JP7636876B2 - Antiviral coating paints, coatings, and laminating films - Google Patents

Description

The present invention relates to a paint for forming an antiviral coating film. More specifically, the present invention relates to a paint capable of forming an antiviral coating film, a coating film formed using the paint, and a laminated film having the coating film.

In recent years, infectious diseases caused by various viruses, particularly those with high infectiousness such as the novel coronavirus, influenza virus, and norovirus, have been highlighted as a serious problem because the infection spreads rapidly over a wide area. For example, mass infections in hospitals and nursing homes have become a social issue. There are many types of viruses to deal with, even just the influenza virus, and viruses often mutate, resulting in the emergence of new species such as the novel coronavirus. Therefore, there is a demand for antiviral agents that can inactivate various viruses (and are generally effective regardless of the type of virus). As an antiviral agent that can inactivate various viruses, an antiviral agent (see Patent Document 1) characterized by containing particles of at least one type of iodide composed of iodine such as cuprous iodide (CuI) and an element of the 4th to 6th periods and groups 8 to 15 of the periodic table as an active ingredient, and a resin member using the antiviral agent (see Patent Document 2) have been proposed.

Conventionally, on the surface of an article, particularly an article used in a place exposed to direct sunlight, a coating film (cured coating film) of a paint containing a thermosetting silicone resin as a binder is often formed because of its excellent weather resistance. However, it has been found that when an antiviral agent such as cuprous iodide (CuI) is blended with a paint containing a thermosetting silicone resin as a binder, there are inconveniences such as a decrease in antiviral properties, difficulty in dispersing the antiviral agent well in the paint, and insufficient transparency of the coating film formed.

International Publication No. WO2010/026730 International Publication No. WO2013/005446

The first object of the present invention is to provide a coating material capable of forming a coating film (cured coating film) having antiviral properties. A further object of the present invention is to provide a coating material capable of forming a coating film (cured coating film) having antiviral properties and excellent transparency.

After extensive research, the inventors discovered that the above objectives can be achieved with a specific paint.

That is, the various aspects of the present invention are as follows.
[1]
(A) 100 parts by mass of a silane compound having a hydrolyzable group;
(B) 0.1 to 150 parts by mass of at least one compound selected from the group consisting of monovalent copper compounds and iodides of iodine and elements of Periods 4 to 6 and Groups 8 to 15 of the Periodic Table; and
(C) 0.01 to 50 parts by mass of at least one compound selected from the group consisting of an amine compound and a silane coupling agent;
Paint containing.
[2]
The coating material according to item [1], further comprising: (D) 10 to 200 parts by mass of low refractive index particles.
[3]
The coating material according to item [1] or [2], wherein the component (C) at least one compound selected from the group consisting of amine compounds and silane coupling agents includes a polyamine or an amine compound having a polyamine structure.
[4]
The coating material according to any one of items [1] to [3], wherein the component (C) at least one compound selected from the group consisting of an amine compound and a silane coupling agent includes an amine compound having a hydrolyzable silyl group.
[5]
The coating material according to any one of items [1] to [4], wherein the component (C) at least one compound selected from the group consisting of an amine compound and a silane coupling agent includes a silane coupling agent having an amino group.
[6]
The paint according to any one of items [1] to [5], wherein at least one compound selected from the group consisting of monovalent copper compounds, iodine, and iodides of elements of periods 4 to 6 and groups 8 to 15 of the periodic table of the component (B) includes cuprous iodide.
[7]
A laminated film comprising a coating film formed using the coating material according to any one of items [1] to [6], wherein the coating film constitutes at least one surface of the laminated film.
[8]
An article comprising a coating film formed using the paint according to any one of items [1] to [6], wherein the coating film constitutes at least a part of the surface of the article.

The coating film (cured coating film) formed using the coating material of the present invention has antiviral properties and is also excellent in transparency. In addition, the coating material of the present invention has an antiviral agent well dispersed in the coating material, and can form a coating film industrially stably. Therefore, articles having a coating film (cured coating film) having antiviral properties formed using the coating material of the present invention on the surface thereof, such as shatterproof films, infrared shielding films, and antireflection films attached to window glass and automobile windows; display faceplate protective films attached to smartphones and tablet terminals; decorative sheets and decorative sheets used for decoration of furniture, home appliances, and building materials; building materials such as handrails, doorknobs, grips, and floorboards; and face shields, partitions, and screens can be suitably used in places where antiviral properties are required, such as hospitals, nursing homes, nurseries, schools, medical instrument production factories, pharmaceutical production factories, and food processing factories.

In this specification, the term "resin" is used to include a resin mixture containing two or more resins, and a resin composition containing components other than resin. In this specification, the term "film" is used interchangeably or interchangeably with "sheet". In this specification, the terms "film" and "sheet" are used to refer to something that can be industrially wound into a roll. The term "plate" is used to refer to something that cannot be industrially wound into a roll. In this specification, laminating a layer and another layer in order includes both directly laminating the layers and laminating the layers with one or more layers, such as an anchor coat, interposed between them.

In this specification, the term "more than" in relation to a numerical range is used to mean a certain number or more than a certain number. For example, 20% or more means 20% or more than 20%. The term "less than" in relation to a numerical range is used to mean a certain number or less than a certain number. For example, 20% or less means 20% or less than 20%. Furthermore, the symbol "to" in relation to a numerical range is used to mean a certain number, more than a certain number and less than another certain number, or another certain number. Here, the other certain number is a number greater than the certain number. For example, 10 to 90% means 10%, more than 10% and less than 90%, or 90%. Furthermore, the upper and lower limits of the numerical range can be arbitrarily combined, and embodiments in which any combination is adopted can be read. For example, from a statement regarding the numerical range of a certain characteristic such as "Usually 10% or more, preferably 20% or more. On the other hand, usually 40% or less, preferably 30% or less" or "Usually 10-40%, preferably 20-30%," it can be inferred that the numerical range of the certain characteristic is 10-40%, 20-30%, 10-30%, or 20-40% in one embodiment.

Other than in the examples, or unless otherwise specified, all numerical values used in the specification and claims should be understood to be modified by the term "about." Without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should be construed in light of the number of significant digits and by applying ordinary rounding techniques.

In this specification, the term "antiviral" is used to include both the meaning of inactivating a virus (reducing or eliminating (deactivating) the infectivity of the virus) and inhibiting the proliferation of the virus.

1. Antiviral coating film forming paint:
The paint of the present invention is a paint that can be suitably used for forming an antiviral coating film. The paint of the present invention includes (A) a silane compound having a hydrolyzable group; (B) at least one compound selected from the group consisting of a monovalent copper compound, and an iodide consisting of iodine and an element of the 4th to 6th periods and the 8th to 15th groups of the periodic table; and (C) at least one compound selected from the group consisting of an amine compound and a silane coupling agent. In one embodiment, the paint of the present invention may further include (D) low refractive index particles. Each component will be described below.

(A) Silane compound having a hydrolyzable group:
The above-mentioned component (A), a silane compound having a hydrolyzable group, condenses and hardens by heat or the like to become a polymer having a silicone skeleton (siloxane bond (Si-O-Si)) as the main skeleton, and functions to form a coating film (cured coating film). The above-mentioned component (A) also functions as a binder, and contains the above-mentioned component (B), a monovalent copper compound, and at least one compound selected from the group consisting of iodine and an iodide consisting of an element of Periods 4 to 6 and Groups 8 to 15 of the Periodic Table. Furthermore, the above-mentioned component (A) functions to improve the weather resistance of the coating film (cured coating film) formed using the paint of the present invention.

The hydrolyzable group contained in the above component (A) may be, for example, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group; an acyloxy group such as an acetoxy group; or a halogen group such as a chloro group. Of these, the hydrolyzable group contained in the above component (A) may preferably be an alkoxy group from the viewpoint of controllability of the hydrolysis reaction.

Examples of the above component (A) include hydrolyzable organic silicon compounds, (partial) hydrolysates of the compounds, and (partial) condensates thereof. Here, the (partial) hydrolysate means a partial hydrolysate, a hydrolysate, or a mixture of a partial hydrolysate and a hydrolysate. Here, the (partial) condensate means a partial condensate, a condensate, or a mixture of a partial condensate and a condensate.

