WO2016031931A1 - Resin composition, coating film, plastic film with coating film, and display device - Google Patents

Abstract

This resin composition is a resin composition in which the surface of the metal oxide particles has been treated with a dispersant having a hydrolyzable group, the resin comprises an acrylic acrylate and/or a urethane acrylate, and the water content is not higher than 3 mass% relative to the content of the metal oxide particles.

Description

Resin composition, coating film, plastic film with coating film, and display device

The present invention relates to a resin composition, a coating film, a plastic film with a coating film, and a display device.
This application claims priority based on Japanese Patent Application No. 2014-176525 filed in Japan on August 29, 2014 and Japanese Patent Application No. 2015-072881 filed in Japan on March 31, 2015. The contents are incorporated herein.

Metal oxide particles such as zirconia, titania, and silica are used by being dispersed in a binder such as a resin.
For example, a plastic film used in a display device such as a liquid crystal display (LCD), a plasma display (PDP), and an electroluminescence display (EL) is required to have transparency, refractive index, mechanical properties, and the like. Therefore, a functional film is provided by applying a composition in which inorganic fine particles having a high refractive index, such as metal oxide particles, and a resin are mixed on the plastic film of these devices.

As a method of combining the metal oxide particles and the binder, for example, the metal oxide particles surface-modified in the presence of water with a dispersant having a hydrolyzable group such as an alkoxide in a solvent such as an organic solvent. A method of mixing a dispersed dispersion and a binder is generally known.
The hydrolyzable group contained in the alkoxide or the like has the property that the hydrolyzed hydroxyl group adsorbs or dehydrates and condenses on the metal oxide particles when coexisting with water under acidic or basic conditions.
The surface of the metal oxide particles is usually hydrophilic. Therefore, in order to maintain high transparency by combining the metal oxide particles and the binder, the surface of the metal oxide particles is hydrophobized with a dispersant or the like, and the metal oxide particles are selected as necessary. It is important to increase the dispersibility in the organic solvent.

As such a dispersion liquid, a metal oxide particle dispersion liquid in which a hydrolysis catalyst is added and metal oxide particles are surface-treated with a silane coupling agent has been proposed (for example, see Patent Documents 1 and 2). ).
Further, the metal oxide fine particles are organicized with a silane coupling agent during the bead mill treatment, that is, an organic portion is given to the particles, and then the ultrasonic treatment, the metal oxide fine particles and an isocyanate compound having a polymerizable functional group, There has been proposed a dispersion in which metal oxide fine particles are dispersed by further reacting (see, for example, Patent Document 3).

JP 2000-256535 A JP 2009-108123 A JP 2010-254889 A

However, the dispersions described in Patent Document 1 and Patent Document 2 described above have many processes because the dispersion treatment is performed by hydrolyzing the silane coupling agent. In addition, since water is contained in the dispersion, a dispersion having a sharp particle size distribution cannot be obtained due to water.
Therefore, when a composition in which the dispersion and the binder are mixed is applied to a plastic film to form a coating film, desired transparency cannot be obtained in the coating film.
In addition, since the dispersion contains a large amount of water, there is a problem in that when it is mixed with a binder component such as a resin to form a coating film, poor appearance due to the generation of foreign matter is likely to occur and the film formability is not excellent. .

Since the dispersion described in Patent Document 3 has not undergone the hydrolysis step, the water content is small. However, since the desired dispersibility cannot be obtained in the first-stage dispersion treatment, an isocyanate compound is added and the dispersion treatment is required again. As described above, the method used is complicated. In addition, since the isocyanate compound reacts with a hydroxyl group, there is a problem that a usable solvent is limited.

Moreover, when using the coating film of the said literature as a touchscreen member, for example, after providing said coating film on a plastic film, a heat treatment process is further required in many cases. However, the plastic film with a coating film may be curled after the heat treatment process. Therefore, there has been a demand for a resin composition that can suppress curling of a plastic film with a coating film even after undergoing a heat treatment step and that can form a coating film with excellent scratch resistance.

The present invention has been made in view of the above circumstances, and has a resin composition, a coating film, and a coating film with low water content and excellent transparency, film forming property, thermal curl suppression, and scratch resistance. An object is to provide a plastic film and a display device.

That is, the resin composition of the present invention is a resin composition comprising metal oxide particles, a basic substance, a resin, and water, wherein the metal oxide particles have a hydrolyzable group. The resin composition is surface-treated with a dispersant having, and the resin contains at least one of acrylic acrylate and urethane acrylate, and the water content is 3% by mass or less of the content of the metal oxide particles. is there.
The resin composition of the present invention comprises a # 0000 steel on a coating film of a coated film formed by applying the resin composition to a polyethylene terephthalate film having a thickness of 50 μm so that the dry film thickness is 0.8 μm. When wool is slid 10 times under a load of 100 g / cm ² , the number of scratches can be reduced to 20 or less. In the resin composition of the present invention, the haze value of the film with a coating film can be 2.0% or less. When the resin composition of the present invention is placed on a horizontal table after leaving the film with a film of 100 mm × 100 mm at 150 ° C. for 1 hour, the horizontal table at the four corners of the film with a film The average value of the amount of lift from can be 20 mm or less.

The coating film of the present invention is formed using the resin composition of the present invention.

The plastic film with a coating film of the present invention is characterized in that the coating film of the present invention is provided on one or both surfaces of a plastic substrate.

The display device of the present invention is provided with either one or both of the coating film of the present invention and the plastic film with a coating film of the present invention.

According to the resin composition of the present invention, it is possible to obtain a resin composition having a small water content and capable of forming a coating film having excellent transparency, film-forming property, thermal curl suppression and scratch resistance.

Since the coating film of the present invention is formed using the resin composition of the present invention, a coating film excellent in transparency, film-forming property, thermal curl suppression and scratch resistance can be obtained.

The plastic film with a coating film of the present invention is excellent in transparency and film formability because the coating film of the present invention is formed, curling of the plastic film with a coating film by heat is suppressed, and excellent in scratch resistance. A plastic film with a coating film can be obtained.

The display device of the present invention is provided with either one or both of the coating film of the present invention and the plastic film with a coating film of the present invention, which is excellent in transparency and scratch resistance. There is almost no variation. For this reason, a display device excellent in visibility and scratch resistance can be obtained.

It is a figure which shows the reflection spectrum of Examples 1-4. It is a figure which shows the reflection spectrum of Examples 5-8. FIG. 6 is a diagram showing reflection spectra of Examples 9 to 11. FIG. 6 is a diagram showing reflection spectra of Comparative Examples 1 to 3.

The preferable form and example for implementing the resin composition of this invention, a coating film, a plastic film with a coating film, and a display apparatus are demonstrated.
The following preferred embodiments are specifically described for better understanding of the gist of the invention, and do not limit the present invention unless otherwise specified. Additions, omissions, modifications, substitutions, and other modifications are possible without departing from the spirit of the present invention.

[Resin composition]
The resin composition of the present invention is a resin composition containing metal oxide particles, a basic substance, a resin, and water. The metal oxide particles are surface-treated with a dispersant having a hydrolyzable group. The resin includes at least one of acrylic acrylate and urethane acrylate. The water content is 3% by mass or less of the metal oxide particle content.

As an example of the resin composition of the present embodiment, metal oxide particles surface-treated with a dispersant, a dispersant having a hydrolyzable group, a basic substance, a resin, an organic dispersion medium, and a small amount of water Preferred examples of the resin composition containing the above will be described below.

"Metal oxide particles"
The metal oxide particles of the present invention are not particularly limited, and metal oxide particles having desired characteristics are appropriately selected and used.
For example, when a high refractive index performance is imparted to the resin composition, metal oxide particles having a refractive index of 1.9 or more are preferably used. Examples of such metal oxide particles include zirconium oxide, zinc oxide, iron oxide, copper oxide, titanium oxide, tin oxide, cerium oxide, tantalum oxide, niobium oxide, tungsten oxide, europium oxide, hafnium oxide, and titanic acid. Metal oxides such as potassium, barium titanate, strontium titanate, potassium niobate, lithium niobate, calcium tungstate, antimony-containing tin oxide (ATO) and tin-containing indium oxide (ITO) are preferably used. Among these, zirconium oxide and titanium oxide are particularly preferable from the viewpoint of high refractive index and little influence by coloring.

In addition, when weather resistance is imparted to the resin composition, metal oxide particles having ultraviolet shielding properties are appropriately selected and used. Preferred examples of such metal oxide particles include zinc oxide, titanium oxide, iron oxide, and cerium oxide.
Moreover, when providing electroconductivity to a resin composition, the metal oxide which has electroconductivity is used. Preferred examples of such metal oxides include antimony-containing tin oxide (ATO) and tin-containing indium oxide (ITO).
The metal oxide particles may be used alone or in combination of two or more.

