the inventor of the present invention speculates as follows.

That is, if the functional coating material is not cured sufficiently, unreacted matter exists in the functional coating material, and the unreacted matter aggregates, causing the coating (hard coat) to become cloudy. Also, if the amount of light irradiation is increased in order to reduce the unreacted matter in the functional coating material, the reaction is likely to become uneven in the functional coating material, and the unreacted matter aggregates in areas where the reaction proceeds slowly, causing the coating (hard coat) to become cloudy.
On the other hand, the functional coating material contains a sensitizer, and thus the curing speed of the functional coating material is increased. This makes it easier for the curing reaction to occur uniformly throughout the functional coating material, reducing 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.

(curable component)
The functional coating material contains a curable component. The curable component may be a photocurable resin composition or a thermosetting resin composition. The curable component may be a photocurable resin composition or a UV-curable resin composition from the viewpoint of increasing the degree of freedom of the substrate to which the functional coating material is applied (in other words, the substrate selectivity of the functional coating material). 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 necessary. The curable component may be a thermosetting resin composition from the viewpoint of improving heat resistance. 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 necessary.

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 containing 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 less cloudiness.

Multifunctional 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, p) bifunctional polymerizable compounds such as 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 dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dimethyloltricyclodecane diacrylate, and dicyclopentanyl diacrylate; trimethylolpropane EO adduct triacrylate; trifunctional polymerizable compounds such as trimethylolpropane tri(meth)acrylate, 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 4 or more polymerizable double bonds, such as methyl ethyl acrylate, ethyl ... 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 less cloudiness. 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 less cloudiness.

The curable component (photocurable resin composition or thermosetting resin composition) may contain a bifunctional polymerizable compound as a polymerizable compound from the viewpoint of improving hardness, 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 polymerizable compounds.

The curable component (photocurable resin composition or thermosetting resin composition) may contain a trifunctional polymerizable compound as a polymerizable compound from the viewpoint of improving hardness, 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 polymerizable compounds.

The polymerizable compound may contain multiple polymerizable compounds with different numbers of functional groups, from the viewpoint of improving hardness and flexibility in a well-balanced manner. For example, the polymerizable compound may contain a bifunctional polymerizable compound and a trifunctional or higher functional polymerizable compound (a polymerizable compound with 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. 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, from the viewpoint of improving hardness and flexibility in a well-balanced manner.

The ratio of the mass-based content of trifunctional or more polymerizable compounds to the mass-based content of bifunctional polymerizable compounds (mass-based content of trifunctional or more polymerizable compounds/mass-based content of bifunctional polymerizable compounds) 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 may be 5 or less, 4 or less, 3 or less, 2 or less, or 1.5 or less from the same viewpoint. The ratio of the mass-based content of trifunctional polymerizable compounds to the mass-based content of bifunctional polymerizable compounds (mass-based content of trifunctional polymerizable compounds/mass-based content of bifunctional polymerizable compounds) 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 may be 5 or less, 4 or less, 3 or less, 2 or less, or 1.5 or less from the same viewpoint. 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 well-balanced manner, and from the same viewpoint, it 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 well-balanced manner, and from the same viewpoint, it may be 5 or less, 4 or less, 3 or less, 2 or less, or 1.5 or less.

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 monofunctional polymerizable compounds 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, 2-acryloyloxyethyl succinic acid, etc.

(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 that can be used is 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-diphenylethane-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, and the like. Non, 4,4'-bis (diethylamino) benzophenone, 2,4-dihydroxybenzophenone, ethyl-4- (dimethylamino) - benzoate, [4- (methylphenylthio) phenyl] - phenyl methane, ethylhexyl-4-dimethylamino benzoate, benzophenone, methyl-o-benzoyl benzoate, 4-methylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, methyl benzoyl 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 of at least one type according to the optimal curing conditions.

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

(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-butyl peroxy-2-ethylhexanoate, t-butyl peroxy isopropyl carbonate, and t-hexyl peroxy isopropyl 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.

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

(Ultraviolet absorber)
The curable component (photocurable resin composition or thermosetting resin composition) may contain an ultraviolet absorbing agent from the viewpoint of improving weather resistance. As the ultraviolet absorbing agent, known ones can be used, and benzotriazole-based compounds, benzophenone-based compounds, triazine-based compounds, etc. can be used. As the ultraviolet absorbing agent, for example, 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.

