JP6911993B1 - Antibacterial active energy ray-curable coating compositions, coating layers, antibacterial components, and articles. - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an antibacterial active energy capable of forming a coating layer having sufficient antibacterial properties, stable expression of antibacterial properties, excellent dispersion stability contributing to improvement of yield, and excellent scratch prevention performance. Provided are a linear curable coating composition, an antibacterial member having a coating layer formed therein, and an article. SOLUTION: The film-forming component is an antibacterial active energy ray-curable coating composition containing a silver-based compound (B), and the film-forming component is a urethane having 6 or more (meth) acryloyl groups. A cured product having a thickness of 3 μm, which contains (meth) acrylate (A) and is formed from an antibacterial active energy ray-curable coating composition on a 100 μm polyethylene terephthalate film, has a Martens hardness of 40 to 80 N / mm 2. It is solved by an antibacterial active energy ray-curable coating composition having an antibacterial activity value of 2 or more in JISZ2801. [Selection diagram] None

Description

The present invention relates to an antibacterial active energy ray-curable coating composition, an antibacterial member having a coating layer formed thereto, and an article.

Conventionally, a coating layer has been formed in order to impart scratch prevention performance (hereinafter, also referred to as scratch resistance) to the surface of an article. In recent years, research and development on various functions such as antistatic property and anti-fingerprint property in addition to scratch prevention performance have been active, but especially in developed countries, bacteria adhering to articles due to the tendency to emphasize cleanliness. And it is required to suppress the propagation of viruses.

In order to satisfy this requirement, a polyvinyl alcohol composition having an amino group having antibacterial and antiviral properties and a coating material containing an ultraviolet curable resin have been proposed. Patent Document 1 describes an amino group in an ultraviolet curable acrylic resin. A coating material in which 5 to 10 parts of containing polyvinyl alcohol is mixed is disclosed.

Further, Patent Document 2 proposes a curable composition containing a compound having an acrylic group or a methacryl group, a silver compound, polyethyleneimine, and a polymerization initiator, and dipenta is added to a silver oxalate-polyethyleneimine complex. A curable composition containing acryloyl hexaacrylate and a polymerization initiator is disclosed.

International Publication No. 2017/171066 Japanese Unexamined Patent Publication No. 2020-045454

However, in the composition of Patent Document 1, since polyvinyl alcohol (PVA) is used as the antibacterial agent, the compatibility with the film-forming component is excellent, but since PVA is inferior in water resistance, stains on the coating layer are hypochlorous acid. Repeated wiping with a cloth soaked with an aqueous solution of chloric acid or alcohol will erode the surface of the coating layer, causing the coating layer to whiten or soften, causing scratches and cloudiness due to subsequent dry wiping. As a result, there is a problem that the visibility is inferior.
Further, in the composition of Patent Document 2, although a silver compound is used as an antibacterial agent, good antibacterial properties are exhibited, but the dispersion stability is insufficient, and agglomerates are generated in a short time after compounding, so that the coating is applied. There is a problem that coating film defects occur during construction.

As described above, it is difficult for these conventional compositions to form a coating layer which is excellent in dispersion stability and has both antibacterial property and scratch prevention performance.

That is, the present invention has sufficient antibacterial properties, has stable expression of antibacterial properties, has excellent dispersion stability that contributes to improvement of yield, and has antibacterial properties capable of forming a coating layer having excellent scratch prevention performance. An object of the present invention is to provide an active energy ray-curable coating composition, an antibacterial member having a coating layer formed from the active energy ray-curable coating composition, and an article.

Further, by using urethane (meth) acrylate (A), which is a reaction product of at least one of an aliphatic polyisocyanate and an alicyclic polyisocyanate, the film-forming component turns yellow even in outdoor use. An object of the present invention is to provide an antibacterial active energy ray-curable coating composition capable of forming a coating layer exhibiting good weather resistance without any problems.

That is, the present invention is an antibacterial active energy ray-curable coating composition containing a film-forming component and a silver-based compound (B), and the film-forming component has 6 or more (meth) acryloyl groups. A cured product having a thickness of 3 μm formed from an antibacterial active energy ray-curable coating composition on a 100 μm polyethylene terephthalate film containing urethane (meth) acrylate (A) has a Martens hardness of 40 to 80 N /. The present invention relates to an antibacterial active energy ray-curable coating composition having an antibacterial activity value of ^{mm 2 and an antibacterial activity value of 2 or more in JISZ2801.}

The present invention also relates to the antibacterial active energy ray-curable coating composition, wherein the cured product has an antiviral activity value of 2 or more in JISL1922.

The present invention also relates to the antibacterial active energy ray-curable coating composition in which the content of the urethane (meth) acrylate (A) is 30% by mass or more in the film-forming component.

Further, in the present invention, the film-forming component contains a reaction product of (meth) acrylate (a1) having a hydroxyl group and polyisocyanate (a2), and the polyisocyanate (a2) has two isocyanate groups. When the isocyanate group / hydroxyl group ratio is 0.2 to 0.7, and the polyisocyanate (a2) is a triisocyanate having three isocyanate groups, the isocyanate group / hydroxyl group ratio is 0.1. The present invention relates to the antibacterial active energy ray-curable coating composition of ~ 0.4.

The present invention also relates to the antibacterial active energy ray-curable coating composition, wherein the polyisocyanate (a2) contains at least one of an aliphatic polyisocyanate and an alicyclic polyisocyanate.

The present invention also relates to the antibacterial active energy ray-curable coating composition in which the content of the silver compound (B) is 0.5 to 10 parts by mass with respect to 100 parts by mass of the film-forming component.

The present invention also relates to a coating layer which is a cured product of the antibacterial active energy ray-curable coating composition.

The present invention also relates to an antibacterial member having the coating layer on a base material.

The present invention also relates to an article including the coating layer.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an antibacterial active energy ray-curable coating composition capable of forming a coating layer having sufficient antibacterial properties, excellent dispersion stability for stably expressing the same, and excellent scratch prevention performance. ..

Further, by using urethane (meth) acrylate (A), which is a reaction product of at least one of an aliphatic polyisocyanate and an alicyclic polyisocyanate, the film-forming component turns yellow even in outdoor use. It is possible to provide an antibacterial active energy ray-curable coating composition capable of forming a coating layer exhibiting good weather resistance without any need.

Embodiments of the present invention will be described in detail below, but the following description is an example (representative example) of embodiments of the present invention, and the present invention is not limited to these contents as long as the gist thereof is not exceeded. In addition, the numerical range specified by using "~" in the present specification shall include the numerical values before and after "~" as the range of the lower limit value and the upper limit value.

In the present specification, "Mw" is a polystyrene-equivalent weight average molecular weight determined by gel permeation chromatography (GPC) measurement, and "Mn" is a polystyrene-equivalent number average molecular weight determined by GPC measurement. These can be measured by the method described in the [Examples] section.

Further, in the present specification, when "(meth) acrylic", "(meth) acryloyl", "(meth) acrylic acid", and "(meth) acrylate" are described, they are used unless otherwise specified. , "Acrylic or methacrylic acid", "acryloyl or methacrylic acid", "acrylic acid or methacrylic acid", "acrylate or methacrylate".
Unless otherwise specified, the various components mentioned in the present specification may be independently used alone or in combination of two or more.
In the present specification, the urethane (meth) acrylate (A) having 6 or more functional groups and the antibacterial active energy ray-curable coating composition are the urethane (meth) acrylate (A) and the coating composition, respectively. May be abbreviated as.