What is necessary is just to select suitably the average primary particle diameter of a metal oxide particle according to a use. For example, in order to obtain a resin composition excellent in transparency, the thickness is preferably 1 nm or more and 30 nm or less, and more preferably 5 nm or more and 25 nm or less. For example, the lower limit value of the particle diameter range may be 1 nm, 3 nm, 5 nm, 8 nm, 10 nm, 12 nm, or the like. The upper limit of the particle diameter range may be 30 nm, 27 nm, 25 nm, 20 nm, 18 nm, 15 nm, or the like. A preferred range can be selected as required. For example, a range of 5 nm to 20 nm and a range of 3 nm to 20 nm can be preferably used.
Metal oxides although the specific surface area of the particles can be selected optionally, it is preferable that the specific surface area used only ^{60 m} 2 / g or more and particles having a 100 m ² / g or less, and a specific surface area of ^70m 2 / g or more 100 m ² / More preferably, only particles that are g or less are used. Use of metal oxide particles within this range is preferable for obtaining a dispersion having a sharp particle size distribution, which will be described later.

In the present invention, the “average primary particle size” means the particle size of each particle itself. As a measuring method of the average primary particle diameter, the major axis of each metal oxide particle, for example, 100 or more metal oxide particles, preferably using a scanning electron microscope (SEM), a transmission electron microscope (TEM), etc. Includes a method of measuring the major axis of each of the 500 metal oxide particles and calculating the arithmetic average value thereof.

What is necessary is just to adjust suitably content of the metal oxide particle in a resin composition according to a use. For example, 10 mass% or more and 90 mass% or less are preferable, 20 mass% or more and 80 mass% or less are more preferable, 30 mass% or more and 75 mass% or less are more preferable, and 40 mass% or more and 70 mass% or less are. Particularly preferred.
By setting the content of the metal oxide particles in the resin composition in the range of 10% by mass to 90% by mass, good dispersion stability of the metal oxide particles in the resin composition can be obtained. it can. In addition, the preferable example of content of a metal oxide particle is not limited only to the above range. Examples of the lower limit of the preferable content range include 10% by mass, 15% by mass, 20% by mass, and 30% by mass. Examples of the upper limit of the preferable content range include 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, and 20% by mass. it can. It can be preferably selected from these. For example, it is also preferable to select a range of 10% by mass to 20% by mass and a range of 10% by mass to 30% by mass according to the required conditions.

"Dispersant with hydrolyzable group"
In the present invention, as the dispersant having a hydrolyzable group, the dispersant has a hydrolyzable group, and the surface of the metal oxide particles is modified to hydrophobize the particle surface. There is no particular limitation as long as it improves the dispersibility in the resin. For example, a dispersant having an alkoxy group is preferably used.
Examples of such a dispersant having an alkoxy group include metal alkoxides, silane coupling agents, silicone compounds, and the like.
As an alkoxy group, a methoxy group and an ethoxy group are preferable.

The metal alkoxide is not particularly limited, but alkoxysilane is preferably used. As the alkoxysilane, tetraalkoxysilane is preferable.
Tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetrat-butoxysilane, tetraphenoxy Examples thereof include silane, monoethoxytrimethoxysilane, monobutoxytrimethoxysilane, monopentoxytrimethoxysilane, monohexoxytrimethoxysilane, dimethoxydiethoxysilane, dimethoxydibutoxysilane and the like.
Among these, tetramethoxysilane and tetraethoxysilane are preferably used because they have a high silicon (Si) content and are easy to adjust the concentration when dispersed in a solvent, and have high hydrolysis and condensation reactivity. be able to.
These tetraalkoxysilanes may be used alone or in combination of two or more.

The silane coupling agent is not particularly limited and can be preferably used as long as it has 1 to 3 alkoxy groups in one molecule.
Vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, 3-acryloxypropyltri Methoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 8-acryloxyoxyoctyltrimethoxysilane, etc. Take as an example.

Silane coupling agents include allyltrimethoxysilane, allyltriethoxysilane, vinylethyldimethoxysilane, vinylethyldiethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropyltriethyldiethoxysilane. P-styrylethyldimethoxysilane, p-styrylethyldiethoxysilane, 3-acryloxypropylethyldimethoxysilane, 3-acryloxypropylethyldiethoxysilane, 3-methacryloxypropylethyldimethoxysilane, 3-methacryloxypropylethyl Examples include diethoxysilane, allylethyldimethoxysilane, and allylethyldiethoxysilane.

Further, as silane coupling agents, vinyldiethylmethoxysilane, vinyldiethylethoxysilane, 3-glycidoxypropyldiethylmethoxysilane, 3-glycidoxypropyldiethylethoxysilane, p-styryldiethylmethoxysilane, p-styryldiethyl Ethoxysilane, 3-acryloxypropyldiethylmethoxysilane, 3-acryloxypropyldiethylethoxysilane, 3-methacryloxypropyldiethylmethoxysilane, 3-methacryloxypropyldiethylethoxysilane, allyldiethylsilane, allyldiethylethoxysilane, etc. As an example.
These silane coupling agents may be used alone or in combination of two or more.

The silicone compound is not particularly limited as long as it has an alkoxy group, and a silicone resin having a methoxy group or an ethoxy group is used.

The amount of the dispersant having a hydrolyzable group used for the surface treatment of the metal oxide particles is appropriately adjusted to such an extent that good dispersibility can be obtained. The amount of the dispersant having a hydrolyzable group is, for example, preferably 5% by mass to 120% by mass with respect to the total mass of the metal oxide particles, and is 10% by mass to 110% by mass. More preferably, it is 15% by mass or more and 100% by mass or less.
In addition, the example of the preferable range of a dispersing agent is not limited only to the said range, It can select arbitrarily. For example, 5 mass%, 7 mass%, 10 mass%, 13 mass%, 15 mass%, 20 mass% as an example of the lower limit of the range of the amount of a preferable dispersing agent with respect to the total mass of metal oxide particles. , 30% by mass, 40% by mass, and 50% by mass. As an example of the upper limit value of the preferable amount range of the dispersant, 120% by mass, 110% by mass, 100% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, And 30% by mass. For example, a range of 5% by mass to 30% by mass can be preferably selected.

"Basic substances"
The basic substance in the present invention is a substance whose hydrogen ion exponent (pH) is greater than 7 when mixed with water, and the water content of the resin composition is a metal oxide contained in the resin composition. Even if it is 3% by mass or less of the content of the product particles, a substance that can be mixed uniformly is preferable. Any such substance can be used without any particular limitation.
Examples of such basic substances include alkali metal or alkaline earth metal hydroxides, amines, and the like, and amines are preferable in terms of easy handling.

Examples of the alkali metal or alkaline earth metal hydroxide include inorganic basic substances such as calcium hydroxide, magnesium hydroxide, manganese hydroxide, aluminum hydroxide, iron hydroxide, potassium hydroxide, and sodium hydroxide. Is mentioned.

Examples of the amines include amines, amides, amine dispersants, amine surfactants, amide type monomers, amine solvents, amide solvents, and the like.
As the amine, any of primary amine, secondary amine, and tertiary amine may be used, and these may be mixed and used, but it is more preferable to use a tertiary amine. Preferred examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, trilaurylamine, tridecylamine, tristearylamine, triisopropylamine, triisobutylamine, tri-2-ethylhexylamine, Dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, triethanolamine, N, N-dimethyloctylamine, N, N-dimethylaniline, N-benzyldimethylamine, Pyridine, N-methylpyridine, N-methylmorpholine, hexamethoxymethylmelamine, 2,4,6-tris (dimethylaminophenol), N-cyclohexyl Dimethylamine, tetramethylguanidine, etc. m- aminophenol.
As the amide type monomer, for example, an acrylamide type monomer or a methacrylamide type monomer is preferably used. Examples of such amide type monomers include hydroxyethyl acrylamide, hydroxyethyl methacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- ( Dimethylamino) propyl] methacrylamide and the like.

The amount of the basic substance contained in the resin composition can be appropriately adjusted so that desired transparency can be obtained. For example, the amount of the basic substance is preferably 0.15% by mass or more and 5% by mass or less, and preferably 0.15% by mass or more and the content of the metal oxide particles contained in the resin composition. It is more preferably 3% by mass or less, and further preferably 0.15% by mass or more and 1.5% by mass or less. However, the amount is not limited.
In the present invention, in the production process of the resin composition, by adding a basic substance to the metal oxide particle dispersion, hydrolysis of the dispersant can be promoted, and the water content can be reduced. Metal oxide particles having a sharp particle size distribution can be obtained.

"resin"
The resin in the present invention contains at least one of acrylic acrylate and urethane acrylate. A coating film made of a resin composition containing this resin is preferably a resin that can suppress thermal curl even when placed in an environment of 150 ° C. for 1 hour. If it is such resin, it will not specifically limit and it can use preferably.
Acrylic acrylate and urethane acrylate are preferably photocurable resins in terms of excellent scratch resistance. Among these, an ultraviolet curable resin is preferable because of its high curing rate.
The weight average molecular weight of the resin is preferably 1000 or more and 28000 or less, more preferably 3000 or more and 25000 or less, still more preferably 8000 or more and 25000 or less, and 10,000 or more and 25000 or less. Is more preferably 15000 or more and 25000 or less. The preferred weight average molecular weights of acrylic acrylate and urethane acrylate are also in the same range as the above range.
By setting the weight average molecular weight of the resin in the above range, it is possible to form a coating film made of the resin composition of the present embodiment, which is excellent in transparency, thermal curl suppression and scratch resistance.
In addition, resin may be used independently or may be used in combination of 2 or more type. In that case, the average weight average molecular weight of the mixture obtained by mixing them may be in the above range, and for example, the average may be in the range of 1000 or more and 28000 or less. However, when a plurality of resins are combined, it is preferable that the acrylate having the largest amount is included in the molecular weight range. It is also preferable that all the molecular weights of the two or more combined resins are within the range.
The weight average molecular weight of the resin can be measured by GPC (Gel Permeation Chromatography).
The total amount of the resin contained in the resin composition can be arbitrarily selected. For example, the total amount of the resin composition is preferably 5% by mass to 65% by mass, and 10% by mass to 55%. More preferably, it is more preferably 15% by mass to 50% by mass.
The amount of acrylic acrylate and / or urethane acrylate can be arbitrarily selected, but for example, it is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass with respect to the total amount of the resin, 80% by mass to 100% by mass is more preferable. It is also preferred that all of the resins included are acrylic acrylate and / or urethane acrylate.
The amount of acrylic acrylate and / or urethane acrylate is preferably 9% by mass to 200% by mass, more preferably 15% by mass to 140% by mass, and more preferably 25% by mass to 110% by mass with respect to the total amount of metal oxide particles. Further preferred.

