KR20170101807A - Coating solution for forming transparent film and substrate with transparent film - Google Patents

Abstract

[PROBLEMS] To provide a coating liquid capable of suppressing curling even when being a thin substrate, and capable of forming a transparent coating film having high hardness and scratch resistance.
(Solution) The coating liquid of the present invention contains a surface-treated metal oxide particle in which a predetermined amount of an organosilicon compound is formed on the surface of metal oxide particles, an alkylene oxide-modified (meth) acrylate resin, and an organic solvent . The alkylene oxide-modified (meth) acrylate resin is a polyfunctional acrylate monomer resin having a (meth) acrylate functional group number of 3 to 10 and an alkylene oxide group number of 3 to 40. The surface-treated metal oxide particles contain 0.1 to 50 parts by mass of the organosilicon compound as R _n -SiO _{(4-n) / 2} with respect to 100 parts by mass of the metal oxide particles. The surface-treated metal oxide particles have an average particle diameter of 5 to 500 nm and are contained in the coating liquid in an amount of 30 to 90% by mass based on the total amount of the solid components of the alkylene oxide-modified (meth) acrylate resin and the surface-

Description

TECHNICAL FIELD [0001] The present invention relates to a coating liquid for forming a transparent film and a transparent film-

The present invention relates to a coating liquid capable of forming a transparent coating film having a low contact angle with water and having a high hardness (pencil hardness) and strength (scratch resistance), and a transparent film-forming base material using the coating liquid.

BACKGROUND ART [0002] A substrate such as a sheet or lens formed of glass, plastic or the like conventionally has a hard coat film formed on the surface of the substrate to improve the scratch resistance of the surface.

The hard coat film is required to have a high contact angle type in order to impart antifouling property to a display used in the outermost surface. On the other hand, in the case of a touch panel such as a tablet or a smart phone, a low contact angle type is required in order to further form a layer on the hard coat film or to bond an adhesive or a resin.

Further, when the coating liquid is dried and cured, there is a problem that the transparent film is shrunk and the substrate is pulled, and the transparent film-forming base material is curled (curved). For example, in the case of a coating liquid having a large amount of solvent, curling tends to occur due to shrinkage from the wet film to the dry film due to solvent volatilization (concentration) at the time of drying. When a resin having a high hardening shrinkage ratio such as a polyfunctional acrylic monomer is used, curling tends to occur due to shrinkage at the time of hardening. In recent years, a thin substrate has been used for further improving the transparency or for reducing the weight of a display device or a cellular phone using a transparent film-forming substrate, and the problem of curling becomes more remarkable.

Thus, Patent Document 1 discloses a hard coat film in which an active energy ray cured resin layer is laminated on at least one side of a base material, and a manufacturing method thereof. In this hard-coated film, the surface hardness of the cured resin layer is not less than H and the contact angle of the water droplet is not more than 60 deg. Specifically, a resin composition for curing such as an unsaturated polyester resin, an acrylic resin, an addition polymerization system, a hybrid system of thiol / acrylic, a cation polymerization system, a hybrid system of cation polymerization and radical polymerization is applied Then, an active energy beam such as ultraviolet rays is irradiated to crosslink and cure the resin composition, and then a gas containing a specific amount of fluorine gas is subjected to a contact treatment to form an active energy ray curable resin layer.

Patent Document 2 discloses a coating material which forms a transparent coating film which is excellent in adhesion to a base material, hardness, scratch resistance, transparency and the like while being a thin base material with a small amount of curling. The coating material comprises a polyfunctional urethane acrylate resin having a functional group number of 4 or more, a low-functionality acrylate resin having a functional group number of 2 or 3, metal oxide fine particles having an average particle diameter of 5 to 500 nm, an organic solvent, urethane concentration ratio (C _B / C _a) of the acrylate resin concentration (C _a) and a low density-functional acrylate resin (C _B) of the is in the range of 0.05 to 0.5.

Japanese Patent Application Laid-Open No. 7-173310 Japanese Laid-Open Patent Publication No. 2013-64038

However, in the structure of the hard coat film of Patent Document 1, the cured resin layer is the main body. For this reason, the hardness of the hard coat film is only about H to 2H, hardening of the hardness is difficult, and a hard coat film having both a low contact angle and a high hardness can not be obtained.

Next, in Patent Document 2, the polyfunctional urethane acrylate resin in the transparent coating film is hydrophobic. Therefore, the surface of the transparent coating film also becomes hydrophobic, and the contact angle with water becomes high. Further, if the content of the surface-treated metal oxide fine particles in the transparent coating film is increased in order to achieve hardening, the obtained transparent coating film is whitened or curled. It is considered that this is because the polyfunctional urethane acrylate resin is hydrophobic while the surface-treated metal oxide fine particles are hydrophilic, so that sufficient compatibility is not obtained. Also, the polyfunctional urethane acrylate resin is a special compound, so it is expensive, and weather resistance and light resistance are low.

The present invention provides a coating liquid (coating liquid for forming a transparent coating film) for obtaining a hard coat transparent coating film which has a low contact angle with water and a high hardness, and which is capable of suppressing curling even by a thin substrate, and a transparent film- .

The coating liquid for a transparent coating film according to the present invention is a coating liquid containing an alkylene oxide-modified (meth) acrylate resin, a surface-treated metal oxide particle having an organosilicon compound formed on the surface of the metal oxide particle, and an organic solvent . The alkylene oxide-modified (meth) acrylate resin is a polyfunctional (meth) acrylate monomer resin having 3 to 10 (meth) acrylate functional groups and 3 to 40 alkylene oxide groups. The surface-treated metal oxide particles are formed in an amount of 0.1 to 50 parts by mass as R _n -SiO _{(4-n) / 2} with respect to 100 parts by mass of the metal oxide particles. The average particle diameter is 5 to 500 nm. The surface-treated metal oxide particles are contained in the coating liquid in an amount of 30 to 90% by mass based on the total amount of the solid components of the alkylene oxide-modified (meth) acrylate resin and the surface-treated metal oxide particles.

It is also preferable that the alkylene oxide-modified (meth) acrylate resin is an ethylene oxide-modified (meth) acrylate resin.

The transparent film-forming base material according to the present invention contains a surface-treated metal oxide particle in which the transparent film has an alkylene oxide-modified (meth) acrylate resin and an organosilicon compound formed on the surface of the metal oxide particle. The average particle diameter of the surface-treated metal oxide particles is 5 to 500 nm. The surface-treated metal oxide particles are contained in the transparent film in an amount of 30 to 90% by mass based on the total amount of the solid components of the alkylene oxide-modified (meth) acrylate resin and the surface-treated metal oxide particles. Here, the transparent coating preferably has a contact angle with water of less than 70 DEG and a pencil hardness of 3H or more.

The contact angle of the transparent coating film is preferably lower than the contact angle of the transparent film film containing no surface-treated oxide particles.

The coating liquid of the present invention contains an alkylene oxide-modified (meth) acrylate resin having an alkylene oxide group having a high polarity. The alkylene oxide-modified (meth) acrylate resin has high compatibility with the surface-treated metal oxide particles. For this reason, the surface-treated metal oxide particles are sufficiently dispersed in the alkylene oxide-modified (meth) acrylate resin. By using this coating liquid, a transparent film-forming base material having a low contact angle and a high degree of hardness and strength and a small degree of curling can be obtained even when a thin substrate having a thickness of 20 to 70 탆 is used.