The hydrolysis or partial hydrolysis of the hydrolyzable organosilicon compound etc. can be carried out by a known method. One example of a method for hydrolyzing or partially hydrolyzing the hydrolyzable organosilicon compound etc. is to mix a predetermined amount of water, typically about 0.1 to 2 moles per mole of hydrolyzable group in the hydrolyzable organosilicon compound etc., with a mixture of the hydrolyzable organosilicon compound etc. and an organic solvent such as diacetone alcohol, and then add a catalyst, if desired, such as an acid or alkali such as phosphoric acid, acetic acid, or formic acid, and react with stirring at a predetermined temperature, typically room temperature (23°C) to about 100°C.

The condensation or partial condensation of the hydrolyzable organosilicon compounds can be carried out by known methods. Examples of methods for condensing or partially condensing the hydrolyzable organosilicon compounds include a method in which the hydrolyzable organosilicon compounds are hydrolyzed or partially hydrolyzed by the above-mentioned method to obtain a (partial) hydrolyzate, and then, if desired, a silanol condensation catalyst, such as a metal chelate compound, an organic acid metal salt, or a metal compound having a hydrolyzable group, is added and reacted with stirring at a predetermined temperature, typically 50°C or higher and about a temperature lower than the boiling point of the organic solvent.

Examples of the hydrolyzable organic silicon compounds include alkoxymonosilane compounds, compounds in which one or more hydrogen atoms in the alkoxymonosilane compounds are replaced with fluorine atoms, bis(alkoxysilyl)alkyl compounds, compounds in which one or more hydrogen atoms in the bis(alkoxysilyl)alkyl compounds are replaced with fluorine atoms, and alkoxysilane compounds such as oligomers or prepolymers of one or more of these.

Examples of the alkoxymonosilane compound include tetraalkoxysilane, alkyltrialkoxysilane, and dialkyldialkoxysilane.

Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane.

Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, and n-decyltrimethoxysilane.

Examples of the dialkyldialkoxysilane include dimethyldimethoxysilane and dimethyldiethoxysilane.

An example of the above alkoxymonosilane compound in which one or more hydrogen atoms have been replaced with fluorine atoms is a compound having the structure of the following general formula (1):

R-SiX ₃ (1)

In formula (1), X is an alkoxy group. R is an alkyl group in which one or more, preferably three or more, hydrogen atoms are substituted with fluorine atoms. R may have usually 1 to 20, preferably 3 to 12, carbon atoms. In one preferred embodiment, R may have a structure represented by the following general formula (1-1).

CF ₃ (CF ₂ )n(CH ₂ ) ₂ - (1-1)

In formula (1-1), n is usually an integer from 0 to 17, preferably from 0 to 9.

Examples of the above alkoxymonosilane compounds in which one or more hydrogen atoms have been replaced with fluorine atoms include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,4,4,5,5,5-heptafluoropentyltrimethoxysilane, 3,3,4,4,5,5,5-heptafluoropentyltriethoxysilane, 1H,1H,2H,2H-heptadecafluorodecyltrimethoxysilane, 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyltrimethoxysilane, and 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyltriethoxysilane.

The bis(alkoxysilyl)alkyl compound may, for example, be a compound having the structure of the following general formula (2):

R' _3-n -SiXn-R-SiX'm-R" _3-m (2)

In formula (2), R is a hydrocarbon group. The hydrocarbon group may be linear or branched, and may contain an aromatic ring, an aliphatic cyclic group, an ether group, an ester group, a nitrogen atom, or an oxygen atom. The number of carbon atoms in the hydrocarbon group is usually 1 to 20, and preferably 2 to 12. X and X' are each an alkoxy group. R' and R" are each an alkyl group. n and m are each an integer of 1 to 3.

The above-mentioned bis(alkoxysilyl)alkyl compounds include, for example, bis(alkoxysilyl)alkanes such as 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,4-bis(trimethoxysilyl)butane, 1-dimethyldimethoxysilyl-4-trimethoxysilylbutane, 1,4-bis(dimethyldimethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,7-bis(trimethoxysilyl)heptane, 1,8-bis(trimethoxysilyl)octane, 1,9-bis(trimethoxysilyl)nonane, and 1,10-bis(trimethoxysilyl)decane; and bis(alkoxysilyl)alkanes having an amine group such as bis[3-(trimethoxysilyl)propyl]amine.

An example of a compound in which one or more hydrogen atoms of the above bis(alkoxysilyl)alkyl compound are replaced with fluorine atoms is a compound having the structure of the following general formula (3).

R' _3-n -SiXn-R-SiX'm-R" _3-m (3)

In formula (3), X and X' are each an alkoxy group. R' and R" are each an alkyl group. n and m are each an integer of 1 to 3. R is a hydrocarbon group in which one or more, preferably two or more, hydrogen atoms are substituted with fluorine atoms. The hydrocarbon group may be linear or branched, and may contain an aromatic ring, an aliphatic cyclic group, an ether group, an ester group, a nitrogen atom, or an oxygen atom. The number of carbon atoms in the hydrocarbon group may usually be 1 to 20, preferably 2 to 12. In one preferred embodiment, R may have a structure represented by the following general formula (3-1):

-(CH ₂ ) ₂ -(CF ₂ )n-(CH ₂ ) ₂ - (3-1)

In formula (3-1), n is a natural number, preferably a natural number from 1 to 20, and more preferably a natural number from 2 to 12.

Examples of the above bis(alkoxysilyl)alkyl compounds in which one or more hydrogen atoms have been replaced with fluorine atoms include 3,3,4,4-tetrafluoro-1,6-bis(trimethoxysilyl)hexane, 3,3,4,4,5,5,6,6-octafluoro-1,8-bis(trimethoxysilyl)octane, 3,3,4,4,5,5,6,6-octafluoro-1,8-bis(triethoxysilyl)octane, 1H,1H,2H,2H,9H,9H,10H,10H-dodecafluoro-1,10-bis(trimethoxysilyl)decane, and 1H,1H,2H,2H,11H,11H,12H,12H-hexadecafluoro-1,12-bis(trimethoxysilyl)dodecane.

When the coating material of the present invention contains the above-mentioned component (D) to make the coating film (cured coating film) formed using the coating material of the present invention a low refractive index layer and to exhibit anti-reflection function, from the viewpoint of lowering the refractive index of the base resin and improving the anti-reflection function, the above-mentioned component (A) is preferably a compound in which one or more hydrogen atoms in the above-mentioned alkoxymonosilane compound are substituted with fluorine atoms, and a compound in which one or more hydrogen atoms in the above-mentioned bis(alkoxysilyl)alkyl compound are substituted with fluorine atoms.

As the above component (A), one or a mixture of two or more of these can be used.

(B) Monovalent copper compounds, etc.:
The component (B) at least one compound selected from the group consisting of monovalent copper compounds and iodides containing iodine and an element of Periods 4 to 6 and Groups 8 to 15 of the periodic table functions to impart antiviral properties to a coating film (cured coating film) formed using the coating material of the present invention.

Examples of the monovalent copper compound include cuprous chloride (CuCl), cuprous bromide (CuBr), cuprous iodide (CuI), cuprous acetate (Cu(CH ₃ COO)), cuprous sulfide (Cu ₂ S), cuprous thiocyanate (CuSCN), and cuprous oxide (Cu ₂ O).

Examples of the iodide containing iodine and an element of the 4th to 6th periods and groups 8 to 15 of the periodic table include iodides of copper, silver, antimony, iridium, germanium, tin, thallium, platinum, palladium, bismuth, gold, iron, cobalt, nickel, zinc, indium, and mercury. Examples of the iodide containing iodine and an element of the 4th to 6th periods and groups 8 to 15 of the periodic table include copper (I) iodide (CuI), silver (I) iodide (AgI), antimony triiodide (SbI ₃ ), iridium tetraiodide (IrI ₄ ), germanium tetraiodide (GeI ₄ ), germanium diiodide (GeI ₂ ), tin diiodide (SnI 2 ), tin tetraiodide (SnI ₄ ), thallium (I ₎ iodide (TlI), platinum diiodide (PtI ₂ ), platinum tetraiodide (PtI ₄ ), palladium diiodide (PdI ₂ ), bismuth triiodide (BiI ₃ ), gold (I) iodide (AuI), gold triiodide (AuI ₃ ), iron diiodide (FeI ₂ ), cobalt diiodide (CoI ₂ ), nickel diiodide (NiI ₂ ), zinc diiodide (ZnI ₂ ), indium triiodide (InI ₃ ), and mercurous iodide (Hg ₂ I ₂ ).

