JP5596920B2 - Paint for forming transparent film and substrate with transparent film - Google Patents

Description

  The present invention provides a coating material and a transparent film for forming a transparent film excellent in mechanical strength, adhesion, transparency, haze, and the like, with excellent balance of water repellency, water resistance, fingerprint resistance, chemical resistance, etc. The present invention relates to an attached substrate.

  It is known to form a transparent film having a hard coat function on the surface of a substrate in order to improve the scratch resistance of a substrate surface such as glass, a plastic sheet, or a plastic lens, or a display device. Specifically, an organic resin film or an inorganic film having transparency is formed on the surface of glass, plastic, a display device substrate or the like. At this time, inorganic particles such as resin particles or silica are blended in the organic resin film or inorganic film to further improve the adhesion to the substrate, scratch resistance, and the like.

  However, the transparent film is required to have chemical resistance, water resistance, water repellency, fingerprint resistance and the like in addition to transparency, adhesion to a substrate, film strength, scratch resistance and the like. For example, when water droplets adhere, there are no traces of water droplets (water resistance), water pens, oil pens, etc. are difficult to scribble, and even if scribbled, they can be easily wiped off (water resistance, water repellency, water repellency) Furthermore, there is a demand for fingerprints that are difficult to adhere to even when touched by a finger, and that they can be easily wiped off (fingerprint resistance).

Conventionally, in order to impart water repellency, oil repellency, water resistance, fingerprint resistance, and the like, a resin having a hydrophobic group, a fluorine-containing resin, or the like has been used for the transparent film. (Patent Document 1: Japanese Patent Laid-Open No. 10-40834)
Japanese Patent Laid-Open No. 10-40834

However, although the oil repellency and fingerprint resistance can be improved to some extent, the adhesion to the substrate and the film strength may be insufficient, or the water repellency may be insufficient.
In addition, even if a resin having a hydrophobic group and a fluorine-containing resin are used in combination, these resins are detached from the transparent film (referred to as bleed-out) and have sufficient chemical resistance, water resistance, In some cases, water repellency, oil repellency, fingerprint resistance, etc. cannot be obtained, and even if obtained, performance may deteriorate over time.

  As a result of intensive studies in view of such problems, the present inventors have an organic resin having a trifunctional or higher functional group as a main component, and a bifunctional organic resin and a monofunctional silicone resin are mixed in a specific ratio. It has been found that it can form a transparent film with excellent chemical resistance, water resistance, water repellency, oil repellency, fingerprint resistance, and reduction of the bleed-out and excellent balance of these characteristics. The present invention has been completed.

The configuration of the present invention is as follows.
[1] (1) an organic resin having a trifunctional or higher functional group;
(2) a bifunctional organic resin and / or a bifunctional silicon resin;
(3) A matrix-forming component consisting of a monofunctional silicone resin and a solvent,
The content of the organic resin having a trifunctional or higher functional group in the obtained transparent film is in the range of 10 to 98% by mass as a solid content, and (2) a bifunctional organic resin and / or a bifunctional silicon. The resin content is in the range of 0.2 to 10% by mass as the solid content, and (3) the monofunctional silicon resin content is in the range of 0.02 to 5% by mass as the solid content. A paint for forming a transparent film.
[2] (2) The bifunctional organic resin and / or the bifunctional silicone resin is a monomer,
(3) The coating material for forming a transparent film according to [1], wherein the monofunctional silicone resin is acrylic modified polysiloxane, methacrylic modified polysiloxane, glycidyl modified polysiloxane, polyester modified polysiloxane, polyether modified polysiloxane, or a mixture thereof.
[3] the and (3) the weight of the monofunctional silicone resin (W _3), wherein (2) the weight of the bifunctional organic resins and / or bifunctional silicone resin (W ₂₎ the weight ratio of (W ₃₎ / ( The paint for forming a transparent film according to [1] or [2], wherein W ₂ ) is in the range of 0.05 to 1.
[4] The transparent film according to [1] to [3], further comprising metal oxide fine particles having an average particle diameter in the range of 5 to 300 nm in the range of 10 to 80% by mass as a solid content in the obtained transparent film. Forming paint.
[5] The paint for forming a transparent film according to [1] to [4], wherein the total solid concentration is in the range of 5 to 50% by mass.
[6] consisting of a base material and a transparent film formed on the base material,
The transparent film comprises (1) an organic resin having a trifunctional or higher functional group, (2) a bifunctional organic resin and / or a bifunctional silicon resin, and (3) a matrix component composed of a monofunctional silicon resin. In the transparent coating, (1) the content of the organic resin having a trifunctional or higher functional group is in the range of 10 to 98% by mass as the solid content, and (2) the bifunctional organic resin and / or the bifunctional silicon resin A base material with a transparent coating in which the content is in the range of 0.2 to 10% by mass as the solid content, and (3) the content of the monofunctional silicon resin is in the range of 0.02 to 5% by mass as the solid content.
[7] The substrate with a transparent coating according to [6], wherein the transparent coating further contains metal oxide fine particles having an average particle diameter in the range of 5 to 300 nm in a range of 10 to 80% by mass as a solid content.

  In the present invention, a transparent film that is excellent in adhesion to a substrate, scratch resistance, film strength, transparency, etc. and can maintain excellent chemical resistance, water resistance, water repellency, and fingerprint resistance over a long period of time. A coating for forming a transparent film and a substrate with a transparent film can be provided.