<< Antibacterial active energy ray-curable coating composition >>
The coating composition in the present invention is used to form a coating layer that imparts antibacterial properties to an article, is an active energy ray-curable type, and has a film-forming component containing urethane (meth) acrylate (A), and a film-forming component. Contains a silver compound (B).
Further, a cured product having a thickness of 3 μm formed from an antibacterial active energy ray-curable coating composition on a 100 μm polyethylene terephthalate film has a maltens hardness of 40 to 80 N / mm ² and an antibacterial activity value in JISZ2801. Is 2 or more.
This makes it possible to obtain an antibacterial active energy ray-curable coating composition capable of forming a coating layer having sufficient antibacterial properties, excellent dispersion stability for stably expressing it, and excellent scratch prevention performance. can.

<Film-forming component>
The film-forming component is a component having active energy ray curability, and contains urethane (meth) acrylate (A) having 6 or more (meth) acryloyl groups, and if necessary, other urethane (meth) acrylate or It may further contain a (meth) acrylic compound or the like.
The content of urethane (meth) acrylate (A) in 100% by mass of the film-forming component is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more and 100% by mass or less. preferable. By containing 10% by mass or more of urethane (meth) acrylate (A), it becomes easy to achieve both scratch resistance and dispersion stability.

The average number of (meth) acryloyl groups in the film-forming component is preferably 3 to 10, and more preferably 4 to 8. At this time, the average number of (meth) acryloyl groups is determined based on the number of (meth) acryloyl groups in all the components of the film-forming component.
When the average number of (meth) acryloyl groups is 3 or more, the scratch resistance is excellent, and when the average number is 10 or less, it becomes easy to suppress deterioration of adhesion to the substrate or generation of cracks in the cured coating film.

(Urethane (meth) acrylate (A))
Urethane (meth) acrylate (A) is a urethane (meth) acrylate having 6 or more (meth) acryloyl groups, that is, having at least one urethane bond and at least 6 (meth) acryloyl groups in the same molecule. It is a compound. The more urethane bonds there are, the better the dispersion stability of the silver compound (B), which will be described later, and the larger the number of (meth) acryloyl groups, the better the scratch resistance, depending on the molecular weight.

As the urethane (meth) acrylate (A), a urethane (meth) acrylate having 6 or more (meth) acryloyl groups is used from the viewpoint of scratch resistance, but it is further necessary to have 9 or more (meth) acryloyl groups. preferable. It is preferable to have an acryloyl group from the viewpoint of curability.

The urethane (meth) acrylate (A) is preferably a reaction product of the (meth) acrylate (a1) having a hydroxyl group and the polyisocyanate (a2), and can be obtained by, for example, the following method.
Method 1: A method of reacting a (meth) acrylate (a1) having a hydroxyl group with a polyisocyanate (a2).
Method 2: A method of reacting a urethane prepolymer having an isocyanate group, which is obtained by reacting a polyol and a polyisocyanate (a2) under a condition of excess isocyanate group, with (meth) acrylates (a1) having a hydroxyl group.
Method 3: A method of reacting a urethane prepolymer having a hydroxyl group, which is obtained by reacting a polyol and a polyisocyanate (a2) under a condition of excess hydroxyl group, with (meth) acrylates having an isocyanate group.
Method 4: A method of reacting a urethane prepolymer having a carboxyl group, which is obtained by reacting a polyol having a carboxyl group and a polyisocyanate (a2) under a condition of excess hydroxyl group, with (meth) acrylates having an epoxy group.
Method 1, which is a simple synthesis method, is preferable because of the number of synthesis steps.

[(Meta) acrylate having a hydroxyl group (a1)]
Examples of the (meth) acrylate (a1) having a hydroxyl group used in the above methods 1 and 2 include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and isocyanuric acid. Examples thereof include (meth) acrylates having a hydroxyl group such as modified diacrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

[Polyisocyanate (a2)]
Examples of the polyisocyanate (a2) used in the above methods 1 to 4 include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

As aromatic polyisocyanates, 1,3-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, 4,4'-toluidin diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and 4,4', 4 "-Triphenylmethane triisocyanate, ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, Examples thereof include 1,4-tetramethylxylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate.

Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodecamethylene. Examples thereof include diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2, Examples thereof include 6-cyclohexanediisocyanate, 4,4′-methylenebis (cyclohexylisocyanate), and 1,4-bis (isocyanatemethyl) cyclohexane.

Further, the polyisocyanate may be a trimethylolpropane adduct body, a biuret body, an allophanate body, a nurate body or the like of the polyisocyanate.

The polyisocyanate (a2) preferably has an aromatic polyisocyanate or an alicyclic polyisocyanate from the viewpoint of scratch resistance. These polyisocyanates may contain a derivative and may have a ring structure such as a nurate form.
From the viewpoint of weather resistance, non-aromatic polyisocyanates are preferable, and aliphatic polyisocyanates or alicyclic polyisocyanates are preferable. In addition, these polyisocyanates also include derivatives.

Examples of the polyol used in the above methods 2 and 3 include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentane glycol, neopentyl glycol, and poly. Examples thereof include tetramethylene glycol, hexanetriol, trimeryl propane, glycerin, pentaerythritol and the like, as well as polypolymers of the polyol with polybasic acid or polybasic acid anhydride. Examples of the polybasic acid and the polybasic acid anhydride include aromatic polybasic acids such as phthalic acid and phthalic anhydride, and aliphatic polybasic acids such as adipic acid and sebacic acid.

Examples of the (meth) acrylates having an isocyanate group used in the above method 3 include 2- (meth) acryloyloxyethyl isocyanate and (meth) acryloyl isocyanate.

Examples of the carboxyl group-containing polyol used in Method 4 include dimethylolbutanoic acid and dimethylolpropionic acid. Further, a polycondensation product of a polyol such as ethylene glycol and propylene glycol, dimethylolbutanoic acid and the like, and a polybasic acid or a polybasic acid anhydride can also be mentioned.

Examples of the epoxy group-containing (meth) acrylates used in Method 4 include glycidyl (meth) acrylate.

The (meth) acrylates having a hydroxyl group, the polyisocyanate, the polyol, and the (meth) acrylates having an isocyanate group may be used alone or in combination of two or more.

The urethane (meth) acrylate (A) preferably has an intramolecular ring structure from the viewpoint of scratch resistance. For example, by having an aromatic ring, an alicyclic structure, or a nurate ring structure, an appropriate hardness can be imparted to the coating layer.

As the urethane (meth) acrylate (A) having an alicyclic structure, a hydrogenated product of isophorone diisocyanate or tolylene diisocyanate, a hydrogenated product of xylylene diisocyanate, a hydrogenated product of methylene diphenyl diisocyanate and derivatives thereof are used as polyisocyanates. Can be obtained by Alternatively, it can be obtained by using cyclohexanedimethanol mono (meth) acrylate as the (meth) acrylate having a hydroxyl group. Alternatively, it can be obtained by using cyclohexanediol as the polyol. Alternatively, it can be obtained by using cyclohexanedicarboxylic acid or its anhydride as the polybasic acid or polybasic acid anhydride.

The urethane (meth) acrylate (A) having a nurate ring can be obtained by using a trimer (nurate) formed from various diisocyanate components as the polyisocyanate in the above methods 1 to 4.

