CN116018364A - Antimicrobial active energy ray-curable coating composition, coating, antimicrobial member, and article - Google Patents

Antimicrobial active energy ray-curable coating composition, coating, antimicrobial member, and article Download PDF

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CN116018364A
CN116018364A CN202180053985.2A CN202180053985A CN116018364A CN 116018364 A CN116018364 A CN 116018364A CN 202180053985 A CN202180053985 A CN 202180053985A CN 116018364 A CN116018364 A CN 116018364A
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meth
acrylate
coating composition
film
energy ray
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高桥隼人
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Toyochem Co Ltd
Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
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Abstract

A coating composition having sufficient antimicrobial properties, excellent dispersion stability that contributes to stable appearance of antimicrobial properties and improvement in yield, and excellent performance of preventing damage can be formed by an antimicrobial active energy ray-curable coating composition comprising a film-forming component and a silver-based compound, wherein the film-forming component comprises a urethane (meth) acrylate having 6 or more (meth) acryloyl groups, and wherein the Mars hardness is 40N/mm in a cured product of thickness 3 [ mu ] m formed from the antimicrobial active energy ray-curable coating composition on a polyethylene terephthalate film of thickness 100 [ mu ] m 2 ～80N/mm 2 And the antibacterial activity value in JIS Z2801 is 2 or more.

Description

Antimicrobial active energy ray-curable coating composition, coating, antimicrobial member, and article
Technical Field
The present invention relates to an antimicrobial active energy ray-curable coating composition, a coating layer formed from the same, an antimicrobial member having the coating layer, and an article.
Background
Since the past, the formation of a coating layer has been performed in order to impart damage-preventing performance (hereinafter, also referred to as scratch resistance) to the surface of an article. In recent years, research and development related to various functional properties such as antistatic properties and fingerprint resistance have been actively conducted in addition to the property of preventing damage, and particularly in developed countries, inhibition of proliferation of bacteria and viruses adhering to articles has been demanded due to the tendency to pay attention to the feeling of cleanliness.
In order to meet the above-mentioned demand, a coating material comprising a polyvinyl alcohol composition having an antibacterial and antiviral property and having an amino group and an ultraviolet curable resin has been proposed, and patent document 1 discloses a coating material in which 5 to 10 parts of an amino group-containing polyvinyl alcohol is mixed with an ultraviolet curable acrylic resin.
Patent document 2 discloses a curable composition containing a compound having an acrylic group or a methacrylic group, a silver compound, a polyethyleneimine, and a polymerization initiator, and a curable composition prepared by blending dipentaerythritol hexaacrylate and a polymerization initiator in a silver oxalate-polyethyleneimine complex.
Prior art literature
Patent literature
Patent document 1: international publication No. 2017/171066
Patent document 2: japanese patent laid-open No. 2020-045454
Disclosure of Invention
Problems to be solved by the invention
However, in the composition of the paint described in patent document 1, since polyvinyl alcohol (PVA) is used as an antibacterial agent, the compatibility with film forming components is excellent, but since PVA is poor in water resistance, if the operation of wiping dirt on the coating layer with a cloth immersed in an aqueous hypochlorous acid solution or alcohol is repeated, the surface of the coating layer is corroded, the coating layer is whitened or softened, damage is easily generated by subsequent dry wiping, and blurring occurs, and as a result, there is a problem in that visibility is low.
In addition, in the composition of the curable composition described in patent document 2, since a silver compound is used as an antibacterial agent, good antibacterial properties are exhibited, but dispersion stability is insufficient, aggregates are generated in a short time after blending, and there is a problem that a coating film is defective at the time of coating.
Thus, it is difficult to obtain a coating layer having excellent dispersion stability and further having both antibacterial properties and damage preventing properties by using these conventional compositions.
That is, an object of the present invention is to provide an antimicrobial active energy ray-curable coating composition capable of forming a coating layer having sufficient antimicrobial properties, excellent dispersion stability contributing to stable development of antimicrobial properties and improvement in yield, and excellent in damage prevention performance, a coating layer formed of the same, an antimicrobial member having the coating layer, and an article.
Further, it is an object of the present invention to provide an antimicrobial active energy ray-curable coating composition capable of forming a coating layer that does not undergo yellowing and exhibits good weather resistance even when used outdoors by using a urethane (meth) acrylate whose film-forming component is a reaction product of at least one selected from the group consisting of aliphatic polyisocyanates and alicyclic polyisocyanates.
Technical means for solving the problems
That is, an embodiment of the present invention relates to an antimicrobial active energy ray-curable coating composition comprising a film-forming component and a silver-based compound (B), wherein the film-forming component comprises 6 or more (meth) propanesAn enoyl urethane (meth) acrylate (A) having a Martin hardness of 40N/mm in a cured product of a polyethylene terephthalate film having a thickness of 100 μm and a thickness of 3 μm formed from the antimicrobial active energy ray-curable coating composition 2 ～80N/mm 2 And the antibacterial activity value in Japanese Industrial Standard (Japanese Industrial Standards, JIS) Z2801 is 2 or more.
Another embodiment of the present invention relates to the above-mentioned antimicrobial active energy ray-curable coating composition, wherein the cured product has an antiviral activity value of 2 or more in JIS L1922.
In addition, another embodiment of the present invention relates to the above-mentioned antimicrobial active energy ray-curable coating composition, wherein the content of the urethane (meth) acrylate (a) in the film-forming component is 30 mass% or more.
In addition, another embodiment of the present invention relates to the antimicrobial active energy ray-curable coating composition, wherein the film-forming component comprises a reaction product of a (meth) acrylate (a 1) having a hydroxyl group and a polyisocyanate (a 2), and the ratio of isocyanate groups/hydroxyl groups is 0.2 to 0.7 when the polyisocyanate (a 2) is a diisocyanate having 2 isocyanate groups, and the ratio of isocyanate groups/hydroxyl groups is 0.1 to 0.4 when the polyisocyanate (a 2) is a triisocyanate having 3 isocyanate groups.
In addition, another embodiment of the present invention relates to the antimicrobial active energy ray-curable coating composition, wherein the polyisocyanate (a 2) contains at least one selected from the group consisting of aliphatic polyisocyanates and alicyclic polyisocyanates.
In addition, another embodiment of the present invention relates to the antimicrobial active energy ray-curable coating composition, wherein the content of the silver-based compound (B) is 0.5 to 10 parts by mass per 100 parts by mass of the film-forming component.
In addition, another embodiment of the present invention relates to a coating layer which is a cured product of the antimicrobial active energy ray-curable coating composition.
In addition, still another embodiment of the present invention relates to an antibacterial member comprising the coating layer on a substrate.
In addition, the invention relates to an article comprising the coating.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the embodiment of the present invention, an antimicrobial active energy ray-curable coating composition capable of forming a coating layer having sufficient antimicrobial properties, excellent dispersion stability for stably exhibiting antimicrobial properties, and excellent damage prevention performance, a coating layer formed of the same, an antimicrobial member having the coating layer, and an article can be provided.
Further, it is possible to provide an antimicrobial active energy ray-curable coating composition which can form a coating layer exhibiting excellent weather resistance without yellowing even when used outdoors by using a urethane (meth) acrylate (A) having a film-forming component which is a reaction product of at least one selected from the group consisting of aliphatic polyisocyanates and alicyclic polyisocyanates.
Detailed Description
The following description is given in detail of the embodiments of the present invention, and is an example (representative example) of the embodiments of the present invention, but the present invention is not limited to these unless exceeding the gist thereof. In the present specification, a numerical range specified using "to" includes a range in which numerical values described before and after "to" are used as a lower limit value and an upper limit value.