Hereinafter, first, the coating material for forming a transparent film according to the present invention will be described.
[Paint for forming transparent film]
The paint for forming a transparent film according to the present invention includes (1) an organic resin having a functional group of three or more functional groups, (2) a bifunctional organic resin and / or a bifunctional silicon resin, and (3) a monofunctional silicon resin. (1) The content of the organic resin having a trifunctional or higher functional group in the obtained transparent film is in the range of 10 to 98% by mass as a solid content, and (2) The content of the bifunctional organic resin and / or the bifunctional silicon resin is in the range of 0.2 to 10% by mass as the solid content, and (3) the content of the monofunctional silicon resin is 0.02 to 5 mass as the solid content. It is characterized by containing so that it may become the range of%.

Matrix-forming component In the matrix-forming component used in the present invention, (1) an organic resin having a trifunctional or higher functional group is used as a main component.

(1) Organic resin having a trifunctional or higher functional group Examples of the functional group include a (meth) acrylic group and an epoxy group. An acrylic resin (acrylate resin) is used as the organic resin.

Specifically, as an organic resin having a trifunctional or higher functional group, a trifunctional acrylate resin such as pentaerythritol triacrylate, trimethylolpropane triacrylate, or trimethylolpropane trimethacrylate, or a tetrafunctional acrylate such as pentaerythritol tetraacrylate. Resin, hexafunctional acrylate resin such as dipentaerythritol hexaacrylate, trifunctional urethane acrylate resin such as pentaerythritol hexamethylene diisocyanate urethane prepolymer, tetrafunctional acrylate resin containing epoxy group such as pentaerythritol polyglycidyl ether acrylate, cresol novolac Type epoxy acrylate, bisphenol A diglycidyl ether acrylic acid adduct, etc. Fat, and the like, it can also be used a mixture thereof suitably.

As the organic resin having a trifunctional or higher functional group, a monomer can be used, but a dimer or higher oligomer or polymer can also be used.
(2) Examples of the functional group constituting the bifunctional organic resin and / or the bifunctional silicon resin and the bifunctional organic resin include a (meth) acryl group and an epoxy group. Moreover, acrylic resin (acrylate resin) is mentioned as resin. Thus, as the bifunctional organic resin, polyethylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, tripropylene glycol dimethacrylate And glycol-based acrylates such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and polypropylene glycol dimethacrylate. Further, 1.4-butanediol dimethacrylate, 1.6-hexanediol dimethacrylate, 1.9-nonanediol dimethacrylate, 1.10-decanediol dimethacrylate, glycerin dimethacrylate, 2hydroxy-3- Non-glycol acrylates such as acryloyloxypropyl methacrylate, 1.6-hexanediol diacrylate, 1.9-nonanediol diacrylate, dimethylol-tricyclodecane diacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate These mixtures can also be used suitably.

  As the bifunctional silicone resin, one represented by the following formula (1) is used.

（但し、Ｒ₁〜Ｒ₅は置換、非置換の炭素数１〜６のアルキル基、Ｘ₁、Ｘ₂はアクリル基、メタクリル基、グリシジル基、を表し、同じであってもよく、異なっていてもよい。ｎは１〜１０の正数）
具体的には、ジアクリレート変性ポリシロキサン、ジメタクリル変性ポリシロキサン、ジグリシジル変性ポリシロキサン、ジポリエステル変性ポリシロキサン、ジポリエーテル変性ポリシロキサンなど、およびこれらの混合物が挙げられる。

(However, R _{1 to} R ₅ represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X ₁ and X ₂ represent an acryl group, a methacryl group, and a glycidyl group, and may be the same or different. N is a positive number from 1 to 10)
Specific examples include diacrylate-modified polysiloxane, dimethacryl-modified polysiloxane, diglycidyl-modified polysiloxane, dipolyester-modified polysiloxane, dipolyether-modified polysiloxane, and the like.

At this time, it is preferable to use a monomer for the bifunctional organic resin and the bifunctional silicone resin.
The use of a monomer promotes bonding between the organic resin having a trifunctional or higher functional group and a monofunctional silicon resin described later, and is excellent in water repellency, oil repellency, fingerprint resistance, chemical resistance, etc. Desorption of monofunctional silicon resin (hereinafter sometimes referred to as bleed-out) can be suppressed, and water repellency, oil repellency, fingerprint adhesion resistance, and chemical resistance can be maintained for a long time.

(3) Monofunctional silicone resin As the monofunctional silicone resin, one represented by the following formula (2) is used.

（但し、Ｒ₁〜Ｒ₅は置換、非置換の炭素数１〜３のアルキル基、Ｘはアクリル基、メタクリル基、グリシジル基、を表す。ｎは１〜２０の整数））
具体的には、アクリル変性ポリシロキサン、メタクリル変性ポリシロキサン、グリシジル変性ポリシロキサン、ポリエステル変性ポリシロキサン、ポリエーテル変性ポリシロキサンなどおよびこれらの混合物が挙げられる。たとえば、片末端(メタ)アクリルシリコンオイル、片末端グリシジルシリコンオイルなどがあげられる。またアクリル系シリコン樹脂モノマーまたはそのポリマー（シリコンオイル）、エポキシ系シリコン樹脂モノマーまたはそのポリマー（シリコンオイル）、ポリエステル系シリコン樹脂モノマーまたはそのポリマー（シリコンオイル）も好適である。

(However, R _{1 to} R ₅ are substituted or unsubstituted alkyl groups having 1 to 3 carbon atoms, X represents an acrylic group, a methacryl group, or a glycidyl group. N is an integer of 1 to 20))
Specific examples include acrylic-modified polysiloxane, methacryl-modified polysiloxane, glycidyl-modified polysiloxane, polyester-modified polysiloxane, polyether-modified polysiloxane, and mixtures thereof. For example, one end (meth) acrylic silicone oil, one end glycidyl silicone oil, and the like can be mentioned. Also suitable are acrylic silicone resin monomers or polymers thereof (silicon oil), epoxy silicone resin monomers or polymers thereof (silicon oil), polyester silicone resin monomers or polymers thereof (silicon oil).