[Coating liquid for forming a transparent film]

The coating liquid of the present invention contains an alkylene oxide-modified (meth) acrylate resin, a surface-treated metal oxide particle having an average particle diameter of 5 to 500 nm in which an organosilicon compound is formed on the surface of the metal oxide particle, and an organic solvent . The coating liquid may further contain an additive such as a polymerization initiator.

The alkylene oxide-modified (meth) acrylate resin is a polyfunctional (meth) acrylate monomer resin having 3 to 10 (meth) acrylate functional groups and 3 to 40 alkylene oxide groups. The surface-treated metal oxide particles are preferably such that the organosilicon compound is present on the surface of the metal oxide particle in an amount of 0.1 to 50 parts by mass as the R _n -SiO _{(4-n) / 2} with respect to 100 parts by mass of the metal oxide particles to be. The surface-treated metal oxide particles have an average particle size of 5 to 500 nm and are contained in the coating liquid in an amount of 30 to 90% by mass based on the sum of the solid content of the alkylene oxide-modified (meth) acrylate resin and the surface-

In general, as a resin having a good hard coat property, a polyfunctional (meth) acrylate monomer resin or a polyfunctional (meth) urethane acrylate oligomer resin is often used. The multifunctional (meth) acrylate monomer resin, although having a relatively low contact angle, is generally prone to curling. The polyfunctional (meth) urethane acrylate oligomer resin generally has a low curling but a high contact angle. On the other hand, the polyfunctional alkylene oxide-modified (meth) acrylate resin has a low hardness but a low curling and a low contact angle by optimizing the ratio of the alkylene oxide group to the (meth) acrylate functional group. As will be described later, the number of acrylate functional groups and alkylene oxide groups in the alkylene oxide-modified (meth) acrylate resin, the surface treatment amount of the surface-treated metal oxide particles with the organosilicon compound, the average particle diameter of the surface- And the amount of the surface-treated organosilicon compound in the coating liquid under the optimum conditions, a hard coat paint realizing all of hardness, low contact angle and low curling property can be obtained.

The main components contained in the coating liquid will be described in detail below.

An " alkylene oxide-modified (meth) acrylate resin "

The alkylene oxide-modified (meth) acrylate resin is liable to exhibit low curling at a relatively low contact angle by optimizing the ratio of the alkylene oxide group to the (meth) acrylate functional group ((meth) acryloyl group). When the number of acrylate functional groups is less than 3, since a bonding site is reduced, a dense and hard film is hardly obtained. Conversely, when the number of acrylate functional groups is larger than 10, the number of couplers for unit volume / unit volume / unit unit becomes relatively large. Therefore, the shrinkage of the film is strong and curling may occur.

The alkylene oxide group is a functional group having a high polarity, and since the obtained film surface is hydrophilic, the water contact angle of the film becomes low. When the alkylene oxide group is smaller than 3, the surface of the coating film is insufficiently hydrophilized and the water contact angle is not sufficiently lowered. Conversely, when the alkylene oxide group is larger than 40, the number of bonding units for unit volume / unit volume / unit unit is relatively small. For this reason, the densification of the film may not be sufficient, and the desired pencil hardness may not be obtained.

As the alkylene oxide (AO) group, an ethylene oxide (EO) group, a propylene oxide (PO) group, and a butylene oxide group are preferable. Particularly, an ethylene oxide group having a high proportion of oxygen atoms in the unit and a high polarity is preferable.

(Meth) acrylate resin having a number of (meth) acrylate functional groups of 3 or more is relatively large in shrinkage, so that a low-functionality (meth) acrylate having a functionality of 2 or less, preferably 1, A late monomer resin is blended. As a result, the shrinkage of the film as a whole can be reduced, the adhesion between the film and the substrate can be further improved, and the residual stress can be relaxed.

Further, the incorporation of a low-functional (meth) acrylate monomer resin improves the compatibility of the alkylene oxide-modified (meth) acrylate resin with the surface-treated metal oxide particles and improves the dispersibility. This is because, by blending a low-functional (meth) acrylate monomer resin, it is possible to inhibit rapid shrinkage during the film formation and to prevent particles in the film from being removed from the film by shrinkage of the film. It is also effective in that it is easy to lower the viscosity of the paint. However, since a high blend of a low-function (meth) acrylate monomer resin leads to a decrease in hardness, the content is preferably as small as possible, and it is preferable to blend with a balance of curling property, adhesiveness and hardness.

As the alkylene oxide-modified (meth) acrylate resin, ethylene oxide modified (meth) acrylate resin, propylene oxide modified (meth) acrylate resin and butylene oxide modified (meth) acrylate resin are preferable.

Examples of the ethylene oxide modified (meth) acrylate resin include ethoxylated glycerin tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated ditrimethyl (Meth) acrylate, ethoxylated dipentaerythritol penta (meth) acrylate, and ethoxylated dipentaerythritol hexa (meth) acrylate. They each have 3 to 40 ethylene oxide groups.

Examples of the propylene oxide modified (meth) acrylate resin include propoxylated glycerin tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tetra (meth) (Meth) acrylate, propoxylated dipentaerythritol penta (meth) acrylate, and propoxylated dipentaerythritol hexa (meth) acrylate. They each have 3 to 40 propylene oxide groups.

Examples of the butylene oxide modified (meth) acrylate resin include butoxyated glycerin tri (meth) acrylate, butoxy pentaerythritol tri (meth) acrylate, butoxy pentaerythritol tetra (meth) acrylate, Trimethylolpropane tetra (meth) acrylate, butoxyated dipentaerythritol penta (meth) acrylate, and butoxyated dipentaerythritol hexa (meth) acrylate. They each have 3 to 40 butylene oxide groups.

These resins may be used alone or in combination of two or more.

&Quot; Surface treated metal oxide particles "

The surface-treated metal oxide particles are obtained by surface-treating conventionally known metal oxide particles with conventionally known organosilicon compounds. Examples of the metal oxide particles include tin oxide doped with tin oxide, Sb or P, indium oxide doped with Sn or F, indium oxide doped with Sn or F, and metal oxide particles doped with at least one element selected from the group consisting of silica, alumina, titania, silica- Conductive particles such as antimony oxide, titanium oxide and the like can be preferably used.

≪ average particle diameter &

The average particle diameter of the surface-treated metal oxide particles is 5 to 500 nm. When the average particle diameter is less than 5 nm, it is difficult to obtain, and even if it is obtained, the surface treatment with the surface treatment agent and the stability of the sol often become insufficient. On the other hand, when the average particle diameter exceeds 500 nm, light scattering occurs on the surface of the film or the haze of the transparent coating deteriorates and the transparency deteriorates, depending on the content of the surface-treated metal oxide particles. The average particle diameter of the surface-treated metal oxide particles is more preferably 10 to 200 nm.

≪ Surface treatment: surface treatment agent, surface treatment amount >

It is preferable to treat the metal oxide particles with an organosilicon compound represented by the following formula (1).

R _n -SiX _4-n ... (One)

In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. Examples of the substituent include an epoxy group, an alkoxy group, a (meth) acryloyloxy group, a mercapto group, a halogen atom, an amino group, and a phenylamino group. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, a hydrogen atom, and n represents an integer of 1 to 3.