In the present specification, "Mw" is a weight average molecular weight in terms of polystyrene obtained by gel permeation chromatography (gel permeation chromatography, GPC), and "Mn" is a number average molecular weight in terms of polystyrene obtained by GPC. These can be measured by the methods described in examples described below.
In the present specification, unless otherwise specified, the expressions "(meth) acrylic group", "(meth) acryl", "(meth) acrylic acid", "(meth) acrylate" are used to denote "acrylic group or methacrylic group", "acryl or methacryl", "acrylic acid or methacrylic acid", "acrylate or methacrylate", respectively.
The respective components described in the present specification may be used singly or in combination of two or more, unless otherwise noted.
In the present specification, the urethane (meth) acrylate (a) having a functional group of 6 or more and the antimicrobial active energy ray-curable coating composition are sometimes simply referred to as a urethane (meth) acrylate (a) and a coating composition, respectively.
Energy-ray-curable coating composition having antibacterial activity
The coating composition according to an embodiment of the present invention is used for forming a coating layer for imparting antimicrobial properties to an article, and is an active energy ray-curable coating composition comprising a film-forming component containing a urethane (meth) acrylate (a), and a silver-based compound (B).
In addition, in the hardened material with the thickness of 3 μm formed by the antimicrobial active energy ray hardening coating composition on the polyethylene terephthalate film with the thickness of 100 μm, the Martin hardness is 40N/mm 2 ～80N/mm 2 And the antibacterial activity value in JIS Z2801 is 2 or more.
Thus, an energy ray-curable coating composition having sufficient antimicrobial properties, excellent dispersion stability for stably exhibiting antimicrobial properties, and excellent anti-damage performance can be formed.
< film Forming ingredient >
The film-forming component is a component having active energy ray hardening properties, and contains a urethane (meth) acrylate (a) having 6 or more (meth) acryloyl groups, and may further contain other urethane (meth) acrylates or (meth) acrylic compounds, if necessary.
The content of the urethane (meth) acrylate (a) in 100 mass% of the film forming component is preferably 10 mass% or more, more preferably 20 mass% or more, and still more preferably 30 mass% or more and 100 mass% or less. By containing 10 mass% or more of the urethane (meth) acrylate (a), it is 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, more preferably 4 to 8. In this case, the average number of (meth) acryloyl groups is determined from the number of (meth) acryloyl groups in all the film-forming components.
When the average number of (meth) acryloyl groups is 3 or more, scratch resistance is more excellent, and when the number is 10 or less, deterioration in adhesion to a substrate or occurrence of cracks in a cured coating film is easily suppressed.
(urethane (meth) acrylate (A))
The urethane (meth) acrylate (a) is a urethane (meth) acrylate having 6 or more (meth) acryloyl groups, that is, a compound having at least one urethane bond and at least six (meth) acryloyl groups in the same molecule. The silver-based compound (B) described later is excellent in dispersion stability as the urethane bond is present more, and the number of (meth) acryloyl groups is larger, which is also dependent on the molecular weight, but can be made excellent in scratch resistance.
From the viewpoint of scratch resistance, urethane (meth) acrylate (a) having 6 or more (meth) acryloyl groups is used, and more preferably 9 or more (meth) acryloyl groups. From the viewpoint of hardenability, it is preferable to have an acryl group.
The urethane (meth) acrylate (a) is preferably a reaction product of a (meth) acrylate (a 1) having a hydroxyl group and a polyisocyanate (a 2), and can be obtained, for example, by the following method.
Method 1: a method of reacting a (meth) acrylate (a 1) having a hydroxyl group with a polyisocyanate (a 2).
Method 2: a method in which a urethane prepolymer having an isocyanate group, which is obtained by reacting a polyol with a polyisocyanate (a 2) under a condition of excess isocyanate groups, is reacted with a (meth) acrylate (a 1) having a hydroxyl group.
Method 3: a method in which a urethane prepolymer having a hydroxyl group, which is obtained by reacting a polyol with a polyisocyanate (a 2) under a condition that the hydroxyl group is excessive, is reacted with a (meth) acrylate having an isocyanate group.
Method 4: a method in which a carboxyl group-containing urethane prepolymer obtained by reacting a carboxyl group-containing polyol with a polyisocyanate (a 2) under a condition that the hydroxyl group is excessive is reacted with an epoxy group-containing (meth) acrylate.
The number of synthesis steps is preferably method 1, which is a simple synthesis method.
[ hydroxyl group-containing (meth) acrylate (a 1) ]
Examples of the (meth) acrylate (a 1) having a hydroxyl group used in the method 1 or the method 2 include: hydroxy-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethylene Oxide (EO) isocyanurate-modified di (meth) acrylate, propylene Oxide (PO) isocyanurate-modified di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.
[ polyisocyanate (a 2) ]
Examples of the polyisocyanate (a 2) used in the methods 1 to 4 include: aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and the like.
Examples of the aromatic polyisocyanate include: 1, 3-Benzenediisocyanate, 4 '-diphenyldiisocyanate, 1, 4-Benzenediisocyanate, 4' -diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4 '-toluidine diisocyanate, 2,4, 6-triisocyanatolylene, 1,3, 5-triisocyanatobenzene, benzidine diisocyanate (dianisidine diisocyanate), 4' -diphenylether diisocyanate, and 4,4', 4' -triphenylmethane triisocyanate, ω '-diisocyanate-1, 3-dimethylbenzene, ω' -diisocyanate-1, 4-diethylbenzene, 1, 4-tetramethylxylylene diisocyanate, 1, 3-tetramethylxylylene diisocyanate, and the like.
Examples of the aliphatic polyisocyanate include: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hexamethylene diisocyanate, HDI), pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, and the like.
Examples of the alicyclic polyisocyanate include: isophorone diisocyanate (isophorone diisocyanate, IPDI), 1, 3-cyclopentane diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), 1, 4-bis (isocyanatomethyl) cyclohexane, and the like.
The polyisocyanate may be a trimethylolpropane adduct, biuret, allophanate, or allophanate of the polyisocyanate.
The polyisocyanate (a 2) is preferably an aromatic polyisocyanate or a cycloaliphatic polyisocyanate from the viewpoint of scratch resistance. These polyisocyanates may also be those containing derivatives and having a cyclic structure such as a allophanate.
From the viewpoint of weather resistance, a non-aromatic polyisocyanate is preferable, and an aliphatic polyisocyanate or a cycloaliphatic polyisocyanate is preferable. These polyisocyanates also include derivatives.
Examples of the polyol used in the method 2 or the method 3 include: examples of the polycondensates of the above-mentioned polyhydric alcohols with a polybasic acid or polybasic acid anhydride include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, polytetramethylene glycol, hexanetriol, trimethylolpropane, glycerin and pentaerythritol. Examples of the polybasic acid or 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) acrylate having an isocyanate group used in method 3 include 2- (meth) acryloyloxyethyl isocyanate and (meth) acryl isocyanate.
Examples of the polyhydric alcohol having a carboxyl group used in the method 4 include dimethylolbutyric acid and dimethylolpropionic acid. Further, polycondensates of polyhydric alcohols such as ethylene glycol and propylene glycol with polybasic acids or polybasic acid anhydrides such as dimethylolbutyric acid can be also mentioned.
Examples of the (meth) acrylate having an epoxy group used in method 4 include glycidyl (meth) acrylate.
The (meth) acrylate having a hydroxyl group, the polyisocyanate, the polyol, and the (meth) acrylate having an isocyanate group may be used singly or in combination of two or more.
From the viewpoint of scratch resistance, the urethane (meth) acrylate (a) preferably has a ring structure in the molecule. For example, having an aromatic ring, an alicyclic structure, or a urethane ring structure can impart moderate hardness to the coating layer.