(1) The concentration of the organic resin having a trifunctional or higher functional group in the coating composition for forming a transparent coating is such that the content of the organic resin having a functional group of (1) the trifunctional or higher in the obtained transparent coating is solid. It is preferable that the content is in the range of 10 to 98% by mass, more preferably 30 to 95% by mass.

  (1) If the amount of the organic resin having a trifunctional or higher functional group is small, the adhesion, strength, scratch resistance, and the like of the resulting transparent coating with the substrate may be insufficient. (1) If the amount of the organic resin having a trifunctional or higher functional group is too large, the amount of the matrix-forming component (2) and / or (3) is small, so that sufficient water repellency, oil repellency, fingerprint resistance, etc. May not be obtained.

  The concentration of the (2) bifunctional organic resin and / or bifunctional silicone resin in the coating for forming a transparent coating is such that the content of the bifunctional organic resin and / or the bifunctional silicone resin in the obtained transparent coating is 0 as a solid content. It is preferable to be in the range of 2 to 10% by mass, more preferably 0.5 to 8% by mass.

  If the amount of the bifunctional organic resin and / or the bifunctional silicone resin is small, (3) the bond with the monofunctional silicone resin becomes insufficient and the water repellency, oil repellency, fingerprint resistance, chemical resistance, etc. are insufficient. In addition, detachment of monofunctional silicon resin (sometimes referred to as bleed-out) occurs, and water repellency, oil repellency, fingerprint resistance, chemical resistance, etc. may deteriorate over time. . If the amount of the bifunctional organic resin and / or the bifunctional silicone resin is too large, (3) the bond with the monofunctional silicone resin does not increase, and therefore water repellency, oil repellency, fingerprint resistance, chemical resistance However, the detachment (bleed out) of the monofunctional silicon resin is not suppressed, but the adhesion to the base material, the film strength, etc. may be insufficient.

The concentration of (3) monofunctional silicon resin in the coating for forming a transparent film is such that the content of the monofunctional silicon resin in the obtained transparent film is 0.01 to 5% by mass, further 0.1 to 3 in terms of solid content. It is preferable to be in the range of mass%. If the amount of monofunctional silicon resin is small, the water repellency, oil repellency, fingerprint resistance, chemical resistance, etc. may be insufficient, although it varies depending on the film thickness of the transparent coating. Even if the content of the monofunctional silicone resin is too large, the water repellency, oil repellency, fingerprint resistance, chemical resistance, etc. will not be further improved. May be sufficient.

And (3) the 1 weight functional silicone resin and (W ₃₎ (2) difunctional weight of the organic resin and / or bifunctional silicone resin (W ₂₎ the weight ratio of (W ₃₎ / (W ₂₎ Is 0.05-1
Furthermore, it is preferable that it exists in the range of 0.1-0.5.

When the weight ratio (W ₃ ) / (W ₂ ) is too small, water repellency, oil repellency, chemical resistance, fingerprint resistance, and the like may be insufficient. Even if the weight ratio (W ₃ ) / (W ₂ ) is too large, the water resistance, oil repellency, chemical resistance, fingerprint resistance and the like are not improved, and the monofunctional silicone resin is detached. Water repellency, oil repellency, fingerprint resistance, chemical resistance, etc. may deteriorate over time.

Metal Oxide Fine Particles Conventionally known metal oxide fine particles can be blended and used in the transparent film-forming paint of the present invention. The metal oxide fine particles are added for further imparting adhesion and strength to the transparent film, and further imparting antistatic performance and the like.

  Examples of the metal oxide fine particles include silica, alumina, titania, silica / alumina, silica / zirconia, etc., tin oxide, tin oxide doped with Sb or P, oxide oxidized with indium oxide, Sn or F. Conductive metal oxide fine particles such as indium, antimony oxide and low-order titanium oxide can also be suitably used.

The metal oxide fine particles can also be used after being subjected to a treatment for improving dispersibility such as a silane coupling agent treatment by a conventionally known method.
The metal oxide fine particles preferably have an average particle diameter in the range of 5 to 300 nm, more preferably 10 to 200 nm. If the metal oxide fine particles are too small, the particles are likely to aggregate in the coating for forming a transparent film, the adhesion of the resulting transparent film to the substrate, the film strength, etc. are insufficient, In such a case, the grain boundary resistance increases, so that the antistatic performance of the obtained transparent film may be insufficient. If the metal oxide fine particles are too large, the transparency of the resulting transparent film may be lowered or haze may be increased. In the case of conductive metal oxide fine particles, it is difficult to form a conductive path in the transparent film, and the antistatic performance may be insufficient.

  When the metal oxide fine particles are included, the concentration of the metal oxide fine particles in the coating for forming a transparent film is such that the content of the metal oxide fine particles in the obtained transparent film is 10 to 80% by mass as a solid content, It is preferable to be in the range of 20 to 60% by mass.

If the amount of the metal oxide fine particles in the resulting transparent film is excessively large, the matrix component is small, and the adhesion to the substrate, film strength, and scratch resistance may be insufficient.
The total solid content concentration of the coating for forming a transparent film is preferably in the range of 5 to 50% by mass, more preferably 10 to 45% by mass. If the total solid content concentration of the coating material for forming a transparent film is small, it may be difficult to obtain a transparent film having a desired film thickness by a single application. The hardness and scratch resistance of the coating become insufficient, the haze or the appearance deteriorates, and the productivity, production reliability, etc. are lowered. If the total solid concentration of the coating material for forming a transparent film is too high, the viscosity of the coating material will increase, the coating property will decrease, the haze of the resulting transparent film will increase, the surface roughness will increase, and the scratch resistance will be increased. It may be insufficient.