When the surface-treated metal oxide particles are contained in an amount of 0.1 to 50 parts by mass as R _n -SiO _{(4-n) / 2} with respect to 100 parts by mass of the metal oxide particles as the solid content, compatibility is improved. If the amount of the organosilicon compound is less than 0.1 part by mass, the dispersibility of the surface-treated metal oxide particles becomes insufficient, and haze may be generated in the obtained transparent coating film. At this time, although the obtained contact angle is lowered, the bonding force with the binder ((meth) acrylate monomer resin) is weakened, so that the adhesion and hardness with the base may become insufficient. On the other hand, if the surface treatment amount is more than 50 parts by mass, the dispersibility is not further improved, and the high-density filling of the surface-treated metal oxide particles may be hindered. At this time, although the contact angle increases, there is a fear that the shrinkage increases, curling, or adhesion becomes insufficient because the number of sites bonded to the binder increases. In addition, it is preferable to reduce unreacted surface treatment agent because the surface treatment agent (organic silicon compound) unreacted (not bonded to the fine particles) binds to each other to shrink.

&Quot; Organic solvent "

As the organic solvent, those capable of dissolving or dispersing additives such as an alkylene oxide-modified (meth) acrylate resin and a polymerization initiator and dispersing the surface-treated metal oxide particles uniformly are used.

For example, a hydrophilic solvent or a polar solvent is preferable. As the hydrophilic solvent, alcohols, esters, glycols, ethers and the like can be used. As the polar solvent, esters, ketones and the like can be used.

Examples of the alcohols include methanol, ethanol, propanol, 2-propanol, butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol and the like. Examples of esters include methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, Glycol monoacetate and the like. The glycols include ethylene glycol, hexylene glycol and the like. Examples of the ethers include diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol mono Methyl ether, propylene glycol monoethyl ether, and the like. Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, methyl pentyl ketone, and diisobutyl ketone. Examples of the polar solvent include dimethyl carbonate and toluene. These may be used alone or in combination of two or more.

Particularly, propylene glycol monomethyl ether, propylene glycol monoethyl ether and diacetone alcohol are effective for control of the film formability and are preferable from the viewpoint of control of appearance (stripe, stain, transparency) of the coating film. In the case of using a triacetylcellulose substrate (TAC substrate), since ethyl acetate, acetone, methyl ethyl ketone, cyclohexanone, dimethyl carbonate or the like is mixed to dissolve the base material, It is preferable in terms of reduction.

The boiling point of the organic solvent is preferably 50 to 200 ° C. If the boiling point of the organic solvent is lower than 50 캜, rapid drying of the coating film causes rapid film formation. Particularly, when packings such as particle components are insufficient, the densification of the film tends to become insufficient, and the film thickness tends to become uneven. Therefore, the hardness of the resulting transparent coating may be insufficient. If the boiling point of the organic solvent is higher than 200 占 폚, the organic solvent may remain, and if it is cured while containing the residual solvent, voids may be generated and the hardness of the resulting transparent coating may become insufficient. The boiling point of the organic solvent is more preferably 55 to 180 ° C.

"Other Ingredients"

To the coating liquid, a photo polymerization initiator may be added as needed. As the polymerization initiator, known ones can be used without particular limitation, and examples thereof include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) Methyl-2-methyl-phenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, and the like. The amount of the polymerization initiator to be used is preferably from 2 to 20 mass%, more preferably from 4 to 16 mass%, of the solid content concentration of the organic resin.

However, conventionally known leveling agents and surfactants, which are additives, tend to be more localized on the surface than metal oxide particles when forming the coating. For this reason, if the amount of use is excessively large, the water contact angle can not be obtained as much as desired, or the additive may precipitate on the surface of the film, causing a problem of bleeding-out. Therefore, when these additives are used, they are preferably used in a range that does not affect the performance of the transparent film-forming base material.

&Quot; Concentration of coating liquid for forming a transparent coating film &

The solid concentration of the coating liquid (the concentration of the solid content of the solid content of the alkylene oxide-modified (meth) acrylate resin and the solid content of the surface-treated metal oxide particles) is preferably from 5 to 70 mass%. When the amount is less than 5% by mass, the concentration stability of the paint is low, so that it is difficult to obtain a uniform film. In addition, the resulting transparent coating film may have insufficient hardness and scratch resistance, haze or appearance deterioration, and may deteriorate productivity, manufacturing reliability, and the like. If it is higher than 70% by mass, the viscosity of the coating liquid tends to be high, the coating property may be lowered, the haze of the obtained transparent coating film may increase, the surface roughness may become large, and scratch resistance may become insufficient.

The solid concentration of the coating liquid is more preferably 10 to 60% by mass.

≪ Concentration of surface-treated metal oxide particles >

The surface-treated metal oxide particles in the coating liquid have a solid content of 30 to 90 mass% with respect to the total amount of the solid content of the alkylene oxide-modified (meth) acrylate resin and the solid content of the surface-treated metal oxide particles. When the amount of the surface-treated metal oxide particles is less than 30% by mass, the effect of inhibiting curling, hardness and scratch resistance becomes insufficient when the coating film is formed, the hydrophilicity of the surface of the coating becomes insufficient, . On the contrary, even if the surface-treated metal oxide particles are more than 90% by mass, cracks sometimes occur in the transparent coating film. In addition, even if a film is obtained, there are cases where the adhesion to the substrate becomes insufficient, and the film strength, scratch resistance, transparency, haze, and the like deteriorate. The surface-treated metal oxide particle component is more preferably from 50 to 85% by mass, and more preferably from 60 to 85% by mass, based on the sum of the solid content of the alkylene oxide-modified (meth) acrylate resin component and the solid content of the surface- By mass to 80% by mass.

<Concentration of alkylene oxide-modified (meth) acrylate resin>

The alkylene oxide-modified (meth) acrylate resin in the coating liquid preferably has a solid content of 10 to 70% by mass, based on the sum of the solid content of the alkylene oxide-modified (meth) acrylate resin and the solid content of the surface- Do.

When the amount of the alkylene oxide-modified (meth) acrylate resin is less than 10% by mass, cracks may occur in the transparent coating film when the coating film is formed. On the other hand, if the amount of the alkylene oxide-modified (meth) acrylate resin is more than 70% by mass, the hard coat and scratch resistance of the transparent coating film may be insufficient. The alkylene oxide-modified (meth) acrylate resin component preferably has an alkylene oxide-modified (meth) acrylate resin component in an amount of 15 to 50% by mass, based on the total amount of the solid content of the alkylene oxide- , And more preferably from 20 to 40 mass%.

In the coating liquid having such a concentration ratio of the surface-treated metal oxide particles and the alkylene oxide-modified (meth) acrylate resin, the concentration of the surface-treated metal oxide particles in the coating liquid is preferably from 1.5 to 63 mass% The alkylene oxide-modified (meth) acrylate resin is preferably contained in an amount of 0.5 to 49% by mass as a solid content.