The urethane (meth) acrylate (a) having an alicyclic structure can be obtained by using, as a polyisocyanate, for example, isophorone diisocyanate or a hydrogenated body of toluene diisocyanate, a hydrogenated body of xylene diisocyanate, a hydrogenated body of methylene diphenyl diisocyanate, and derivatives of these. Alternatively, it can be obtained by using, for example, cyclohexanedimethanol mono (meth) acrylate as the (meth) acrylate having a hydroxyl group. Alternatively, it can be obtained by using, for example, cyclohexane diol as a polyol. Alternatively, it can be obtained by using, for example, cyclohexane dicarboxylic acid and its anhydride as the polybasic acid and polybasic acid anhydride.
The urethane (meth) acrylate (a) having a urethane ring can be obtained by using, as the polyisocyanate in methods 1 to 4, a trimer (a urethane body) formed from various diisocyanate components.
When the urethane (meth) acrylate (a) is obtained by the methods 1 to 4, the following components are contained in addition to the desired urethane (meth) acrylate (a).
Method 1 is described as an example.
For example, there are also (meth) acrylates having 1 hydroxyl group as a raw material, and those which are supplied in a mixed state with (meth) acrylates having no hydroxyl group, and therefore, in the case of using such a mixture, the product obtained by the method 1 contains (meth) acrylates having no hydroxyl group in addition to the desired urethane (meth) acrylate (a). In general, since a (meth) acrylate having a hydroxyl group is used in excess of a polyisocyanate, an unreacted (meth) acrylate having one hydroxyl group is also included in the product obtained by the method 1.
Further, a compound produced and sold as a (meth) acrylate having 1 hydroxyl group may contain a small amount of a (meth) acrylate having 2 or more hydroxyl groups or a (meth) acrylic acid as a raw material of the (meth) acrylate.
Therefore, a part of the (meth) acryloyl group in the urethane (meth) acrylate (a) is desirably contained in the product obtained by the reaction between a part of the (meth) acryloyl group in the unreacted (meth) acrylate having 1 hydroxyl group and the (meth) acryloyl group in the (meth) acrylate having no hydroxyl group, or the product obtained by the reaction between the (meth) acrylate having 2 or more hydroxyl groups and the (meth) acrylate having 1 hydroxyl group and the polyisocyanate, and the product obtained by the reaction between the product obtained by 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 methods 2 to 4.
Therefore, a method for determining the average number of (meth) acryloyl groups in a film-forming component including urethane (meth) acrylate (a) was performed such that the ratio of (meth) acryloyl groups was 1:1 (molar ratio) of a composition comprising dipentaerythritol pentaacrylate (hereinafter, referred to as DPPA (dipentaerythritol pentaacrylate). Molecular weight: 524) which is a (meth) acrylate having a hydroxyl group and having 5 (meth) acryloyl groups, and dipentaerythritol hexaacrylate (hereinafter, referred to as DPHA (dipentaerythritol hexaacrylate). Molecular weight: 578) which is a (meth) acrylate having no hydroxyl group and having 6 (meth) acryloyl groups: 1052g of an urethane body with hexamethylene diisocyanate containing 21.8% by weight of isocyanate groups (hereinafter referred to as HDI-urethane): a reaction of 37g (about 0.19 mol. = (37X 0.218/42). Times.100 in terms of NCO groups) is illustrated.
DPPA has 1 hydroxyl group per molecule and HDI urethane has 3 NCO groups per molecule, so 3 molecules of DPPA are believed to react with 1 molecule of HDI urethane. Thus, it is considered that DPPA contained in 1052g of the composition is 500g (about 0.95 mol), wherein about 95g of DPPA corresponding to about 0.19 mol is reacted with the HDI urethane (molecular weight: 504), and as a result, in the resultant,
theoretical molecular weight: 2076 (=504+524×3), assuming that it contains: urethane (meth) acrylate (a) having 15 (meth) acryloyl groups: about 132g,
Unreacted DPPA with 5 (meth) acryloyl groups: about 405g
DPHA having 6 (meth) acryloyl groups: about 552g.
Therefore, the average number of (meth) acryloyl groups of the film-forming component including the urethane (meth) acrylate (a) is (132×15+405×5+552×6)/(1052+37) =6.8.
That is, the average number of (meth) acryloyl groups in the film-forming component is a theoretical value.
On the other hand, the whole product is considered to be an aggregate of molecular species of various structures and molecular weights as described above, but it is practically impossible to determine the content of each molecular species and each content of each molecular species in total.
Therefore, the properties of the whole product are determined by the theoretical average number of (meth) acryloyl groups and the mass average molecular weight (Mw).
The mass average molecular weight can be obtained by the method described below.
The mass average molecular weight (Mw) of the film-forming component comprising the urethane (meth) acrylate (A) is preferably 1000 to 6000, more preferably 1200 to 4000, and even more preferably 1400 to 3500. By setting the mass average molecular weight (Mw) to 1000 to 6000, scratch resistance and dispersion stability can be easily achieved.
The (meth) acrylic equivalent Mw/f of the film-forming component comprising the urethane (meth) acrylate (A) is preferably 200 to 900, more preferably 300 to 800, still more preferably 400 to 700. By setting the (meth) acrylic equivalent Mw/f to 200 to 900, the balance between scratch resistance and dispersion stability can be easily achieved.
The term "f" as used herein means the average number of (meth) acryloyl groups in the film-forming component containing the urethane (meth) acrylate (a).
In one embodiment of the present invention, a product containing urethane (meth) acrylate (a) may be used as the film-forming component, or a compound having a polymerizable unsaturated double bond group typified by a (meth) acrylic compound may be further added to the product after the product containing urethane (meth) acrylate (a) is obtained.
The (meth) acrylic compound that can be added to the film-forming component may have no functional group other than a (meth) acryloyl group, as in DPHA, or may have a functional group such as a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, or a silanol group.
Examples of the compound having a polymerizable unsaturated double bond group other than the (meth) acrylic compound include a fatty acid vinyl ester compound, an alkyl vinyl ether compound, an α -olefin compound, a vinyl compound, and an acetylene compound.
The content of the urethane (meth) acrylate (a) contained in the product containing the urethane (meth) acrylate (a) can be changed by changing the ratio of isocyanate groups to hydroxyl groups when reacting the component having hydroxyl groups with the component having isocyanate groups.
Specifically, when a diisocyanate component having 2 isocyanate groups is used as the component having isocyanate groups, the ratio of isocyanate groups to hydroxyl groups is set to 0.2 to 0.7, and further, 0.2 to 0.6, and particularly, 0.4 to 0.6, and when a triisocyanate component having 3 isocyanate groups is used as the component having isocyanate groups, the ratio of isocyanate groups to hydroxyl groups is set to 0.1 to 0.4, and further, 0.1 to 0.3, and particularly, 0.2 to 0.3, the urethane (meth) acrylate (a) excellent in dispersion stability and antibacterial property can be obtained.
((meth) acrylic Compound)
When a film-forming component is produced by obtaining a product containing urethane (meth) acrylate (a) and then adding a (meth) acrylic compound or the like, the average number of (meth) acryloyl groups or average (meth) acryloyl equivalent weight of the film-forming component can be obtained in the same manner as in the case of the product containing urethane (meth) acrylate (a).
Examples of the (meth) acrylic compound include alkyl (meth) acrylates, alkylene glycol (meth) acrylates, compounds having carboxyl groups and polymerizable unsaturated double bonds, hydroxyl group-containing (meth) acrylic compounds, nitrogen-containing (meth) acrylic compounds, benzyl (meth) acrylate, and the like. From the viewpoint of scratch resistance of the coating layer, a polyfunctional compound is preferable.
The polyfunctional acrylic compound is preferably a compound having three or more acryl groups, and examples thereof include: dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, pentapentaerythritol triacrylate, trimethylolpropane triacrylate, isocyanuric acid modified triacrylate, ethylene oxide modified or propylene oxide modified versions thereof, and the like.
