JP2023145395A - Active energy ray-curable composition with reduced bacterial adhesion, coating agent composition, and laminate - Google Patents

Abstract

To provide an active energy ray-curable composition with reduced bacterial adhesion and a coating agent composition, which can yield a cured coating with excellent resistance to bacterial adhesion; a laminate with excellent resistance to bacterial adhesion; and an article with excellent resistance to bacterial adhesion.SOLUTION: An active energy ray-curable composition with reduced bacterial adhesion includes methacryl methacrylate (A) with 2 or more repetitions of polyoxyalkylene structure. In ATP measurement, the Relative Light Unit (ELU) of Escherichia coli is 1,000 or less, and the ELU of Staphylococcus aureus is 50,000 or less.SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable composition with low bacterial adhesion, a coating composition, and a laminate.

Generally plastic products, e.g. polycarbonate, polymethyl methacrylate,
Polyethylene terephthalate, vinyl chloride resin, ABS resin, cellulose acetate, polypropylene, etc. are used for various purposes because they are lightweight, easy to process, and have excellent impact resistance. However, these plastic products are easily scratched due to their low surface hardness.
It has the disadvantage that it significantly impairs the appearance, and depending on the application, it is coated with a hard coat layer to protect the plastic substrate.

On the other hand, in recent years, cleanliness has been required for various industrial products. There is a particularly strong demand for cleanliness in industrial products that are touched or approached by an unspecified number of people. Nutrient sources for microorganisms such as sweat, grime, and food scraps tend to adhere to these industrial products, which can lead to explosive growth of bacteria. For example, there is a demand for products with excellent cleanliness, ranging from industrial products to daily necessities in medical facilities, food factories, clothing manufacturing factories, schools, stations, banks, convenience stores, various public facilities, and the like.
Therefore, by using a composition containing an active energy ray-curable resin, an antibacterial agent, and a fungicide,
It has been proposed to provide a cured coating film having antibacterial and antifungal properties on the surface of an article (Patent Document 1).

Japanese Patent Application Publication No. 2011-57855

In general, in articles having antibacterial and antifungal properties, bacteria adhering to the surface are killed, but dead bodies and debris of microorganisms generated by the antibacterial action remain on the surface of the article. Therefore, with the passage of time, new microorganisms and the like accumulate on the dead bodies, forming a mass of microorganisms and bacteria called a biofilm.
Biofilms formed in this way are difficult to remove from the surfaces of articles, etc., impairing cleanliness. Therefore, in the case of cured coating films using conventional antibacterial agents and antifungal agents, patent documents describe how to make it easier to remove lumps of microorganisms from the surface of the article and make it difficult for microorganisms to remain (low bacterial adhesion). 1 cannot meet the performance currently required, and there is room for improvement.

The present invention provides a low-bacteria-adhesive active energy ray-curable composition and a coating agent composition capable of producing a cured coating film with an excellent low-bacterial adhesion; a laminate with an excellent low-bacterial adhesion; and an article with an excellent low-bacterial adhesion. provide.

The present invention has the following aspects.
[1] (Meth)acrylic (meth) with a repeating number of polyoxyalkylene structure of 2 or more
A low-bacteria-adherent active energy ray-curable composition containing acrylate (A) and characterized in that the luminescence amount of Escherichia coli is 1000 or less and the luminescence amount of Staphylococcus aureus is 50000 or less when measuring ATP. thing.
[2] The low bacterial adhesion active energy according to [1], wherein the polyoxyalkylene structure is at least one selected from the group consisting of polyoxymethylene, polyoxyethylene, polyoxypropylene, and polyoxytetramethylene. Line curable composition.
[3] The low bacterial adhesion active energy ray curing according to [1] or [2], further containing a (meth)acrylic acid ester compound (B) in addition to the (meth)acrylate (A). mold composition.
[4] The low-bacteria-adhesive active energy ray-curable composition according to any one of [1] to [3], which further contains a photopolymerization initiator (C).
[5] A cured coating film of the low bacterial adhesion active energy ray-curable composition according to any one of [1] to [4].
[6] A laminate having the cured coating film according to [5] on at least one surface of a base material.

According to the active energy ray-curable composition and coating agent composition with low bacterial adhesion of the present invention, a cured coating film with excellent low bacterial adhesion can be obtained.
The laminate of the present invention has excellent low bacterial adhesion.
The article of the present invention has excellent low bacterial adhesion.

The meanings of the following terms in this specification are as follows.
(Meth)acrylic means a generic term for acrylic and methacrylic.
(Meth)acrylate means a general term for methacrylate and acrylate.
(Meth)acryloyl group means a general term for methacryloyl group and acryloyl group.
"~" indicating a numerical range means that the numerical values written before and after it are included as lower and upper limits.