When the urethane (meth) acrylate (A) is obtained by the above methods 1 to 4, various components such as the following are included in addition to the ideal urethane (meth) acrylate (A).
Method 1 will be described as an example.
For example, some (meth) acrylates having one hydroxyl group as a raw material are provided in a mixed state with (meth) acrylates having no hydroxyl group. In addition to the ideal urethane (meth) acrylate (A), the product according to Method 1 also contains (meth) acrylates having no hydroxyl group. Further, since (meth) acrylates having a hydroxyl group are generally used in excess as compared with polyisocyanate, (meth) acrylates having one unreacted hydroxyl group are also included in the product according to Method 1. Become.
Further, among those manufactured and sold as (meth) acrylates having one hydroxyl group, (meth) acrylates having two or more hydroxyl groups and (meth) acrylic acid which is a raw material of (meth) acrylates are used. It may be contained in small amounts.
Therefore, some of the (meth) acryloyl groups in the ideal urethane (meth) acrylate (A) do not have the (meth) acryloyl group or the hydroxyl group in the (meth) acrylates having one unreacted hydroxyl group. Those in which (meth) acryloyl groups in (meth) acrylates have reacted one after another, or those in which (meth) acrylates having two or more hydroxyl groups and (meth) acrylates having one hydroxyl group have reacted with polyisocyanate. However, the product according to the method 1 is included in the product according to the method 1, and the product according to the method 1 is an aggregate of molecules having various structures and molecular weights and exhibits a relatively wide molecular weight distribution. The same applies to the cases according to methods 2 to 4.

Therefore, the method of determining the average number of (meth) acryloyl groups of the film-forming component containing urethane (meth) acrylate (A) is a (meth) acrylate having a hydroxyl group and five (meth) acryloyl groups. Dipentaerythritol pentaacrylate (hereinafter referred to as DPPA, molecular weight: 524) and dipentaerythritol hexaacrylate (hereinafter referred to as DPHA, which is a (meth) acrylate having 6 (meth) acryloyl groups without a hydroxyl group and having a molecular weight. Composition containing 1: 578) in a ratio of 1: 1 (molar ratio): 1052 g of hexamethylene diisocyanate containing 21.8 wt% of isocyanate groups (hereinafter referred to as HDI-nurate): 37 g (about as NCO group). A case of reacting with 0.19 mol = (37 × 0.218 / 42) × 100)) will be described as an example.
Since DPPA has one hydroxyl group per molecule and HDI nurate has three NCO groups per molecule, it is considered that three DPPA molecules react with one HDI nurate molecule. Therefore, it is considered that the DPPA contained in 1052 g of the composition is 500 g (about 0.95 mol), of which about 95 g of DPPA corresponding to about 0.19 mol reacts with the HDI nurate (molecular weight: 504). As a result, the product is
Theoretical molecular weight: 2076 (= 504 + 524 × 3), urethane (meth) acrylate (A) having 15 (meth) acryloyl groups: about 132 g, and
Unreacted DPPA with 5 (meth) acryloyl groups: about 405 g and
It is assumed that DPHA having 6 (meth) acryloyl groups: contains about 552 g.
Therefore, the average number of (meth) acryloyl groups of the film-forming component containing urethane (meth) acrylate (A) is (132 × 15 + 405 × 5 + 552 × 6) / (1052 + 37) = 6.8.
That is, the average number of (meth) acryloyl groups contained in the film-forming component referred to here is a theoretical value.

On the other hand, the entire product is considered to be an aggregate of molecular species having various structures and molecular weights as described above, but it is virtually impossible to specify each molecular species and the content of each. be.
Therefore, the properties of the product as a whole are specified by the above-mentioned average number of theoretical (meth) acryloyl groups and the mass average molecular weight (Mw).
The mass average molecular weight can be determined according to the method described later.

The mass average molecular weight (Mw) of the film-forming component containing urethane (meth) acrylate (A) is preferably 1000 to 6000, more preferably 1200 to 4000, and further preferably 1400 to 3500. preferable. By setting the mass average molecular weight (Mw) to 1000 to 6000, it is easy to achieve both scratch resistance and dispersion stability.

The (meth) acrylic equivalent Mw / f of the film-forming component containing urethane (meth) acrylate (A) is preferably 200 to 900, more preferably 300 to 800, and even more preferably 400 to 700. By setting the (meth) acrylic equivalent Mw / f to 200 to 900, it is easy to balance scratch resistance and dispersion stability.
The "f" here means the average number of (meth) acryloyl groups of the film-forming component containing the urethane (meth) acrylate (A) described above.

In the present invention, a product containing urethane (meth) acrylate (A) can be used as a film-forming component, and after a product containing urethane (meth) acrylate (A) is obtained, the product is added to the product. Optionally, a compound having a polymerizable unsaturated double bond group typified by a (meth) acrylic compound can be added and used as a film-forming component.
As the (meth) acrylic compound that can be added to the film-forming component, even if it does not have a functional group other than the (meth) acryloyl group like the DPHA, a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, etc. It may have a functional group such as a silanol group.
Examples of the compound having a polymerizable unsaturated double bond group other than the (meth) acrylic compound include fatty acid vinyl compounds, alkyl vinyl ether compounds, α-olefin compounds, vinyl compounds, and ethynyl compounds.

The content of urethane (meth) acrylate (A) contained in the product containing urethane (meth) acrylate (A) is the isocyanate group / hydroxyl group when the component having a hydroxyl group and the component having an isocyanate group are reacted. It can be changed by changing the ratio.
Specifically, when a diisocyanate component having two isocyanate groups is used as the component having an isocyanate group, the isocyanate group / hydroxyl group ratio is 0.2 to 0.7, more preferably 0.2 to 0.6, particularly. By setting it to 0.4 to 0.6, when a toisocyanate component having three isocyanate groups is used as the component having an isocyanate group, the isocyanate group / hydroxyl group ratio is 0.1 to 0.4, and further 0. By setting the value to 1 to 0.3, particularly 0.2 to 0.3, a urethane (meth) acrylate (A) having excellent dispersion stability and antibacterial properties can be obtained.

((Meta) acrylic compound)
When a product containing urethane (meth) acrylate (A) is obtained and then a (meth) acrylic compound or the like is further added to form a film-forming component, the average number of (meth) acryloyl groups of the film-forming component is obtained. And the average (meth) acryloyl group equivalent can be determined in the same manner as in the case of the above-mentioned product containing urethane (meth) acrylate (A).

Examples of the (meth) acrylic compound include an alkyl-based (meth) acrylate, an alkylene glycol-based (meth) acrylate, a compound having a carboxyl group and a polymerizable unsaturated double bond, a (meth) acrylic compound having a hydroxyl group, and nitrogen. Examples thereof include (meth) acrylic compounds and benzyl (meth) acrylates. From the viewpoint of scratch resistance of the coating layer, a polyfunctional one is preferable.

As the polyfunctional acrylic compound, those having three or more acryloyl groups are preferable, and dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, and tri. Examples thereof include methylolpropane triacrylate, isocyanuric acid-modified triacrylate, and ethyleneoxy-modified or propyloxy-modified products thereof.

In the embodiment of the present invention, an acrylic compound having two acryloyl groups can also be used. Specifically, polyethylene glycol diacrylate, polypropylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, nonanediol diacrylate, bisphenol A diacrylate, bisphenol F diacrylate and their ethyleneoxy modified products or propyloxy. Denatured products and the like can be mentioned.