Among these, from the viewpoint of stability in air, cuprous chloride (CuCl), cuprous bromide (CuBr), cuprous iodide (CuI), cuprous thiocyanate (CuSCN), silver iodide (AgI), and tin tetraiodide (SnI ₄ ) are preferred, and from the viewpoint of antiviral activity, cuprous iodide (CuI) is more preferred.

As component (B), one or a mixture of two or more of these can be used.

The shape of the above component (B) is not particularly limited. From the viewpoint of the coatability of the paint, the shape of the above component (B) may be preferably particulate (including spherical, fibrous, scaly, ribbon-like, etc.).

When the component (B) is particulate, the average particle size of the component (B) may be usually 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less, from the viewpoint of film-forming properties. When it is desired to impart a clear and transparent feel to the film, the average particle size of the component (B) may be usually 300 nm or less, preferably 200 nm or less, and more preferably 120 nm or less. On the other hand, there is no particular lower limit for the average particle size, but from the viewpoint of productivity in producing the component (B), it may usually be 1 nm or more.

In this specification, the average particle size of particles is the particle size at which the cumulative total from the smallest particles is 50% by mass in a particle size distribution curve measured by a laser diffraction/scattering method. The particle size distribution curve can be measured, for example, using a laser diffraction/scattering particle size analyzer "MT3200II (product name)" manufactured by Nikkiso Co., Ltd.

The amount of the above component (B) may be, from the viewpoint of reliably expressing antiviral properties, usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 3 parts by mass or more, and most preferably 5 parts by mass or more, per 100 parts by mass of the above component (A) a silane compound having a hydrolyzable group. On the other hand, from the viewpoint of maintaining the coatability of the paint and the transparency of the coating film, it may be usually 150 parts by mass or less, preferably 100 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 30 parts by mass or less, and most preferably 20 parts by mass or less.

(C) Amine compounds, etc.:
The at least one compound selected from the group consisting of component (C) amine compounds and silane coupling agents functions to ensure that the at least one compound selected from the group consisting of component (B) monovalent copper compounds and iodides containing iodine and an element of Periods 4 to 6 and Groups 8 to 15 of the periodic table can exhibit antiviral properties as an antiviral agent.

The amine compound is a compound in which the hydrogen atom of ammonia is replaced with a hydrocarbon group or an aromatic atomic group. Preferred examples of the amine compound include polyamines, amine compounds having a polyamine structure, and amine compounds having a hydrolyzable silyl group.

The silane coupling agent is a silane compound having one or more hydrolyzable groups and one or more organic polymerizable functional groups in one molecule. Examples of the hydrolyzable groups include alkoxy groups such as methoxy and ethoxy groups; acyloxy groups such as acetoxy groups; and halogen groups such as chloro groups. Examples of the organic polymerizable functional groups include vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, amino groups, mercapto groups, isocyanate groups, ureido groups, and isocyanurate groups. The silane coupling agent may contain one or more of these hydrolyzable groups and one or more of these organic polymerizable functional groups in one molecule.

The silane coupling agent is a chemical substance that can be classified as a silane compound having a hydrolyzable group, component (A), in that it is a silane compound having a hydrolyzable group, but in this specification, it is classified as component (C). In other words, the above-mentioned component (A) excludes substances that also fall under component (C), i.e., compounds having the above-mentioned organic polymerizable functional group.

(C1) Polyamine or compound containing a polyamine structure:
In one preferred embodiment, the component (C) may include (C1) a polyamine or an amine compound having a polyamine structure. A polyamine is a hydrocarbon compound having two or more amino groups in a molecule. A compound having a polyamine structure is a compound having one or more hydrocarbon groups having two or more amino groups in a molecule. From the viewpoint of transparency, the compound having a polyamine structure may be an ammonium compound having one or more hydrocarbon groups having two or more amino groups in a molecule. The "hydrocarbon" referred to here may be an aliphatic hydrocarbon, an aromatic hydrocarbon, or an aliphatic and aromatic hydrocarbon, or a mixture thereof. The "hydrocarbon" referred to here is typically an aliphatic hydrocarbon.

Without intending to be bound by theory, polyamines are also present in viruses and are involved in the synthesis of nucleic acids and proteins. For this reason, it is predicted that viruses remain in the vicinity of the above-mentioned component (C1) polyamine or a compound containing a polyamine structure, and as a result, they are more likely to be attacked by the above-mentioned component (B) monovalent copper compound or the like as an antiviral agent.

(C2) Amine compound having a hydrolyzable silyl group:
In another preferred embodiment, the component (C) may contain (C2) an amine compound having a hydrolyzable silyl group. The component (C2) is a compound in which the hydrogen atom of ammonia is substituted with a hydrocarbon group or an aromatic atomic group, and has one or more hydrolyzable silyl groups in one molecule.

In one embodiment, the above component (C2) may be a compound having one or more hydrocarbon groups having one or more amino groups in the molecule and having one or more hydrolyzable silyl groups in the molecule. The "hydrocarbon" referred to here may be an aliphatic hydrocarbon, an aromatic hydrocarbon, or an aliphatic and aromatic hydrocarbon, or a mixture thereof. The "hydrocarbon" referred to here is typically an aliphatic hydrocarbon.

A compound having one or more hydrocarbon groups with two or more amino groups in the molecule and one or more hydrolyzable silyl groups in the molecule is a chemical substance that has both the characteristics of the above-mentioned component (C1) in that it has a polyamine structure and the characteristics of the above-mentioned component (C2) in that it has a hydrolyzable silyl group, and is more preferable as the above-mentioned component (C) from the viewpoint of antiviral properties.

The hydrolyzable silyl group of the component (C2) is a functional group having a structure in which a hydrolyzable group is directly bonded to a silicon atom. Examples of the hydrolyzable silyl group include alkoxysilyl groups such as methoxysilyl, ethoxysilyl, propoxysilyl, and isopropoxysilyl groups; acyloxysilyl groups such as acetoxysilyl; and functional groups having a structure in which a halogen group such as a chloro group is directly bonded to a silicon atom. Among these, the hydrolyzable silyl group of the component (C2) may preferably be an alkoxysilyl group (a functional group having a structure in which an alkoxy group is directly bonded to a silicon atom) from the viewpoint of controllability of the hydrolysis reaction. The component (C2) may contain one or more of these hydrolyzable silyl groups in one molecule.

The above component (C2) has a hydrolyzable silyl group and is therefore polymerizable, and even when incorporated in large quantities, it does not significantly impair the film-forming properties (curability of the wet film). Therefore, the above component (C2) can be incorporated in large quantities into the paint to ensure that antiviral properties are expressed. Furthermore, without intending to be bound by theory, it is expected that the above component (C2) forms a polyamine structure by polymerization, and that the same mechanism of antiviral activity as the above component (C1) is at work.

The above silane coupling agents include, for example, silane coupling agents having a vinyl group (silane compounds having a vinyl group and a hydrolyzable group), silane coupling agents having an epoxy group (silane compounds having an epoxy group and a hydrolyzable group), silane coupling agents having a (meth)acryloxy group (methacryloxy group or acryloxy group) (silane compounds having a (meth)acryloxy group and a hydrolyzable group), silane coupling agents having an amino group (silane compounds having an amino group and a hydrolyzable group), silane coupling agents having a mercapto group (silane compounds having a mercapto group and a hydrolyzable group), silane coupling agents having an isocyanate group (silane compounds having an isocyanate group and a hydrolyzable group), silane coupling agents having a ureido group (silane compounds having a ureido group and a hydrolyzable group), and silane coupling agents having an isocyanurate group (silane compounds having an isocyanurate group and a hydrolyzable group).