As the acrylic acrylate, a dendritic polymer (dendritic polymer) is preferably used. Examples of the dendritic polymer include a dendrimer structure and a hyperbranch structure. By using a dendritic polymer as the acrylic acrylate, effects of suppressing thermal curl and improving scratch resistance can be obtained. The molecular weight of the dendritic polymer, which is an acrylic acrylate, is preferably in the range of the molecular weight described above, but is preferably 10000 or more and 25000 or less, more preferably 15000 or more and 25000 or less, It is particularly preferably 17000 or more and 23000 or less. The amount of the dendritic polymer can be arbitrarily selected. For example, the resin composition is preferably contained in an amount of 1 to 50% by mass, more preferably 1 to 35% by mass, and more preferably 1 to 15% by mass. Things are more preferable.
In the resin composition of the present invention, polyester acrylate or a polymerizable acrylic copolymer may be mixed as an acrylate other than acrylic acrylate and urethane acrylate in order to suppress thermal curl. As the polyester acrylate, a dendritic polymer is preferably used.
The conditions for these polymers may be further selected from the above ranges as necessary.
For example, the amount of the dendritic polymer of polyester acrylate is preferably 1 to 30% by mass, more preferably 1 to 15% by mass, and more preferably 1 to 8% by mass in the resin composition. More preferred. The molecular weight can also be arbitrarily selected, but is preferably 800 to 15000, more preferably 1000 to 8000, and preferably 1000 to 4000.
The amount of polymerizable acrylic copolymer can also be selected as needed. For example, the resin composition preferably contains 0.3 to 20% by mass, more preferably 0.4 to 15% by mass, and more preferably 0.5 to 5% by mass. The molecular weight is preferably 300 or more and 25000 or less, and more preferably 3000 or more and 23000 or less.
Moreover, you may add resin other than an acrylate to a resin composition in the range which does not inhibit the objective of this invention. Examples of resins other than acrylates include epoxy, polyester, polyurethane, polystyrene, polyethylene, phenol, polyimide, melamine, and the like.

The addition amount of the resin in the resin composition of the present invention is appropriately adjusted so as to obtain a desired thermal curl suppressing effect and scratch resistance.
The addition amount of the resin in the resin composition is preferably in the range where the mass ratio of the metal oxide particles to the resin is 1: 9 to 9: 1, and preferably in the range of 2: 8 to 8: 2. More preferably, the range is from 3: 7 to 7: 3.

In the resin composition of the present invention, the water content is 3% by mass or less of the content of the metal oxide particles. That is, in the present invention, when the content of the metal oxide particles in the metal oxide particle dispersion is 100% by mass, the water content in the metal oxide particle dispersion is It means 3% by mass or less of the content of metal oxide particles. In addition, content of water here is the quantity also including the adhesion water of metal oxide particles, and bound water.
The water content is preferably 2.5% by mass or less, and more preferably 2.0% by mass or less, based on the total content of the metal oxide fine particles.

If the water content exceeds 3% by mass of the total content of metal oxide particles, the stability over time in the metal oxide particle dispersion may be impaired. Also, since water and acrylate are not compatible with each other, when forming a coating film using the resin composition of the present invention, the metal oxide particles may aggregate as the solvent volatilizes from the coating film. There is a risk of segregation.

If the resin composition of the present invention contains water in an amount necessary for hydrolysis of the dispersant having a hydrolyzable group, the water content is preferably as small as possible.
Here, the required amount of water is an amount required for the hydrolysis of the hydrolyzable group of the dispersant, which is required for the surface treatment of the metal oxide particles. If the surface treatment of the metal oxide particles is performed, the amount of water may be smaller than the amount of water necessary for the hydrolysis of all hydrolyzable groups to proceed (hydrolysis rate 100%). In addition, the surface treatment reaction can be performed using attached water or bound water of metal oxide particles.

When the metal oxide particles to be used contain a large amount of adhering water, it is preferable to remove moisture in advance with a dryer or the like. On the other hand, when the amount of water adhering to the metal oxide particles is too small, it is preferable to add the necessary amount. In these cases, the water content is preferably 0.05% by mass or more based on the metal oxide content.

"Organic solvent"
The organic solvent is not particularly limited as long as it can disperse the metal oxide particles and has good compatibility with the resin, and can be selected as necessary. For example, aliphatic hydrocarbons such as hexane, heptane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol and propanol, halogenated hydrocarbons such as methylene chloride and ethylene chloride, acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone and isophorone, esters such as ethyl acetate and butyl acetate, cellosolves such as ethyl cellosolve, ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, amides Examples of the solvent include ether solvents and ether ester solvents. These solvents may be used alone or in combination of two or more.
The addition amount of the organic solvent is appropriately adjusted so that desired metal oxide particle dispersibility and the viscosity of the resin composition described later can be obtained. The same dispersion medium as described later may be used, or may be different. The organic solvent may contain water within a range of 3% by mass or less of the content of the metal oxide fine particles, and if included, it is preferably contained in a trace amount, and more preferably does not contain water.

The resin composition of the present invention has one or more functional groups within a range not inhibiting the effects of the present invention, and is not included in the above resin. , Antistatic agent, refractive index modifier, antioxidant, ultraviolet absorber, light stabilizer, leveling agent, antifoaming agent, inorganic filler, coupling agent, preservative, plasticizer, flow regulator, thickening Various general additives such as an agent, a pH adjuster, and a polymerization initiator may be appropriately contained. These amounts can be arbitrarily selected. For example, it may be used in an amount of 0.01 to 10% by mass, preferably 0.1 to 5% by mass, and preferably 0.1 to 3% by mass with respect to the total amount of the resin composition. More preferred is 0.1 to 1.5% by mass. However, it is not limited only to the range of these amounts.

Examples of the dispersant include anionic surfactants such as sulfate esters, carboxylic acids, and polycarboxylic acids, cationic surfactants such as quaternary salts of higher aliphatic amines, higher fatty acid polyethylene glycol esters, and the like. Nonionic surfactants, silicon surfactants, fluorine surfactants, and polymer surfactants having an amide ester bond.

The polymerization initiator can be appropriately selected according to the type of monomer used. When using the monomer of a photocurable resin, a photoinitiator can be used. The kind and amount of the photopolymerization initiator are appropriately selected according to the monomer of the photocurable resin to be used. Examples of the photopolymerization initiator include benzophenone, diketone, acetophenone, benzoin, thioxanthone, quinone, benzyldimethyl ketal, alkylphenone, acyl phosphine oxide, and phenyl phosphine oxide. And known photopolymerization initiators.

The resin composition of the present invention is preferably used as a composition that is applied to a film to form a coating film. Accordingly, in order to facilitate coating, the viscosity is preferably 0.2 mPa · s or more and 500 mPa · s or less, more preferably 0.3 mPa · s or more and 350 mPa · s or less, and More preferably, it is 5 mPa · s or more and 200 mPa · s or less.
If the viscosity of the resin composition is 0.2 mPa · s or more, it is preferable because the film thickness when formed into a coating film does not become too thin and the film thickness can be easily controlled. On the other hand, if the viscosity of the resin composition is 500 mPa · s or less, it is preferable because the viscosity is not too high and handling of the resin composition at the time of coating becomes easy.

"Abrasion resistance"
When the resin composition of the present invention is applied to a polyethylene terephthalate (PET) film having a thickness of 50 μm so that the dry film thickness is 0.8 μm, the resin composition of the present invention has a coating film. When the steel wool of # 0000 is slid back and forth 10 times under a load of 100 g / cm ² , the number of scratches can be 20 or less.

"transparency"
In the resin composition of the present invention, when this resin composition is applied to a 50 μm-thick polyethylene terephthalate film so that the dry film thickness is 0.8 μm, the haze value of the obtained film with a coating film is 2. It can be 0% or less. The haze value of the film with a coating film is preferably 1.5% or less, and more preferably 1.3% or less.
The haze value of a film with a coating film is measured based on Japanese Industrial Standard JIS-K-7136 using a haze meter NDH-2000 (manufactured by Nippon Denshoku Co., Ltd.) on the basis of air.