In the embodiment of the present invention, a monofunctional (meth) acrylic compound can also be used. Specific examples of the monofunctional (meth) acrylic compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and octyl (meth) acrylate. ) Acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate, etc. Examples thereof include alkyl (meth) acrylates of 1 to 22.

Examples of the monofunctional alkylene glycol-based (meth) acrylate include ethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, tetramethylene glycol (meth) acrylate, and the like. Mono (meth) acrylate having polyoxyalkylene chain; methoxyethylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, propoxyethylene glycol (meth) acrylate, n-butoxy Tetraethylene glycol (meth) acrylate, n-pentoxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol ( Meta) acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol ( Mono (meth) acrylate having an alkoxy group at the end and a polyoxyalkylene chain such as meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and ethoxypolyethylene glycol (meth) acrylate. Phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate , Phenoxytetrapropylene ethylene glycol (meth) acrylate and the like, polyoxyalkylene-based (meth) acrylate having a phenoxy group or an aryloxy group at the end, and the like can be mentioned.

Compounds having a carboxyl group and a polymerizable unsaturated double bond include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, β- (meth) acryloxyethyl monoester of phthalates. , Isophthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, citraconic acid and the like.

Examples of the hydroxyl group-containing (meth) acrylic compound (excluding the mono (meth) acrylate having a hydroxyl group at the terminal and a polyoxyalkylene chain described above) include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (excluding the above-mentioned mono (meth) acrylate having a hydroxyl group and a polyoxyalkylene chain). Examples thereof include meta) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like.

Examples of nitrogen-containing (meth) acrylic compounds include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, and N-propoxymethyl- ( Monoalkylol (meth) acrylamide, N, N-di (methylol) acrylamide, N, N-di (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, etc. Acrylamide-based unsaturated compounds such as dialchirole (meth) acrylamide such as methylol) acrylamide;
There are unsaturated compounds having a dialkylamino group such as dimethylaminoethyl (meth) acrylate.

Further, examples of the monofunctional (meth) acrylic compound include perfluoroalkyloxyalkyl (meth) acrylates having a perfluoroalkyl group having 1 to 20 carbon atoms, such as perfluoromethyl (meth) acrylate. ..

Further, examples of the compound having a polymerizable unsaturated double bond group include an alkoxysilyl group such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, and γ- (meth) acryloxipropyltrimethoxysilane. Containing vinyl compounds and derivatives thereof;
Glycidyl group-containing acrylates such as glycidyl acrylate and 3,4-epoxycyclohexyl acrylate;
Examples thereof include perfluoroalkyls such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene and perfluorodecylethylene, and perfluoroalkyl group-containing vinyl monomers such as alkylenes.

<Silver compound (B)>
The silver-based compound (B) component in the present invention is a compound containing silver. The silver-based compound (B) functions as an antibacterial agent, and can also function as an active ingredient of an antiviral agent, an antifungal agent, or a deodorant.
Therefore, the antibacterial coating layer using the silver-based compound (B) can also exert an antiviral effect.

The following can be considered as a mechanism by which the antibacterial active energy ray-curable compound of the present invention has excellent antibacterial properties. When the silver-based compound (B) comes into contact with water, the water is permeated into the inside of the silver-based compound due to the slight moisture permeability of the urethane (meth) acrylate (A). This water elutes silver ions. The amount of silver ions eluted is almost constant during a certain period, and the silver ions are positively charged, and the silver ions are attracted to the surface of negatively charged bacteria and viruses. Then, the electrical balance of the surface of bacteria and the like is lost, the cell membrane is broken, and the bacteria are killed. Furthermore, silver ions permeate into the cell and bind to the intracellular enzyme to lose the enzyme activity. It also reacts with DNA from bacteria and the like, losing its function and reducing fertility. It is presumed that such antibacterial action of silver ions can completely prevent the growth of bacteria and the like on the surface of the coating layer.

By containing the silver-based compound (B), the coating composition of the present invention has antibacterial properties and can exert an effect of suppressing the growth of microorganisms and the like and a deodorizing effect. Examples of the silver compound (B) include, in addition to antibacterial properties, antivirus, antifungal, and deodorant effects, silver alone; silver oxide; silver carbonate, silver chloride, silver nitrate, silver sulfate, silver sulfonate, etc. Inorganic silver salts; those containing silver compounds such as organic silver salts such as silver formate and silver acetate can be mentioned. Further, the above silver salt may be supported on zeolite, silica gel, small molecule glass, calcium phosphate, silicate, molybdenum oxide, titanium oxide or the like.
Examples of the carrier include a zeolite-based silver-supporting compound supporting a silver compound such as silver alone, silver oxide, an inorganic silver salt, and an organic silver salt, a silica gel-based silver-supporting compound, a silicate-based silver-supporting compound, and a molybdenum oxide-based carrier. Examples thereof include silver-supported compounds and titanium oxide-based silver-supported compounds.

From the viewpoint of dispersion stability, the silver-based compound (B) is preferably a carrier in which an inorganic silver salt such as silver alone, silver oxide, and silver nitrate is supported on a carrier, and a zeolite in which a silver compound is supported on zeolite or molybdenum oxide. A silver-based silver-supported compound or a molybdenum oxide-based silver-supported compound is more preferable.
Zeolite-based silver-supported compounds or molybdenum oxide-based silver-supported compounds are preferable because they have excellent antiviral properties.

The average primary particle size of the silver-based compound (B) used in the present invention is preferably 5 to 100 nm. The average primary particle size can be measured by directly observing the particles themselves, for example, using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). When the average primary particle size is 5 nm or more, the dispersibility becomes better, and when the average primary particle size is 100 nm or less, a cured film having more excellent transparency can be formed.

The content of the silver-based compound (B) with respect to 100 parts by mass of the film-forming component containing the urethane (meth) acrylate (A) of the present invention is preferably 0. It is 1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and further preferably 1.0 to 7 parts by mass. When the content is 0.1 part by mass or more, a better antibacterial coating film can be obtained, and when the content is 20 parts by mass or less, a coating film having excellent dispersion stability can be easily formed.

The silver-based compound (B) is prepared as a suspension (slurry) in which a powdery compound is previously dispersed in a non-aqueous vehicle such as an organic solvent, and then blended with a film-forming component containing urethane (meth) acrylate (A). It is preferable to do so. A dispersant can also be used for slurrying. _{The dispersed particle size D 50} of the silver compound (B) in the slurry is preferably 300 nm or less, more preferably 200 nm or less. The dispersed particle size D ₅₀ can be measured by "Nanotrack UPA" manufactured by Nikkiso Co., Ltd. using a dynamic light scattering method. When the dispersed particle size D ₅₀ is 300 nm or less, the dispersion stability can be further improved.

For dispersion of silver compound (B) in non-aqueous vehicles such as organic solvents, paint conditioners (manufactured by Red Devil), ball mills, sand mills ("Dyno Mill" manufactured by Symmar Enterprises, etc.), attritors, pearl mills, etc. (Eich's "DCP mill", etc.), Coball mill, homomixer, homogenizer (M-Technique's "Clearmix", etc.), Wet jet mill (Genus's "Genus PY", Nanomizer's "Nammizer"), Dispersers such as micro bead mills (“Super Apec Mill” and “Ultra Apec Mill” manufactured by Kotobuki Kogyo Co., Ltd.) can be used. When media is used for the disperser, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads and the like. With regard to dispersion, two or more types of dispersers or two or more types of media having different sizes may be used and used in stages.