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

(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, rosary, pearl necklace, chain, cocoon, association, and confetti. The shape of the silica particles may be spherical. The silica particles may be colloidal silica or fumed silica.

The silica particles may have crosslinkable functional groups on a portion of their surface. Examples of crosslinkable functional groups include amino groups, sulfo groups, epoxy groups, oxetanyl groups, acryloyl groups, methacryloyl groups, vinyl groups, methylol groups, and maleimide groups.

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. The dispersion medium for silica particles may be water from the viewpoint of versatility.

The pH of the silica particle dispersion may be 2 to 10, 4 to 9, 6 to 8, or 2 to 5. The pH of the silica particle dispersion can be measured with a pH meter (e.g., 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, pH: 4.01 (25°C), neutral phosphate pH buffer, pH: 6.86 (25°C), borate pH buffer, pH: 9.18 (25°C)), and then the electrode is placed in the dispersion and the value is taken after stabilization for at least two minutes.

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. By having the zeta potential of the silica particles be -50 to -11 mV, or 11 to 40 mV, the silica particles will be more likely to repel each other in the dispersion, making it easier to suppress aggregation of the silica particles.

The zeta potential of silica particles can be measured with a zeta potential meter (e.g., Beckman Coulter, model number: Coulter Delsa 440). The zeta potential is measured by adding a dispersion medium to a dispersion of silica particles so that the concentration of silica particles is 5 ppm based on the total amount of the test solution, and preparing a test solution in which the silica particles are dispersed by ultrasonic treatment. The test solution is then placed in a measurement cell with platinum electrodes attached to both sides, and a voltage of 10 V is applied to both electrodes, causing the charged silica particles to move to the electrode with the opposite polarity to their charge. The zeta potential can be calculated from the movement speed of the charged silica particles.

As the colloidal silica dispersion, a commercially available product 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.), IP A-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.) Nissan Chemical Industries, Ltd.), NMP-ST (Nissan Chemical Industries, Ltd.), TOL-ST (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-A C-2140Z (manufactured by Nissan Chemical Industries, Ltd.), MEK-AC-4130Y (manufactured by Nissan Chemical Industries, Ltd.), MEK-AC-5140Z (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. (manufactured by Nissan Chemical Co., Ltd.), ST-S (manufactured by Nissan Chemical Co., Ltd.), ST-OS (manufactured by Nissan Chemical Co., Ltd.), ST-NS (manufactured by Nissan Chemical Co., Ltd.), ST-30 (manufactured by Nissan Chemical Co., 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.), ST-OYL (manufactured by Nissan Chemical Co., Ltd.), ST-AK-YL (manufactured by Nissan Chemical Co., Ltd.), ST-ZL (manufactured by Nissan Chemical Co., Ltd.), MP-1040 (manufactured by Nissan Chemical Co., Ltd.), MP-2040 (manufactured by Nissan Chemical Co., Ltd.), MP-4540M (manufactured by Nissan Chemical Co., Ltd.), PL-1-IPA (manufactured by Fuso Chemical Co., Ltd.), PL-1-TOL (manufactured by Fuso Chemical Co., Ltd.), PL-2L-PGME (manufactured by Fuso Chemical Co., Ltd.), PL- 2L-MEK (manufactured by Fuso Chemical Co., Ltd.), PL-2L (manufactured by Fuso Chemical Co., 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.) Co., Ltd.), PL-3-C (Fuso Chemical Co., Ltd.), PL-3-D (Fuso Chemical Co., Ltd.), TCSOL800 (Tama Chemical Industry Co., Ltd.), SI-40 (JGC Catalysts & Chemicals Co., Ltd.), SI-50 (JGC Catalysts & Chemicals Co., Ltd.), SI-45P (JGC Catalysts & Chemicals Co., Ltd.), SI-80P (JGC Catalysts & Chemicals Co., Ltd.), SIK-23 (JGC Catalysts & Chemicals Co., Ltd.), S-30H (JGC Catalysts & Chemicals Co., Ltd.), SIK-15 (JGC Catalysts & Chemicals Co., Ltd.), SI-550 (JGC Catalysts & Chemicals Co., Ltd.), etc.

The average particle size (average secondary particle size) of the silica particles may be 1 to 1000 nm. The average particle size of the silica particles may be 3 nm or more, 5 nm or more, or 10 nm or more, and may be 700 nm or less, 500 nm or less, 300 nm or less, 200 nm or less, or 100 nm or less.