"Heat curl suppression"
In the resin composition of the present invention, this resin composition is applied to a polyethylene terephthalate film having a thickness of 50 μm so that the dry film thickness is 0.8 μm, and the film is further molded to a size of 100 mm × 100 mm. When the obtained film with a coating film was allowed to stand at 150 ° C. for 1 hour and then the film was placed on a horizontal table, the average value of the amount of lift from the horizontal table at the four corners of the film with a coating film was 20 mm or less. can do.
The average value of the lifting amount is preferably 15 mm or less, and more preferably 4 mm or less.
When the average value of the lifting amount is 20 mm or less, it becomes possible to suppress problems caused by lifting in the post-process, for example, a sputtering process or an annealing process, in which heat is applied to the plastic film with a coating film, The yield of mounting on a display device can be increased.

`` Film formation ''
When the resin composition of the present invention is applied to a polyethylene terephthalate film having a thickness of 50 μm so that the dry film thickness is 0.8 μm, the obtained film with a coating film has a wavelength range of 500 nm to 750 nm. The difference between the maximum value and the minimum value of the reflectance is preferably 0.80% or less, more preferably 0.75% or less, and further preferably 0.70% or less.
Since the difference between the maximum value and the minimum value of the reflectance within the range of 500 nm to 750 nm is 0.80% or less, the occurrence of ripples due to light interference is suppressed, and color unevenness is suppressed and coating with good film formability is achieved. It is preferable because a film is obtained.

When the resin composition of the present invention is applied to a polyethylene terephthalate film having a thickness of 50 μm so that the dry film thickness is 0.8 μm, the obtained film with a coating film has a wavelength range of 450 nm to 800 nm. The difference between the maximum value and the minimum value of the reflectance is preferably 4% or less, more preferably 2% or less, and even more preferably 1.5% or less.
Thus, since the difference in reflectance over the range of the visible light region is small, it is preferable because a coating film with excellent film formability in which color unevenness is suppressed can be obtained.

When a coating film is formed using the resin composition of the present invention, the reason why the coating film has excellent reflection characteristics in addition to the film forming property as described above is considered as follows.
In the resin composition of the present invention, metal oxide particles having a sharp particle size distribution can be obtained by adding a basic substance to reduce the water content. In other words, since the size of the metal oxide particles is substantially uniform in the resin composition of the present embodiment, the metal oxide particles are contained in the coating film obtained from the resin composition of the present embodiment. Easy to fill uniformly without gaps. Therefore, the resin composition of the present embodiment is excellent in the film formability of the coating film, and as a result, the coating film formed using the resin composition of the present embodiment has a performance at all points in the film surface. Becomes uniform. Therefore, for example, since the refractive index in the film surface of the coating film becomes almost uniform, the reflectance of the coating film becomes almost constant within the wavelength range of 450 nm to 800 nm, and the occurrence of ripple due to light interference is suppressed. As a result, the occurrence of color unevenness in the coating film is suppressed. Therefore, when the coating film formed using the resin composition of this embodiment is applied to a display apparatus etc., it is thought that visibility can be improved.

In the coating film formed using the resin composition of the present invention, metal oxide particles having a sharp particle size distribution, that is, having the same particle size in the composition are used. Yes. Therefore, the metal oxide particles are uniformly filled in the coating film, and there are few voids in the coating film. Therefore, for example, when it is desired to improve the refractive index by using metal oxide particles having a refractive index of 1.9 or more, the amount of metal oxide particles necessary to improve the refractive index is reduced as compared with the conventional case. Can do. Therefore, even in a thin film having a film thickness of 10 nm to 200 nm, the entire inside of the coating film is uniformly filled with metal oxide particles, and the voids in the coating film, that is, the portion where no metal oxide particles exist , Can be reduced or eliminated. For this reason, the refractive index of a coating film can be improved.
Here, the sharp particle size distribution is sufficient if the metal oxide particles in the resin composition have the same size so that the metal oxide particles can be uniformly filled in the coating film. For example, when the particle size distribution of the resin composition is measured with a particle size distribution meter (trade name: Microtrac UPA150, manufactured by Nikkiso Co., Ltd.), the particle size (D90) when the cumulative volume percentage of the particle size distribution is 90% The value divided by the particle size (D50) when the cumulative volume percentage of the distribution is 50% is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less. More preferably.
Moreover, in the coating film formed using the resin composition of this invention, the performance in all the places in a film surface can be made uniform. For this reason, even if a thick film having a thickness of 1 μm or more is formed, the occurrence of optical unevenness can be suppressed. In particular, when the dispersant having a hydrolyzable group has a functional group having a polymerizable unsaturated group, the metal oxide particles are bonded to the acrylate in the composition by the polymerizable unsaturated group during curing. For this reason, it is preferable because the metal oxide particles can be aggregated in the film at the time of curing, or the particle distribution can be prevented from being different between the surface and the inside of the film. Thus, when forming a thick film of 1 μm or more, the application of the present invention is particularly suitable.
That is, the coating film formed using the resin composition of the present embodiment can be used as a thin film for adjusting the refractive index, or can be adjusted in refractive index and has a hard coat property. It may be used as a membrane. It can be appropriately selected and used depending on the application.

[Method for Producing Resin Composition]
The method for producing the resin composition of the present invention is not particularly limited. For example, a method of mechanically mixing the above-described resin, the organic solvent, and the metal oxide particle dispersion appropriately may be mentioned. As the metal oxide particle dispersion used in the present invention, the metal oxide particles are dispersed in a dispersion medium by a dispersant having a hydrolyzable group, and further contain a basic substance and have a water content of metal. It is preferably 3% by mass or less of the content of oxide particles. It is preferable that the organic solvent and the resin other than the dispersion liquid contain no water.
Examples of the mixing device include a stirrer, a self-revolving mixer, a homogenizer, and an ultrasonic homogenizer.

[Metal oxide particle dispersion]
The metal oxide particle dispersion in the present invention that can be used in the above production method is, for example, a dispersion in which metal oxide particles are dispersed in a dispersion medium using a dispersant having a hydrolyzable group. As described above, this dispersion preferably contains a basic substance, and the water content is preferably 3% by mass or less based on the total content of the metal oxide particles.

The water content of the metal oxide particle dispersion in the present invention is preferably 3% by mass or less, more preferably 2.5% by mass or less, and more preferably 2% by mass or less of the content of the metal oxide particles. Is more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less. The lower limit value is selected as necessary, and for example, it is necessary to be greater than 0% by mass. For example, the content of water is preferably 0.01% by mass or more, and preferably 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more.
When the content of water in the metal oxide particle dispersion exceeds 3% by mass of the content of the metal oxide particles, not only a dispersion having a sharp particle size distribution can be obtained, but also long-term storage stability. Becomes worse. For this reason, it is preferable that the content of water in the metal oxide particle dispersion is as small as possible.
The water content in this embodiment means a value titrated with a Karl Fischer moisture meter (model number: AQL-22320, manufactured by Hiranuma Sangyo Co., Ltd.).

In the metal oxide particle dispersion according to the present invention, the particle size (D90) when the cumulative volume percentage of the particle size distribution is 90% is divided by the particle size (D50) when the cumulative volume percentage of the particle size distribution is 50%. The measured value is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or more and 2 or less. Here, the particle size distribution is the particle size distribution of the metal oxide particles contained in the metal oxide particle dispersion.
By dividing the particle size (D90) when the cumulative volume percentage of the particle size distribution is 90% by the particle size (D50) when the cumulative volume percentage of the particle size distribution is 50%, within the above range The metal oxide particles can be uniformly dispersed in the resin, and the refractive index distribution in the film can be made uniform. As a result, color unevenness such as interference fringes can be reduced. Moreover, since coarse particles are reduced, there is also an effect that generation of foreign matters during coating can be suppressed.

In addition, D50 and D90 in this embodiment mean the value measured with the particle size distribution meter (brand name: Microtrac UPA150, Nikkiso Co., Ltd.) which uses a dynamic light scattering system as a measurement principle.

In this embodiment, D50 in the metal oxide particle dispersion is preferably 1 nm or more and 45 nm or less, more preferably 1 nm or more and 30 nm or less from the viewpoint of improving the transparency of the metal oxide particle dispersion. Preferably, it is 1 nm or more and 20 nm or less.

As a preferred example of the metal oxide particle dispersion in the present invention, a metal oxide particle dispersion comprising metal oxide particles, a dispersant having a hydrolyzable group, a basic substance, and a dispersion medium. The liquid will be described.
The metal oxide particles, the dispersant having a hydrolyzable group, the kind of the basic substance, and the like are exactly the same as those described in the description of the resin composition, and thus the description thereof is omitted. To do. Hereinafter, preferred addition amounts of these components and preferred dispersion media will be described.

"Content of each component in the dispersion"
The content of the metal oxide particles in the metal oxide particle dispersion is appropriately adjusted according to the application. For example, 5 mass% or more and 50 mass% or less are preferable, 7 mass% or more and 45 mass% or less are more preferable, and 10 mass% or more and 40 mass% or less are more preferable. However, other ranges are also preferable depending on the conditions, and for example, a range of 20% by mass to 50% by mass or 30% by mass to 50% by mass may be preferably used. By setting the content of the metal oxide particles in the metal oxide particle dispersion within the above range, better dispersion stability of the metal oxide particles in the metal oxide particle dispersion can be obtained.

The amount of the dispersant having a hydrolyzable group is appropriately adjusted so that good dispersibility can be obtained. The addition amount of the dispersant having a hydrolyzable group is preferably 5% by mass or more and 120% by mass or less, for example, based on the total mass of the metal oxide particles, and is 10% by mass or more and 110% by mass or less. More preferably, it is 15 mass% or more and 100 mass% or less.