The constitution of the coating liquid of the present invention is such that, as described above, the surface treatment metal oxide (B) having an average particle diameter of 5 to 500 nm, in which an alkylene oxide modified (meth) acrylate resin and an organosilicon compound are formed on the surface of the metal oxide particle Particles, and an organic solvent. The alkylene oxide-modified (meth) acrylate resin contains 3 to 10 (meth) acrylate functional groups and 3 to 40 alkylene oxide groups. The surface-treated metal oxide particles contain 0.1 to 50 parts by mass of the organosilicon compound as R _n -SiO _{(4-n) / 2} with respect to 100 parts by mass of the metal oxide particles. In the coating liquid, the surface-treated metal oxide particles are contained in an amount of 30 to 90% by mass based on the total amount of the solid components of the alkylene oxide-modified (meth) acrylate resin and the surface-treated metal oxide particles.

For example, in the alkylene oxide-modified (meth) acrylate resin, the number of (meth) acrylate functional groups is 4 to 8 and the number of alkylene oxide groups is 6 to 30. Next, the surface-treated metal oxide particles contain an organic silicon compound in an amount of 1 to 30 parts by mass as R _n -SiO _{(4-n) / 2} with respect to 100 parts by mass of the metal oxide particles. In the coating liquid, the surface-treated metal oxide particles are contained in an amount of 50 to 85 mass% with respect to the total amount of the solid components of the alkylene oxide-modified (meth) acrylate resin and the surface-treated metal oxide particles.

For example, first, the alkylene oxide-modified (meth) acrylate resin contains 4 to 6 (meth) acrylate functional groups and 12 to 24 alkylene oxide groups. Next, the surface-treated metal oxide particles contain an organic silicon compound in an amount of 5 to 20 parts by mass as R _n -SiO _{(4-n) / 2} with respect to 100 parts by mass of the metal oxide particles. In the coating liquid, the surface-treated metal oxide particles are contained in an amount of 60 to 80 mass% with respect to the total amount of the solids of the alkylene oxide-modified (meth) acrylate resin and the surface-treated metal oxide particles.

[Transparent film-forming substrate]

Using the above-mentioned coating liquid, a transparent coating film is formed directly or indirectly on the substrate. The transparent coating film is formed mainly of the surface-treated metal oxide particles and the resin component. The transparent coating film of the present invention is particularly useful when an upper layer such as a resin layer is formed on the coating film of the present invention because the contact angle with water is low. That is, the transparent film-forming substrate of the present invention is preferably a structure in which a transparent film is formed on a substrate and an upper layer such as a resin layer is further formed on the transparent film.

"materials"

As the substrate, known ones can be used without any particular limitation, and examples thereof include a polycarbonate, an acrylic resin, a polyethylene terephthalate (PET), a triacetyl cellulose (TAC), a polymethyl methacrylate resin (PMMA), a cycloolefin polymer COP) and the like are preferable. These resin base materials can obtain a transparent film-forming base material excellent in adhesion with the transparent film formed by the above-described coating liquid and excellent in hardness and scratch resistance. Therefore, it can be preferably used for a thin substrate. The thickness of the substrate is preferably 20 to 70 mu m. Among them, the TAC substrate is liable to be curled if the substrate is thin. For this reason, it is preferable to use the coating liquid for a transparent coating film of the present invention in order to suppress curling.

The thickness of the substrate is more preferably 30 to 60 mu m.

&Quot; Transparent film &quot;

In the transparent coating according to the present invention, the ratio of the amount of the alkylene oxide-modified (meth) acrylate resin component to the amount of the surface-treated metal oxide particle component in the coating liquid is the same as that in the coating film.

That is, the ratio of the alkylene oxide-modified (meth) acrylate resin in the transparent coating film is preferably such that the solid content of the alkylene oxide-modified (meth) acrylate resin component and the average particle diameter of the alkylene oxide- (Meth) acrylate resin component with respect to the total amount of the solid content of the surface-treated metal oxide particle component having an average particle diameter of 200 nm to 200 nm. The proportion of the alkylene oxide-modified (meth) acrylate resin in the transparent coating film is preferably 10 to 70% by mass as solid content. When the amount of the alkylene oxide-modified (meth) acrylate resin is less than 10% by mass, cracks may occur in the transparent coating film. On the other hand, when the amount of the alkylene oxide-modified (meth) acrylate resin is more than 70% by mass, the hard coat and scratch resistance of the transparent coating film may be insufficient. The alkylene oxide-modified (meth) acrylate resin component preferably has an alkylene oxide-modified (meth) acrylate resin component in an amount of 15 to 50% by mass, based on the total amount of the solid content of the alkylene oxide- , And more preferably from 20 to 40 mass%.

On the other hand, the ratio of the surface-treated metal oxide particles in the transparent coating film is preferably in the range of from the solid amount of the alkylene oxide-modified (meth) acrylate resin component in the above-mentioned coating liquid to the solid amount of the surface- Expressed as a ratio of the solid content of the treated metal oxide particle component. The proportion of the surface-treated metal oxide particles in the transparent coating film is preferably 30 to 90% by mass as solid content. Here, if the surface-treated metal oxide particles are less than 30 mass%, the effect of inhibiting curling, hardness, and scratch resistance may be insufficient. In addition, the surface of the coating film becomes insufficient in hydrophilicity, and a water contact angle as low as desired may not be obtained. On the contrary, even if the surface-treated metal oxide particles are more than 90% by mass, cracks sometimes occur in the transparent coating film. In addition, even if a film is obtained, there are cases where the adhesion to the substrate becomes insufficient, and the film strength, scratch resistance, transparency, haze, and the like deteriorate. The surface-treated metal oxide particle component is more preferably in the range of 50 to 85% by mass as solid content with respect to the sum of the solid content of the alkylene oxide-modified (meth) acrylate resin component and the solid content of the surface-treated metal oxide particle component , And more preferably 60 to 80 mass%.

It is difficult to obtain the surface-treated metal oxide particles having an average particle diameter smaller than 5 nm. Even if such particles are obtained, the surface treatment with the surface treatment agent and the stability of the sol often become insufficient. If the average particle diameter of the surface-treated metal oxide particles is larger than 500 nm, it may vary depending on the content of the surface-treated metal oxide particles, but light scattering occurs on the surface of the film or the haze of the transparent coating deteriorates, . The obtained transparent coating film has a lower contact angle than that of the coating film containing the surface-treated metal oxide particles in the case of the coating film composed of the resin component alone in general. However, the coating film containing the surface-treated metal oxide particles of the present invention is characterized in that the contact angle is lower than that of the coating film composed of the resin component alone. The reason is not clear, but it is considered to be one of the factors that the particles exist on the surface of the film to form a texture on the surface of the film, the film surface area is relatively increased, and the low contact angle is promoted (Wenzel effect).

The thickness of the transparent coating film is preferably 1 to 10 mu m. If the transparent coating film is thinner than 1 占 퐉, hardness and scratch resistance of the transparent coating film may be insufficient. If the transparent coating is thicker than 10 占 퐉, shrinkage of the film becomes large, curling tends to occur, and adhesion with the substrate may become insufficient. In addition, when the shrinkage is very large, cracks may occur. The transparent coating preferably has a thickness of 2 to 10 mu m.

The contact angle of the transparent coating is preferably less than 70 DEG with respect to water. When the contact angle is 70 DEG or more, the hydrophilicity is insufficient and the adhesiveness with the upper layer is lowered in some cases. It is more preferable that the contact angle of the transparent coating film is less than 50 DEG with respect to water.