[Active energy ray-curable composition with low bacterial adhesion]
The low-bacteria-adhesive active energy ray-curable composition of the present invention (hereinafter referred to as "the present low-bacteria-adhesive active energy ray-curable composition") comprises a specific (meth)acrylic (meth)acrylate (A). Contains.
The present low bacterial adhesion active energy ray-curable composition can further contain a (meth)acrylic acid ester (B) other than the specific (meth)acrylate (meth)acrylate (A) and a photopolymerization initiator (C). .
In addition, the present low bacterial adhesion active energy ray-curable composition may contain (meth)acrylic (meth)acrylate (A), (meth)acrylic acid ester (B), as long as the effects of the present invention can be obtained. and may further contain other components than the photopolymerization initiator (C).

The low-bacteria-adhesive active energy ray-curable composition refers to the ATP measurement kit (Kikk
The luminescence amount (Relative L
A low-bacteria-adhesive active energy ray-curable composition in which the luminescence amount of Escherichia coli is 1000 or less and the luminescence amount of Staphylococcus aureus is 50000 or less during ATP measurement to measure the amount of attached bacteria by light unit (RLU). point to something

<(Meth)acrylic (meth)acrylate (A)>
(Meth)acrylic (meth)acrylate (A) contains a (meth)acryloyl group and a polyoxyalkylene structure in the side chain of a radical polymer containing (meth)acrylic acid or (meth)acrylic acid ester as a monomer. It is characterized by:

The polyoxyalkylene structure contained in (meth)acrylate (A) includes polyoxymethylene, polyoxyethylene, polyoxypropylene, polyoxybutylene, and at least one of block copolymerization and random copolymerization thereof. It has a seed structure.

The repeating number of the polyoxyalkylene structure is preferably 2 to 10,0000, 3 to 5,
000 is more preferable, and 4 to 1,000 is even more preferable. When the number of repeats of the polyoxyalkylene structure is below the lower limit, it is difficult to exhibit low bacterial adhesion, and when it is above the upper limit,
The hardness of the coating may decrease.

The (meth)acryloyl group concentration per 1 g of (meth)acrylate (A) is preferably 0.1 mmol/g or more, and 0.3 mmol/g from the viewpoint of the scratch resistance of the cured film. It is more preferably at least 1.0 mmol/g, and even more preferably at least 1.0 mmol/g.

The (meth)acryloyl equivalent may be determined using the results of quantitative determination of the (meth)acryloyl group using a conventional analytical device such as IR or NMR. In addition, the (meth)acryloyl equivalent is
When substantially all of the raw material for the (meth)acryloyl group is consumed for introducing the (meth)acryloyl group, it may be calculated from the amount of the raw material compound used.

(Meth)acrylic (meth)acrylate having an acryloyl group in the side chain of a (meth)acrylic polymer is generally a radical polymer containing a (meth)acrylic acid ester having an epoxy group as a monomer. A method of adding an acid (method 1), a method of adding a (meth)acrylic acid ester having an epoxy group to a radical polymer containing (meth)acrylic acid etc. as a monomer having a carboxyl group (method 2), a method of adding an isocyanate group. have (meta)
A method of adding a (meth)acrylic ester having a hydroxyl group to a radical polymer containing an acrylic ester as a monomer (Method 3), a radical polymer containing a (meth)acrylic ester having a hydroxyl group as a monomer having an isocyanate group It can be obtained by a method of adding (meth)acrylic acid ester (Method 4).

Examples of the (meth)acrylic acid ester monomer having an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,
Examples include 4-epoxycyclohexylmethyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred. The (meth)acrylic acid ester monomer having an epoxy group may be used alone or in combination of two or more.

Examples of the monomer having a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, and the like. Among these, (meth)acrylic acid is preferred. Note that the (meth)acrylate monomer having a carboxyl group may be used alone or in combination of two or more.

As the (meth)acrylic acid ester monomer having an isocyanate group, for example, 2
-Isocyanatoethyl (meth)acrylate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)
Examples include ethyl isocyanate. Among these, 2-isocyanatoethyl (meth)
Acrylate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate is preferred. The (meth)acrylic acid ester monomer having an isocyanate group may be used alone or in combination of two or more.

Examples of (meth)acrylic acid ester monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, -Hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate and (meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide. Among these, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-
Hydroxybutyl (meth)acrylate is preferred. The (meth)acrylic acid ester monomer having a hydroxyl group may be used alone or in combination of two or more.