In one embodiment of the present invention, an acrylic compound having two acryl groups may also be used. Specifically, examples thereof include: polyethylene glycol diacrylate, polypropylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, nonanediol diacrylate, bisphenol A diacrylate, bisphenol F diacrylate, ethylene oxide modified products or propylene oxide modified products of these, and the like.
In one embodiment of the present invention, a monofunctional (meth) acrylic compound may be further 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, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.
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, having a hydroxyl group at the terminal and a polyoxyalkylene chain; methoxy ethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy ethylene glycol (meth) acrylate, propoxy ethylene glycol (meth) acrylate, n-butoxy tetraethylene glycol (meth) acrylate, n-pentoxy tetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy tetrapropylene glycol (meth) acrylate, ethoxy tetrapropylene glycol (meth) acrylate, propoxy tetrapropylene glycol (meth) acrylate, n-butoxy tetrapropylene glycol (meth) acrylate, n-pentoxy tetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, and the like have alkoxy groups at the ends and have polyoxyalkylene chains; and polyoxyalkylene-based (meth) acrylates having a phenoxy group or an aryloxy group at the terminal end, such as phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenoxytetrapropylene glycol (meth) acrylate.
Examples of the compound having a carboxyl group and a polymerizable unsaturated double bond include: maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters of these, β - (meth) acryloyloxyethyl phthalate, β - (meth) acryloyloxyethyl isophthalate, β - (meth) acryloyloxyethyl succinate, acrylic acid, methacrylic acid, crotonic acid, cinnamic 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) include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like.
Examples of the nitrogen-containing (meth) acrylic compound include: an acrylamide-based unsaturated compound such as a monohydroxy alkyl (meth) acrylamide such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, or a dihydroxyalkyl (meth) acrylamide such as N, N-bis (hydroxymethyl) acrylamide;
Unsaturated compounds having a dialkylamino group such as dimethylaminoethyl (meth) acrylate and the like.
Examples of the monofunctional (meth) acrylic compound include: and perfluoroalkyl oxyalkyl (meth) acrylates having a perfluoroalkyl group of 1 to 20 carbon atoms such as perfluoromethyl (meth) acrylate.
Examples of the compound having a polymerizable unsaturated double bond group include: alkoxysilane group-containing vinyl compounds such as vinyltrichlorosilane, vinyltris (. Beta. -methoxyethoxy) silane, vinyltriethoxysilane, and γ - (meth) acryloxypropyl trimethoxysilane, and derivatives thereof;
glycidyl group-containing acrylates such as glycidyl acrylate and 3, 4-epoxycyclohexyl acrylate;
perfluoroalkyl-containing vinyl monomers such as perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluorodecyl ethylene, and alkylene.
< silver-based Compound (B) >)
The silver-based compound (B) is a compound containing silver. The silver-based compound (B) can function as an antibacterial agent, and further can function as an active ingredient of an antiviral agent, a mildew preventive, or a deodorant.
Therefore, the antibacterial coating using the silver-based compound (B) can also exert an antiviral effect.
The following can be considered as a mechanism of excellent antibacterial activity in the antibacterial active energy ray-curable compound of the present invention. The silver-based compound (B) is brought into contact with moisture, whereby the moisture is allowed to permeate into the silver-based compound by utilizing a small moisture permeability of the urethane (meth) acrylate (a). And (3) dissolving out silver ions through the moisture. The elution amount of silver ions, which are positively charged and are attracted to the surfaces of negatively charged bacteria and viruses (hereinafter, referred to as bacteria and the like), is substantially constant over a constant period of time. Thus, the electric balance of the surface of bacteria and the like is broken, the cell membrane is ruptured, and bacteria and the like die. Further, silver ions permeate into cells, bind to enzymes in the cells, and lose enzymatic activity. In addition, it reacts with deoxyribonucleic acid (deoxyribonucleic acid, DNA) of bacteria and the like, and loses its function, thereby reducing the proliferation potency. It is presumed that the proliferation of bacteria and the like on the surface of the coating layer can be completely prevented by such an antibacterial action of silver ions.
The coating composition according to an embodiment of the present invention contains the silver-based compound (B) and thus has antibacterial properties and can exhibit a growth inhibitory effect or deodorizing effect on microorganisms and the like. The silver-based compound (B) may be, for example, an elemental silver having an antibacterial property, an antiviral, antifungal, and deodorizing effect; silver oxide; inorganic silver salts such as silver carbonate, silver chloride, silver nitrate, silver sulfate, silver sulfonate, etc.; silver compound-containing substances such as organic silver salts of silver formate and silver acetate. The silver salt may be supported on zeolite, silica gel, low molecular glass, calcium phosphate, silicate, molybdenum oxide, titanium oxide, or the like.
Examples of the carrier include zeolite-based silver-carrying compounds, silica-based silver-carrying compounds, silicate-based silver-carrying compounds, molybdenum oxide-based silver-carrying compounds, and titanium oxide-based silver-carrying compounds on which silver compounds such as elemental silver, silver oxide, inorganic silver salts, and organic silver salts are carried.
The silver-based compound (B) is preferably a carrier obtained by supporting an inorganic silver salt such as elemental silver, silver oxide, or silver nitrate on a carrier, and more preferably a zeolite-based silver-supported compound or molybdenum oxide-based silver-supported compound obtained by supporting a silver compound on zeolite or molybdenum oxide, from the viewpoint of dispersion stability.
In view of excellent antiviral properties, a zeolite-based silver-supported compound or a molybdenum oxide-based silver-supported compound is preferable.
The average primary particle diameter of the silver-based compound (B) is preferably 5nm to 100nm. The average primary particle diameter can be measured by directly observing the particles themselves using, for example, a transmission electron microscope (transmission electron microscope, TEM) or a scanning electron microscope (scanning electron microscope, SEM). When the average primary particle diameter is 5nm or more, dispersibility becomes more excellent, and when the average primary particle diameter is 100nm or less, a cured film having more excellent transparency can be formed.
The content of the silver-based compound (B) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1.0 to 7 parts by mass, per 100 parts by mass of the film-forming component containing the urethane (meth) acrylate (a). When the content is 0.1 part by mass or more, a more excellent antibacterial coating film can be obtained, and when the content is 20 parts by mass or less, a coating film excellent in dispersion stability can be easily formed.
The silver-based compound (B) is preferably formulated into a suspension (slurry) comprising a powdery substance dispersed in a nonaqueous medium (vehicle) such as an organic solvent, and then blended into a film-forming component containing the urethane (meth) acrylate (a). Dispersants may also be used in slurrying. The dispersion particle diameter D50 of the silver-based compound (B) in the slurry is preferably 300nm or less, more preferably 200nm or less. The dispersion particle diameter D50 can be measured by "nano-turbo" UPA manufactured by daily mechanical packaging (strand) using a dynamic light scattering method. When the dispersion particle diameter D50 is 300nm or less, the dispersion stability can be further improved.
As the dispersion of the silver-based compound (B) in a nonaqueous medium such as an organic solvent, a paint conditioner (Red Devil), a ball Mill, a sand Mill (Dyno-Mill) manufactured by new pill company (SHINMARU ENTERPRISES), a grinding Mill, a pearl Mill (pearl) manufactured by Eirich company, "DCP Mill" or the like), a co-ball Mill (Coball Mill), a homomixer, a homogenizer (eimuque science (M-techniqu) manufactured by kulai mixer (Clearmix) or the like), a wet jet Mill (Ji Nasu (Genus) PY manufactured by Ji Nasu (Genus), a nanocone drill (nanomizer) manufactured by nanocone drill (nanomizer), a Super Apex Mill (Super Apex Mill) manufactured by life industry (Super Apex Mill), "Super Apex (Ultra Apex) Mill, or the like, can be used. In the case of using a medium in the dispersing machine, glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, or the like are preferably used. For dispersion, two or more dispersing machines or two or more mediums having different sizes may be used separately and used stepwise.