<Photopolymerization initiator (C)>
The coating composition according to the embodiment of the present invention may contain a photopolymerization initiator (C). The photopolymerization initiator may have a function of initiating the polymerization of an active energy ray-curable functional group such as a (meth) acryloyl group in a film-forming component containing urethane (meth) acrylate (A) by photoexcitation. However, the present invention is not particularly limited, and for example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl compound, and other compounds can be used.

Specifically, examples of the monocarbonyl compound include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 3,3', 4,4'-. Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone, 2-iso-propylthioxanthone, 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. ..

Examples of the dicarbonyl compound include 2-ethylanthraquinone, 9,10-phenanthrenequinone, methyl-α-oxobenzene acetate and the like.

Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-. Hydroxy-cyclohexylphenylketone, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 1,1'- (Methylene-di-1,4-phenylene) bis (2-hydroxy-2-methylpropan-1-one), 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxymethylpropan-1-one , Oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime and the like. Be done.

Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin normal butyl ether and the like.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide and the like.

Examples of the aminocarbonyl compound include ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate, Examples thereof include 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, and 2,5'-bis (4-diethylaminobenzal) cyclopentanone.

Examples of other compounds include (bis (2,4-cyclopentadienyl) bis "2,6-difluoro-3- (1-pyryl) phenyl" titanium (IV)).

Commercially available photopolymerization initiators include IGM-Resins B.I. V. Omnirad 184 (1-hydroxy-cyclohexylphenylketone), 651 (2,2-dimethoxy-1,2-diphenylethane-1-one), 500,907 (2-methyl-1- [4- (methylthio)) Phenyl] -2-morpholinopropan-1-one), 127 (1,1'-(methylene-di-1,4-phenylene) bis (2-hydroxy-2-methylpropan-1-one), 369 (2) -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one), 784 (bis (2,4-cyclopentadienyl) bis "2,6-difluoro-3- (1-pyril)" ) Phenyl "titanium (IV)), 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxymethylpropan-1-one), Esacure One (oligo [2-hydroxy-2-methyl-1-one] [4- (1-Methylvinyl) phenyl] propanone]), Lucillin TPO (2,4,6-trimethylbenzoyldiphenylphosphenyl oxide) manufactured by BASF, etc., in particular, yellowing resistance after active energy ray curing. From this point of view, Omnirad 184 and Esacure One are preferable.

The photopolymerization initiator is not limited to the above compounds, and may be any photopolymerization initiator as long as it has the ability to initiate polymerization with active energy rays. The amount of the photopolymerization initiator used is not particularly limited, but it is preferably used within the range of 1 to 20 parts by mass with respect to 100 parts by mass of the film-forming component. As a sensitizer, a known organic amine or the like can be added. Further, although the photopolymerization initiator is for radical polymerization, an initiator for cationic polymerization can also be used in combination.

The coating composition according to the embodiment of the present invention may further contain arbitrary components such as various additives as long as the object and effect of the present invention are not impaired. As an optional component, a resin other than a film-forming component, and as an additive, for example, a polymerization inhibitor, a photosensitizer, a leveling agent, a slip agent, a defoaming agent, a surfactant, an antiblocking agent, a plasticizer, and an ultraviolet absorber. Examples thereof include agents, infrared absorbers, antioxidants, silane coupling agents, conductive polymers, conductive surfactants, inorganic fillers, pigments, dyes and the like.
In addition, for example, those that exhibit an antistatic function to prevent the adhesion of dust and pollen, an antifogging function to prevent fogging due to sighs and sweat, and an antifouling function to prevent fogging due to cosmetics such as lipstick. Various additives may be used in combination. By using these additives in combination with the coating composition of the present invention, it is possible to exhibit a plurality of functions in a single layer at the same time as antibacterial performance.

When a solvent is added, it is preferable to carry out a curing treatment with active energy rays after volatilizing the solvent. The solvent is not particularly limited, and various known organic solvents can be used. Specifically, for example, cyclohexanone, methylisobutylketone, methylethylketone, acetone, acetylacetone, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol. , 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol monon-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethylene Glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, butyl acetate, tetrahydrofuran, methylpyrrolidone and the like can be mentioned.

Among these, a solvent having a hydroxyl group is particularly preferable because it works in a direction of stabilizing the dispersibility of the silver compound (B) in the solution. Further, when an additive such as silicone or fluorine that lowers the surface tension is contained, it is preferable because it is excellent in defoaming property against bubbles generated after mixing various materials and stirring or during coating. It is preferable to include a solvent having a hydroxyl group in the solvent composition because the dispersion is stabilized, the coating film defect is suppressed, and the yield is improved.
The content of the solvent having a hydroxyl group in 100% by mass of the total solvent is preferably 25 to 100% by mass, more preferably 50 to 100% by mass, and further preferably 75 to 100% by mass. .. Specifically, as the hydroxyl group-containing solvent, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol Examples thereof include monomethyl ether, ethylene glycol monon-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, and propylene glycol monomethyl ether. In particular, propylene glycol monomethyl ether and ethylene glycol monomethyl ether are preferable because they are excellent in defoaming property and volatility as a slow-moving solvent (solvent having low volatility) and have a better coated surface.

<Manufacturing method of antibacterial active energy ray-curable coating composition>
The coating composition of the present invention can be obtained by a known production method and is not particularly limited. For example, first, a film-forming component containing urethane (meth) acrylate (A) and a silver-based compound (B) are mixed and dispersed to obtain a stable dispersion, and then a photopolymerization initiator (C) and various other substances are obtained. Examples thereof include a method of adding, preparing and producing various additives.
Further, as described above, the powdery silver-based compound (B) is formed into a suspension (slurry) in which the powdery silver-based compound (B) is previously dispersed in a non-aqueous vehicle such as an organic solvent, and then the urethane (meth) acrylate (A) is contained in a film-forming property. It can also be blended with the ingredients to form a coating composition.

<< Antibacterial member >>
The antibacterial member is used to join the article to form an article provided with the antibacterial member. For example, it is obtained by coating the base material with the antibacterial active energy ray-curable coating composition of the present invention and curing it to form a coating layer.
The antibacterial member may have another functional layer in addition to the coating layer. For example, an antistatic layer for preventing adhesion of dust, pollen, etc., and an antifogging layer for preventing fogging due to breathing, sweat, etc. Examples thereof include those that exhibit an antifouling function for preventing stains caused by cosmetics such as layers and lipsticks.

<Coating layer>
The coating layer is a cured product of the antibacterial active energy ray-curable coating composition of the present invention.
For example, the coating composition can be applied to various substrates, dried when it contains an organic solvent, and then irradiated with active energy rays to form a coating layer which is a cured coating film.
The thickness of the cured product is preferably 0.5 to 20 μm, more preferably 1.0 to 15 μm, from the viewpoint of avoiding deterioration of adhesion to the substrate or generation of cracks in the cured coating film. It is more preferably 2 to 10 μm.

<Base material>
The base material can be appropriately selected from the group consisting of plastic, metal, wood and paper. Furthermore, a composite base material composed of a plurality of base materials can also be selected. These base materials may have a flat shape such as a film or paper, or may have a three-dimensional shape. The coating layer may be provided on both sides of the base material.