Examples of the silane coupling agent having the vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane.

Examples of the silane coupling agent having an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.

Examples of the silane coupling agent having the (meth)acryloxy group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

Examples of the silane coupling agent having an amino group include compounds having one hydrocarbon group having one amino group in the molecule and having one or more hydrolyzable groups in the molecule, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane; and compounds having one hydrocarbon group having two amino groups in the molecule and having one or more hydrolyzable groups in the molecule, such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane.

Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

An example of a silane coupling agent having an isocyanate group is 3-isocyanatepropyltriethoxysilane.

Examples of the silane coupling agent having a ureido group include 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane.

An example of the silane coupling agent having an isocyanurate group is tris-(trimethoxysilylpropyl) isocyanurate.

Among these silane coupling agents, the silane coupling agents having the above amino group are preferred from the viewpoint of antiviral properties. The silane coupling agents having the above amino group are also compounds that fall under the category of the amine compounds having a hydrolyzable silyl group (C2).

The amine value of the amine compound may be, from the viewpoint of antiviral properties, usually 1 mgKOH/g or more, preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, even more preferably 30 mgKOH/g or more, and most preferably 40 mgKOH/g or more, although it depends on the amount of the compound. On the other hand, from the viewpoint of the pot life of the paint, the amine value of the amine compound may be, from the viewpoint of antiviral properties, usually 500 mgKOH/g or less, preferably 200 mgKOH/g or less, although it depends on the amount of the compound.

The amine value is the amount of potassium hydroxide (KOH: molecular weight 56.11) (mg) required to neutralize 1 g of sample, equivalent to the amount of acid. In this specification, the amine value is calculated by dissolving 5 g of sample in 50 mL of ethanol (95) and titrating with 0.5 mol/L aqueous hydrochloric acid solution by electrometric titration (potentiometric titration).

As the above component (C), one or a mixture of two or more of these can be used.

The amount of the above component (C) may be, from the viewpoint of reliably expressing antiviral properties, usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, and most preferably 3 parts by mass or more, per 100 parts by mass of the above component (A) a silane compound having a hydrolyzable group. On the other hand, from the viewpoint of suppressing bleed whitening or from the viewpoint of the pot life of the paint, it may be usually 50 parts by mass or less, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 12 parts by mass or less, and most preferably 8 parts by mass or less.

(D) Low refractive index particles:
In one embodiment, the coating material of the present invention may further contain (D) low refractive index particles. The above component (D) is a particle that serves to lower the refractive index of the coating film (cured coating film) formed using the coating material of the present invention. By including the above component (D) in the coating material of the present invention, the coating film (cured coating film) formed using the coating material of the present invention can be made into a low refractive index layer, thereby exhibiting an anti-reflection function.

The refractive index (RL) of the low refractive index layer may be usually 1.5 or less, preferably 1.45 or less, and more preferably 1.4 or less, from the viewpoint of exhibiting a good anti-reflection function. On the other hand, from the viewpoint of the transparency of the anti-reflection film (laminated film having the low refractive index layer), it may be preferably 1.2 or more, more preferably 1.25 or more, more preferably 1.28 or more, and even more preferably 1.3 or more.

The refractive index (RL) is a value measured using an Abbe refractometer according to JIS K7142:2008 Method A, using sodium D line (wavelength 589.3 nm), 1-bromonaphthalene as the contact liquid, the surface of the sample that was the biaxially oriented polypropylene resin film side when the sample was made is the surface that is in contact with the prism, and the bar coater operation direction of the sample is the length direction of the test piece. For the sample, the paint used to form the low refractive index layer is applied to the surface of a 20 μm thick biaxially oriented polypropylene resin film using a bar coater so that the thickness after curing is 2 μm, and the coating film obtained by drying and curing is peeled off from the biaxially oriented polypropylene resin film.

Examples of the above component (D) include particles (solid particles) of low refractive index materials such as silica, magnesium fluoride, fluorine resin, and silicone resin; and hollow particles.

The hollow particles have an outer shell layer and are porous or hollow (single-hole) inside. The hollow particles contain air (refractive index 1.0) in the pores of the porous or hollow (single-hole), which is highly effective in lowering the refractive index of the coating film.

The material constituting the hollow particles is not particularly limited as long as it forms the above-mentioned structure. Examples of materials constituting the hollow particles include low refractive index materials such as silica, magnesium fluoride, fluorine resin, and silicone resin. Among these, silica is preferred from the viewpoint of productivity in producing hollow particles.

The average particle diameter of the above component (D) is appropriately determined taking into consideration the thickness of the low refractive index layer (the coating film (cured coating film) formed using the coating material of the present invention containing the above component (D)) and the productivity when producing the low refractive index particles. The average particle diameter of the above component (D) may be usually 1 to 150 nm, preferably 5 to 100 nm, more preferably 10 to 80 nm, and even more preferably 15 to 60 nm.

In this specification, the average particle size is the particle size at which the cumulative particle size distribution curve measured by a laser diffraction/scattering method using a laser diffraction/scattering particle size analyzer is 50% by mass, starting from the smallest particles. As the laser diffraction/scattering particle size analyzer, for example, the "MT3200II (product name)" manufactured by Nikkiso Co., Ltd. can be used.

Among these, hollow particles are preferred as the above component (D), and hollow silica (hollow silica particles) is more preferred. As the above component (D), one or a mixture of two or more of these can be used.

When the above component (D) is used, the amount of the above component (D) is appropriately determined from the viewpoint of setting the refractive index (RL) in the above-mentioned range, taking into consideration the type of the above component (D). The amount of the above component (D) may be usually 10 to 200 parts by mass, preferably 20 to 100 parts by mass, and more preferably 30 to 80 parts by mass, per 100 parts by mass of the above component (A) silane compound having a hydrolyzable group, from the viewpoint of setting the refractive index (RL) in the above-mentioned range.

The coating material of the present invention may further contain a solvent from the viewpoint of productivity when forming a wet coating film using the coating material of the present invention. Examples of the solvent include 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 2-methoxyethanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, methyl cellosolve, ethyl cellosolve, diacetone alcohol, and acetone. The solvent may be one of these or a mixture of two or more of them.

The amount of the solvent to be added is determined appropriately from the viewpoint of productivity when forming a wet coating film using the coating material of the present invention, and from the viewpoint of productivity of the process of drying the wet coating film and recovering the solvent after the wet coating film is formed.

When the coating material of the present invention is an embodiment that contains the above-mentioned component (D) low refractive index particles, that is, when the coating film (cured coating film) formed using the coating material of the present invention is a low refractive index layer, the blend amount of the above-mentioned solvent may be preferably 600 parts by mass or more, more preferably 1200 parts by mass or more, and even more preferably 1800 parts by mass or more, where the sum of the blend amounts of the above-mentioned components (A) to (D) is 100 parts by mass, from the viewpoint of productivity when forming a wet coating film using the coating material of the present invention. On the other hand, from the viewpoint of productivity of the process of drying the wet coating film and recovering the solvent after forming the wet coating film using the coating material of the present invention, the blend amount may be preferably 6000 parts by mass or less, more preferably 4000 parts by mass or less, and even more preferably 3000 parts by mass or less.

The coating material of the present invention may further contain optional components other than the above components (A) to (D) and the solvent, to the extent that it does not contradict the object of the present invention. Examples of the optional components include defoamers, leveling agents, surfactants, thixotropic agents, antistatic agents, antifouling agents, water repellents, printability improvers, antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, and dyes. The optional components may be one or a mixture of two or more of these. The amount of the optional components to be blended may be usually 10 parts by mass or less, or about 0.01 to 10 parts by mass, per 100 parts by mass of the component (A) silane compound having a hydrolyzable group.

The paint of the present invention can be obtained by mixing and stirring these components.