Polymerization initiator In the present invention, a polymerization initiator may be contained together with the matrix-forming component and, if necessary, the metal oxide fine particles. As the polymerization initiator, known ones can be used without particular limitation. For example, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2, 4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-methyl-2-methyl-phenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy- Examples include cyclohexyl-phenyl-ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one. The amount of the polymerization initiator used is desirably 2 to 15 mol, more preferably 4 to 10 mol, based on the weight of the organic resin.

Solvent As the solvent used in the present invention, a conventionally known solvent capable of dissolving or dispersing the matrix forming component and the polymerization initiator and uniformly dispersing the metal oxide fine particles can be used.

  Specifically, water; alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol; methyl acetate, ethyl acetate, isopropyl acetate, and propyl acetate , Esters such as isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol monoacetate, glycols such as ethylene glycol and hexylene glycol; diethyl ether, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol Hydrophilic solvents including ethers such as rumonomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether and purpylene glycol ethyl ether, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate Esters such as 2-ethylbutyl acetate, cyclohexyl acetate, and ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, and diisobutyl ketone; Examples include polar solvents such as toluene. These may be used singly or in combination of two or more.

The transparent film-forming method using such a transparent film-forming coating is a known method such as dipping, spraying, spinner, roll coating, bar coating, gravure printing, or micro gravure printing. A transparent coating film can be formed by applying to a substrate, drying, and curing by an ordinary method such as ultraviolet irradiation or heat treatment.
The film thickness of the transparent coating of the obtained substrate with a transparent coating is preferably in the range of 30 nm to 20 μm.

[Base material with transparent coating]
The substrate with a transparent coating according to the present invention comprises a substrate and a transparent coating formed on the substrate. The transparent coating comprises (1) an organic resin having a trifunctional or higher functional group, (2) a bifunctional organic resin and / or a bifunctional silicon resin, and (3) a matrix component comprising a monofunctional silicon resin. And (1) the content of the organic resin having a trifunctional or higher functional group in the transparent film is in the range of 10 to 98% by mass as the solid content, and (2) the bifunctional organic resin and / or the bifunctional silicon resin. The content of is in the range of 0.2 to 10% by mass as the solid content, and (3) the content of the monofunctional silicone resin is in the range of 0.02 to 5% by mass as the solid content.

Substrate As the substrate used in the present invention, a known substrate can be used without particular limitation, and glass, polycarbonate, acrylic resin, plastic sheet such as PET, TAC, plastic film, etc. Panel etc. Among these, a resin-based substrate can be preferably used.

The transparent film The transparent film comprises (1) an organic resin having a trifunctional or higher functional group, (2) a bifunctional organic resin and / or a bifunctional silicon resin, and (3) a matrix component composed of a monofunctional silicon resin. It has become.

  As the organic resin having a functional group of 3 or more functional groups, the bifunctional organic resin and / or the bifunctional silicone resin and the monofunctional silicone resin, the same resins as described above are used, but these resins are polymerized in the transparent film. It is cured.

It is preferable that the content of the organic resin having a functional group of (1) trifunctional or higher in the transparent film is in the range of 10 to 98% by mass, more preferably 30 to 95% by mass as the solid content.
If the content of the organic resin having a functional group of (1) trifunctional or higher in the transparent film is small, the adhesiveness, strength, scratch resistance, etc. of the transparent film obtained may be insufficient. . Moreover, even if the content of the organic resin having a functional group of (1) trifunctional or higher in the transparent film is too large, the water repellent sufficient to reduce the matrix component (2) and / or (3) described later. In some cases, oil repellency, fingerprint resistance and the like cannot be obtained.

The content of (2) bifunctional organic resin and / or bifunctional silicon resin in the transparent coating is preferably in the range of 0.2 to 10% by mass, more preferably 0.5 to 8% by mass as the solid content. If the content of (2) bifunctional organic resin and / or bifunctional silicon resin in the transparent coating is low,
(3) Bonding with monofunctional silicone resin, which will be described later, is insufficient, and water repellency, oil repellency, fingerprint resistance, chemical resistance, etc. may be insufficient. (Sometimes referred to as bleed-out), water repellency, oil repellency, fingerprint resistance, chemical resistance, etc. may decrease over time. Even if the content of (2) bifunctional organic resin and / or bifunctional silicone resin in the transparent film is too large, (3) the bond with monofunctional silicone resin does not increase. Oiliness, fingerprint resistance, chemical resistance and the like are not improved, and detachment (bleed out) of the monofunctional silicone resin is not suppressed. Furthermore, the adhesion to the substrate, the film strength, etc. may be insufficient.

The content of (3) monofunctional silicon resin in the transparent coating is preferably in the range of 0.01 to 5% by mass, more preferably 0.1 to 3% by mass as the solid content. If the content of (3) monofunctional silicone resin in the transparent coating is small, the water repellency, oil repellency, fingerprint adhesion, chemical resistance, etc. may be insufficient, depending on the film thickness of the transparent coating. is there. Even if there is too much content of (3) monofunctional silicone resin in the transparent coating, the water repellency, oil repellency, fingerprint resistance, chemical resistance, etc. will not be further improved. The film strength may be insufficient.

And (3) the 1 weight functional silicone resin and (W ₃₎ (2) difunctional weight of the organic resin and / or bifunctional silicone resin (W ₂₎ the weight ratio of (W ₃₎ / (W ₂₎ Is 0.05-1
Furthermore, it is preferable that it exists in the range of 0.1-0.5.