The addition amount of the basic substance is the particle size (D90) when the cumulative volume percentage of the particle size distribution of the metal oxide particles is 90%, and the particle size (D50) when the cumulative volume percentage of the particle size distribution is 50%. What is necessary is just to adjust suitably so that the value which remove | divided may be 1 or more and 4 or less. The added amount of the basic substance is, for example, preferably 0.01% by mass or more and 1% by mass or less of the basic substance in the metal oxide particle dispersion, and 0.1% by mass or more and 0.8% by mass. It is more preferable that the amount is not more than mass%.
When the metal oxide particle dispersion contains a basic substance, it has an alkoxy group such as a silane coupling agent even if the water content is 3% by mass or less of the metal oxide particle content. Hydrolysis of the dispersant is promoted, and the metal oxide particles can be dispersed in the dispersion medium in a state where the particle diameters are uniform.

"Dispersion medium"
The dispersion medium is not particularly limited as long as the metal oxide particles are easily dispersed and is other than water. Examples of the dispersion medium include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, and propanol, and halogenation such as methylene chloride and ethylene chloride. Hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as 2-pentanone and isophorone, esters such as ethyl acetate and butyl acetate, cellosolves such as ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. Ethers, amide solvents, ether ester solvents, resin monomers, resin oligomers, and the like. One type of dispersion medium may be used, or two or more types may be used in combination. The dispersion medium may contain water within a range of 3% by mass or less of the content of the metal oxide fine particles, and if included, it is preferably contained in a trace amount, and more preferably does not contain water.

"Method of manufacturing dispersion"
The method for producing the metal oxide particle dispersion in the present invention is selected as necessary. For example, a method of mechanically mixing the above-described materials as constituents of the metal oxide particle dispersion and dispersing the metal oxide particles in a solvent can be mentioned.
Examples of the dispersing device include a stirrer, a self-revolving mixer, a homogenizer, and an ultrasonic homogenizer.

According to the resin composition of the present invention, in the dispersion treatment of the metal oxide particles, by using a basic substance, the metal oxide particles are surface-treated and dispersed, thereby minimizing the adsorption water of the metal oxide particles. Surface treatment can be performed with a limited amount of water. Further, a resin that suppresses thermal curl and has excellent scratch resistance can be selected and used. For this reason, it is possible to form a coating film having a small water content and excellent in transparency, film-forming property, thermal curl suppression, and scratch resistance.

[Coating]
The coating film of the present invention is formed using the resin composition of the present invention.
The film thickness of this coating film is appropriately adjusted according to the application. For example, it is usually preferably 0.01 μm or more and 30 μm or less, more preferably 0.01 μm or more and 20 μm or less, further preferably 0.1 μm or more and 15 μm or less, 0.5 μm or more and 10 μm or less. Is more preferably 0.5 μm or more and 6 μm or less, and most preferably 0.5 μm or more and 2 μm or less. However, it is not limited only to this range.

The manufacturing method of the coating film of this invention has preferably the process of forming a coating film by apply | coating said resin composition on a to-be-coated object, and the process of hardening this coating film.
Examples of the coating method for forming a coating film include a bar coating method, a flow coating method, a dip coating method, a spin coating method, a roll coating method, a spray coating method, a meniscus coating method, a gravure coating method, a suction coating method, A brush coating method or the like and a normal wet coating method are used.

The curing method for curing the coating film is appropriately selected according to the type of the resin, but generally, a method of thermal curing or photocuring is used.
The energy ray used for photocuring is not particularly limited as long as the coating is cured, but for example, ultraviolet rays, far infrared rays, near ultraviolet rays, infrared rays, X rays, γ rays, electron rays, proton rays, neutron rays, etc. Energy rays are used. Among these energy rays, it is preferable to use ultraviolet rays because the curing speed is fast and the device is easily available and handled.

In the case of curing by ultraviolet irradiation, ultraviolet rays are irradiated at an energy of 100 to 3,000 mJ / cm ² using a high pressure mercury lamp, metal halide lamp, xenon lamp, or chemical lamp that generates ultraviolet rays in a wavelength band of 200 nm to 500 nm. And the like.

According to the coating film of the present invention, since it is formed using the resin composition of the present embodiment, a coating film excellent in transparency, film forming property, thermal curl suppression and scratch resistance can be obtained.

[Plastic film with paint film]
The plastic film with a coating film of the present invention has a film body (plastic film) formed using a resin material, and the coating film of the present invention provided on at least one surface of the film body.

The plastic film with a coating film can be obtained by coating the resin composition of the present invention on the film body using a known coating method to form a coating film and curing the coating film.

If a film main body is a plastic film, it will not specifically limit, It can select as needed. For example, those formed from plastics such as polyethylene terephthalate, triacetyl cellulose, acrylic, acrylic-styryl copolymer, acrylonitrile-butadiene-styrene copolymer, polystyrene, polyethylene, polypropylene, polycarbonate, and vinyl chloride are used.
When used for a display device, it is preferable to use a plastic film having optical transparency as the film body. The thickness of the plastic film used can be selected as required. For example, for example, the thickness is preferably 12 μm to 100 μm, more preferably 25 μm to 100 μm, and even more preferably 50 μm to 100 μm. The thickness of the coating can also be selected as necessary. For example, for example, it is preferably 0.05 μm to 2 μm, preferably 0.5 μm to 2 μm, and more preferably 0.5 μm to 1 μm.

In the plastic film with a coating film of the present invention, the number of scratches is preferably 20 or less when the coating film surface is slid 10 times with # 0000 steel wool under a load of 100 g / cm ² .
The plastic film with a coating film of the present embodiment has a haze value of preferably 2.0% or less, more preferably 1.5% or less when measured on the basis of air. More preferably, it is% or less.
When the plastic film with a coating film of this embodiment is 100 mm × 100 mm in size and heat-treated at 150 ° C. for 1 hour and then placed on a horizontal table, the amount of lift from the horizontal table at the four corners of the film Is preferably 20 mm or less, more preferably 15 mm or less, and even more preferably 4 mm or less.

Here, the “haze value” is a ratio (%) of diffuse transmitted light to total light transmitted light, and a haze meter NDH-2000 (manufactured by Nippon Denshoku Co., Ltd.) is used on the basis of air. It means a value measured based on the standard JIS-K-7136.

In the plastic film with a coating film of the present invention, the difference between the maximum value and the minimum value of the reflectance within the wavelength range of 500 nm to 650 nm is preferably 1% or less, more preferably 0.9% or less, More preferably, it is 0.8% or less.
In the plastic film with a coating film of this embodiment, the difference between the maximum value and the minimum value of the reflectance within the wavelength range of 450 nm to 800 nm is preferably 4% or less, more preferably 2% or less. More preferably, it is 5% or less.
Here, “reflectance” means the value of the reflection spectrum measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technology Corporation).

In the plastic film with a coating film of the present invention, a hard coat film may be provided between the plastic film and the coating film, or a film having a different performance such as a refractive index from the coating film may be laminated.

According to the plastic film with a coating film of the present invention, since the coating film of this embodiment is formed, it is excellent in transparency, film formability and scratch resistance, and curling of the plastic film with a coating film due to heat is suppressed. In addition, a plastic film with a coating film can be obtained.

[Display device]
The display device of the present invention comprises either or both of the coating film of the present invention and the plastic film with a coating film of the present invention.
Although a display apparatus is not specifically limited, In this embodiment, the preferable example of the liquid crystal display device for touchscreens is demonstrated.

[Touch panel]
In the touch panel, when the refractive index difference between the ITO electrode and the transparent base material (plastic film such as polyethylene terephthalate) is large, a so-called bone appearance phenomenon occurs in which the ITO electrode portion is easily visible.
Therefore, the difference in the refractive index between the transparent substrate and the ITO electrode is obtained by providing the coating film of the present invention, in which the metal oxide particles having a refractive index of 1.9 or more are selected, as a layer between the transparent substrate and the ITO electrode. It is possible to relax the bone appearance phenomenon.
The method of providing either one or both of the coating film of the present invention and the plastic film with a coating film of the present invention on the touch panel is not particularly limited, and may be implemented by a known method. For example, the structure etc. which patterned the ITO electrode on the coating-film surface of the plastic film with a coating film of this embodiment, and laminated | stacked the alignment film and the liquid-crystal layer are mentioned.

According to the display device of the present invention, the display device of the present invention is provided with either one or both of the coating film of the present invention and the plastic film with a coating film of the present invention, which is excellent in transparency, film formability, thermal curl suppression and scratch resistance. Therefore, there is almost no variation in optical characteristics within the coating surface. For this reason, the display apparatus excellent in visibility can be obtained.

Hereinafter, examples of the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to only these examples.

[Example 1]
"Metal oxide particle dispersion"
Zirconium oxide (average primary particle size 12 nm, manufactured by Sumitomo Osaka Cement Co., Ltd.) is 40.0% by mass as metal oxide particles, 6.0% by mass of 3-acryloxypropyltrimethoxysilane as a dispersant, and alkyl as a salt substance 0.3% by mass of dimethylamine, 0.6% by mass of water, and 53.1% by mass of methyl isobutyl ketone as a dispersion medium were mixed. Then, the dispersion process was performed using the bead mill and the metal oxide particle dispersion liquid of Example 1 was obtained.