2. Laminated film:
The laminated film of the present invention includes a coating film formed using the coating material of the present invention. In the laminated film of the present invention, the coating film formed using the coating material of the present invention usually constitutes at least one surface of the laminated film. The laminated film of the present invention typically has a coating film formed using the coating material of the present invention and a layer of a film substrate, and the surface that becomes the surface in the actual use state (which may be one surface or both surfaces depending on the article) is constituted by the coating film. Here, the actual use state refers to the state in which the laminated film of the present invention is used as a member of various articles (for example, in the case of a shatterproof film, it is attached to a window glass, etc.; in the case of a decorative sheet, it is used to decorate the surface of an article; in the case of a face shield, it is set in the frame of the face shield and used to protect the face).

When the coating material of the present invention is an embodiment that contains the above-mentioned component (D) low refractive index particles, i.e., when the coating film (cured coating film) formed using the coating material of the present invention is a low refractive index layer, the low refractive index layer usually forms the surface that is the surface on which sunlight or external light is incident in actual use (this may be one surface or both surfaces depending on the article). Here, the actual use state refers to the state in which the laminate film of the present invention is used as a component of various articles.

The coating material of the present invention has been described above. The method of forming a coating film using the coating material of the present invention is not particularly limited, and known web coating methods can be used. Examples of the web coating method include rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, dip coating, spray coating, spin coating, air knife coating, and die coating. Among these methods, from the viewpoint of applying the coating material with good productivity by the roll-to-roll method, rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating are preferred, and from the viewpoint of making the coating film thickness uniform, rod coating is more preferred, and rod coating using a Mayer bar as the rod (hereinafter sometimes abbreviated as "Mayer bar method") is even more preferred.

The coating film (cured coating film) formed using the coating material of the present invention may be laminated directly onto the surface of the layer of the above-mentioned film substrate, or may be laminated via an anchor coat to improve adhesion.

The thickness of the coating film (cured coating film) formed using the coating material of the present invention is appropriately determined taking into consideration the flex resistance and the productivity when forming the coating film. From the viewpoint of maintaining good flex resistance of the laminated film and making it easy to handle as a film roll, the thickness of the coating film (cured coating film) formed using the coating material of the present invention may be usually 60 μm or less, preferably 30 μm or less, more preferably 20 μm or less, even more preferably 10 μm or less, and most preferably 5 μm or less. On the other hand, from the viewpoint of productivity when forming the coating film, it may be usually 0.1 μm or more, preferably 0.5 μm or more, and more preferably 1 μm or more.

When the coating material of the present invention is an embodiment containing the above-mentioned component (D) low refractive index particles, i.e., when the coating film (cured coating film) formed using the coating material of the present invention is a low refractive index layer, the thickness of the low refractive index layer is appropriately determined taking into consideration the desired reflectance and the productivity when forming the low refractive index layer. From the viewpoint of reducing reflectance, the thickness of the low refractive index layer may be usually 300 nm or less, preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less. On the other hand, from the viewpoint of productivity when forming the low refractive index layer, the thickness may be usually 10 nm or more, preferably 20 nm or more, more preferably 40 nm or more, and even more preferably 60 nm or more.

The above-mentioned film substrate layer is made of any resin film, and is the layer that serves as the film substrate for forming the coating film (cured coating film) formed using the coating material of the present invention.

Examples of the resin film include polyvinyl chloride resins; polyester resins such as aromatic polyesters and aliphatic polyesters; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; acrylic resins; polycarbonate resins; poly(meth)acrylimide resins; styrene resins such as polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), styrene-ethylene-butadiene-styrene copolymer, styrene-ethylene-propylene-styrene copolymer, and styrene-ethylene-ethylene-propylene-styrene copolymer; cellulose resins such as cellophane, triacetyl cellulose, diacetyl cellulose, and acetyl cellulose butyrate; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride; and other resin films such as polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, and polyethersulfone. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. These films also include multilayer films in which one or more of these types are laminated in two or more layers.

The thickness of the resin film is not particularly limited and can be any thickness as desired. When the laminate film of the present invention is used for applications that do not require high rigidity, the thickness of the resin film may be typically 10 μm or more, preferably 30 μm or more, and more preferably 50 μm or more, from the viewpoint of handleability and compliance with standards for glass shatterproof films. On the other hand, the thickness of the resin film may be typically 250 μm or less, preferably 150 μm or less, and more preferably 100 μm or less, from the viewpoint of economy.

When the laminated film of the present invention is used for applications requiring high rigidity, the thickness of the resin film may be typically 200 μm or more, preferably 300 μm or more, and more preferably 400 μm or more. On the other hand, in order to meet the demand for thinner articles, the thickness of the resin film may be typically 1500 μm or less, preferably 1000 μm or less, and more preferably 700 μm or less.

When the laminate film of the present invention is used for applications requiring transparency, such as shatterproof films, infrared shielding films, and ultraviolet shielding films attached to window panes of buildings and automobile windows; display panel protection films attached to smartphones, tablet terminals, car navigation systems, and the like; and face shields, the resin film is preferably one having high transparency, and a transparent resin film that is highly transparent and uncolored is more preferred.

The total light transmittance of the transparent resin film may usually be 80% or more, preferably 85% or more, more preferably 88% or more, and even more preferably 90% or more. The higher the total light transmittance, the better. The total light transmittance is measured in accordance with JIS K7136:2000. An example of an apparatus used for the measurement is the turbidity meter "NDH2000 (product name)" manufactured by Nippon Denshoku Industries Co., Ltd.

The yellowness index of the transparent resin film is usually 5 or less, preferably 3 or less, more preferably 2 or less, and even more preferably 1 to -1. The yellowness index is measured in accordance with JIS K7105:1981. An example of an apparatus used for the measurement is a colorimeter "SolidSpec-3700 (product name)" manufactured by Shimadzu Corporation.

The transparent resin film may be, for example, a cellulose ester resin such as triacetyl cellulose; a polyester resin such as polyethylene terephthalate; a cyclic hydrocarbon resin such as an ethylene norbornene copolymer; an acrylic resin such as polymethyl methacrylate, polyethyl methacrylate, or a vinylcyclohexane-methyl (meth)acrylate copolymer; an aromatic polycarbonate resin; a polyolefin resin such as polypropylene or 4-methyl-pentene-1; a polycarbonate resin; a poly(meth)acrylimide resin; a polyamide resin; a polyarylate resin; a polymeric urethane acrylate resin; or a polyimide resin. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. These films also include multilayer films in which one or more of these films are laminated in two or more layers.

When the laminate film of the present invention is used for applications in which transparency is not required, such as decorative sheets and decorative films, the resin film may be colored, opaque, or transparent.

When the coating material of the present invention is an embodiment that contains the above-mentioned component (D) low refractive index particles, i.e., when the coating film (cured coating film) formed using the coating material of the present invention is a low refractive index layer, the laminate film of the present invention may, in one embodiment, have a low refractive index layer, a high refractive index layer, and a film substrate layer in this order.

The low refractive index layer and the film substrate layer have been described above.

By providing the high refractive index layer, the anti-reflection function can be improved. The refractive index (RH) of the high refractive index layer is usually 1.55 or more, preferably 1.6 or more, and more preferably 1.65 or more, from the viewpoint of increasing the refractive index difference with the refractive index (RL) of the low refractive index layer and allowing the anti-reflection film (laminate film having the low refractive index layer) to exhibit good anti-reflection function. On the other hand, from the viewpoint of the transparency of the laminate film, it is preferably 2.0 or less, more preferably 1.9 or less, and even more preferably 1.8 or less.

The refractive index (RH) is a value measured using an Abbe refractometer according to JIS K7142:2008 Method A, using sodium D line (wavelength 589.3 nm), 1-bromonaphthalene as the contact liquid, the surface of the sample that was the biaxially oriented polypropylene resin film side when the sample was made is the surface that is in contact with the prism, and the direction of operation of the bar coater of the sample is the length direction of the test piece. For the sample, the paint used to form the high refractive index layer is applied to the surface of a 20 μm thick biaxially oriented polypropylene resin film using a bar coater so that the thickness after curing is 2 μm, and the coating film obtained by drying and curing is peeled off from the biaxially oriented polypropylene resin film for use.