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

Silica particles may be used alone or in combination of two or more different shapes depending on the filling rate and structural thickness of the molded product. The total content of silica particles may be 10 to 100 parts by mass, or 25 to 60 parts by mass, per 100 parts by mass of the total amount of polymerizable compounds, from the viewpoint of improving hardness and flexibility in a well-balanced manner.

(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.

Examples of silane coupling agents having an acryloyl group include 3-acryloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd., etc.), 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.).

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

(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.

A polysiloxane compound can also be described as a compound in which some of the structural units that make up the siloxane chain are replaced with structural units that have amino groups.

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

In the formula, R ¹ represents an alkyl group or a phenyl group. Multiple R ^1s may be the same or different.

R 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.

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

Rx in formulas (1-X) and (1-Z) may be an alkyl group having 1 to 10 carbon atoms, or a phenyl group, or a methyl group, or an ethyl group, or may be a methyl group. R ¹ in formulas (1-X), (1-Y), and (1-Z) may be an alkyl group having 1 to 6 carbon atoms, or a phenyl group, or a methyl group, or an ethyl group, or may be a methyl group. Multiple R ^1s may be the same or different.

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.

In the formula, ^R2 represents an alkyl group, and ^L1 represents a divalent group.

^R2 may be an alkyl group having 1 to 6 carbon atoms, a methyl group or an ethyl group, or may be a methyl group.

Examples of ^L1 include an alkanediyl group and an alkanediyl group in which at least one of -CH ₂ - is replaced with -NH- or -O-. The number of carbon atoms in the alkanediyl group may be, for example, 2 to 12, or 4 to 8.

Examples of ^L1 include a group represented by ^-R21 -NH- ^R22- , where ^R21 and ^R22 each independently represent an alkanediyl group. In this group, ^R21 is a group that bonds to Si, and ^R22 is a group that bonds to _NH2 .

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

The polysiloxane compound may have a 2-[(2-aminoethyl)amino]propyl group in the side chain in order to improve water repellency and stain resistance.

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

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

The average number of silicon atoms in one molecule of the polysiloxane compound may be, for example, 10 or more, 50 or more, 100 or more, 200 or more, or 300 or more. 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 coating (hard coat) formed tends to be improved.

In addition, 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.

The polysiloxane compound may have an alkyl group having 12 to 50 carbon atoms (hereinafter, long-chain alkyl group) from the viewpoint of water repellency and viscosity. 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 preferable.

The polysiloxane compound may have a long-chain alkyl group at the end 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 end of the siloxane chain.

The end 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 directly bonded to the oxygen atom end of the siloxane chain, and may be bonded to the silicon atom end via an oxygen atom.

In the formula, R ³¹ , R ³² and R ³³ each independently represent an alkyl group, and multiple R ³¹ may be the same or different.

R ³¹ 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.

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.

R ³³ may be an aralkyl group, a long-chain alkyl group having 12 to 50 carbon atoms, or a long-chain alkyl group having 15 to 17 carbon atoms (for example, a cetearyl group [CH ₃ (CH ₂ ) _15-17 -]). When R ³³ is an aralkyl group, R ³³ may be the following (iii).

The end of the siloxane chain of the polysiloxane compound may be a structural unit represented by formula (3-2) from the viewpoint of water repellency.

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. If the weight average molecular weight of the polysiloxane compound is large, the water repellency of the coating (hard coat) formed tends to be improved.

In addition, 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. This tends to further improve dispersibility in the curable component.

The weight average molecular weight is calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is approximated by a third-order 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" (product name, Tosoh Corporation)
Detector: Ultraviolet absorption detector "UV-8320" (product name, Tosoh Corporation)
Columns: Guard column: TSKgel guardcolumn Super (HZ)-M+, column: TSKgel SuperMultipore HZ-M (2 columns), reference column: TSKgel SuperH-RC (2 columns) (all product names of Tosoh Corporation)
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: 0.35mL/min Measurement temperature: 40℃

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 stain resistance, and may be 1000 to 1500 g/mol from the viewpoint of further improving the transparency, scratch resistance, and stain resistance of the coating (hard coat).

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 of the polysiloxane compound having an amino group per 100 parts by mass of the curable component, from the viewpoint of scratch 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 parts by mass of the polysiloxane compound having an amino group per 100 parts by mass of the polymerizable compound, from the viewpoint of scratch resistance and water repellency.