Examples of the plastic material include transparent polymers such as polyester-based polymers, cellulosic-based polymers, polycarbonate-based polymers, and acrylic-based polymers. Examples of the polyester-based polymer include polyethylene terephthalate (PE) and polyethylene naphthalate. Examples of the cellulosic polymer include diacetyl cellulose and triacetyl cellulose (TAC). Examples of the acrylic polymer include polymethylmethacrylate and the like.

Examples of the plastic material include transparent polymers such as styrene-based polymers, olefin-based polymers, vinyl chloride-based polymers, and amide-based polymers. Examples of the styrene polymer include polystyrene, acrylonitrile / styrene copolymer and the like. Examples of the olefin polymer include polyethylene, polypropylene, polyolefin having a cyclic or norbornene structure, ethylene / propylene copolymer and the like. Examples of the amide polymer include nylon and aromatic polyamide.

Furthermore, imide-based polymers, sulfone-based polymers, polyether sulfone-based polymers, polyether ketone-based polymers, polyphenyl sulfide-based polymers, vinyl alcohol-based polymers, vinylidene chloride-based polymers, vinyl butyral-based polymers, allylate-based polymers, and polyoxymethylene. Examples include based polymers, epoxy polymers, and transparent polymers such as blends of the polymers.

When a plastic film is used as a base material, the surface on which the cured coating film is formed is selected from the group of acrylic resin, copolymerized polyester resin, polyurethane resin, styrene-maleic acid graft polyester resin, acrylic graft polyester resin and the like. A so-called easy-adhesion type film provided with a resin layer can also be used.

Of the base materials, the thickness of the base material having a flat shape can be appropriately determined, but in the case of a plastic film, it is generally about 10 to 20,000 μm from the viewpoint of workability such as strength and handling. Is preferable. When the base material has a three-dimensional shape, the thickness is not limited.

The coating composition may be applied by a conventional method, for example, by a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or a spray method. When a solvent is contained, it is preferable to dry the coating film at about 50 to 150 ° C. after applying the coating composition.

Curing of the coating composition after coating can be performed by irradiating with active energy rays as described above. Examples of the active energy ray include ultraviolet rays and electron beams. When ultraviolet rays are used, a light source such as a high-pressure mercury lamp, an electrodeless lamp, or a xenon lamp is used, and the ultraviolet irradiation amount is preferably ^{, for example, about 100 to 2000 mJ / cm 2.} When an electron beam is used, the electron beam irradiation amount is preferably 60 to 150 kV, 1 to 10 mad, for example, under the condition that the oxygen concentration is 100 ppm or less.

<< Article with coating layer >>
The article provided with the antibacterial member of the present invention may be formed by coating the base material with the antibacterial active energy ray-curable coating composition of the present invention in the same manner as the antibacterial member, and may be used as the article. ..
Further, by using an antibacterial member and joining it to an article such as another base material, it can be used as an article provided with an antibacterial coating layer.
Articles with a coating layer are provided with another coating layer or another substrate via a bonding material on the coating layer side (including between the coating layer and the substrate) and / or on the substrate side without the coating layer. May be good.
By having the coating layer of the present invention, it is possible not only to protect or reinforce the article, but also to have an antibacterial function. In addition to the coating layer, it may have another functional layer.

Other functional layers include, for example, an antistatic function to prevent the adhesion of dust and pollen, an antifogging function to prevent fogging due to sighs and sweat, and an antifouling function to prevent fogging due to cosmetics such as lipstick. And the like that expresses. These functions can be expressed in a single layer at the same time as the antibacterial performance by using a functional material exhibiting the functions in combination with the coating composition of the present invention.
As another base material via the bonding material, the above-mentioned base material can be bonded to each other for the purpose of protection, reinforcement, or the like via a bonding material such as an adhesive or an adhesive.

<Article>
The article in the present invention is not limited as long as it requires antibacterial properties, and is used as a tangible object having the above coating layer. For example, transparent resin partitions, face guards, flexible packaging materials containing alcohol for disinfection and sheets, bottles and their cap members, smartphones, tablets, PCs, TVs, car navigation systems, information boards for commercial facilities, and transportation ticket vending machines. Examples include touch panel members mounted on such devices, door knobs, hanging leather, PC mice and keyboards, and other items that people directly touch in their daily lives.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. In addition, in Synthesis Examples and Examples, the number of parts of the material compounded is in terms of non-volatile content, excluding the solvent. Further, in the following Examples and Comparative Examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.

The molecular weight of urethane (meth) acrylate, the average primary particle size of the silver-based compound, and the dispersed particle size of the silver-based compound were measured by the following methods.
[Molecular weight of urethane (meth) acrylate]
The mass average molecular weight (Mw) and the number average molecular weight (Mn) were measured by the gel permeation chromatography (GPC) method. The measurement conditions are as follows. Both Mw and Mn are polystyrene-equivalent values.
Equipment: SHIMADZU Prominence (manufactured by Shimadzu Corporation),
Column: SHODEX LF-804 (manufactured by Showa Denko KK) connected in series,
Detector: Differential refractometer,
Solvent: tetrahydrofuran (THF),
Flow velocity: 1.0 mL / min,
Solvent temperature: 40 ° C,
Sample concentration: 0.2%,
Sample injection volume: 100 μL.

[Average primary particle size of silver compounds]
The average primary particle size is observed by a transmission electron microscope (TEM) using a transmission electron microscope JEM-2010 manufactured by JEOL Ltd., and 10 minor axis diameters and major axis diameters of the primary particles are measured, and the average thereof is measured. The value was taken as the average primary particle size.

[Dispersed particle size of silver-based compound]
The dispersed particle size D ₅₀ was measured by "Nanotrack UPA" manufactured by Nikkiso Co., Ltd. using a dynamic light scattering method.

<Synthesis of urethane (meth) acrylate (A)>
(Film-forming component (X1))
(A1): Anix M403: 1052 g (molecular weight: 524 dipentaerythritol pentaacrylate (DPPA) 500 g (about 0.95) in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping funnel. A composition containing 552 g (about 0.95 mol) of dipentaerythritol hexaacrylate (DPHA) having a molecular weight of 578 (mol) and Neostan U-810 (tin catalyst, Nitto Kasei (tin catalyst, manufactured by Toa Synthetic Co., Ltd.)). (Manufactured by Co., Ltd.) 0.1 g and 467 g of butyl acetate were added to bring the liquid temperature to 50 ° C., and then a nurate body (HDI-nurate body) of hexamethylene diisocyanate having about 21.8% by mass of an isocyanate group: 37 g (isocyanate). (Having about 0.19 mol of groups) was added dropwise from the dropping funnel over 30 minutes. After the temperature rise has subsided, the temperature is raised to 80 ° C. and reacted for 3 hours. After confirming that the peak of the isocyanate group has disappeared on FT-IR, butyl acetate is added while cooling to dilute, and DPPA and HDI- A solution of a film-forming component (X1) containing a urethane (meth) acrylate (A1) with a diluent was obtained. The solid content was 70% by mass.
The mass average molecular weight of the film-forming component (X1) containing urethane (meth) acrylate (A1) of DPPA and HDI-nurate is 1930, and the average number of functional groups (f _{C = C} ) obtained by the above method is 6. 8. The product acrylic equivalent Mw / f was 285. The film-forming component (X1) theoretically contains about 50.7% by mass of DPHA.

(Film-forming component (X2-12))
According to the composition and compounding ratio in Table 1, a film-forming component (X2 to 12) containing urethane (meth) acrylate (A) was obtained in the same manner as in the production of the film-forming component (X1).