The paint used to form the high refractive index layer is not particularly limited except that the refractive index (RH) falls within the above-mentioned range, and any paint can be used. As the paint used to form the high refractive index layer, a paint containing an active energy ray curable resin as a binder is preferred because it has high hardness, a short curing time, and high productivity. Hereinafter, a high refractive index layer forming paint containing an active energy ray curable resin as a binder (hereinafter sometimes abbreviated as "paint (H)") will be described.

(H1) Active energy ray curable resin:
The active energy ray curable resin (H1) functions to polymerize and cure by active energy rays such as ultraviolet rays and electron beams to form a coating film (cured coating film).

The above-mentioned component (H1) may, for example, be polyurethane (meth)acrylate, polyester (meth)acrylate, polyacryl (meth)acrylate, epoxy (meth)acrylate, polyalkylene glycol poly(meth)acrylate, or polyether (meth)acrylate, or other (meth)acryloyl group-containing prepolymers or oligomers; methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, or other (meth)acryloyl group-containing prepolymers or oligomers; Acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, phenyl (meth)acrylate, phenyl cellosolve (meth)acrylate, 2-methoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth)acrylate, trifluoroethyl (meth)acrylate, and trimethylsiloxyethyl. (meth)acryloyl group-containing monofunctional reactive monomers such as diethyl methacrylate; N-vinylpyrrolidone, styrene, and other monofunctional reactive monomers; diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2,2'-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl)propane, and 2,2'-bis(4-(meth)acryloyloxypolypropyleneoxyphenyl)propane, etc. Examples of the monomers include one or more selected from the group consisting of (meth)acryloyl group-containing bifunctional reactive monomers such as trimethylolpropane tri(meth)acrylate and trimethylolethane tri(meth)acrylate; (meth)acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra(meth)acrylate; and (meth)acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate, or resins containing one or more of the above as constituent monomers. In this specification, (meth)acrylate means acrylate or methacrylate.

The above component (H1) can be one of these or a mixture of two or more of them.

(H2) High refractive index particles:
The high refractive index particles of the component (H2) are particles that act to increase the refractive index of the coating film formed using the coating material (H).

Examples of the above component (H2) include metal oxides such as titanium oxide, zinc oxide, indium oxide, tin oxide, zirconium oxide, and aluminum oxide; and composite oxides in which these metal oxides are doped with different elements such as antimony and tin.

As the above component (H2), it is preferable to use high refractive index particles whose surfaces have been treated with silane-based coupling agents such as vinyl silane and amino silane; titanate-based coupling agents; aluminate-based coupling agents; organic compounds having ethylenically unsaturated bond groups such as (meth)acryloyl groups, vinyl groups, and allyl groups, and reactive functional groups such as epoxy groups; and surface treatment agents such as fatty acids and fatty acid metal salts. The interaction between the above component (H2) and the above component (H1) is strengthened, and the weather resistance of the coating film can be improved.

The average particle size of the above component (H2) is appropriately determined taking into consideration the need to maintain the transparency of the coating film and the productivity when producing high refractive index particles. The average particle size of the above component (H2) may usually be 1 to 300 nm, preferably 5 to 200 nm, more preferably 10 to 150 nm, and even more preferably 15 to 100 nm. The method for measuring and the definition of the average particle size are described above in the explanation of the above component (D) low refractive index particles.

As the above component (H2), one or a mixture of two or more of these can be used.

The amount of component (H2) is determined appropriately, taking into consideration the type of component (H2) and from the viewpoint of keeping the refractive index (RH) in the above-mentioned range. The amount of component (H2) may be usually 10 to 300 parts by mass, preferably 30 to 200 parts by mass, more preferably 45 to 150 parts by mass, and even more preferably 60 to 120 parts by mass, per 100 parts by mass of component (H1) in order to keep the refractive index (RH) in the above-mentioned range.

(H3) Photopolymerization initiator:
The coating material (H) may preferably further contain (H3) a photopolymerization initiator. The component (H3) is a compound that generates active species such as radicals when irradiated with active energy rays. The component (H3) generates active species such as radicals, thereby polymerizing and curing the component (H1) active energy ray curable resin.

The above-mentioned component (H3) may, for example, be benzophenone-based compounds such as benzophenone, methyl o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; benzoin-based compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl} acetophenone compounds such as 2-methyl-propan-1-one; alkylphenone compounds such as α-hydroxyalkylphenone and acetophenone dimethyl ketal; anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, and 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; biimidazole compounds; titanocene compounds; oxime ester compounds; oxime phenylacetate compounds; hydroxyketone compounds; triazine compounds; and aminobenzoate compounds.

The above component (H3) can be one of these or a mixture of two or more of them.

The amount of component (H3) is appropriately determined from the viewpoint of reliably obtaining the effect of using component (H3) and from the viewpoint of suppressing discoloration of the coating film (cured coating film). From the viewpoint of reliably obtaining the effect of using component (H3), the amount of component (H3) may be typically 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of component (H1). On the other hand, from the viewpoint of suppressing discoloration of the coating film (cured coating film), the amount may be typically 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less.

The coating material (H) may further contain a solvent from the viewpoint of productivity when forming a wet coating film using the coating material (H). Examples of the solvent include 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 2-methoxyethanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, methyl cellosolve, ethyl cellosolve, diacetone alcohol, and acetone. The solvent may be one or a mixture of two or more of these.

The coating material (H) may further contain optional components other than the components (H1) to (H3) as long as the purpose of the present invention is not violated. Examples of the optional components include defoamers, leveling agents, surfactants, thixotropy agents, antistatic agents, printability improvers, antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, and dyes. The optional components may be one or a mixture of two or more of these. The amount of the optional components to be added may be typically 10 parts by mass or less, or about 0.01 to 10 parts by mass, per 100 parts by mass of the component (H1).

The above-mentioned paint (H) can be obtained by mixing and stirring these components.

The method of forming the high refractive index layer on the surface of the film substrate using the coating material (H) is not particularly limited, and any known web coating method can be used. Examples of the web coating method include rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, dip coating, spray coating, spin coating, air knife coating, and die coating. Among these methods, from the viewpoint of applying the coating material with good productivity by the roll-to-roll method, rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating are preferred, and from the viewpoint of making the coating film thickness uniform, rod coating is more preferred, and rod coating using a Mayer bar as a rod (hereinafter sometimes abbreviated as "Mayer bar method") is even more preferred.

The high refractive index layer may be laminated directly onto the surface of the film substrate layer, or may be laminated via an anchor coat to improve adhesion.

The thickness of the high refractive index layer is appropriately determined taking into consideration the desired reflectance and the productivity when forming the high refractive index layer. From the viewpoint of anti-reflection function, the thickness of the high refractive index layer may be usually 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 1.5 μm or more. On the other hand, from the viewpoint of maintaining good bending resistance of the laminated film and making it easy to handle as a film roll, and from the viewpoint of suppressing curling, the thickness may be usually 60 μm or less, preferably 30 μm or less, more preferably 20 μm or less, even more preferably 10 μm or less, and most preferably 5 μm or less.

When the surface of the coating film (cured coating film) of the laminated film of the present invention is exposed to the Hong Kong influenza virus A (A/Hong Kong/8/68 (H3N2)) at a temperature of 25°C for 240 minutes, the log reduction in infectivity may be preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. From the viewpoint of antiviral properties, a higher log reduction in infectivity is preferable. Here, the log reduction in infectivity is measured according to the measurement method (a) Antiviral properties in the examples below.

When the laminated film of the present invention is used for applications requiring transparency, the haze of the laminated film of the present invention may be usually 5% or less, preferably 4% or less, more preferably 3% or less, and even more preferably 2.5% or less. From the viewpoint of obtaining a clear transparency, a lower haze is preferable. The total light transmittance of the laminated film of the present invention may be usually 80% or more, preferably 85% or more, more preferably 88% or more, and even more preferably 90% or more. A higher total light transmittance is preferable. Here, the total light transmittance and haze are measured according to JIS K7136:2000. An example of an apparatus used for the measurement is the turbidity meter "NDH2000 (product name)" manufactured by Nippon Denshoku Industries Co., Ltd.