 The pencil hardness of the transparent coating is preferably 3H or more. At a pencil hardness of less than 3H, the hardness of the hard coat film is insufficient. The transparent hard coat preferably has a pencil hardness of 4H or more.

The transparency film preferably has a curling property of less than 20 mm, more preferably less than 10 mm.

The light transmittance of the transparent film-forming base material is preferably 90.0% or more.

When the light transmittance of the transparent film-forming base material is lower than 90.0%, the sharpness of the image may become insufficient when used in a display device or the like. It is more preferable that the light transmittance of the transparent film-forming base material is 91.5% or more.

Such a transparent film-forming substrate is preferable for applications requiring thinness and light weight for light-weighting of photovoltaic cells, liquid crystal display cells, cellular phones, PCs and the like.

Example

Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

In the examples, silica-alumina fine particles or silica fine particles were used as the metal oxide fine particles.

(Example 1)

&Quot; Preparation of coating liquid (1) &quot;

Methacryloxypropyltrimethoxysilane 6.08 (trade name)) was added to 100 g of a silica alumina sol dispersion (OSCAL 1132, average particle diameter 12 nm, solid content concentration 40.5 mass%, dispersion medium: methanol sol, particle refractive index 1.46, (KBM-503, manufactured by Shin-Etsu Silicone Co., Ltd., 81.2% by mass of SiO ₂ component) were mixed, and 8.80 g of ultrapure water was added, and 0.40 g of 5% ammonia water was added and stirred at 50 캜 for 6 hours. Thus, a surface-treated 12 nm silica alumina sol dispersion was obtained (solid content concentration: 40.4 mass%).

Subsequently, the product was subjected to solvent replacement with propylene glycol monomethyl ether (PGME) using a rotary evaporator to obtain a silica sol PGME dispersion (1) having a solid content of 46.6 mass%. Subsequently, 60.11 g of the silica sol PGME dispersion (1), 12.00 g of an EO-modified acrylate binder (NK Ester A-DPH-18E, manufactured by Shin-Nakamura Chemical Co., Ltd.) Manufactured by Irgacure 184), 13.59 g of PGME and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid (1) for forming a transparent coating film having a solid content concentration of 41.8% by mass. The composition of this coating liquid (1) is shown in Table 1.

&Quot; Measurement of average particle diameter &quot;

The average particle diameter was obtained as an average value of particle diameters measured for any 100 particles by taking an electron microscope photograph.

&Quot; Preparation of transparent film-forming base material (1) &quot;

The coating liquid 1 for forming a transparent film was applied to a TAC film (FT-PB40UL-M manufactured by Fuji Film Co., Ltd., thickness: 40 占 퐉, refractive index: 1.51) by a bar coater method (# 16) For 120 seconds, and then irradiated with ultraviolet rays of 300 mJ / cm &lt; 2 &gt; in an N ₂ atmosphere to be cured to obtain a transparent film-forming base material (1). The thickness of the transparent coating film was 8 占 퐉.

The film thickness, pencil hardness, contact angle, curling property, scratch resistance, haze, total light transmittance, adhesion, and appearance of the transparent film-forming substrate (1) were evaluated by the following methods and evaluation criteria. The evaluation results are shown in Table 2.

&Quot; Measurement of film thickness &

The film thickness was measured by a digital gauge (Gauge Stand ST-0230 manufactured by Ono Sangyo Co., Ltd. and digital gauge counter DG-5100).

"Measurement of pencil hardness"

The pencil hardness was measured by a pencil hardness tester in accordance with JIS-K-5600. The pencil hardness is preferably 3H or more.

&Quot; Measurement of contact angle &quot;

The contact angle was measured by an automatic contact angle meter (DM700, manufactured by Kyowa Interface Science Co., Ltd.). The contact angle to water is preferably less than 70 DEG.

&Quot; Evaluation of curling property &quot;

The coating liquid 1 was applied on a TAC film base material of 14 cm x 25 cm x 40 m (thickness) so as to form a transparent coating film having a thickness of 8 m and left to stand for 20 hours. Thereafter, the film was cut into a size of 10 cm x 10 cm, and the film was placed on a flat plate with the application side down, and the height of the vertex of the floated base material curled (curved) was measured. The curling property was evaluated by the following criteria.

<Evaluation Criteria>

Less than 10 ㎜ : ◎

Less than 10 ~ 20 ㎜ : ○

Less than 20 ~ 30 ㎜ : △

More than 30 ㎜ : ×

"Evaluation of scratch resistance"

# 0000 steel wool at a load of 500 g / cm &lt; 2 &gt; ten times, and the surface of the film was visually observed. The scratch resistance was evaluated by the following criteria.

<Evaluation Criteria>

No scratches on stripes are identified : ◎

There are some scratches on the stripes. : ○

Many scratches on stripes are identified : △

The face is entirely trimmed. : ×

&Quot; Total light transmittance, measurement of haze &quot;

The total light transmittance and haze were measured by a haze meter (NDH-5000 manufactured by Nippon Telegraph Co., Ltd.). The uncoated TAC film had a total light transmittance of 93.0% and a haze of 0.3%. The total light transmittance is preferably 90.0% or more, and the haze is preferably 0.5% or less.

&Quot; Adherence &quot;

Eleven parallel scratches were formed on the surface of the transparent film-forming substrate with a knife at intervals of 1 mm in width and 100 squares, and a cellophane tape was adhered thereto. Subsequently, when the cellophane tape was peeled off, the number of cells remaining without peeling the film was counted. The adhesion was evaluated by classifying into the following four levels.

<Evaluation Criteria>

Number of remaining squares 100 : ◎

Number of remaining cells 90 to 99 : ○

Number of remaining spaces 85 to 89 : △

Number of remaining spaces 84 or less : ×

"Exterior"

The surface of the transparent film-forming base material was visually observed. The appearance was evaluated by the following criteria.

<Evaluation Criteria>

You can not check the appearance of streaks, smudges, cracks, or bleedouts on the surface. : ◎

Almost no appearance of streaks, smudges, cracks, or bleedouts on the surface : ○

Appearance defects of stripes, stains, cracks, and bleed-outs were slightly observed on the surface : △

Appearance defects of stripes, stains, cracks, and bleed-outs were clearly observed on the surface : ×

(Example 2)

&Quot; Preparation of transparent coating film forming coating liquid (2) &quot;

A coating liquid (2) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1 except that the EO-modified acrylate binder was changed to NK Ester A-DPH-24E manufactured by Shin-Nakamura Chemical Co., The composition of the obtained coating liquid (2) is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (2) &quot;

A transparent-film-forming base material (2) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (2) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 3)

&Quot; Preparation of transparent coating film forming coating liquid (3) &quot;

A coating liquid (3) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1 except that the EO-modified acrylate binder was changed to NK Ester A-DPH-12E manufactured by Shin-Nakamura Chemical Co., The composition of the obtained coating liquid (3) is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (3) &quot;

A transparent-film-forming base material (3) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (3) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 4)

&Quot; Preparation of transparent coating film forming coating liquid (4) &quot;

A coating liquid (4) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1 except that the EO-modified acrylate binder was changed to NK Ester ATM-35E manufactured by Shin-Nakamura Chemical Co., The composition of the obtained coating liquid (4) is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (4) &quot;

A transparent-film-forming base material (4) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (4) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 5)

&Quot; Preparation of transparent coating film forming coating liquid (5) &quot;