(Sensitizer)
The functional coating material contains a sensitizer. By containing a sensitizer in the functional coating material, a coating film (hard coat) in which cloudiness is suppressed can be formed.

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. The sensitizer may contain at least one selected from the group consisting of anthracene compounds, benzophenone compounds, and pyrazoline compounds, from the viewpoint of easily forming a coating (hard coat) with less cloudiness. The sensitizer is preferably a sensitizer with an absorption wavelength of 350 to 450 nm, from the viewpoint of being particularly useful for high-pressure mercury lamps with a narrow irradiation wavelength range.

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 less cloudiness, the sensitizer may contain at least one selected from the group consisting of 9,10-dibutoxyanthracene and 9,10-diethoxyanthracene.

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 easily forming a coating (hard coat) with less cloudiness, 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.

Examples of pyrazoline compounds 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-isopropylphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-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-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- phenyl)-pyrazoline, 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)- styryl)-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.

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, and may be 400 nm or less, 390 nm or less, 380 nm or less, or 370 nm or less, from the viewpoint of reducing the amount of unreacted material remaining during UV curing.

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 500 or less, 450 or less, 400 or less, or 350 or less, from the viewpoint of easily forming a coating (hard coat) with less cloudiness.

The amount 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 less cloudiness. The amount 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 speed of the functional coating material.

The amount 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 less cloudiness. The amount 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 speed of the functional coating material.

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 less 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 speed of the functional coating material. The functional coating material may contain a single sensitizer or multiple sensitizers.

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

The liquid medium may be, for example, water, an organic solvent, or a mixture of these. 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 may be used alone or in a mixture of two or more.

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

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.

The functional coating material of this embodiment may contain various additives such as polymerization inhibitors, silane coupling agents, antioxidants, light stabilizers, thickeners, dew condensation inhibitors, and snow-adhesion inhibitors, as necessary, within the range in which the desired effects are obtained.

The functional coating material may be 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, a stain-resistant hard coat material, or a water-repellent and stain-resistant hard coat material.

<Hard court>
The hard coat of this embodiment is made of the cured product of the functional coating material of this embodiment described above.

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

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 include automobile components such as body exteriors, glass exteriors, headlamps, sensor lenses and window glass, image display devices such as liquid crystal display devices, CRT display devices, plasma display devices, EL (electroluminescence) display devices 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 textiles for clothing and tents.

Examples of application methods 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.

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

The irradiation of ultraviolet rays may be performed using a halogen lamp or a high-pressure mercury lamp. The amount of ultraviolet irradiation may be, for example, 1000 mJ/cm ² or more, 3000 mJ/cm ² or more, or 5000 mJ/cm 2 or more from the viewpoint of accelerating the curing speed of the functional coating material, and may be, for example, 5000 mJ/cm 2 or less, 3000 mJ/cm ² or ^less , or 1000 mJ/cm ² or less from the viewpoint of easily forming a coating (hard coat) with more suppressed ^cloudiness .

The hard coat may be one that has both water repellency and stain resistance. In other words, the hard coat may be a water repellent and stain resistant hard coat.

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.

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.

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.

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.

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.

<Structure>
The structure of the present embodiment includes a substrate and the hard coat of the present 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.

The substrate can be any of those mentioned above.

The present invention will be explained in more detail below with reference to examples. However, the present invention is not limited to these examples.

<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-added triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: AT-20E), 50 g of 2-hexamethylene acrylate, and 14 g of 2-hydroxy-2-methylpropiophenone (photopolymerization initiator, rich 4 g of 2,4-dihydroxybenzophenone (photopolymerization initiator, Fujifilm Wako Pure Chemical Industries, Ltd.), 4 g of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (ultraviolet absorber, Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.1 g of X-12-1050 (acrylic silane coupling agent, Shin-Etsu Chemical Co., Ltd.) were mixed. The resulting mixture was then distilled with stirring at 80° C. for 2 hours to remove IPA, and curable component A1 was obtained.

<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), 17 g of 2-hydroxy-4-(2-hydroxyethoxy)-1,3-dimethyl-2,4-dimethyl-1,5-dimethyl-2,6-dimethyl-1,7-dimethyl-2,8-dimethyl-1,9-dimethyl-2,9-dimethyl-1,5-dimethyl-2,6-dimethyl-1,7-dimethyl-2,8-dimethyl-1,7-dimethyl-2,6 ... 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (ultraviolet absorbing agent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 4 g of 2,4-dihydroxybenzophenone (photopolymerization initiator, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 8 g of 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (ultraviolet absorbing agent, 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 IPA, and a curable component A2 was obtained.