Figure 1 is a conceptual diagram of a cross section showing an example of an embodiment of the laminated film of the present invention. The laminated film of this embodiment has, in order from the surface on which sunlight or external light is incident in actual use, a low refractive index layer 1 formed using the coating material of the present invention containing the above-mentioned component (D) low refractive index particles, a high refractive index layer 2, a first anchor coat 3, a transparent resin film layer 4, a second anchor coat 5, and a hard coat 6. A touch sensor is then formed directly on the surface of the hard coat 6 to produce a two-layer touch panel (often called a "one plastic glass solution"), which is then incorporated into car navigation systems, etc.

3. Items:
The article of the present invention includes a coating film (cured coating film) formed using the coating material of the present invention. In the article of the present invention, the coating film (cured coating film) formed using the coating material of the present invention usually constitutes at least a part of the surface of the article. In one embodiment of the article of the present invention, the coating film (cured coating film) formed using the coating material of the present invention may constitute the entire surface of the article.

In a typical embodiment, the article of the present invention may be an article in which the laminate film of the present invention is used as a component (e.g., window glass to which a shatterproof film is attached, furniture decorated with a decorative sheet, and a face shield, etc.).

In another typical embodiment, the article of the present invention may be one in which a coating film (cured coating film) is formed using the paint of the present invention on a part or all of the surface of a three-dimensional substrate of the article (e.g., the housing of an electrical appliance, the instrument panel of an automobile, etc.). The coating film may be formed by directly applying the paint of the present invention to the substrate, by laminating a laminate film containing the coating film, or by transferring the coating film from a laminate film containing the coating film to the substrate.

Examples of a method for forming a coating film by directly applying the coating material of the present invention to a part or all of the surface of the substrate include methods such as dip coating, spray coating, spin coating, and air knife coating, in which the coating material of the present invention is applied once or repeatedly two or more times to form a coating film.

Examples of methods for molding the above-mentioned base body include so-called three-dimensional molding methods such as membrane press molding, compressed air press molding, vacuum molding, and vacuum compressed air molding of a thermoplastic resin sheet; injection molding, blow molding, and extrusion molding of a thermoplastic resin; and a method of injecting a curable resin into a mold of a desired shape and curing it.

The present invention will be described below with reference to examples, but the present invention is not limited to these.

Measurement method (a) Antiviral activity:
(a1) Antiviral activity a:
(A-1) Measurement of the infectivity value of antiviral film:
The test was performed according to the method of ISO 21702 "Measurement of antiviral activity of plastic and non-porous surfaces". Specifically, the test was performed in the following procedure. First, a 5 cm x 5 cm test piece was taken from the laminated film (antiviral film) and placed in a plastic petri dish, and 100 μL of a virus solution (hereinafter sometimes referred to as "original solution") of the A Hong Kong influenza virus (A/Hong Kong/8/68 (H3N2)) was dropped onto the surface of the antiviral coating of the test piece, and allowed to act at room temperature (25°C) for 60 minutes. At this time, in order to keep the contact area between the test piece and the virus solution constant, the upper surface of the test piece was covered with a polyethylene terephthalate film (size 4 cm x 4 cm). Next, 10 mL of SCDLP medium was added, and the virus was washed out by pipetting to stop the action. The virus solution was then diluted with MEM dilution solution until the concentration of the virus solution after each action was 10 ^-2 to 10 ^-5 of the original solution (until the amount of virus solution after each action was 10 ² to 10 ⁵ times the amount of original solution (100 μL) dropped), and sample solutions (5 types of original solution, with virus solution concentrations of 10 ^-2 , 10 ^-3 , 10 ^-4 , and 10 ^-5 of the original solution) were prepared. Next, for each sample solution, 100 μL of the sample solution was inoculated into MDCK cells (Madin-Darby canine kidney cells) cultured in a 6-well plate dish, and the sample was allowed to stand for 60 minutes to allow the virus to be adsorbed to the MDCK cells. A 0.7% by mass agar medium was overlaid, and the cells were cultured for 48 hours at 34° C. and 5% CO ₂ in an incubator. After that, formalin fixation and methylene blue staining were performed, and the number of plaques formed was counted. From the results of each sample solution, the common logarithm of the virus infectivity (PFU (plaque-forming unit)/0.1 mL) was calculated.

(A-2) Preparation of control film:
The following components (A-1) 3333 parts by mass (100 parts by mass in terms of solid content), (C-1) 6 parts by mass, (D-1) 200 parts by mass (40 parts by mass in terms of solid content), (E-1) 4.2 parts by mass, and (F-1) 4400 parts by mass were mixed and stirred to obtain a coating material for forming a coating film of a control film. Next, the coating material was applied to one side of a 50 μm-thick double-sided easy-adhesion biaxially stretched polyethylene terephthalate resin film "Lumirror" (product name) of Toray Industries, Inc., using a Meyer bar type coating device so that the thickness after curing was 0.1 μm, dried, and cured by ultraviolet irradiation to form a coating film, thereby obtaining a control film.

(A-3) Measurement of the infectivity value of the control film:
The common logarithm of the infectivity titer of the control film was calculated in the same manner as in (A-1) above, except that a 5 cm × 5 cm test piece was taken from the control film obtained in (A-2) above.

(I-4) Evaluation of antiviral properties:
The difference between the common logarithm of the infectivity titer of the control film and the common logarithm of the infectivity titer of the antiviral film (hereinafter sometimes referred to as the "log reduction value") was calculated as an index of antiviral activity. Note that a log reduction value of 3 means that the infectivity titer of the antiviral film was 1/1000 of the infectivity titer of the control film.

(a2) Antiviral activity b:
The test was carried out in the same manner as in Test (a1) Antiviral Activity a, except that the time for which the virus solution was allowed to act was changed to 240 minutes.

(b) Total light transmittance, haze:
In accordance with JIS K7136:2000, the total light transmittance and haze were measured using a turbidity meter "NDH2000 (product name)" manufactured by Nippon Denshoku Industries Co., Ltd., under the condition that light was incident from the antiviral coating surface of the laminate film (antiviral film).

(C) Minimum reflectance:
A spectrophotometer "SolidSpec-3700 (product name)" and a reflection unit "Absolute reflectance measurement device, incident angle 5° (product name)" manufactured by Shimadzu Corporation were used, and a black adhesive sheet was attached to the surface of the laminate film (antiviral film) opposite the antiviral coating film surface, and the reflectance spectrum of visible light (wavelength 380 to 780 nm) was measured under the condition of 5 degree regular reflection (the reflection unit was installed in front of the integrating sphere) in accordance with the instructions for the spectrophotometer. The lowest reflectance was read as the minimum reflectance from the spectrum obtained by smoothing the spectrum using a polynomial approximation method. The black adhesive sheet was obtained by mixing 20 parts by mass of a black acrylic adhesive master batch "Black-OT-1338 (trade name)" from Resino Color Kogyo Co., Ltd. and 100 parts by mass of an adhesive "LKU-01 (trade name)" from Fujikura Kasei Co., Ltd. on one side of a 25 μm thick biaxially oriented polyethylene terephthalate resin film "E5431 (trade name)" from Toyobo Co., Ltd., and applying the mixture using an applicator so that the thickness after drying would be 35 μm. The L* value obtained by measuring the color of the adhesive layer of the black adhesive sheet was 3.13. The L* value was measured in accordance with JIS Z 8722:2009 using a spectrophotometer "CM600d" from Konita Minolta Japan Co., Ltd. under standard light D65 illumination, geometric condition c, and conditions including components that become specular reflection, and was converted to L*a*b* coordinates.

Raw materials used : (A) Silane compound having a hydrolyzable group:
(A-1) "X-12-2510A (trade name)" an organosilane compound having a hydrolyzable group in which one or more hydrogen atoms are substituted with a fluorine atom, manufactured by Shin-Etsu Chemical Co., Ltd. Solid content: 3% by mass.