Photopolymerization initiator (C) >)
The coating composition of the embodiment of the present invention may include a photopolymerization initiator (C). The photopolymerization initiator is not particularly limited as long as it has a function of initiating polymerization of an active energy ray-curable functional group such as a (meth) acryloyl group in a film-forming component containing the urethane (meth) acrylate (a) by light excitation, and for example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl compound, or 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', 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4-diethyl thioxanthone, 2, 4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, and the like.
Examples of the dicarbonyl compound include: 2-ethyl anthraquinone, 9, 10-phenanthrenequinone, methyl alpha-oxo-phenylacetate, and the like.
Examples of the acetophenone compound include: 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxy-cyclohexylphenyl ketone, diethoxyacetophenone, dibutoxyacetophenone, 2-dimethoxy-1, 2-diphenylethane-1-one, 2-diethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butan-1-one, 1' - (methylene-di-1, 4-phenylene) bis (2-hydroxy-2-methylpropan-1-one), 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxymethylpropane-1-one, oligo [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone ], 1-phenyl-1, 2-dipropyleneoxime, and the like.
Examples of the benzoin ether compound include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, and the like.
Examples of the acylphosphine oxide compound include: 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 4-n-propylphenyl-bis (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) ethyl benzoate, 4' -bis-4-dimethylaminobenzophenone, 4' -bis-4-diethylaminobenzophenone, 2,5' -bis (4-diethylaminobenzylidene) cyclopentanone, and the like.
Examples of the other compound include bis (2, 4-cyclopentadienyl) bis [2, 6-difluoro-3- (1-pyridyl) phenyl ] titanium (IV).
Examples of commercial products of photopolymerization initiators include: the production of (1-hydroxy-cyclohexylphenyl ketone) ONDE (Omnirad) 184 (1-hydroxy-cyclohexylphenyl ketone) by IGM-resin (IGM-Resins) B.V., 500, 907 (2, 2-dimethoxy-1, 2-diphenylethane-1-ONE), 500, 907 (2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-ONE), 127 (1, 1' - (methylene-bis-1, 4-phenylene) bis (2-hydroxy-2-methylpropan-1-ONE), 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-ONE), 784 (bis (2, 4-cyclopentadienyl) bis [2, 6-difluoro-3- (1-pyridyl) phenyl ] titanium (IV)), 2959 (1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxymethylpropane-1-ONE), ai Sagu Wang (Esacure) (oligo [ 2-hydroxy-2-methyl-1- [4- (4-morpholinophenyl) butan-1-ONE), and especially (Tri) 4-hydroxy-phenyl) 2, 6-phenylphosphine (BAS) 2, 6-hydroxy-phenyl) N (BAS) 2, BAS (BAS) phosphine oxide (BAS) and the like, from the viewpoint of yellowing resistance after active energy ray hardening, preferably, ornided (Omnirad) 184 and Ai Sagu (Esacure ONE) are used.
The photopolymerization initiator is not limited to the above-mentioned compound, and may be any one if it has an ability to start polymerization by an active energy ray. The amount of the photopolymerization initiator to be used is not particularly limited, but is preferably in the range of 1 to 20 parts by mass based on 100 parts by mass of the film-forming component. As the sensitizer, a known organic amine or the like may be added. Further, the photopolymerization initiator is used for radical polymerization, but other than the radical polymerization initiator, a cationic polymerization initiator may be used.
The coating composition according to one embodiment of the present invention may further contain any component such as various additives within a range that does not impair the object and effect of the present invention. The optional component may be a resin other than the film-forming component, and the additive may be, for example: polymerization inhibitors, photosensitizers, leveling agents, slip aids, defoamers, surfactants, antiblocking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, silane coupling agents, conductive polymers, conductive surfactants, inorganic fillers, pigments, dyes, and the like.
In addition, various additives such as a substance exhibiting an antistatic function for preventing adhesion of dust, pollen, etc., an antifogging function for preventing blurring caused by wheezing, sweat, etc., and an antifouling function for preventing contamination caused by cosmetics such as lipstick may be used in combination. By combining these additives in the coating composition of an embodiment of the present invention, various functions can be exhibited in a single layer while exhibiting antibacterial properties.
In the case of adding the solvent, it is preferable to carry out the hardening treatment by the active energy ray after volatilizing the solvent. The solvent is not particularly limited, and various known organic solvents can be used. Specifically, examples thereof include: cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetylacetone, toluene, xylene, n-butanol, isobutanol, t-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono-n-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, methyl pyrrolidone, and the like.
Among these, particularly, a solvent having a hydroxyl group is preferable because it acts in a direction to stabilize the dispersibility of the silver-based compound (B) in a solution. In addition, when an additive such as silicone or fluorine is contained to reduce the surface tension, it is preferable to use the foam-removing agent because foam-removing property is excellent after the various materials are blended and stirred or foam is generated during coating. The solvent composition containing a solvent having a hydroxyl group is preferable because dispersion stabilization is very effective in suppressing defects in the coating film and improving the yield.
The content of the solvent having a hydroxyl group in 100% by mass of the total solvent is preferably 25% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, and still more preferably 75% by mass to 100% by mass. Specifically, examples of the hydroxyl group-containing solvent include: n-butanol, isobutanol, t-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, propylene glycol monomethyl ether, and the like. In particular, propylene glycol monomethyl ether and ethylene glycol monomethyl ether are preferable because they are excellent in defoaming property and volatility as slow-drying solvents (solvents having low volatility) and thus are more excellent in coating.
Method for producing energy ray-curable coating composition
The coating composition according to an embodiment of the present invention can be obtained by a known production method, and is not particularly limited. For example, the following methods are exemplified: first, a film-forming component containing urethane (meth) acrylate (a) and a silver compound (B) are mixed and dispersed to obtain a stable dispersion, and then a photopolymerization initiator (C) and other various additives are added and prepared.
As described above, the coating composition may be prepared by preparing a suspension (slurry) of the powdery silver-based compound (B) dispersed in a nonaqueous medium such as an organic solvent, and then blending the suspension into a film-forming component containing the urethane (meth) acrylate (a).
Antibacterial Member
The antimicrobial component is for engagement with an article to make an article comprising the antimicrobial component. For example, the coating composition is obtained by applying an antimicrobial active energy ray-curable coating composition onto a substrate and curing the composition to form a coating layer.
The antibacterial member may have other functional layers in addition to the coating layer, and examples thereof include an antistatic layer for preventing adhesion of dust, pollen, etc., an antifogging layer for preventing blurring caused by wheezing, sweat, etc., and a layer exhibiting an antifouling function for preventing contamination caused by cosmetics such as lipstick, etc.
Coating layer
The coating layer is a cured product of the antimicrobial active energy ray-curable coating composition according to an embodiment of the present invention.
For example, a coating layer, which is a cured coating film, can be formed by applying the coating composition to various substrates, drying the substrates in the presence of an organic solvent, and then irradiating the substrates with an active energy ray.
The thickness of the cured product is preferably 0.5 μm to 20 μm, more preferably 1.0 μm to 15 μm, and even more preferably 2 μm to 10 μm, from the viewpoint of avoiding the decrease in adhesion to the substrate or the occurrence of cracks in the cured coating film.
< substrate >
The substrate may be suitably selected from the group consisting of plastic, metal, wood and paper. Further, a composite substrate including a plurality of substrates may be selected. These substrates may be flat, such as films and papers, or may be three-dimensional. Coatings may also be included on both sides of the substrate.