"Evaluation of metal oxide particle dispersion"
As a result of measuring the moisture content of the obtained metal oxide particle dispersion with a Karl Fischer moisture meter (model number: AQL-22320, manufactured by Hiranuma Sangyo Co., Ltd.), the water content was 0.6% by mass. Since the content of water was 0.6% by mass with respect to the content of metal oxide particles 40.0% by mass, the content of water when the content of metal oxide particles was 100% by mass was 1.5% by mass.
Moreover, as a result of measuring the particle size distribution of the obtained metal oxide particle dispersion with a particle size distribution meter (trade name: Microtrac UPA150, manufactured by Nikkiso Co., Ltd.), D50 is 15 nm, D90 is 20 nm, and D90 / D50 is 1. .3.

"Resin composition"
40.6% by mass of the obtained metal oxide particle dispersion of Example 1 and urethane acrylate having a weight average molecular weight of 23200 as a resin (trade name: EXP-141, 55% by mass of resin component, methyl isobutyl ketone (diluting solvent) ) 45% by mass, 13.6% by mass of Dainichi Seika Kogyo Co., Ltd., 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl as a polymerization initiator } 0.4% by mass of 2-methyl-propan-1-one and 45.4% by mass of methyl isobutyl ketone as an organic solvent were mixed to obtain a resin composition of Example 1.
The content rate of the resin component (urethane acrylate) in the resin composition of Example 1 was 7.5 mass%.
In this resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

The obtained resin composition of Example 1 was applied to a polyethylene terephthalate film having a thickness of 50 μm by a bar coating method so that the dry film thickness was 0.8 μm. Then, it heated and dried at 90 degreeC and formed the coating film.
Next, using a high-pressure mercury lamp (120 W / cm), the coating film was exposed to ultraviolet light with an energy of 250 mJ / cm ² to cure the coating film, and the film with a hard coat film of Example 1 was obtained. .

"Evaluation of plastic film with paint film"
"Total light transmittance and haze value of plastic film with coating film"
The total light transmittance and haze value of the coated plastic film were measured based on Japanese Industrial Standard JIS-K-7136 using a haze meter NDH-2000 (manufactured by Nippon Denshoku Co., Ltd.) based on air.
For the measurement of the total light transmittance and haze value, a test piece of 100 mm × 100 mm was produced from the produced plastic film with a coating film, and the test piece was used. The evaluation results are shown in Table 1.
In addition, as a result of measuring the haze value of a 50-micrometer-thick polyethylene terephthalate film by said method, the haze value of the polyethylene terephthalate film itself was 1.2%.

"Color unevenness of plastic film with paint film"
The color unevenness of the plastic film with a coating film was evaluated by visually observing with a gap of 30 cm between the film and the eyes, and when there was no color unevenness or almost inconspicuous, and x when there was color unevenness.
The evaluation results are shown in Table 1.

"Thermal curling properties of plastic films with coatings"
For evaluation of the thermal curl property, a test piece of 100 mm × 100 mm was produced from the produced plastic film with a coating film, and the test piece was used.
This test piece was heat-treated at 150 ° C. for 1 hour, then placed on a horizontal base, the height of the lift from the four corners of the film was measured with a ruler, and the average value of the lift was calculated. The evaluation results are shown in Table 1.

"Measurement of reflection spectrum"
The reflection spectrum in the visible light region of the plastic film with a coating film of Example 1 was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technology Corporation).
The results are shown in FIG.
In this reflection spectrum, the difference between the maximum value and the minimum value of the reflectance within the range of 500 nm to 750 nm was determined. The results are shown in Table 1.

"Abrasion resistance of coating film"
On the coating film of the plastic film with a coating film, # 0000 steel wool was slid back and forth 10 times under a load of 100 g / cm ² . The surface of the coating film after reciprocation was visually observed, and the scratch resistance was evaluated according to the following criteria.
Those with an evaluation result of 0 are non-defective products, and as the evaluation result is from 1 to 6, the scratch resistance is low.
0: 0 wounds 1: 1-5 wounds 2: 6-10 wounds 3: 11-15 wounds 4: 16-20 wounds 5: 21-25 wounds 6: 26 or more wounds

[Example 2]
"Resin composition, plastic film with paint film"
Instead of using urethane acrylate having a weight average molecular weight of 23200, urethane acrylate having a weight average molecular weight of 26300 (trade name: EXP-142, 55% by mass of resin component, 45% by mass of methyl isobutyl ketone, manufactured by Dainichi Seika Kogyo Co., Ltd.) Except having been used, the resin composition of Example 2 was obtained using the metal oxide particle dispersion obtained in Example 1 in exactly the same manner as in Example 1. Moreover, the plastic film with a coating film of Example 2 was obtained using this composition. The content rate of the resin component (urethane acrylate) in the resin composition of Example 2 was 7.5 mass%.
In the resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

"Evaluation of plastic film with paint film"
About the plastic film with a coating film of Example 2, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1 and FIG.

[Example 3]
"Resin composition, plastic film with paint film"
Instead of using urethane acrylate having a weight average molecular weight of 23200, urethane acrylate having a weight average molecular weight of 18600 (trade name: EXP-14, resin component 55% by mass, methyl isobutyl ketone 45% by mass, manufactured by Dainichi Seika Kogyo Co., Ltd.) Except having been used, the resin composition of Example 3 was obtained using the metal oxide particle dispersion obtained in Example 1 in exactly the same manner as in Example 1. Moreover, the plastic film with a coating film of Example 3 was obtained using this composition. The content of the resin component (urethane acrylate) in the resin composition of Example 3 was 7.5% by mass.
In the resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

"Evaluation of plastic film with paint film"
About the plastic film with a coating film of Example 3, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1 and FIG.

[Example 4]
"Resin composition, plastic film with paint film"
Instead of using urethane acrylate having a weight average molecular weight of 23200, a dendritic polymer having a weight average molecular weight of 20000 (trade name: SUBARRU-501, resin component 50 mass%, ethyl acetate 50 mass%, manufactured by Osaka Organic Chemical Industry Co., Ltd., Acrylic acrylate) and a dendritic polymer having a weight average molecular weight of 1950 (manufactured by Osaka Organic Chemical Industry Co., Ltd., resin component 100 mass%, polyester acrylate) were mixed at a resin component ratio of 1: 9, Resin composition of Example 4 using the metal oxide particle dispersion obtained in Example 1 in substantially the same manner as in Example 1 except that an acrylate having a weight average molecular weight of 3755 (calculated value) was used. Got. A plastic film with a coating film of Example 4 was obtained using this composition.
That is, 40.6% by mass of the metal oxide particle dispersion of Example 1, 1.5% by mass of SUBARU-501, 6.75% by mass of dendritic polymer having a weight average molecular weight of 1950, 2-hydroxy- 0.4% by mass of 1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one and 50.75% by mass of methyl isobutyl ketone By mixing, the resin composition of Example 4 was obtained. The content rate of the resin component (acryl acrylate and polyester acrylate) in the resin composition of Example 4 was 7.5% by mass.
In the resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

"Evaluation of plastic film with paint film"
About the plastic film with a coating film of Example 4, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1 and FIG.

[Example 5]
"Resin composition, plastic film with paint film"
Instead of using urethane acrylate having a weight average molecular weight of 23200, a dendritic polymer having a weight average molecular weight of 20000 (trade name: SUBARRU-501, resin component 50 mass%, ethyl acetate 50 mass%, manufactured by Osaka Organic Chemical Industry Co., Ltd., Acrylic acrylate) and a dendritic polymer having a weight average molecular weight of 1950 (manufactured by Osaka Organic Chemical Industry Co., Ltd., resin component 100 mass%, polyester acrylate) were mixed at a resin component ratio of 2: 8 mass ratio, Resin composition of Example 5 using the metal oxide particle dispersion obtained in Example 1 in substantially the same manner as Example 1 except that an acrylate having a weight average molecular weight of 5560 (calculated value) was used. Got. Moreover, the plastic film with a coating film of Example 5 was obtained using this composition.
That is, 40.6% by mass of the metal oxide particle dispersion of Example 1, 3.0% by mass of SUBARU-501, 6.0% by mass of dendritic polymer having a weight average molecular weight of 1950, 2-hydroxy- 0.4% by mass of 1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one and 50.0% by mass of methyl isobutyl ketone By mixing, the resin composition of Example 5 was obtained. The content rate of the resin component (acryl acrylate and polyester acrylate) in the resin composition of Example 5 was 7.5% by mass.
In this resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

"Evaluation of plastic film with paint film"
About the plastic film with a coating film of Example 5, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1 and FIG.