When the weight ratio (W ₃ ) / (W ₂ ) is small, water repellency, oil repellency, chemical resistance, fingerprint resistance, and the like may be insufficient.
Even if the weight ratio (W ₃ ) / (W ₂ ) is larger than the above range, the water resistance, oil repellency, chemical resistance, fingerprint resistance and the like are not improved, and the monofunctional silicone resin May occur and the water repellency, oil repellency, fingerprint resistance, chemical resistance, and the like may deteriorate over time.

The metal oxide fine particle transparent film may contain metal oxide fine particles as required, and specifically, as described above. The content of the metal oxide fine particles in the transparent film is preferably in the range of 10 to 80% by mass, more preferably 20 to 60% by mass as the solid content.

The film thickness of the transparent coating is preferably in the range of 0.3 to 20 μm, more preferably 0.5 to 10 μm. If the film thickness of the transparent coating is thin, sufficient scratch resistance may not be obtained. Even if the film thickness of the transparent coating is too thick, curling may occur due to the shrinkage of the film, or the adhesion to the substrate may be insufficient.

Such a transparent film is formed by the above-described method using the above-described transparent film-forming coating material.
As described above, in the present invention, by using a specific amount of three kinds of resins having different functional groups as the matrix component and having different functional groups such as reactivity, oil repellency and water repellency, Forms a transparent film capable of maintaining excellent chemical resistance, water resistance, water repellency, oil repellency, and fingerprint resistance over a long period of time, as well as excellent adhesion to materials, scratch resistance, film strength, transparency, etc. Therefore, it is possible to provide a coating material for forming a transparent film and a substrate with a transparent film.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.

[Example 1]
Preparation of Transparent Film Forming Paint (1 ) 25.5 g of tetrafunctional acrylate resin pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-4A) as trifunctional or higher organic resin and silicon as bifunctional silicone resin 0.3 g of diacrylate (manufactured by Daicel Cytec Co., Ltd .: EBECRYL350), 1.5 g of 1,6-hesandiol diacrylate (manufactured by Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) as a bifunctional organic resin, 0.4 g of mono-terminal methacrylic silicone oil (Shin-Etsu Chemical Co., Ltd .: X-22-174DX) as monofunctional silicone resin, 39.6 g of isopropyl alcohol, 15 g of isopropyl glycol, 10 g of butyl cellosolve, and photopolymerization initiator 2.4 .6-Trimethylbenzoyldiphenylphosphine oxy A transparent coating film forming liquid (1) was prepared by mixing 2.2 g of side (manufactured by BIAS JAPAN KK: Lucillin TPO).

Production of substrate with transparent coating (F-1) Coating solution (1) for forming a transparent coating was applied to an easily adhesive PET film (Toyobo: Cosmo Shine A-4).
300, thickness 188 μm, total light transmittance 92.0%, haze 0.7%) by bar coater method (bar # 12), dried at 80 ° C. for 1 minute, and then high pressure mercury lamp (120 W / cm) Was cured by irradiation with 600 mJ / cm ² using an ultraviolet irradiation device (manufactured by Nippon Batteries: UV irradiation device CS30L21-3), to prepare a substrate with transparent coating (F-1). At this time, the thickness of the transparent film was 4 μm.

The total light transmittance and haze of the transparent coating obtained were measured with a haze meter (Nippon Denshoku Co., Ltd .: NDH-2000), and the results are shown in Table 1.
Further, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping property, magic repellency, magic wiping property were evaluated by the following methods and evaluation criteria, and the results are shown in Table 1. .

Measurement of pencil hardness It measured with the pencil hardness tester according to JIS-K-5400.

Measurement of Scratch Resistance Using # 0000 steel wool, sliding 50 times at a load of 500 g / cm ² , visually observing the surface of the film, and evaluating according to the following criteria, the results are shown in Table 1.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×

11 parallel scratches were made on the surface of the substrate with adhesive transparent coating (F-1) with a 1mm vertical and horizontal interval with a knife.
00 cells were made, cellophane tape (registered trademark) was adhered to this, and then the cellophane tape (registered trademark) was peeled off, and the number of cells remaining without peeling off was determined by the following four steps. The adhesion was evaluated by classifying into The results are shown in Table 1.
Number of remaining cells: 95 or more: ◎
Number of remaining squares 90-94: ○
Number of remaining squares: 85-89:
Number of remaining squares: 84 or less: ×

A water drop was dropped on the water- repellent transparent coating, and the contact angle between the transparent coating and the water droplet was measured using a fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd .: DM700).

A fingerprint is attached to the surface of the transparent anti- fingerprint coating, the state of fingerprint attachment is visually observed, and evaluated according to the following criteria. Table 1 shows the results.
Fingerprint is not recognized: ○
Slight fingerprints are found: △
Fingerprints are clearly recognized: ×

Fingerprint wiping (fingerprint wiping test)
Fingerprints were attached to the surface of the transparent coating, wiped back and forth on the fingerprint-attached transparent coating three times with a clean room wipe (Asahi Kasei Co., Ltd .: Bencotton), and the presence or absence of the remaining fingerprint was visually observed. The results are shown in Table 1.
No fingerprint mark is found: ○
Fingerprint marks are recognized: ×

With magic magic repellency magic (Mitsubishi Pencil Co., Ltd .: Mitsubishi oil marker fine piece A-5E), draw a line on the surface of the transparent coating, visually observe the state of repellency, and evaluate it according to the following criteria. It is shown in 1.
Ink is dotted and noticeable repelling is observed: ○
The line remains almost intact: ×