A coating liquid (5) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1 except that the EO-modified acrylate binder was changed to NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., The composition of the obtained coating liquid (5) is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (5) &quot;

A transparent-film-forming base material (5) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (5) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 6)

&Quot; Preparation of transparent coating film forming coating liquid (6) &quot;

A coating liquid (6) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1 except that the EO-modified acrylate binder was changed to NK Ester A-DPH-16P manufactured by Shin-Nakamura Chemical Co., The composition of the obtained coating liquid (6) is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (6) &quot;

A transparent-film-forming base material (6) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (6) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 7)

&Quot; Preparation of transparent coating film forming coating liquid (7) &quot;

64.41 g of the silica sol PGME dispersion (1) having a solid content concentration of 46.6% by mass obtained in Example 1, 10.00 g of EO-modified acrylate (NK Ester A-DPH-18E manufactured by Shin Nakamura Chemical Co., 1.50 g of an initiator (Irgacure 184, manufactured by Chiba Japan K.K.), 11.59 g of PGME and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid 7 having a solid content concentration of 41.5% by mass. The composition of the obtained coating liquid (7) is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (7) &quot;

A transparent-film-forming base material (7) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (7) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 8)

&Quot; Preparation of transparent coating film forming coating liquid (8) &quot;

42.94 g of the silica sol PGME dispersion (1) having a solid content concentration of 46.6% by mass obtained in Example 1, 20.00 g of EO-modified acrylate (NK Ester A-DPH-18E manufactured by Shin-Nakamura Chemical Co., 3.00 g of an initiator (Irgacure 184 manufactured by Chiba Japan K.K.), 21.56 g of PGME and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid (8) having a solid content concentration of 43.0% by mass. The composition of the obtained coating liquid (8) is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (8) &quot;

A transparent-film-forming base material (8) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (8) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 9)

&Quot; Preparation of transparent coating film forming coating liquid (9) &quot;

25.76 g of the silica sol PGME dispersion (1) having a solid content concentration of 46.6% by mass obtained in Example 1, 28.00 g of EO-modified acrylate (NK Ester A-DPH-18E manufactured by Shin Nakamura Chemical Co., 4.20 g of an initiator (Irgacure 184, manufactured by Chiba Japan K.K.), 29.54 g of PGME and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid (9) having a solid content concentration of 44.2% by mass. The composition of the obtained coating liquid (9) is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (9) &quot;

A transparent film-forming base material (9) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (9) was applied by a bar coater method (# 20). The thickness of the transparent coating film was 10 mu m.

(Example 10)

&Quot; Preparation of transparent coating film forming coating liquid (10) &quot;

Methacryloxypropyltrimethoxysilane 12.15 (trade name, manufactured by Nippon Shokubai Seiyaku Co., Ltd.) (OSCAL 1132, average particle diameter 12 nm, solid content concentration 40.5 mass%, dispersion medium: methanol sol, particle refractive index 1.46) (KBM-503, manufactured by Shin-Etsu Silicone Co., Ltd., 81.2% by mass of SiO ₂ component) were mixed, and 17.60 g of ultrapure water was added, and 0.40 g of 5% ammonia water was added. A 12 nm silica alumina sol dispersion was obtained (solid content concentration 40.5 mass%).

Subsequently, the product was solvent-substituted with propylene glycol monomethyl ether (PGME) by a rotary evaporator to obtain silica sol PGME dispersion (2) having a solid content of 52.7 mass%.

Subsequently, 53.18 g of a silica sol PGME dispersion (2) having a solid content concentration of 52.7% by mass, 12.00 g of an EO-modified acrylate binder (NK Ester A-DPH-18E manufactured by Shin Nakamura Chemical Co., (Irgacure 184, manufactured by Chiba Japan Co., Ltd.), 20.52 g of PGME and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid 10 having a solid content concentration of 41.8% by mass. The composition of the obtained coating liquid 10 is shown in Table 1.

&Quot; Preparation of transparent film-forming substrate 10 &quot;

A transparent-film-forming base material (10) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (10) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 11)

&Quot; Preparation of transparent coating film forming coating liquid (11) &quot;

Methacryloxypropyltrimethoxysilane 1.22 (trade name, manufactured by Nikkiso Catalysts Co., Ltd., OSCAL 1132, average particle diameter 12 nm, solid content concentration 40.5 mass%, dispersion medium: methanol sol, particle refractive index 1.46) g (manufactured by Shin-Etsu silicone Co., Ltd. Preparation: KBM-503, SiO ₂ component 81.2% by weight) and mixed, ultra-pure water to 1.76 g was added, and a 5% aqueous ammonia 0.40 g were added and surface treatment by stirring at 50 ℃ 6 time To obtain a 12 nm silica sol dispersion (solid content concentration: 40.4 mass%).

Subsequently, the solvent was replaced with propylene glycol monomethyl ether (PGME) by a rotary evaporator to obtain a silica sol PGME dispersion (3) having a solid content of 41.7 mass%.

Subsequently, 67.12 g of a silica sol PGME dispersion (3) having a solid content concentration of 41.7% by mass, 12.00 g of an EO-modified acrylate binder (NK Ester A-DPH-18E manufactured by Shin Nakamura Chemical Co., (Irgacure 184, manufactured by Chiba Japan Co., Ltd.), 6.58 g of PGME and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid 11 having a solid content concentration of 41.8% by mass. The composition of the obtained coating liquid 11 is shown in Table 1.

&Quot; Preparation of transparent film-forming substrate 11 &

A transparent-film-forming base material (11) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (11) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 12)

&Quot; Preparation of transparent coating film forming coating liquid (12) &quot;

6.08 g of? -Acryloxypropyltrimethoxysilane was added to 100 g of a silica alumina sol dispersion (OSCAL 1132; average particle diameter 12 nm, solid content concentration 40.5 mass%, dispersion medium: methanol sol, particle refractive index 1.46, (KBM-5103, manufactured by Shin-Etsu Silicone Co., Ltd .; 81.2% by mass of SiO ₂ component) were mixed and added with 8.80 g of ultrapure water, 0.40 g of 5% ammonia water was added and stirred at 50 캜 for 6 hours, Of silica alumina sol dispersion (solid content concentration: 40.4 mass%).

Subsequently, the solvent was replaced with propylene glycol monomethyl ether (PGME) as a rotary evaporator to obtain a silica sol PGME dispersion (4) having a solid content of 46.6 mass%.

Subsequently, 60.11 g of a silica sol PGME dispersion (4) having a solid content concentration of 46.6% by mass, 12.00 g of an EO-modified acrylate binder (NK Ester A-DPH-18E manufactured by Shin-Nakamura Chemical Co., (Irgacure 184, manufactured by Chiba Japan Co., Ltd.), 13.59 g of PGME and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid 12 having a solid content concentration of 46.6% by mass. The composition of the coating liquid 12 thus obtained is shown in Table 1.