Examples of the raw material of the plastic include: transparent polymers such as polyester polymers, cellulose polymers, polycarbonate polymers, and acrylic polymers. Examples of the polyester polymer include: polyethylene terephthalate (polyethylene terephthalate, PE), polyethylene naphthalate, and the like. The cellulose-based polymer may be: diacetyl cellulose, triacetyl cellulose (triacetyl cellulose, TAC), and the like. Examples of the acrylic polymer include polymethyl methacrylate.
Examples of the raw material of the plastic include: transparent polymers such as styrene polymers, olefin polymers, vinyl chloride polymers, and amide 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-based polymer include: nylon, aromatic polyamide, and the like.
Further, examples of the material of the plastic include: and transparent polymers such as imide-based polymers, sulfone-based polymers, polyethersulfone-based polymers, polyetherketone-based polymers, polyphenylene sulfide-based polymers, vinyl alcohol-based polymers, vinylidene chloride-based polymers, vinyl butyral-based polymers, aryl ester-based polymers, polyoxymethylene-based polymers, and epoxy-based polymers, and blends of these polymers.
When a plastic film is used as the base material, a film of a so-called easy-to-attach type may be used in which a resin layer selected from the group consisting of an acrylic resin, a copolyester resin, a polyurethane resin, a styrene-maleic acid graft polyester resin, an acrylic acid graft polyester resin, and the like is provided on the surface on which the cured coating film is formed.
The thickness of the flat substrate can be suitably determined, and in the case of a plastic film, it is generally about 10 μm to 20,000 μm in view of strength, workability in handling, and the like. In the case where the substrate is three-dimensionally shaped, the thickness is not limited.
The coating of the coating composition may be carried out by a conventional method, for example, bar coating, blade coating, roll coating, blade coating, die coating, gravure coating, or spray coating. When the solvent is contained, it is preferable that the coating composition is applied and then the coating film is dried at about 50 to 150 ℃.
As described above, the hardening of the coated coating composition after coating can be performed by irradiation with an active energy ray. Examples of the active energy ray include ultraviolet rays and electron beams. In the case of using ultraviolet rays, a light source such as a high-pressure mercury lamp, an electrodeless lamp, or a xenon lamp is used, and the irradiation amount of ultraviolet rays is preferably, for example, 100mJ/cm 2 ～2000mJ/cm 2 Left and right. In the case of electron beam, in the case of oxygen concentrationThe electron beam irradiation amount is preferably 60kV to 150kV and 1Mrad to 10Mrad, for example, at a temperature of 100ppm or less.
Articles comprising a coating
An article comprising the antibacterial member according to one embodiment of the present invention can be formed by applying the antibacterial active energy ray-curable coating composition according to the present invention to a substrate, similarly to the antibacterial member, and can be used as an article.
In addition, the use of the antibacterial member can be used as an article including an antibacterial coating by bonding with other articles such as a substrate.
Articles comprising a coating may comprise other coatings or other substrates via a bonding material on the coated side (including between the coating and the substrate) and/or the uncoated substrate side.
By having the coating of an embodiment of the present invention, not only the article can be protected or reinforced, but also the function of antibacterial property can be provided. In addition, other functional layers may be provided in addition to the coating layer.
Examples of the other functional layer include a layer exhibiting an antistatic function for preventing adhesion of dust, pollen, etc., an antifogging function for preventing blurring caused by wheezing, sweat, etc., and an antifouling function for preventing contamination caused by cosmetics such as lipstick. By using a functional material exhibiting functions in combination with the coating composition according to an embodiment of the present invention, these functions can be exhibited as a single layer while exhibiting antibacterial performance.
As another base material via a bonding material, the base material may be bonded for protection, reinforcement, and the like via a bonding material such as an adhesive or an adhesive.
< article >)
The article according to one embodiment of the present invention is not limited as long as it is an article requiring antibacterial properties, and is used as a tangible article including the coating layer. Examples include: transparent resin partition, face shield, soft packaging material containing sterilizing alcohol or sheet, bottle and its cover member, smart phone, tablet, personal computer (Personal Computer, PC), television, car navigator, guidance board for business facility, etc., touch screen member mounted on traffic ticket vending machine, door handle, hanging ring, mouse for PC, keyboard, etc., and articles directly contacted by people in daily life.
Examples (example)
The present invention will be described below by way of examples, but the present invention is not limited to the examples. In the synthesis examples and examples, the blending ratio of the materials was calculated as non-volatile components except for the solvent. In the following examples and comparative examples, "part" and "%" represent "part by mass" and "% by mass", respectively, unless otherwise specified.
The molecular weight of the urethane (meth) acrylate, the average primary particle diameter of the silver-based compound, and the dispersion particle diameter 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) are measured by a Gel Permeation Chromatography (GPC) method. The measurement conditions are as follows. Further, mw and Mn are polystyrene equivalent values.
The device comprises: excellent Shimadzu (SHIMADZU Prominence) (manufactured by Shimadzu corporation),
And (3) pipe column: 3 Shodes (SHODEX) LF-804 (manufactured by Showa electric Co., ltd.) were connected in series,
A detector: a differential refractive index detector,
A solvent: tetrahydrofuran (THF),
Flow rate: 1.0 mL/min,
Solvent temperature: 40 ℃ of,
Sample temperature: 0.2 percent,
Sample injection amount: 100. Mu.L.
[ average primary particle diameter of silver-based Compound ]
Regarding the average primary particle diameter, a short axis diameter and a long axis diameter of 10 primary particles were measured by observation with a Transmission Electron Microscope (TEM) using a transmission electron microscope JEM-2010 manufactured by japan electron (strand), and the average value thereof was taken as the average primary particle diameter.
[ particle diameter of silver-based Compound dispersed therein ]
The dispersion particle diameter D50 was measured by "nano-turbo" UPA manufactured by daily mechanical packaging (strand) using a dynamic light scattering method.
< Synthesis of urethane (meth) acrylate (A) >)
(film Forming component (X1))
(A1) The method comprises the following steps In a four-necked flask including a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, aronix (Aronix) M403 was placed: 1052g (composition comprising 500g (about 0.95 mol) of dipentaerythritol pentaacrylate (DPPA) having a molecular weight of 524 and 552g (about 0.95 mol) of dipentaerythritol hexaacrylate (DPHA) having a molecular weight of 578 manufactured by Toyase Synthesis (Co., ltd.), 0.1g of Neostan (Neostan) U-810 (tin catalyst manufactured by Niastan chemical Co., ltd.) and 467g of butyl acetate were added dropwise from a dropping funnel over 30 minutes after the liquid temperature was set to 50 ℃, su Midu (Sumidule) N3300 (an urethane body (HDI-urethane body) of hexamethylene diisocyanate having an isocyanate group of about 21.8 mass%): 37g (having about 0.19 mole of isocyanate groups). After the completion of the temperature rise, the reaction was allowed to proceed to 80℃for 3 hours, after which the disappearance of the peak of the isocyanate group was confirmed by a Fourier transform infrared spectrometer (Fourier Transform Infrared Spectrometer, FT-IR), butyl acetate was added while cooling, and dilution was performed to obtain a solution of DPPA and HDI-urethane body containing the film-forming component (X1) of urethane (meth) acrylate (A1). The solid content was 70 mass%.
The film-forming component (X1) comprising urethane (meth) acrylate (A1) of DPPA and HDI-urethane body has a mass average molecular weight of 1930, and the average number of functional groups (f) obtained by the method C＝C ) The acrylic acid equivalent Mw/f of the resultant was 6.8, 285. Furthermore, the film-forming component (X1) theoretically contains about 50.7 mass% DPHA.
(film Forming Components (X2-X12))
Film-forming components (X2 to X12) containing urethane (meth) acrylate (a) were obtained by the same method as the production of film-forming component (X1) according to the compositions and the blending ratios shown in table 1.