Magic Wipeability Magic (Mitsubishi Pencil Co., Ltd .: Mitsubishi Oil-based Marker Fine Piece A-5E) draws a line on the surface of the transparent coating, wipes it with Kimwipe, and evaluates it according to the following criteria. Show.
Magic mark disappeared: ○
Magic marks remained: ×

[Example 2]
Preparation of Transparent Film Forming Paint (2) In Example 1, 12 g of pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-4A) as a tetrafunctional acrylate resin, pentaerythritol triacrylate as a trifunctional acrylate resin (Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-3A) 11.9 g, difunctional silicon resin as silicon diacrylate (Daicel Cytec Co., Ltd .: EBECRYL350) 0.7 g, bifunctional organic resin 1,6- 2 g of Hesandiol diacrylate (Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) 1.1 g of mono-terminal methacrylic silicone oil (Shin-Etsu Chemical Co., Ltd .: X-22-174DX) as a monofunctional silicone resin The coating liquid for forming a transparent film (2) was similarly used except that it was used. Prepared.

Production of substrate with transparent coating (F-2) A substrate with transparent coating (F-2) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (2) was used.

  Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Example 3]
Preparation of Transparent Film Forming Paint (3) In Example 1, 15.27 g of pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-4A) as a tetrafunctional acrylate resin, pentaerythritol triacrylate as a trifunctional acrylate resin Acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-3A) 11.9 g, difunctional silicon resin, silicon diacrylate (manufactured by Daicel Cytec Co., Ltd .: EBECRYL350) 0.1 g, bifunctional organic resin 1, 6 -Hessandiol diacrylate (Nippon Kayaku Co., Ltd. product: Kayrad KS-HDDA) 0.4g, One terminal methacryl silicone oil as monofunctional silicone resin (Shin-Etsu Chemical Co., Ltd. product: X-22-174DX) 0. For forming a transparent film in the same manner except using 03 g A coating solution (3) was prepared.

Production of substrate with transparent film (F-3) A substrate with transparent film (F-3) was prepared in the same manner as in Production Example 1 except that the coating liquid for forming a transparent film (3) was used. Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Example 4]
Preparation of paint for forming transparent film (4) Transparent in the same manner as in Example 1, except that 25.5 g of pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-3A) was used as the trifunctional acrylate resin. A coating solution (4) for film formation was prepared.

Production of substrate with transparent film (F-4) A substrate with transparent film (F-4) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (4) was used. Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Example 5]
Preparation of paint for forming transparent film (4) In Example 1, 15.5 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A) was used as the hexafunctional acrylate resin. A coating solution (5) for forming a transparent film was prepared.

Production of substrate with transparent coating (F-5) A substrate with transparent coating (F-5) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (5) was used. Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Example 6]
Preparation of paint for forming transparent film (6) 25.5 g of pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd .: urethane acrylate UA-306H) as a urethane acrylate resin of a tri- or higher functional organic resin; 2 g of triethylene glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate 3EG-A) as a bifunctional organic resin and one-terminal glycidyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X-22) as a monofunctional silicone resin 173DX) 0.2 g, isopropyl alcohol 39.6 g, isopropyl glycol 15 g, butyl cellosolve 10 g, photopolymerization initiator 2.4.6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BIAS JAPAN KK: Lucillin TP) O) 2.2 g was mixed to prepare a coating solution (6) for forming a transparent film.

Production of substrate with transparent film (F-6) A substrate with transparent film (F-6) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (6) was used. Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Example 7]
Preparation of Transparent Film Forming Paint (7) In Example 1, 0.5 g of silicon diacrylate (manufactured by Daicel Cytec Co., Ltd .: EBECRYL350) as a bifunctional organic resin, and 1,6-hesandiol as a bifunctional organic resin 2 g of diacrylate (manufactured by Nippon Kayaku Co., Ltd .: Kayarad KS-HDDA) and 1.3 g of one-terminal methacrylic silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-174DX) as a monofunctional silicone resin are used. A coating solution (7) for forming a transparent film was prepared in the same manner except that.

Production of substrate with transparent film (F-7) A substrate with transparent film (F-7) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (7) was used.
Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Example 8]
Preparation of Transparent Film Forming Coating Material (8) In Example 1, 0.39 g of silicon diacrylate (manufactured by Daicel Cytec Co., Ltd .: EBECRYL350) as a bifunctional organic resin and 1,6-hesandiol as a bifunctional organic resin 1.7 g of diacrylate (manufactured by Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA),
A coating solution for forming a transparent film (8) in the same manner except that 0.11 g of one-end methacrylic silicon oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-174DX) is used as the monofunctional silicone resin.
Was prepared.

Production of substrate with transparent coating (F-8) A substrate with transparent coating (F-8) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (8) was used.
Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Example 9]
Preparation of paint for forming transparent film (9) A coating liquid for forming a transparent film (1) was prepared in the same manner as in Example 1.
Separately, silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SN, SiO ₂ concentration 20 mass%, average particle diameter 12 nm, dispersion medium: water) was replaced with a methanol solvent using an ultrafiltration membrane. 2000 g of this methanol-substituted silica sol (SiO ₂ concentration 20% by mass) was added as a coupling agent to γ-acrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-51).
03, SiO ₂ component 81.2% by mass) 40 g, methanol 2000 g, and 0.14 g of 28% ammonia water were added and stirred at 50 ° C. for 18 hours for surface treatment. Thereafter, a silica particle dispersion was prepared by subjecting the solvent to isopropyl alcohol and subjecting it to a surface treatment with a silane coupling agent having a solid concentration of 30% by mass.