In Table 1, f _OH represents the number of hydroxyl groups, f _NCO represents the number of isocyanate groups, and f _{C = C} represents the number of (meth) acryloyl groups.

[material]
The materials used are as follows.
"(Meta) acrylate having a hydroxyl group (a1)"
(A1-1) A composition containing Aronix M403 (dipentaerythritol pentaacrylate (DPPA) having a molecular weight of 524 and dipentaerythritol hexaacrylate (DPHA) having a molecular weight of 578). Penta / hexa = 1/1 (molar ratio). ), Toa Synthetic Co., Ltd.).
(A1-2) A-TMPT (Pentaerythritol triacrylate having a molecular weight of 298, manufactured by Shin-Nakamura Chemical Co., Ltd.).

"Polyisocyanate (a2)"
(A2-1) Sumijour N3300 (hexamethylene diisocyanate-nulate form, NCO% = 21.8 (solid content 100%), aliphatic polyisocyanate-nurate form manufactured by Sumika Cobestrourethane Co., Ltd.),
(A2-2) Death Module H (hexamethylene diisocyanate, NCO% = 50.0 (solid content 100%), manufactured by Sumika Cobestrourethane Co., Ltd., aliphatic polyisocyanate),
(A2-3) Death module Z4470BA (isophorone diisocyanate-neurate butyl acetate solution, NCO% = 16.9 (solid content 100% conversion), alicyclic polyisocyanate manufactured by Sumika Cobestrourethane Co., Ltd.) ),
(A2-4) Death module T-80 (tolylene diisocyanate, NCO% = 48.0 (solid content 100%), aromatic polyisocyanate manufactured by Sumika Cobestrourethane Co., Ltd.).

<Manufacturing of dispersion of silver compound>
(Silver compound dispersion 1)
A dispersion of silver ion-supported zeolite was produced by the following method.
Mix 200 parts of silver ion-supporting zeolite (Novalon AGT330, manufactured by Toa Synthetic Co., Ltd.), 10 parts of DisperBYK-111 (manufactured by Big Chemie Japan Co., Ltd.) as a dispersant, and 800 parts of methyl ethyl ketone, and disperse under the following conditions. Dispersion 1 containing a silver compound (B1) having an average primary particle size of 30 nm, a dispersion particle size D ₅₀ of 80 nm, and a solid content of 21% (the active ingredient as a silver compound is 20% in the dispersion). Was produced.
Pre-dispersion: Using zirconia beads (1.25 mm) as media, disperse with a paint shaker for 1 hour.
Main dispersion: Using zirconia beads (0.1 mm) as a medium, dispersion was performed for 1 hour with a disperser UAM-015 manufactured by Kotobuki Kogyo Co., Ltd.

(Silver compound dispersion 2)
A dispersion of silver ion-supported molybdenum oxide was produced by the following method.
195 parts of sodium molybdenate dihydrate (Kanto Kagaku Co., Ltd.) was dissolved in 3000 parts of ion-exchanged water, and a solution of 273 parts of silver nitrate (Kanto Kagaku Co., Ltd.) dissolved in 3000 parts of ion-exchanged water was stirred. While dropping over 30 minutes, a precipitate was obtained. This was filtered, washed with ion-exchanged water, and 200 parts sufficiently dried at 100 ° C. were used in place of Novalon AGT330 of the silver compound dispersion 1 in the same manner as the silver compound dispersion 1 on average. A dispersion 2 containing a silver-based compound (B2) having a primary particle size of 25 nm, a dispersion particle size D ₅₀ of 70 nm, and a solid content of 21% was prepared.

(Silver compound dispersion 3)
A dispersion of silver ion-supported zeolite was produced by the following method.
Instead of Novaron AGT330, except for using Zeomic AJ10N as silver ion-loaded zeolite (Co. Sinanen Zeomic made Mick) in the same manner as the silver compound dispersion 1, average primary particle diameter of 30 nm, a dispersion particle diameter _{D 50} A dispersion 3 containing a silver-based compound (B3) having a solid content of 90 nm and a solid content of 21% was prepared.

(Silver compound dispersion 4)
A dispersion of silver ion-supported silicate was produced by the following method.
Similar to silver compound dispersion 1, except that AIS-NAZ320 (manufactured by JGC Catalysts and Chemicals Co., Ltd.) was used as the silver ion-supporting silicate instead of Novalon AGT330, the average primary particle size was 40 nm, and the dispersed particles were dispersed. A dispersion 4 containing a silver-based compound (B4) having a diameter D _{50 of 110 nm and a solid content of 21% was prepared.}

(Example 1)
Dispersion 2 containing 100 parts by mass (nonvolatile content) of a film-forming component (X1) containing urethane (meth) acrylate (A) and 3 parts by mass (nonvolatile content) of a silver compound (B2), a photopolymerization initiator ( 5 parts by mass of Esacure One (manufactured by IGM-Resins BV) as C), 0.1 parts by mass of BYK349 (silicone-based additive, manufactured by Big Chemie Japan Co., Ltd.) as a leveling agent, insufficient as a diluting solvent 60 parts of polyethylene glycol monoethyl ether (PGME) and 20 parts of butyl acetate were mixed and dispersed to obtain a coating composition 1.

(Examples 2 to 12)
Coating compositions 1 to 12 were obtained in the same manner as in Example 1 except that the film-forming component (X1) was changed to the film-forming component (X2 to 12).

(Examples 13 to 18)
The amount of the silver compound (B2) was 0.2 parts, 0.5 parts, 1 part, 5 parts, 7 parts, and 12 parts (nonvolatile content), except that the dispersion 2 was used. Coating compositions 13-18 were obtained in the same manner as in Example 3. Table 3 also shows Example 3.

(Examples 19 to 21)
Coating compositions 19 to 21 were obtained in the same manner as in Example 4 except that the film-forming component (X4) was used and the dispersion containing the silver compounds (B1), (B3) and (B4) was used.
The table shows the content (nonvolatile content) of silver compounds.

(Example 22)
A coating composition 22 was obtained in the same manner as in Example 4 except that Omnirad 184 (manufactured by IGM Resins VV) was used as the photopolymerization initiator.

(Example 23)
A coating composition 23 was obtained in the same manner as in Example 4 in which 80 parts of butyl acetate was used without using polyethylene glycol monoethyl ether (PGME) as the diluting solvent.

(Comparative Example 1)
A coating composition was obtained in the same manner as in Example 3 except that Neofix RP-70 (polyethylene polyamine resin, manufactured by NICCA CHEMICAL CO., LTD.) Was used instead of the silver compound.

(Comparative Example 2)
A coating composition was obtained in the same manner as in Example 1 except that 100 parts of dipentaerythritol hexaacrylate (DPHA) was used as a film-forming component.

[material]
The materials used are as follows.
"Film-forming component"
DPHA (dipentaerythritol hexaacrylate, manufactured by Daicel Ornex Co., Ltd., molecular weight: 578, Mw / f _{C = C} = 96.3)

"others"
PR-70; Neofix RP-70 (polyethylene polyamine resin, manufactured by NICCA CHEMICAL CO., LTD.)
"Photopolymerization Initiator (C)"
Esacure One (oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, manufactured by IGM Resins BV),
Omnirad 184 (1-hydroxycyclohexylphenyl ketone, manufactured by IGM Resins BV)

The following physical property values were measured and evaluated using the obtained antibacterial active energy ray-curable composition. The results are shown in Tables 2-4.