Figure BDA0004103212990000151
/>
F in Table 1 OH Represents the hydroxyl number, f NCO Represents the number of isocyanate groups, f C＝C The number of (meth) acryloyl groups is represented.
[ Material ]
The materials used are as follows.
"hydroxy group-containing (meth) acrylate (a 1)",
(a 1-1) Aronix (Aronix) M403 (composition comprising dipentaerythritol pentaacrylate (DPPA) having molecular weight 524 and dipentaerythritol hexaacrylate (DPHA) having molecular weight 578 dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate=1/1 (molar ratio), manufactured by east Asia Synthesis (Co.).
(a 1-2) A-TMPT (pentaerythritol triacrylate (PET 3A) having a molecular weight of 298, manufactured by Xinzhou Chemie (Co., ltd.).
"polyisocyanate (a 2)",
(a 2-1) Su Midu (Sumidule) N3300 (hexamethylene diisocyanate-urethane (HDI-urethane), NCO% = 21.8 (solid content 100%), litsea Corp. Manufactured by Kagaku Kogyo polyurethane (Sumika Covestro Urethane) (Stra), aliphatic polyisocyanate-urethane),
(a 2-2) Desmodur (Desmodur) H (hexamethylene diisocyanate (HDI), NCO% = 50.0 (solid content 100%), litsea Corp. Polyurethane (Sumika Covestro Urethane) (manufactured by Strand), aliphatic polyisocyanate),
(a 2-3) Desmodur Z4470BA (butyl acetate solution of isophorone diisocyanate-allophanate (IPDI-allophanate), NCO% = 16.9 (100% solids basis), litsea Corp. Manufactured by Kadsura polyurethane (Sumika Covestro Urethane) (strand)), an alicyclic polyisocyanate,
(a 2-4) Desmodur T-80 (toluene diisocyanate (tolylene diisocyanate, TDI), NCO% = 48.0 (solid content 100%), aromatic polyisocyanate manufactured by Kaschin polyurethane (Sumika Covestro Urethane) (Stra)).
Production of dispersion of silver-based Compound
(Dispersion 1)
A dispersion of the silver-ion-supported zeolite was produced by the following method.
200 parts of silver ion-supported zeolite (Novaron (NOVARON) AGT330, manufactured by east Asia Synthesis (stock)), 10 parts of DisperBYK-111 (manufactured by BYK-Chemie Japan (stock)) as a dispersant, and 800 parts of methyl ethyl ketone were mixed and dispersed under the following conditions to prepare a dispersion 1 containing a silver compound (B1) having an average primary particle diameter of 30nm, a dispersed particle diameter D50 of 80nm, and a solid content of 21% (20% as an active ingredient of the silver compound in the dispersion).
Pre-dispersing: using zirconia beads (1.25 mm) as a medium, the dispersion was performed for 1 hour using a paint mixer (paint shaker).
Formally dispersing: using zirconia beads (0.1 mm) as a medium, dispersion was performed for 1 hour using a disperser UAM-015 manufactured by the longevity industry (strand).
(Dispersion 2)
A dispersion of silver-ion-supported molybdenum oxide was produced by the following method.
195 parts of sodium molybdate dihydrate (kanto chemical (strand)) was dissolved in 3000 parts of ion-exchanged water, and a solution obtained by dissolving 273 parts of silver nitrate (kanto chemical (strand)) in 3000 parts of ion-exchanged water was added dropwise thereto with stirring over 30 minutes, to obtain a precipitate. A dispersion 2 containing a silver compound (B2) having an average primary particle diameter of 25nm, a dispersed particle diameter D50 of 70nm, and a solid content of 21% was produced in the same manner as in the silver compound dispersion 1 except that 200 parts of the mixture, which was sufficiently dried at 100 ℃, was used in place of the NOVARON AGT330 of the dispersion 1, after filtration and washing with ion-exchanged water.
(Dispersion 3)
A dispersion of the silver-ion-supported zeolite was produced by the following method.
A dispersion 3 containing a silver-based compound (B3) having an average primary particle diameter of 30nm, a dispersed particle diameter D50 of 90nm, and a solid content of 21% was produced in the same manner as in the dispersion 1, except that jieshimei (Zeomic) AJ10N (manufactured by Sinanen Zeomic) (strand) was used as the silver-ion-supported zeolite in place of the NOVARON AGT 330.
(Dispersion 4)
A dispersion of silver-ion-supported silicate was produced by the following method.
A dispersion 4 containing a silver-based compound (B4) having an average primary particle diameter of 40nm, a dispersed particle diameter D50 of 110nm, and a solid content of 21% was produced in the same manner as in the dispersion 1, except that AIS-NAZ320 (manufactured by daily volatile catalyst conversion (strand)) was used as the silver-ion-supporting silicate instead of NOVARON (NOVARON) AGT 330.
Example 1
100 parts by mass of a film forming component (X1) containing a urethane (meth) acrylate (a) (nonvolatile component), 3 parts by mass of a silver compound (B2) (nonvolatile component), 5 parts by mass of Ai Sagu (Esacure ONE) (IGM-resin (manufactured by IGM-Resins) b.v. company) as a photopolymerization initiator, 0.1 part by mass of pick (BYK) 349 (silicone-based additive manufactured by BYK-Chemie Japan) company, 60 parts of polyethylene glycol monoethyl ether (polyethylene glycol monoethyl ether, PGME) as a shortage of a dilution solvent, and 20 parts of butyl acetate were mixed and dispersed to obtain a coating composition 1.
Example 2 to example 12
Coating compositions 2 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 components (X2 to X12).
Example 13 to example 18
Coating compositions 13 to 18 were obtained in the same manner as in example 3, except that the dispersion 2 was used so that the amount of the silver-based compound (B2) was 0.2 part, 0.5 part, 1 part, 5 parts, 7 parts, and 12 parts (nonvolatile components). Example 3 is also shown in table 3.
Example 19 to example 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 a dispersion containing the silver compound (B1), the silver compound (B3) and the silver compound (B4) was used.
The content (nonvolatile content) of the silver-based compound is shown in the table.
Example 22
Coating composition 22 was obtained in the same manner as in example 4, except that ornida (Omnirad) 184 (IGM resin) b.v. company) was used as a photopolymerization initiator.
Example 23
Coating composition 23 was obtained in the same manner as in example 4, except that Polyethylene Glycol Monoethyl Ether (PGME) was not used as a diluting solvent and butyl acetate was used as 80 parts.
Comparative example 1
A coating composition was obtained in the same manner as in example 3 except that Neofine (NEOFIX) RP-70 (polyethylene polyamine-based resin, manufactured by Nikka chemical (Co., ltd.) was used instead of the silver-based 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 ingredient "
DPHA (dipentaerythritol hexaacrylate, manufactured by Daicel Ornex Co., ltd., molecular weight 578, mw/f C＝C ＝96.3)
"other"
PR-70: neofine (NEOFIX) RP-70 (polyethylene polyamine-based resin manufactured by Nippon chemical (Co., ltd.)
"photopolymerization initiator (C)") "
Ai Sagu (Esacure ONE) (oligo { 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone, IGM resin (manufactured by IGM Resins) B.V. Co.),
ornithle (Omnirad) 184 (1-hydroxycyclohexyl phenyl ketone, manufactured by IGM resin (IGM Resins) B.V. Co., ltd.)
The following physical property values were measured and evaluated using the obtained antimicrobial active energy ray-curable composition. The results are shown in tables 2 to 4.
(Martin hardness)
The obtained coating compositions were applied to a polyethylene terephthalate film (PET; cosmosine A4100 manufactured by Toyo-Co., ltd.) having a thickness of 100 μm and easy to be adhered, using a bar coater, dried and the solvent was removed, and then irradiated with a high-pressure mercury lamp at 200mJ/cm 2 Is cured into a cured product of 3 μm.