Next, 30.0 g of the coating liquid for forming a transparent film (5) prepared in the same manner as in Example 5 was mixed with 30.0 g of a silica particle dispersion surface-treated with a silane coupling agent having a solid content concentration of 30% by mass. Thus, a coating solution (9) for forming a transparent film was prepared.

Production of substrate with transparent film (F-9) A substrate with transparent film (F-9) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (9) was used.
Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Example 10]
Preparation of paint for transparent film formation (10)
Preparation of P-doped tin oxide fine particles 80 g of pure water was charged with 13 g of ammonium nitrate and 20 g of 15% aqueous ammonia, and the temperature was raised to 50 ° C. A solution obtained by dissolving 1519 g of potassium stannate in 4290 g of pure water was added with a roller pump over 10 hours. At this time, nitric acid having a concentration of 10% by mass was added and adjusted so as to keep the pH at 8.8 with a pH controller. After keeping the addition at 50 ° C. for 1 hour after the addition, nitric acid having a concentration of 10% by mass was added to lower the pH to 3.0. Next, it was washed with pure water until the filtered water conductivity reached 10 μS / cm with an ultrafiltration membrane, and then concentrated with an ultrafiltration membrane. The amount of liquid taken out at this time was 6000 g, and the solid content (SnO ₂ ) concentration was 12% by mass. To this slurry, 264 g of a phosphoric acid aqueous solution having a concentration of 16% by mass was added and stirred for 0.5 hour. This was dried and fired at 700 ° C. for 2 hours to prepare P-doped tin oxide fine particles. The obtained P-doped tin oxide fine particles had an average particle diameter of 15 nm and a volume resistance of 5000 Ω · cm.

Preparation of surface-treated P-doped tin oxide fine particle dispersion 217 g of P-doped tin oxide fine particles and 335 g of ion-exchanged water were placed in a 2 L glass beaker, and after adding 50 g of 20% by weight KOH aqueous solution, 1000 g of quartz beads (0.15 mm) , Pulverize and disperse thoroughly with a bead mill, then separate the quartz beads and the dispersion with a 325 mesh (44 micron mesh) stainless steel wire mesh, and ion exchange the quartz beads remaining on the wire mesh. The liquid washed with 1560 g of water was mixed well, this liquid was heat-treated at 90 ° C. for 1 hour, cooled to room temperature, 96 g of anion exchange resin was added and stirred for 1 hour, and then the anion exchange resin was separated. After adding 96 g of cation exchange resin and stirring for 1 hour, the cation resin was separated to obtain a P-doped tin oxide fine particle aqueous dispersion (concentration: 10% by mass).

Next, 2000 g of a 10% by weight concentration of P-doped tin oxide fine water spray was added as a coupling agent to normal ethyl silicate (ethyl silicate 28 SiO ₂ component 28.8%, manufactured by Tama Chemical).
8 g (weight ratio with P-doped tin oxide fine particles = 100/3) and 2000 g of methanol were added and stirred at 50 ° C. for 18 hours for surface treatment. Thereafter, an ethanol dispersion of P-doped tin oxide fine particles which was solvent-substituted with ethanol and surface-treated with a silane coupling material having a concentration of 30% by mass was prepared.

Separately, a coating liquid for forming a transparent film (1) was prepared in the same manner as in Example 1.
Subsequently, 30 g of the coating solution for forming a transparent film (1) and 70 g of an ethanol dispersion of P-doped tin oxide fine particles having a solid content concentration of 30% by mass were mixed to prepare a coating solution for forming a transparent film (10). .

Production of substrate with transparent film (F-10) A substrate with transparent film (F-10) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (10) was used. Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Comparative Example 1]
Preparation of Transparent Film Forming Paint (R1 ) 27.7 g of hexafunctional acrylate resin dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) and 39.6 g of isopropyl alcohol 15 g of isopropyl glycol, 10 g of butyl cellosolve and 2.2 g of photopolymerization initiator 2.4.6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BIAS JAPAN KK: Lucyrin TPO) are mixed to form a coating solution for forming a transparent film. (R1) was prepared.

Production of substrate with transparent coating (RF-1) A substrate with transparent coating (RF-1) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R1) was used.
Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Comparative Example 2]
Preparation of paint for forming transparent film (R2 ) 27.42 g of hexafunctional acrylate resin dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A) as trifunctional or higher organic resin and piece as monofunctional silicone resin Terminal methacrylic silicon oil (Shin-Etsu Chemical Co., Ltd .: X-22-174DX) 0.28 g, isopropyl alcohol 39.6 g, isopropyl glycol 15 g, butyl cellosolve 10 g and photopolymerization initiator 2.4.6-trimethylbenzoyldiphenyl A coating solution (R2) for forming a transparent film was prepared by mixing 2.2 g of phosphine oxide (manufactured by BES Japan Co., Ltd .: Lucillin TPO).

Production of substrate with transparent coating (RF-2) A substrate with transparent coating (RF-2) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R2) was used. Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Comparative Example 3]
Preparation of paint for forming transparent film (R3 ) 25.9 g of tetrafunctional acrylate resin pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-4A) as trifunctional or higher organic resin and silicon as bifunctional organic resin 0.3 g of diacrylate (manufactured by Daicel Cytec Co., Ltd .: EBECRYL350), 1.5 g of 1,6-hesandiol diacrylate (manufactured by Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) as a bifunctional organic resin, 39.6 g of isopropyl alcohol, 15 g of isopropyl glycol, 10 g of butyl cellosolve and 2.2 g of photopolymerization initiator 2.4.6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BIAS JAPAN KK: Lucillin TPO) A coating solution (R3) for forming a transparent film was prepared.