&Quot; Preparation of transparent film-forming substrate 12 &quot;

A transparent-film-forming base material (12) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (12) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 13)

&Quot; Preparation of transparent coating film forming coating liquid (13) &quot;

100 g of a silica alumina sol dispersion (manufactured by Nikki Catalysts Co., Ltd., OSCAL 1132; average particle size 12 nm, solid content concentration 40.5 mass%, dispersion medium: methanol sol, particle refractive index 1.46), 2.74 g of tetraethoxysilane ) manufactured by the normal acid ethyl -A, SiO ₂ ingredient 28.80%) was mixed with deionized water to 4.33 g was added, and a 5% aqueous ammonia 0.40 g were added and the mixture was stirred at 50 ℃ 6 sigan surface treatment of the silica-alumina sol and a 12 ㎚ To obtain a dispersion (solid content concentration: 38.4 mass%).

Subsequently, the solvent was replaced with propylene glycol monomethyl ether (PGME) as a rotary evaporator to obtain a silica sol PGME dispersion (5) having a solid content of 41.3 mass%.

Subsequently, 67.78 g of a silica sol PGME dispersion (5) having a solid content concentration of 41.3% by mass, 12.00 g of an EO-modified acrylate binder (NK Ester A-DPH-18E manufactured by Shin Nakamura Chemical Co., (Irgacure 184, manufactured by Chiba Japan Co., Ltd.), 5.92 g of PGME and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid 13 having a solid content concentration of 41.8% by mass. The composition of the coating liquid 13 thus obtained is shown in Table 1.

&Quot; Preparation of Transparent Film-Forming Substrate 13 &

A transparent-film-forming base material (13) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (13) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 14)

&Quot; Preparation of transparent coating film forming coating liquid (14) &quot;

6000 g of ion-exchanged water was added to 1000 g of a silica sol dispersion (SI-30; average particle diameter 12 nm, SiO ₂ concentration 40.5 mass%, manufactured by Nikki Catalysts Co., Ltd.), followed by addition of a cation exchange resin (available from Mitsubishi Chemical Corporation) Manufactured by SK-1BH Co., Ltd.) was added, and the mixture was dealkalized by stirring for 1 hour.

Next, after separating the cation exchange resin, 400 g of an anion exchange resin (SANUPC, manufactured by Mitsubishi Chemical Corporation) was added, and the mixture was stirred for 1 hour to effect deanion treatment. Subsequently, 400 g of a cation exchange resin (SK-1BH, manufactured by Mitsubishi Chemical Corporation) was further added and the mixture was stirred for 1 hour to carry out a dealkalization treatment to prepare a silica particle dispersion (A) having an SiO ₂ concentration of 5 mass%.

This dispersion was subjected to solvent substitution with methanol using an ultrafiltration membrane to obtain a methanol dispersion (A) having a solid content concentration of 40.5% by mass.

6.08 g of? -Methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Silicone Co., Ltd., 81.2 mass% of SiO ₂ component) was mixed with 100 g of the silica-methanol dispersion (A) , 0.40 g of 5% ammonia water was added, and the mixture was stirred at 50 캜 for 6 hours to obtain a 12 nm silica sol dispersion (solid content concentration: 40.5 mass%).

Subsequently, the product was solvent-substituted with propylene glycol monomethyl ether (PGME) by a rotary evaporator to obtain a silica sol PGME dispersion (6) having a solid content of 46.6 mass%.

A coating liquid (14) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1 except that the silica alumina sol was changed to the silica sol PGME dispersion (6). The composition of the coating liquid 14 thus obtained is shown in Table 1.

&Quot; Preparation of transparent film forming base material 14 &quot;

A transparent-film-forming base material (14) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (14) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 15)

&Quot; Preparation of transparent coating film forming coating liquid (15) &quot;

6000 g of ion-exchanged water was added to 1000 g of a silica sol dispersion (SI-80P; average particle diameter 80 nm, SiO ₂ concentration 40.5 mass%) manufactured by Nikki Catalysts Co., Ltd. Then, a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) Manufactured by SK-1BH Co., Ltd.) was added, and the mixture was dealkalized by stirring for 1 hour.

Next, after separating the cation exchange resin, 400 g of an anion exchange resin (SANUPC, manufactured by Mitsubishi Chemical Corporation) was added, and the mixture was stirred for 1 hour to effect deanion treatment. Subsequently, 400 g of a cation exchange resin (SK-1BH, manufactured by Mitsubishi Chemical Corporation) was further added and the mixture was stirred and agitated for 1 hour to prepare a silica particle dispersion (B) having an SiO ₂ concentration of 5% by mass.

This dispersion was subjected to solvent substitution with methanol using an ultrafiltration membrane to obtain a methanol dispersion (B) having a solid content concentration of 40.5% by mass.

A surface-treated metal oxide fine particle resin PGME dispersion (7) comprising silica having a solid concentration of 46.6% by mass was prepared in the same manner as in Example 1 except that 100 g of the silica methanol dispersion (B) was used.

A coating liquid (15) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1 except that the silica alumina sol was changed to the silica sol PGME dispersion (7). The composition of the obtained coating liquid 15 is shown in Table 1.

&Quot; Preparation of transparent film forming substrate (15) &quot;

A transparent film-forming base material (15) was prepared and evaluated in the same manner as in Example 1, except that the coating liquid (15) for forming a transparent film was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 16)

&Quot; Preparation of transparent coating film forming coating liquid (16) &quot;

Methacryloxypropyltrimethoxysilane 6.08 (trade name)) was added to 100 g of a silica alumina sol dispersion (OSCAL 1132, average particle diameter 12 nm, solid content concentration 40.5 mass%, dispersion medium: methanol sol, particle refractive index 1.46, g (manufactured by Shin-Etsu silicone Co., Ltd. Preparation: KBM-503, SiO ₂ component 81.2% by mass) were mixed by adding 8.80 g of ultrapure water, added 0.40 g of 5% ammonia water, and the surface treatment by stirring at 50 ℃ 6 hours 12 Nm silica sol alumina sol dispersion (solid content concentration: 40.4 mass%).

Subsequently, the solvent was replaced with propylene glycol monomethyl ether (PGME) as a rotary evaporator to obtain a silica alumina sol PGME dispersion (8) having a solid content of 60.0 mass%.

Subsequently, 64.17 g of a silica alumina sol PGME dispersion (8) having a solid content concentration of 60.0% by mass and 16.50 g of an EO-modified acrylate binder (NK Ester A-DPH-18E manufactured by Shin Nakamura Chemical Co., (Irgacure 184, manufactured by Chiba Japan Co., Ltd.), 4.36 g of PGME and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid 16 having a solid content concentration of 57.5% by mass. Table 1 shows the composition of the coating liquid 16 obtained.

&Quot; Preparation of transparent film-forming substrate 16 &quot;

A transparent-film-forming base material 16 was prepared and evaluated in the same manner as in Example 1 except that the coating liquid 16 was applied by a bar coater method (# 12). The thickness of the transparent coating film was 8 占 퐉.

(Example 17)

&Quot; Preparation of transparent coating film forming coating liquid (17) &quot;

30.06 g of a silica sol PGME dispersion (1) having a solid content concentration of 46.6% by mass prepared in Example 1 and 6.00 g of an EO-modified acrylate binder (NK Ester A-DPH-18E manufactured by Shin Nakamura Chemical Co., 0.90 g of a polymerization initiator (Irgacure 184, manufactured by Chiba Japan K.K.), 50.54 g of PGME and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid 17 having a solid content concentration of 20.9% by mass. The composition of the coating liquid (17) thus obtained is shown in Table 1.