[Example 6]
"Resin composition, plastic film with paint film"
Instead of using urethane acrylate having a weight average molecular weight of 23200, a dendritic polymer having a weight average molecular weight of 20000 (trade name: SUBARRU-501, resin component 50 mass%, ethyl acetate 50 mass%, manufactured by Osaka Organic Chemical Industry Co., Ltd., Acrylic acrylate) and a dendritic polymer having a weight average molecular weight of 1950 (Osaka Organic Chemical Industries, Ltd., resin component 100 mass%, polyester acrylate) were mixed at a resin component ratio of 5: 5, Resin composition of Example 6 using the metal oxide particle dispersion obtained in Example 1 in substantially the same manner as in Example 1 except that an acrylate having a weight average molecular weight of 10975 (calculated value) was used. Got. Moreover, the plastic film with a coating film of Example 6 was obtained using this composition.
That is, 40.6% by mass of the metal oxide particle dispersion of Example 1, 7.5% by mass of SUBARU-501, 3.75% by mass of dendritic polymer having a weight average molecular weight of 1950, 2-hydroxy- 0.4% by mass of 1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one and 47.75% by mass of methyl isobutyl ketone By mixing, the resin composition of Example 6 was obtained. The content rate of the resin component (acryl acrylate and polyester acrylate) in the resin composition of Example 6 was 7.5% by mass.
In the resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

"Evaluation of plastic film with paint film"
For the plastic film with a coating film of Example 6, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1 and FIG.

[Example 7]
"Resin composition, plastic film with paint film"
Instead of using urethane acrylate having a weight average molecular weight of 23200, a dendritic polymer having a weight average molecular weight of 20000 (trade name: SUBARRU-501, resin component 50 mass%, ethyl acetate 50 mass%, manufactured by Osaka Organic Chemical Industry Co., Ltd., Acrylic acrylate) and a dendritic polymer having a weight average molecular weight of 1950 (manufactured by Osaka Organic Chemical Industry Co., Ltd., resin component 100 mass%, polyester acrylate) were mixed at a resin component ratio of 8: 2 mass ratio. Resin composition of Example 7 using the metal oxide particle dispersion obtained in Example 1 in substantially the same manner as Example 1 except that an acrylate having a weight average molecular weight of 16390 (calculated value) was used. Got. Using this composition, a plastic film with a coating film of Example 7 was obtained.
That is, 40.6% by mass of the metal oxide particle dispersion of Example 1, 12.0% by mass of SUBARU-501, 1.5% by mass of dendritic polymer having a weight average molecular weight of 1950, 2-hydroxy- 0.4% by mass of 1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one and 45.5% by mass of methyl isobutyl ketone By mixing, the resin composition of Example 7 was obtained. The content rate of the resin component (acryl acrylate and polyester acrylate) in the resin composition of Example 7 was 7.5% by mass.
In the resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

"Evaluation of plastic film with paint film"
For the plastic film with a coating film of Example 7, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1 and FIG.

[Example 8]
"Resin composition, plastic film with paint film"
Instead of using urethane acrylate having a weight average molecular weight of 23200, a dendritic polymer having a weight average molecular weight of 20000 (trade name: SUBARRU-501, resin component 50 mass%, ethyl acetate 50 mass%, manufactured by Osaka Organic Chemical Industry Co., Ltd., Acrylic acrylate) and urethane acrylate having a weight average molecular weight of 400 (trade name: U-2PPA, resin component 100 mass%, manufactured by Shin-Nakamura Chemical Co., Ltd.) are mixed at a resin component ratio of 9: 1. The resin of Example 8 was obtained using the metal oxide particle dispersion obtained in Example 1 in substantially the same manner as in Example 1 except that the acrylate having a weight average molecular weight of 18040 (calculated value) was used. A composition was obtained. A plastic film with a coating film of Example 8 was obtained using this composition.
That is, 40.6% by mass of the metal oxide particle dispersion of Example 1, 13.5% by mass of SUBARU-501, 0.75% by mass of U-2PPA, 2-hydroxy-1- {4- [4 0.4% by mass of-(2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one and 44.75% by mass of methyl isobutyl ketone were mixed. A resin composition was obtained. The content rate of the resin component (acryl acrylate and urethane acrylate) in the resin composition of Example 8 was 7.5% by mass.
In the resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

"Evaluation of plastic film with paint film"
For the plastic film with a coating film of Example 8, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1 and FIG.

[Example 9]
"Metal oxide particle dispersion"
Zirconium oxide (average primary particle size 12 nm, manufactured by Sumitomo Osaka Cement Co., Ltd.) 40.0% by mass, 3-acryloxypropyltrimethoxysilane 4.0% by mass, alkyldimethylamine 0.3% by mass, water 0% After mixing 6 mass% and methyl isobutyl ketone 55.1 mass%, the dispersion process was performed using the bead mill, and the metal oxide particle dispersion liquid of Example 9 was obtained.

"Evaluation of metal oxide particle dispersion"
As a result of measuring the moisture content of the obtained metal oxide particle dispersion with a Karl Fischer moisture meter (model number: AQL-22320, manufactured by Hiranuma Sangyo Co., Ltd.), the water content was 0.6% by mass. When the content of the metal oxide particles was 100% by mass, the content of water was 1.5% by mass. That is, when the content of metal oxide particles was 100% by mass, the content of water was 1.5% by mass.
Moreover, as a result of measuring the particle size distribution of the obtained metal oxide particle dispersion with a particle size distribution meter (trade name: Microtrac UPA150, manufactured by Nikkiso Co., Ltd.), D50 is 14 nm, D90 is 25 nm, and D90 / D50 is 1. .8.

"Resin composition"
The resulting metal oxide particle dispersion of Example 9 was 40.6% by mass, a dendritic polymer having a weight average molecular weight of 20000 (trade name: SUBARRU-501, resin component 50% by mass, ethyl acetate 50% by mass, Polymeric acrylic copolymer (trade name: GH9903, resin component 100% by mass, Shin-Nakamura Chemical Co., Ltd.) having 13.5% by mass and acrylic acid acrylate (produced by Osaka Organic Chemical Industry Co., Ltd.) and a weight average molecular weight of 10500 is 0.75. % By mass, 0.4% by mass of 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, methyl isobutyl A resin composition of Example 9 was obtained by mixing 44.75% by mass of ketone.
A dendritic polymer having a weight average molecular weight of 20000 and a polymerizable acrylic copolymer having a weight average molecular weight of 10500 are mixed at a resin component ratio of 9: 1, and the weight average molecular weight is 19050 (calculated value). ) Acrylate. The content rate of the resin component (acryl acrylate and acrylic copolymer) in the resin composition of Example 9 was 7.5% by mass.
In the resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

The obtained resin composition of Example 9 was applied to a 50 μm thick polyethylene terephthalate film by a bar coating method so as to have a dry film thickness of 0.8 μm, dried by heating at 90 ° C. Formed.
Next, using a high-pressure mercury lamp (120 W / cm), the coating film was exposed to ultraviolet light with an energy of 250 mJ / cm ² to cure the coating film, thereby obtaining a plastic film with a coating film of Example 9. .

"Evaluation of plastic film with paint film"
For the plastic film with a coating film of Example 9, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1 and FIG.

[Example 10]
"Metal oxide particle dispersion"
Zirconium oxide (average primary particle size 12 nm, manufactured by Sumitomo Osaka Cement Co., Ltd.) 40.0% by mass, 8-methacryloxyoctyltrimethoxysilane 4.0% by mass, alkyldimethylamine 0.3% by mass, water 0% After mixing 6 mass% and methyl isobutyl ketone 55.1 mass%, the dispersion process was performed using the bead mill, and the metal oxide particle dispersion liquid of Example 10 was obtained.

"Evaluation of metal oxide particle dispersion"
As a result of measuring the moisture content of the obtained metal oxide particle dispersion with a Karl Fischer moisture meter (model number: AQL-22320, manufactured by Hiranuma Sangyo Co., Ltd.), the water content was 0.6% by mass. That is, when the content of metal oxide particles was 100% by mass, the content of water was 1.5% by mass.
Moreover, as a result of measuring the particle size distribution of the obtained metal oxide particle dispersion with a particle size distribution meter (trade name: Microtrac UPA150, manufactured by Nikkiso Co., Ltd.), D50 is 15 nm, D90 is 25 nm, and D90 / D50 is 1. .7.

"Resin composition"
The resulting metal oxide particle dispersion of Example 10 was 40.6% by mass and the dendritic polymer having a weight average molecular weight of 20000 (trade name: SUBARRU-501, resin component 50% by mass, ethyl acetate 50% by mass, Polymeric acrylic copolymer (trade name: GH9903, resin component 100% by mass, Shin-Nakamura Chemical Co., Ltd.) having 13.5% by mass and acrylic acid acrylate (produced by Osaka Organic Chemical Industry Co., Ltd.) and a weight average molecular weight of 10500 is 0.75. % By mass, 0.4% by mass of 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, methyl isobutyl A resin composition of Example 10 was obtained by mixing 44.75% by mass of ketone.
A dendritic polymer having a weight average molecular weight of 20000 and a polymerizable acrylic copolymer having a weight average molecular weight of 10500 are mixed at a resin component ratio of 9: 1, and the weight average molecular weight is 19050 (calculated value). ) Acrylate. The content rate of the resin component (acryl acrylate and acrylic copolymer) in the resin composition of Example 10 was 7.5% by mass.
In the resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

The obtained resin composition of Example 10 was applied to a polyethylene terephthalate film having a thickness of 50 μm by a bar coating method so that the dry film thickness was 0.8 μm, and dried by heating at 90 ° C. Formed.
Next, using a high-pressure mercury lamp (120 W / cm), the coating film was exposed to ultraviolet rays so as to have an energy of 250 mJ / cm ² , and the coating film was cured to obtain a plastic film with a coating film of Example 10. .