For the hardened material on 100. Mu.m PET, a micro hardness charging Gaucher lens (Fischer) HM2000 (Fisher instrument (Fischer Instruments) (strand) was used, a Vickers indenter, an application speed of 0.5 mN/sec, a maximum load of 10mN, and a holding time of 5 sec), and a Mars hardness (N/mm) calculated based on the specifications of International organization for standardization (International Organization for Standardization, ISO) 14577 was measured 2 ) The measurement was performed.
A：50N/mm 2 ～70N/mm 2
B：40N/mm 2 Is less than 50N/mm 2 Or over 70N/mm 2 ～80N/mm 2
C: less than 40N/mm 2 Or more than 80N/mm 2
(antibacterial Property)
The antibacterial properties of the cured product obtained at the time of measurement of the mahalanobis hardness were tested according to the test method of JIS Z2801.
A: the antibacterial activity value is more than 3
B: an antibacterial activity value of 2 or more and less than 3
C: an antibacterial activity value of less than 2
(antiviral Property)
The cured product obtained at the time of measurement of the mahalanobis hardness was tested for antiviral properties according to the test method of JIS L1922.
A: the antiviral activity value is above 3
B: an antiviral activity value of 2 or more and less than 3
C: an antiviral activity value of less than 2
Evaluation of energy ray-curable composition for antibacterial Activity
(dispersion stability)
After 50 parts by mass of the coating composition was placed in 70mL covered containers and sealed, each container was left to stand in an oven at 40 ℃ for 1 week. Then, the container was taken out of the oven, air-cooled for 1 hour, and subjected to visual observation and redispersion test by shaking the container.
[ evaluation criterion ]
3: no sedimentation and good effect.
2: even if there is sedimentation, the container may be redispersed by shaking, and may be used.
1: even if the container is shaken, the container will not be redispersed, which is undesirable.
< evaluation of coating >
(formation of antibacterial Member)
The obtained coating compositions were applied to a polyethylene terephthalate film (PET; cosmosine A4100 manufactured by Toyo-Co., ltd.) having a thickness of 100 μm and easy to be adhered, using a bar coater, dried and the solvent was removed, and then irradiated with a high-pressure mercury lamp at 200mJ/cm 2 To form a cured product of 3 μm, thereby forming an antibacterial member.
(scratch resistance)
A square mat of 1 square cm with #0000 steel wool attached was placed on the coated surface of the cured product of the antibacterial member, and after a load of 500g was reciprocated 10 times, the appearance was evaluated visually, and the number of scratches was measured.
[ evaluation criterion ]
3: scratch is 0, and is good.
2: the number of scratches is 1-2, and the scratch can be used.
1: the number of scratches is more than 3, and the scratch is bad.
(weather resistance)
The antibacterial member was placed in an atmosphere having a temperature of 63℃and a humidity of 45% using a daylight carbon arc weather tester (sunshine carbon weather meter) (model: S80), and a weather resistance test was performed for 500 hours, and the change in yellowing of the coating layer before and after the test was measured using a colorimeter.
[ evaluation criterion ]
3: the Δb value is preferably 1 or less.
2: the Δb value exceeds 1 and is 3 or less, and can be used.
1: the Δb value exceeds 3, which is undesirable.
Figure BDA0004103212990000201
/>
Figure BDA0004103212990000211
/>
Figure BDA0004103212990000221
From tables 2 to 4, it can be confirmed that: a coating composition comprising a urethane (meth) acrylate (A) having 6 or more (meth) acryloyl groups, which has a cured product of an antimicrobial active energy ray-curable coating composition having a thickness of 3 [ mu ] m and a hardness of 40N/mm on a polyethylene terephthalate film of 100 [ mu ] m, can form a coating layer having sufficient antimicrobial properties, excellent dispersion stability for stably exhibiting antimicrobial properties, and excellent damage prevention performance 2 ～80N/mm 2 And the antibacterial activity value in JIS Z2801 is 2 or more.
As shown in table 4, in comparative example 2 in which the film-forming component does not contain urethane (meth) acrylate (a), the film becomes a brittle coating film due to excessive hardness, and as a result, the dispersion stability is also poor.
Evaluation of article comprising coating
On the surface opposite to the cured product of the coating composition, 100 parts by mass of an acrylic adhesive (TOYO CHEM) (manufactured by TOYO CHEM.); 41% nonvolatile matter) was applied to the mixture of 100 parts by mass of an isocyanate curing agent (TOYO CHEM.); 1.2 parts by mass of the TOYO CHEM.; 37.5% nonvolatile matter) and 1.2 parts by mass of the TOYO BHS8515 (manufactured by TOYO CHEM.); and after drying and removal of the solvent, a separation film (super De Koch (super tec) SP-PET38 manufactured by Lintec (manufactured by Lintec.)) was bonded, and curing was performed in a 50% Rh environment at 23℃for 1 week. After curing, the separation film was peeled off and then attached to an acrylic separator (manufactured by friendly carpentry (strand); spray-protected acrylic plate) so that air did not enter.
Regarding the article (acrylic separator) including the coating layer formed from the coating composition obtained in the examples, it was confirmed that both antibacterial properties and scratch resistance were compatible.
Industrial applicability
The antimicrobial active energy ray-curable coating composition according to an embodiment of the present invention can be used for transparent resin separators, face masks, flexible packaging materials containing sterilizing alcohol or sheets, bottles and their cover members, smart phones, tablet personal computers, PCs, televisions, car navigation devices, guide boards for other commercial facilities, touch panel members mounted on traffic ticket vending machines, door handles, hanging rings, mice for PCs, keyboards, and other articles in direct contact with people in daily life.

Claims (9)

1. An antimicrobial active energy ray-curable coating composition comprising a film-forming component and a silver-based compound, wherein,
the film-forming component comprises a urethane (meth) acrylate having 6 or more (meth) acryloyl groups,
in a cured product of a thickness of 3 μm formed from an antimicrobial active energy ray-curable coating composition on a polyethylene terephthalate film of a thickness of 100 μm,
hardness of 40N/mm 2 ～80N/mm 2 And the antibacterial activity value in Japanese Industrial Standard Z2801 is 2 or more.
2. The antimicrobial active energy ray-curable coating composition according to claim 1, wherein the cured product has an antiviral activity value of 2 or more in japanese industrial standard L1922.
3. The antimicrobial active energy ray-curable coating composition according to claim 1 or 2, wherein the content of the urethane (meth) acrylate is 30 mass% or more in the film-forming component.
4. The antimicrobial active energy ray-curable coating composition according to any one of claims 1 to 3, wherein the film-forming component comprises a reaction product of a (meth) acrylate having a hydroxyl group and a polyisocyanate, the ratio of isocyanate groups/hydroxyl groups is 0.2 to 0.7 when the polyisocyanate is a diisocyanate having 2 isocyanate groups, and the ratio of isocyanate groups/hydroxyl groups is 0.1 to 0.4 when the polyisocyanate is a triisocyanate having 3 isocyanate groups.
5. The antimicrobial active energy ray-curable coating composition according to claim 4, wherein the polyisocyanate comprises at least one selected from the group consisting of aliphatic polyisocyanates and alicyclic polyisocyanates.
6. The antimicrobial active energy ray-curable coating composition according to any one of claims 1 to 5, wherein the content of the silver-based compound is 0.5 to 10 parts by mass per 100 parts by mass of the film-forming component.
7. A coating layer which is a cured product of the antimicrobial active energy ray-curable coating composition according to any one of claims 1 to 6.
8. An antimicrobial component comprising the coating of claim 7 on a substrate.
9. An article comprising the coating of claim 7.
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