(B) Monovalent copper compounds, etc.:
(B-1) Commercially available copper(I) iodide (CuI) powder (manufactured by Wako Pure Chemical Industries, Ltd.) was pre-dispersed in ethanol, and then crushed and dispersed in a bead mill to obtain a copper(I) iodide slurry having an average particle size of 120 nm. The solid content of this slurry was adjusted to 11% by mass.

(C) amine compounds, etc.;
(C-1) 3-aminopropyltriethoxysilane "KBE903 (product name)" from Shin-Etsu Chemical Co., Ltd.
(C-2) BYK-9076 (trade name), an amine-based dispersant from BYK Japan Co., Ltd. An alkyl ammonium salt of a high molecular weight copolymer containing a polyamine structure. Amine value: 44 mg KOH/g. Solid content: 100% by mass.
(C-3) BYK Japan's amine-based dispersant "DISPER BYK-145" (trade name). Phosphate salt of a high molecular weight copolymer containing a polyamine structure. Amine value 71 mg KOH/g. Solid content 100% by mass.
(C-4) N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane "KBM602 (trade name)" manufactured by Shin-Etsu Chemical Co., Ltd.
(C-5) N-(2-aminoethyl)-3-aminopropyltrimethoxysilane "KBM603 (trade name)" from Shin-Etsu Chemical Co., Ltd.
(C-6) Vinyltrimethoxysilane "KBM1003 (product name)" from Shin-Etsu Chemical Co., Ltd.
(C-7) 3-methacryloxypropylmethyldimethoxysilane "KBM502 (trade name)" from Shin-Etsu Chemical Co., Ltd.

(D) Low refractive index particles:
(D-1) Hollow silica dispersion "THRULYA4320 (product name)" from JGC Catalysts and Chemicals. The amount of hollow silica in the dispersion is 20% by mass. The average particle size of the hollow silica is 60 nm.

(E) Optional Components:
(E-1) An acrylic-silicone copolymer-based stain prevention agent "Simac US270 (product name)" manufactured by Toagosei Co., Ltd. Solid content: 100% by mass.

(F) Solvent:
(F-1) A mixed solvent of 2-methoxyethanol, 1-methoxy-2-propanol, and methyl isobutyl ketone in a volume ratio of 2:1:1.

(L) Antiviral coating film forming paint:
(L-1) 3,333 parts by mass of the component (A-1) (100 parts by mass in terms of solid content), 136 parts by mass of the component (B-1) (11 parts by mass of solid content), 6 parts by mass of the component (C-1), 200 parts by mass of the component (D-1) (40 parts by mass in terms of solid content), 4.2 parts by mass of the component (E-1), and 4,400 parts by mass of the component (F-1) were mixed and stirred to obtain an anti-viral coating film-forming paint (L-1).

(L-2) to (L-8): Except for changing the paint formulation as shown in Table 1, antiviral coating film-forming paints (L-2) to (L-8) were obtained in the same manner as (L-1) above.

The number of parts of each component in the antiviral coating paint listed in the table is calculated as the solid content for components other than the solvent (component (F-1) above).

Example 1
On one side of a 50 μm thick double-sided easy-adhesion biaxially stretched polyethylene terephthalate resin film "Lumirror (trade name)" manufactured by Toray Industries, Inc., the above (L-1) was applied using a film Mayer bar type coating device so that the thickness after curing would be 0.1 μm, and the film was dried and cured in a drying oven to form a cured coating film, thereby obtaining a laminated film. The above tests (a) to (c) were carried out. The results are shown in Table 1.

Examples 2 to 8
A laminated film was obtained in the same manner as in Example 1, except that the paint shown in Table 1 was used instead of the above (L-1) as the paint for forming an antiviral coating film. The above tests (a) to (c) were carried out. The results are shown in Table 1.

The coating film (cured coating film) formed using the paint of the present invention had good antiviral properties. In addition, the laminated film having the coating film (cured coating film) formed using the preferred paint of the present invention also had good transparency.

Raw materials used in the preparation of the coating material for forming the high refractive index layer (H1-1) were a polyfunctional urethane (meth)acrylate "Art Resin UN-954 (product name)" from Negami Chemical Industries, Ltd., with a solid content of 60% by mass and a functionality of 6.
(H2-1) Zirconium oxide methyl isobutyl ketone dispersion "ZRMIBK15WT%-P01 (product name)" by CIK Nanotech Co., Ltd. The amount of zirconium oxide in the dispersion is 15 mass%. The average particle size of zirconium oxide is 30 nm.
(H3-1) "Omnirad 184 (trade name)" an α-hydroxyalkylphenone photopolymerization initiator (1-hydroxycyclohexyl-phenyl ketone) from IGM Resins.

(H) Coating material for forming high refractive index layer:
(H-1) 167 parts by mass of the above component (H1-1) (100 parts by mass in terms of solid content), 600 parts by mass of the above component (H2-1) (90 parts by mass in terms of zirconium oxide), and 3 parts by mass of the above component (H3-1) were mixed and stirred to obtain a coating material (H-1) for forming a high refractive index layer.

Example H1
On one side of a 50 μm thick double-sided easy-adhesion biaxially stretched polyethylene terephthalate resin film "Lumirror (trade name)" manufactured by Toray Industries, Inc., the above (H-1) was applied using a film Mayer bar type coating device so that the thickness after curing was 1.7 μm, and the film was dried in a drying oven, and then irradiated with ultraviolet light to form a cured coating film (high refractive index layer). Next, the above (L-1) was applied on the surface of the high refractive index layer so that the thickness after curing was 0.1 μm, and the film was dried and cured in a drying oven to form a cured coating film, thereby obtaining a laminated film. The above tests (a) to (c) were performed. The results were antiviral a 1.39, antiviral b ≧ 4.12, total light transmittance 92%, haze 1.9%, and minimum reflectance 0.30%.

It has been found that a laminate film having a low refractive index layer, a high refractive index layer, and a film substrate layer in this order, formed using a preferred coating material of the present invention, has good antiviral properties and is excellent in transparency and antireflection properties.

1 is a schematic cross-sectional view showing an example of an embodiment of a laminated film of the present invention.

1: low refractive index layer 2: high refractive index layer 3: first anchor coat 4: transparent resin film layer 5: second anchor coat 6: hard coat

Claims (7)

(A) 100 parts by mass of a silane compound having a hydrolyzable group (excluding compounds having an organic polymerizable functional group);
(B) 5 to 150 parts by mass of at least one compound selected from the group consisting of monovalent copper compounds and iodides of iodine and elements of Periods 4 to 6 and Groups 8 to 15 of the Periodic Table; and
(C) 0.01 to 50 parts by mass of at least one compound selected from the group consisting of polyamines, amine compounds having a polyamine structure, amine compounds having a hydrolyzable silyl group, silane coupling agents having an amino group, vinyltrimethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane;
Paint containing.
(A) 100 parts by mass of a silane compound having a hydrolyzable group (excluding compounds having an organic polymerizable functional group);
(B) 0.1 to 150 parts by mass of at least one compound selected from the group consisting of monovalent copper compounds and iodides of iodine and elements of Periods 4 to 6 and Groups 8 to 15 of the Periodic Table; and
(C) 0.01 to 50 parts by mass of at least one compound selected from the group consisting of polyamines, amine compounds having a polyamine structure, amine compounds having a hydrolyzable silyl group, silane coupling agents having an amino group, vinyltrimethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane;
wherein the component (C) comprises a polyamine or an amine compound having a polyamine structure .
3. The coating material according to claim 2, wherein the amine value of the polyamine or the amine compound having a polyamine structure is 1 to 500 mgKOH/g.
The coating material according to any one of claims 1 to 3, further comprising: (D) 10 to 200 parts by mass of low refractive index particles.
The paint according to any one of claims 1 to 4, wherein at least one compound selected from the group consisting of monovalent copper compounds of component (B) and iodides of iodine and elements of periods 4 to 6 and groups 8 to 15 of the periodic table comprises cuprous iodide.
A laminated film comprising a coating film formed using the coating material according to any one of claims 1 to 5 , wherein the coating film constitutes at least one surface.
An article, comprising a coating film formed using the coating material according to any one of claims 1 to 5 , wherein the coating film constitutes at least a part of the surface of the article.