&Quot; Preparation of Transparent Film-Forming Substrate 17 &

A transparent-film-forming base material 17 was prepared and evaluated in the same manner as in Example 1 except that the coating liquid 17 was applied by a bar coater method (# 32). The thickness of the transparent coating film was 8 占 퐉.

(Example 18)

&Quot; Preparation of transparent coating film forming coating liquid (18) &quot;

Except that 0.001 g of an acrylic silicone leveling agent (UVX-3750, solid content 50.0%, manufactured by Kusumoto Chemical Co., Ltd.) was added and mixed to prepare a coating liquid 18 having a solid content concentration of 41.8 mass% Lt; / RTI &gt; The composition of the coating liquid 18 obtained is shown in Table 1.

&Quot; Preparation of transparent film forming substrate 18 &quot;

A transparent-film-forming base material (18) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (18) was used. The thickness of the transparent coating film was 8 占 퐉.

(Example 19)

&Quot; Preparation of transparent film forming base material (19) &quot;

A coating liquid 1 was applied in the same manner as in Example 1 except that the substrate was changed to a 50 탆 PET film (Cosmo Shine A4300, manufactured by TOYOBO CO., LTD.) To prepare a transparent film forming base material 19, Respectively. The thickness of the transparent coating film was 8 占 퐉.

(Comparative Example 1)

&Quot; Preparation of transparent coating film forming coating liquid (R1) &quot;

, 16.5 g of a silica sol PGME dispersion (1) having a solid content concentration of 46.6 mass%, 16.00 g of dipentaerythritol hexaacrylate (Light Acrylate DPE-6A, manufactured by Kyowa Chemical Industry Co., Ltd.) (Irgacure 184, manufactured by Japan KK), 17.58 g of PGME and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid (R1) having a solid content concentration of 42.4% by mass. The composition of the obtained coating liquid (R1) is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (R1) &quot;

A transparent film-forming substrate (R1) was produced and evaluated in the same manner as in Example 1 except that the coating liquid (R1) was used. The thickness of the transparent coating film was 8 占 퐉.

(Comparative Example 2)

&Quot; Preparation of transparent coating film forming coating liquid (R2) &quot;

(NK Oligo UA-33H manufactured by Shin-Nakamura Chemical Co., Ltd., functional group: urethane acrylate, number of functional groups: 9, molecular weight: 4,000, solid content concentration: 100%) was changed to urethane acrylate , A coating liquid (R2) having a solid content concentration of 42.4% by mass was prepared in the same manner as in Comparative Example 1. The composition of the obtained coating liquid (R2) is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (R2) &quot;

A transparent film-forming substrate (R2) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (R2) was used. The thickness of the transparent coating film was 8 占 퐉.

(Comparative Example 3)

&Quot; Preparation of transparent coating film forming coating liquid (R3) &quot;

A coating liquid (R3) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1 except that the EO-modified acrylate binder was changed to NK Ester A-DPH-48E manufactured by Shin Nakamura Chemical Co., The composition of the coating liquid (R3) thus obtained is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (R3) &quot;

A transparent film-forming substrate (R3) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (R3) was used. The thickness of the transparent coating film was 8 占 퐉.

(Comparative Example 4)

&Quot; Preparation of transparent coating film forming coating liquid (R4) &quot;

A coating liquid (R4) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1 except that the EO-modified acrylate binder was changed to NK Ester A-1000 manufactured by Shin-Nakamura Chemical Co., The composition of the obtained coating liquid (R4) is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (R4) &quot;

A transparent film-forming substrate (R4) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (R4) was used. The thickness of the transparent coating film was 8 占 퐉.

(Comparative Example 5)

&Quot; Preparation of transparent coating film forming coating liquid (R5) &quot;

40.00 g of an EO-modified acrylate binder (NK Ester A-DPH-18E, manufactured by Shin-Nakamura Chemical Co., Ltd.) and 6.00 g of a photopolymerization initiator (Irgacure 184 manufactured by Chiba Japan K.K.) And 12.50 g of acetone were thoroughly mixed to prepare a coating liquid (R5) having a solid content concentration of 46.0% by mass. The composition of the coating liquid (R5) obtained is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (R5) &quot;

A transparent film-forming substrate (R5) was prepared and evaluated in the same manner as in Example 1 except that the coating liquid (R5) was used. The thickness of the transparent coating film was 8 占 퐉.

Compared with the transparent film-forming base material 1 of Example 1 in which the surface-treated metal oxide particles were contained, the transparent film-forming base material 1 had higher pencil hardness, scratch resistance, total light transmittance and adhesiveness, And the appearance was good.

(Comparative Example 6)

&Quot; Preparation of transparent coating film forming coating liquid (R6) &quot;

59.26 g of a silica alumina sol dispersion (OSCAL 1132, average particle diameter 12 nm, solid content concentration 40.5 mass%, dispersion medium: methanol sol, particle refractive index 1.46, manufactured by Nikki Catalysts Co., Ltd.) and an EO-modified acrylate binder (Shin Nakamura Chemical Industries 16.00 g of NK Ester A-DPH-18E) and 2.40 g of a photopolymerization initiator (Irgacure 184 manufactured by Chiba Japan K.K.), 9.84 g of PGME and 12.50 g of acetone were sufficiently mixed to obtain a solid content concentration of 42.4 mass% % Of a coating liquid (R6). The composition of the obtained coating liquid (R6) is shown in Table 1.

&Quot; Preparation of transparent film-forming base material (R6) &quot;

(R6) was prepared and evaluated in the same manner as in Example 1, except that the coating liquid (R6) was used. The thickness of the transparent coating film was 8 占 퐉.

Claims (5)

An alkylene oxide-modified (meth) acrylate resin,
A surface-treated metal oxide particle having an organosilicon compound formed on the surface of the metal oxide particle and having an average particle diameter of 5 to 500 nm,
An organic solvent,
The alkylene oxide-modified (meth) acrylate resin is a polyfunctional acrylate monomer resin having a (meth) acrylate functional group number of 3 to 10 and an alkylene oxide group number of 3 to 40,
Wherein the organosilicon compound is at least one selected from the group consisting of R _n -SiO _{(4-n) / 2} (wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, N is an integer of 1 to 3) and is contained in the surface-treated metal oxide particle,
Treated metal oxide particles are contained in an amount of 30 to 90% by mass based on the total amount of the solid components of the alkylene oxide-modified (meth) acrylate resin and the surface-treated metal oxide particles. The method according to claim 1,
Wherein the alkylene oxide-modified (meth) acrylate resin is an ethylene oxide-modified (meth) acrylate resin. 1. A transparent film-forming substrate having a transparent film formed on a substrate,
The transparent coating film contains an alkylene oxide-modified (meth) acrylate resin and a surface-treated metal oxide particle having an organosilicon compound formed on the surface of the metal oxide particle,
The surface-treated metal oxide particles have an average particle diameter of 5 to 500 nm and are contained in an amount of 30 to 90 mass% with respect to the total amount of the solid components of the alkylene oxide-modified (meth) acrylate resin and the surface- To form a transparent film-forming substrate. The method of claim 3,
Wherein the transparent coating film has a contact angle with water of less than 70 ° and a pencil hardness of 3H or more. The method according to claim 3 or 4,
Wherein the contact angle of the transparent coating film is lower than the contact angle of the transparent coating film not containing the surface treated oxide particles.