<Preparation of Curable Component A3>
200 g of MEK-dispersed spherical nanosilica (manufactured by Nissan Chemical Industries, Ltd., product 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., product name: A-GLY-9E), 50 g of 1,9-nonanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product 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 with stirring at 60° C. for 1 hour to remove MEK, and curable component A3 was obtained.

<Preparation of Curable Component A4>
200 g of MEK-dispersed spherical nanosilica (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 (Shin-Nakamura Chemical Co., Ltd., trade name: A-GLY-9E), 50 g of 1,9-nonanediol diacrylate (Shin-Nakamura Chemical Co., Ltd., trade name: A-NOD-N), 7 g of t-butylperoxy-2-ethylhexanate (NOF Corporation, trade name: Perocta O), and 8 g of 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (ultraviolet absorber, Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed. Next, the resulting mixture was distilled with stirring at 60 ° C. for 1 hour to remove MEK, and curable component A4 was obtained.

<Preparation of Curable Component A5>
100 g of PGM-dispersed spherical nanosilica (Nissan Chemical Industries, Ltd., product name: PGM-AC-4130Y, average particle size 45 nm, solid content of spherical nanosilica 30 g), 120 g of trimethylolpropane EO adduct triacrylate (Shin-Nakamura Chemical Co., Ltd., product name: A-TMPT-9EO), and 100 g of 1,9-nonanediol diacrylate (Shin-Nakamura Chemical Co., Ltd., product 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. Next, the resulting mixture was distilled with stirring at 60°C for 1 hour to remove the PGM, and a curable component A5 was obtained.

<Preparation of Polysiloxane Compound B>
100 parts by mass of styrene (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 carried out for 1 hour to obtain an alkyl-modified polyorganosiloxane represented by the following formula (ii). In addition, in formula (ii), R ^B represents an aralkyl group represented by (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)

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 solution of tetramethylammonium hydroxide (manufactured by Nacalai Tesque, Inc.) was added as an active ingredient, and the mixture was stirred at 90 ° C. for 3 hours. Next, 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 average molar ratio (C 2 /C 1 ) of the content C ₂ of the structural unit represented by formula (2-1) to the content C ₁ of the structural unit represented by formula ( _1-1 ) in _the siloxane chain was 0.06.

<Sensitizer>
As the sensitizer, the following compounds were used.
9,10-dibutoxyanthracene (manufactured by Air Water Performance Chemicals, product name: Anthracure UVS1331, maximum absorption wavelength: 368 nm, 388 nm, 410 nm)
4,4'-bis(diethylamino)benzophenone (Kanto Chemical Co., Ltd., 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.)

<Preparation of functional coating material>
(Examples 1 to 5 and Comparative Example 1)
The components in the compositions (parts by mass) shown in Table 1 were mixed at 40° C. to obtain functional coating materials.

<Hard court evaluation>
A functional coating material was applied onto 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.

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

(Hayes)
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.).

(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.).

(Scratch resistance)
A scratch resistance test was carried out on the hard-coated substrate. The hard-coated substrate was placed on the stand 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 weight of 500 g was placed on it, and the hard coat was scratched under the following conditions: abrasion distance: 50 mm one way, abrasion speed: 6000 mm/min, and number of reciprocations: 10 times. The haze before and after scratching was measured using a spectroscopic haze meter SH7000, and the difference in haze was calculated.

As shown in Table 1, the functional coating materials of Examples 1 to 5 can form a coating (hard coat) with sufficiently low haze and sufficiently suppressed cloudiness.

Claims (9)

A functional coating material containing a curable component, a polysiloxane compound having an amino group, and a sensitizer. The functional coating material according to claim 1, wherein the curable component is a photocurable resin composition. 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. The functional coating material according to claim 1, wherein the sensitizer is an anthracene compound. The functional coating material according to claim 1, wherein the sensitizer is a benzophenone compound. The functional coating material according to claim 1, which is a hard coat material. A hard coat comprising a cured product of the functional coating material according to any one of claims 1 to 6. The hard coat according to claim 7, having a haze of 2 or less. A structure comprising a substrate and the hard coat according to claim 7 provided on the substrate.