"Evaluation of plastic film with paint film"
About the plastic film with a coating film of Example 10, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1 and FIG.

[Example 11]
"Resin composition, plastic film with paint film"
Instead of using urethane acrylate having a weight average molecular weight of 23200, acrylic acrylate having a weight average molecular weight of 6500 (trade name: EXP-185 resin component 55% by mass, mixture of methyl isobutyl ketone and propylene glycol monomethyl ether acetate 45% by mass, Except for using Dainichi Seika Kogyo Co., Ltd.), a resin composition of Example 11 was obtained using the metal oxide particle dispersion obtained in Example 1 in exactly the same manner as in Example 1. Moreover, the plastic film with a coating film of Example 11 was obtained using this composition. The content rate of the resin component in the resin composition of Example 11 was 7.5 mass%.
In this resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

"Evaluation of plastic film with paint film"
For the plastic film with a coating film of Example 11, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1 and FIG.

[Comparative Example 1]
Instead of using 13.6% by mass of urethane acrylate having a weight average molecular weight of 23200 and 45.4% by mass of methyl isobutyl ketone, acrylic acrylate having a weight average molecular weight of 578 (trade name: DPHA, resin component 100% by mass, Nippon Kayaku) Using the metal oxide particle dispersion obtained in Example 1 in exactly the same manner as in Example 1 except that 7.5% by mass (made by Yakuhin) and 51.5% by mass of methyl isobutyl ketone were used. The resin composition of Comparative Example 1 was obtained. Moreover, the plastic film with a coating film of the comparative example 1 was obtained using this resin composition. The content rate of the resin component (acryl acrylate) in the resin composition of Comparative Example 1 was 7.5% by mass.
In the resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

"Evaluation of plastic film with paint film"
About the plastic film with a coating film of Comparative Example 1, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 2 and FIG.

[Comparative Example 2]
Instead of using 13.6% by mass of urethane acrylate having a weight average molecular weight of 23200 and 45.4% by mass of methyl isobutyl ketone, urethane acrylate having a weight average molecular weight of 400 (trade name: U-2PPA, resin component 100% by mass, Shin Nakamura Chemical Co., Ltd.) 7.5% by mass and methyl isobutyl ketone 51.5% by mass were used in exactly the same manner as in Example 1, except that the resin composition of Comparative Example 2 and the coating film of Comparative Example 2 were used. A plastic film was obtained. The content rate of the resin component (urethane acrylate) in the resin composition of Comparative Example 2 was 7.5% by mass.
In the resin composition, since the content of water was 0.2% by mass, the content of water was 1.5% by mass when the content of the metal oxide particles was 100% by mass.

"Evaluation of plastic film with paint film"
About the plastic film with a coating film of Comparative Example 2, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 2 and FIG.

[Comparative Example 3]
Instead of using 13.6% by mass of urethane acrylate having a weight average molecular weight of 23200 and 45.4% by mass of methyl isobutyl ketone, acrylic acrylate having a weight average molecular weight of 30000 (trade name: V-6840, resin component 50% by mass, The resin composition of Comparative Example 3 and Comparative Example were the same as Example 1 except that 15.0% by weight of methyl isobutyl ketone (made by DIC Corporation) and 14.0% by weight of methyl isobutyl ketone were used. 3 plastic film with a coating film was obtained. The content rate of the resin component (acryl acrylate) in the resin composition of Comparative Example 3 was 7.5% by mass.
In the resin composition, when the content of the metal oxide particles was 100% by mass, the content of water was 1.5% by mass.

"Evaluation of plastic film with paint film"
About the plastic film with a coating film of Comparative Example 3, the total light transmittance, haze value, color unevenness, thermal curl property, reflection spectrum, and scratch resistance of the coating film were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 2 and FIG.

[Reference Example 1]
"Metal oxide particle dispersion"
Zirconium oxide (average primary particle size 12 nm, manufactured by Sumitomo Osaka Cement Co., Ltd.) 40.0% by mass, 3-acryloxypropyltrimethoxysilane 6.0% by mass, 1% by mass acetic acid aqueous solution 3% by mass, methyl isobutyl ketone Was mixed with 51.0% by mass, and dispersion treatment was performed using a bead mill. However, zirconium oxide was not dispersed because no basic substance was contained.

 
 

 

The present invention provides a resin composition, a coating film, a plastic film with a coating film, and a display device that have a low water content and are excellent in transparency, film-forming properties, thermal curl suppression, and scratch resistance.
The resin composition of the present invention can be applied to all industrial uses in which a metal oxide particle dispersion is conventionally used. For example, it can be applied to optical film uses, house exterior uses, heat ray shielding uses, etc. Can do.

Claims (19)

1. Metal oxide particles,
   A basic substance,
   Resin,
   water and,
   A resin composition comprising:
   The metal oxide particles are surface-treated with a dispersant having a hydrolyzable group,
   The resin includes at least one of acrylic acrylate and urethane acrylate,
   The water content is 3% by mass or less of the content of the metal oxide particles,
   On the coating film of a film with a coating film obtained by applying the resin composition to a polyethylene terephthalate film having a thickness of 50 μm so as to have a dry film thickness of 0.8 μm, the weight of # 0000 steel wool is 100 g / cm ² . The number of scratches when sliding back and forth 10 times below is 20 or less,
   The haze value of the film with a coating film is 2.0% or less,
   When the film with a coated film is left at 150 ° C. for 1 hour in a size of 100 mm × 100 mm and then placed on a horizontal table, the average value of the amount of lift from the horizontal table at the four corners of the film with a coated film is A resin composition characterized by being 20 mm or less.
2. The resin composition according to claim 1, wherein the resin has a weight average molecular weight of 1000 or more and 28000 or less.
3. 2. The resin composition according to claim 1, wherein the difference between the maximum value and the minimum value of the reflectance within the range of 500 nm to 750 nm of the film with a coating film is 0.80% or less.
4. A coating film formed using the resin composition according to claim 1.
5. A plastic film with a coating film, wherein the coating film according to claim 4 is provided on one or both surfaces of the plastic film.
6. A display device comprising the coating film according to claim 4.
7. The display device according to claim 6, further comprising a plastic film, wherein the coating film is provided on one surface or both surfaces of the plastic film.
8. The resin composition according to claim 1, wherein the content of the metal oxide particles in the resin composition is in the range of 10% by mass to 30% by mass.
9. The resin composition according to claim 1, wherein the metal oxide particles are at least one of zirconium oxide and titanium oxide having an average primary particle diameter of 5 nm or more and 25 nm or less.
10. The amount of the basic substance is 0.15% by mass or more and 1.5% by mass or less with respect to the content of the metal oxide particles contained in the resin composition,
    The resin composition according to claim 1, wherein the basic substance is a tertiary amine.
11. The resin composition according to claim 1, wherein the acrylic acrylate and urethane acrylate have a weight average molecular weight of 3000 or more and 25000 or less.
12. The resin composition according to claim 1, wherein the acrylic acrylate and urethane acrylate have a weight average molecular weight of 15000 or more and 25000 or less.
13. The resin composition according to claim 1, wherein the acrylic acrylate is a dendritic polymer.
14. The resin composition is
    A metal oxide particle, a dispersant having a hydrolyzable group, a basic substance, a dispersion medium, and water are mixed to form a dispersion,
    Thereafter, the dispersion is a resin composition obtained by mixing a resin and an organic solvent,
    The water content of the resin composition is
    The resin composition according to claim 1, wherein the resin composition is a value calculated based on a value obtained by measuring the dispersion with a Karl Fischer moisture meter.
15. The resin composition according to claim 14, wherein the amount of water contained for forming the dispersion is 3% by mass or less of the content of the metal oxide particles.
16. The resin composition according to claim 14, wherein the amount of water contained for forming the dispersion is 2% by mass or less of the content of the metal oxide particles.
17. The dispersant is a silane coupling agent having 1 to 3 alkoxy groups in one molecule, and the dispersant is in the range of 5% by mass to 30% by mass with respect to the total mass of the metal oxide particles. The resin composition of Claim 1 contained.
18. The content of the metal oxide particles in the resin composition is in the range of 10% by mass to 30% by mass,
    The metal oxide particles are at least one of zirconium oxide and titanium oxide having an average primary particle diameter of 5 nm or more and 25 nm or less,
    The basic substance is a tertiary amine, and the amount of the basic substance is 0.15% by mass or more and 1.5% by mass or less with respect to the content of the metal oxide particles contained in the resin composition. Yes,
    The acrylic acrylate and urethane acrylate have a weight average molecular weight of 3000 or more and 25000 or less,
    The dispersant is a silane coupling agent having 1 to 3 alkoxy groups in one molecule, and the dispersant is in the range of 5% by mass to 30% by mass with respect to the total mass of the metal oxide particles. Included,
    The resin composition is water in an amount of 3% by mass or less based on the content of metal oxide particles, a hydrolyzable group-containing dispersant, a basic substance, a dispersion medium, and metal oxide particles. To form a dispersion, and then the dispersion is a resin composition obtained by mixing a resin and an organic solvent,
    The resin composition according to claim 1, wherein the water content of the resin composition is a value calculated based on a value obtained by measuring the dispersion with a Karl Fischer moisture meter.
19. The plastic film with a coating film according to claim 6, wherein the plastic film is a polyethylene terephthalate film.

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