Production of substrate with transparent coating (RF-3) A substrate with transparent coating (RF-3) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R3) was used. Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Comparative Example 4]
Preparation of paint for forming transparent film (R4) In Example 1, a tetrafunctional acrylate resin pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-4A) as a trifunctional or higher functional organic resin 27
. 665 g, 0.01 g of silicon hexaacrylate (manufactured by Daicel Cytec Co., Ltd .: EBECRYL1360) as a bifunctional organic resin, and 1,6-hesandiol diacrylate (manufactured by Nippon Kayaku Co., Ltd .: Kayarad as a bifunctional organic resin) KS-HDDA) For forming a transparent film in the same manner except that 0.02 g and 0.005 g of one-terminal methacrylic silicon oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-174DX) are used as a monofunctional silicone resin. A coating solution (R4) was prepared.

Production of substrate with transparent coating (RF-4) A substrate with transparent coating (RF-4) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R4) was used. Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

[Comparative Example 5]
Preparation of paint for forming transparent film (R5) In Example 1, a tetrafunctional acrylate resin pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-4A) 20 as a trifunctional or higher functional organic resin 20
. 2g and silicon hexaacrylate (Daicel Cytec) as a bifunctional organic resin
Co., Ltd .: EBECRYL1360) 1.4 g, 1,6-Hesandiol Diacrylate (Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) 4.2 g as a bifunctional organic resin, and one terminal as a monofunctional silicone resin A coating solution (R5) for forming a transparent film was prepared in the same manner except that 1.9 g of methacrylic silicon oil (Shin-Etsu Chemical Co., Ltd .: X-22-174DX) was used.

Production of substrate with transparent coating (RF-5) A substrate with transparent coating (RF-5) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R5) was used. Evaluate the thickness of the transparent coating, total light transmittance, haze, pencil hardness, scratch resistance, adhesion, water repellency, fingerprint resistance, fingerprint wiping, magic repellency, and magic wiping. Table 1 shows.

Claims (6)

(1) A trifunctional or higher functional acrylate resin having a (meth) acrylate group as a functional group ;
(2) Polyethylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, tripropylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate Methacrylate, triethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1.4-butanediol dimethacrylate, 1.6-hexanediol dimethacrylate, 1.9-nonanediol dimethacrylate, 1.10-decanedioldi Methacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl Methacrylate, 1,6-hexanediol diacrylate, 1.9- nonanediol Zia crate, dimethylol - diacrylate, difunctional organic selected from 2-hydroxy-3-acryloyloxy propyl methacrylate or mixtures thereof Resin monomers, and
A bifunctional silicone resin monomer represented by the following formula (1) :

(However, R _{1 to} R ₅ represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X ₁ and X ₂ represent an acryl group, a methacryl group, and a glycidyl group, and may be the same or different. N may be 1 to 10).
(3) A matrix-forming component composed of a monofunctional silicone resin selected from acrylic-modified polysiloxane and methacryl-modified polysiloxane, and a solvent.
The content of (1) trifunctional or higher functional acrylate resin in the obtained transparent film is in the range of 10 to 98% by mass as solid content, and (2) the content of bifunctional organic resin monomer and bifunctional silicon resin monomer The amount is in the range of 0.2 to 10% by mass as the solid content, and (3) the monofunctional silicone resin is contained so that the content is in the range of 0.02 to 5% by mass as the solid content. A coating for forming a transparent film. Wherein (3) the weight of the monofunctional silicone resin (W _3), wherein (2) the weight of the bifunctional organic resin monomer and a difunctional silicone resin monomer (W ₂₎ the weight ratio of (W ₃₎ / (W ₂₎ The paint for forming a transparent film according to claim 1, wherein is in the range of 0.05 to 1.   The metal oxide fine particles having an average particle diameter in the range of 5 to 300 nm are further contained in the range of 10 to 80% by mass as a solid content in the obtained transparent film. Paint for forming transparent film.   The coating composition for forming a transparent film according to any one of claims 1 to 3, wherein the total solid concentration is in the range of 5 to 50 mass%. It consists of a base material and a transparent film formed on the base material,
Transparent coating,
(1) a trifunctional or higher functional acrylate resin;
(2) Polyethylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, tripropylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate Methacrylate, triethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1.4-butanediol dimethacrylate, 1.6-hexanediol dimethacrylate, 1.9-nonanediol dimethacrylate, 1.10-decanedioldi Methacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl Bifunctional organic selected from tacrylate, 1.6-hexanediol diacrylate, 1.9-nonanediol diacrylate, dimethylol-tricyclodecane diacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, or mixtures thereof A resin monomer and a polymer of a bifunctional silicone resin monomer represented by the following formula (1) (that is, a bifunctional organic resin and a bifunctional silicone resin),

(However, R _{1 to} R ₅ represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X ₁ and X ₂ represent an acryl group, a methacryl group, and a glycidyl group, and may be the same or different. N may be 1 to 10).
(3) It consists of a matrix component consisting of a monofunctional silicone resin selected from acrylic-modified polysiloxane and methacryl-modified polysiloxane ,
It is in the range of 10 to 98 mass% content of (1) tri- or more functional acrylate resin in the transparent coating film as solids, as solids content (2) difunctional organic resin and the bifunctional silicone resin A substrate with a transparent coating, which is in the range of 0.2 to 10% by mass, and (3) the content of the monofunctional silicone resin is in the range of 0.02 to 5% by mass as the solid content.   6. The substrate with a transparent coating according to claim 5, wherein the transparent coating further contains metal oxide fine particles having an average particle diameter in the range of 5 to 300 nm in a range of 10 to 80% by mass as a solid content. .