(Martens hardness)
Each of the obtained coating compositions is coated on a 100 μm-thick easy-adhesion-treated polyethylene terephthalate film (PET; “Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) using a bar coater, and dried to remove the solvent. ^{After that, an ultraviolet ray of 200 mJ / cm 2} was irradiated using a high-pressure mercury lamp to form a cured product of 3 μm.
For the cured product on 100 μm PET, a microhardness meter Fisherscope HM2000 (manufactured by Fisher Instruments Co., Ltd., indenter; Vickers indenter, application speed; 0.5 mN / sec, maximum load; 10 mN, holding time; 5 seconds) was used. The Martens hardness (N / mm ² ) calculated based on the ISO14577 standard was measured.
A: 50-70N / mm ²
B: 40 to less than 50, or more than 70 to 80 N / mm ²
C: Less than 40 or more than 80 N / mm ²

(Antibacterial)
According to the test method of JISZ2801, the antibacterial property of the cured product obtained at the time of measuring the Martens hardness was tested.
A: Antibacterial activity value 3 or more B: Antibacterial activity value 2 or more and less than 3 C: Antibacterial activity value less than 2

(Anti-virus)
According to the test method of JISL1922, the antiviral property of the cured product obtained at the time of measuring the Martens hardness was tested.
A: Anti-virus activity value 3 or more B: Anti-virus activity value 2 or more and less than 3 C: Anti-virus activity value less than 2

<Evaluation of antibacterial active energy ray-curable composition>
(Dispersion stability)
After 50 parts by mass of the coating composition was placed in a 70 mL container with a lid and sealed, the whole container was allowed to stand in an oven at 40 ° C. for 1 week. After that, the container was taken out of the oven, air-cooled for 1 hour, visually observed, and a redispersion test was performed by shaking the container.
[Evaluation criteria]
〇: No sedimentation, good.
Δ: Although there is sedimentation, it can be redispersed and used by shaking the container.
X: Defective, not redispersed even when the container is shaken.

<Evaluation of coating layer>
(Formation of antibacterial member)
Each of the obtained coating compositions is coated on a 100 μm-thick easy-adhesion-treated polyethylene terephthalate film (PET; “Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) using a bar coater, and dried to remove the solvent. ^{After that, an ultraviolet ray of 200 mJ / cm 2} was irradiated using a high-pressure mercury lamp to form a cured product of 3 μm, and an antibacterial member was formed.

(Scratch resistance)
A 1-square-centimeter square pad equipped with # 0000 steel wool was placed on the coated surface of the cured product of the antibacterial member, reciprocated 10 times with a load of 500 g, and then visually evaluated for appearance and the number of scratches. Was measured.
[Evaluation criteria]
〇: No scratches, good.
Δ: 1-2 scratches, usable.
X: 3 or more scratches, defective.

(Weatherability)
Using a sunshine carbon weather meter (manufactured by Suga Test Instruments Co., Ltd., model: S80), the antibacterial member was placed in an atmosphere at a temperature of 63 ° C. and a humidity of 45%, and a weather resistance test was conducted for 500 hours before and after the test. The change in yellowness of the coating layer was measured using a color difference meter.
[Evaluation criteria]
〇: Δb ^* Value 1 or less, good.
Δ: Δb ^* Value 1 to 3 or less, can be used.
×: Δb ^* Value over 3, defective.

From Tables 2 to 4, the coating composition of the present invention contains a urethane (meth) acrylate (A) having 6 or more (meth) acryloyl groups, and is an antibacterial active energy ray-curable type on a 100 μm polyethylene terephthalate film. A cured product having a thickness of 3 μm formed from the coating composition has a martens hardness of 40 to 80 N / mm ² and an antibacterial activity value of 2 or more in JISZ2801 to ensure sufficient antibacterial properties and stabilize it. It was confirmed that a coating layer having excellent dispersion stability and scratch prevention performance can be formed.

As shown in Table 4, Comparative Example 2 in which the film-forming component did not contain urethane (meth) methacrylate (A) had a brittle coating film due to excessive hardness, resulting in inferior dispersion stability. ..

<Evaluation of articles with a coating layer>
On the surface opposite to the cured product of the coating composition, 100 parts by mass of an acrylic adhesive (manufactured by Toyochem Co., Ltd .; Oliveine BPS6421, non-volatile content 41%), an isocyanate curing agent (manufactured by Toyochem Co., Ltd .; Oliveine BHS8515, non-volatile) Minutes 37.5%) 1.2 parts by mass of the mixture is applied and dried to remove the solvent, and then a separator film (Super Stick SP-PET38 manufactured by Lintec Co., Ltd.) is bonded to 23 ° C. and 50% Rh. It was cured for one week in the environment. After curing, the separator film was peeled off and then attached to an acrylic partition (manufactured by Tomozawa Woodworking Co., Ltd .; splash guard acrylic panel) so that air would not enter.

It was confirmed that all the articles (acrylic partitions) provided with the coating layer formed by the coating composition obtained in the examples had both antibacterial properties and scratch resistance.

The antibacterial active energy ray-curable coating composition of the present invention includes transparent resin partitions, face guards, flexible packaging materials containing alcohol for disinfection and sheets, bottles and their cap members, smartphones, tablets, PCs, televisions, and the like. It can be used for items that people touch in their daily lives, such as touch panel members, door knobs, hanging leather, PC mice and keyboards mounted on information boards of car navigation systems and other commercial facilities and transportation ticket vending machines.

Claims (8)

An antibacterial active energy ray-curable coating composition containing a film-forming component and a silver-based compound (B).
The film-forming component contains urethane (meth) acrylate (A) having 6 or more (meth) acryloyl groups.
The content of the silver-based compound (B) is 0.5 to 10 parts by mass with respect to 100 parts by mass of the film-forming component.
A cured product having a thickness of 3 μm formed from an antibacterial active energy ray-curable coating composition on a 100 μm polyethylene terephthalate film is:
The Martens hardness is 40 to 80 N / mm2, and the antibacterial activity value in JISZ2801 is 2 or more.
Antibacterial active energy ray-curable coating composition. The cured product has an antiviral activity value of 2 or more in JIS L1922, claim 1.
The antibacterial active energy ray-curable coating composition according to the above. The antibacterial active energy ray-curable coating composition according to claim 1 or 2, wherein the content of the urethane (meth) acrylate (A) is 30% by mass or more in the film-forming component. The film-forming component contains a reaction product of a (meth) acrylate (a1) having a hydroxyl group and a polyisocyanate (a2), and when the polyisocyanate (a2) is a diisocyanate having two isocyanate groups, it has an isocyanate group. / Hydroxyl group ratio is 0.2 to 0.
7. The polyisocyanate (a2) is a triisocyanate having three isocyanate groups, and the isocyanate group / hydroxyl group ratio is 0.1 to 0.4.
~ 3 The antibacterial active energy ray-curable coating composition according to any one of the above items. The antibacterial active energy ray-curable coating composition according to claim 4, wherein the polyisocyanate (a2) contains at least one of an aliphatic polyisocyanate and an alicyclic polyisocyanate. A coating layer which is a cured product of the antibacterial active energy ray-curable coating composition according to any one of claims 1 to 5. An antibacterial member comprising the coating layer according to claim 6 on a base material. An article comprising the coating layer according to claim 6.