In order to introduce a polyoxyalkylene structure into the side chain of (meth)acrylic (meth)acrylate (A), one can copolymerize a monomer having a (meth)acryloyl group and a polyoxyalkylene structure in one molecule, or It can be obtained by reacting the reactive functional group of a compound containing a polyoxyalkylene structure in one molecule with the functional group of the side chain of a (meth)acrylic polymer.

Examples of monomers having a (meth)acryloyl group and a polyoxyalkylene structure in one molecule used for copolymerization include polymethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, and polytetra Examples include methylene glycol (meth)acrylate, methoxypolymethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolytetramethylene glycol (meth)acrylate, and the like. These may be used alone or in combination of two or more.

Examples of reactive functional groups of compounds having a polyoxyalkylene structure in one molecule used for reaction with functional groups of side chains of (meth)acrylic polymers include polymethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, and polyethylene glycol (meth)acrylate. ) acrylate, polypropylene glycol (meth)acrylate, polytetramethylene glycol (meth)acrylate, α
-hydroxy-ω-methoxypolymethylene glycol, α-hydroxy-ω-methoxypolyethylene glycol, α-hydroxy-ω-methoxypropylene glycol, α-hydroxy-ω-methoxypolytetramethylene glycol, and the like. These may be used alone or in combination of two or more.

Monomers of (meth)acrylic (meth)acrylate (A) include (meth)acrylic acid and (meth)acrylic acid ester, but may also contain other radically polymerizable monomers. The (meth)acrylic acid and (meth)acrylic ester are contained in an amount of 30 mol% or more in the monomer of the radical polymer from the viewpoint of solubility in the polymerization solvent during the synthesis of (meth)acrylic (meth)acrylate. It is preferably 50 mol% or more, more preferably 80 mol% or more.

Other monomers of (meth)acrylic (meth)acrylate (A) include, for example,
Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate,
iso-butyl (meth)acrylate, sec-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (
meth)acrylate, n-decyl(meth)acrylate, lauryl(meth)acrylate, n-tridecyl(meth)acrylate, stearyl(meth)acrylate, benzyl(
meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, butoxyethyl (meth)acrylate, cyanoethyl (meth)acrylate (Meth)acrylates such as acrylate; N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-ethylmethyl (meth)acrylamide, N-methoxy (meth)acrylamide; ) acrylamide, N,N-dimethoxy(meth)acrylamide, N-ethoxy(meth)acrylamide, N,N-diethoxy(meth)acrylamide, diacetone(meth)acrylamide, N-methylol(meth)acrylamide, N,N-dimethyl Aminomethyl (meth)
Acrylamide, N-(2-dimethylamino)ethyl(meth)acrylamide, N,N-
Examples include (meth)acrylamides such as methylenebis(meth)acrylamide and N,N-ethylenebis(meth)acrylamide. These may be used alone or in combination of two or more. As other monomers, alkyl (meth)acrylates having an alkyl group having 1 to 12 carbon atoms are preferred.

The copolymerization reaction for obtaining (meth)acrylate (A) used in the present invention is usually a radical reaction, and specifically, it is carried out in an organic solvent in the presence of a radical polymerization initiator. I can do it. The reaction time for this reaction is usually 1 to 50 hours, preferably 3 to 50 hours.
It is 12 hours. The organic solvent and radical polymerization initiator that can be used here are as follows.

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, and propylene glycol monomethyl ether. Examples include ester solvents such as acetate and 2-ethoxyethyl acetate; aromatic hydrocarbon solvents such as toluene; and alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), n-butanol, and isobutanol. These organic solvents may be used alone or in combination of two or more.

As the radical polymerization initiator, for example, known initiators generally used for radical polymerization can be used, including organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; Examples include azo compounds such as lonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more.

The reaction used in the above-mentioned methods 1 and 2 to obtain (meth)acrylate (meth)acrylate (A) is an addition reaction between an epoxy group and a carboxyl group. In this reaction, the reaction temperature is preferably 50 to 110°C, more preferably 55 to 100°C. Further, the reaction time is preferably 3 to 50 hours, more preferably 4 to 30 hours.

In order to accelerate the addition reactions in Methods 1 and 2, a catalyst can be used. As a catalyst, triethylamine, tributylamine, triethylenediamine, N,N
-dimethylbenzylamine, benzyltrimethylammonium chloride, triphenylphosphine, triparatolylphosphine and the like. The amount of catalyst used is preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight based on the total amount of raw materials. In addition, in this reaction, the organic solvent used in the reaction in the production of (meth)acrylic (meth)acrylate (A) may be used as is, or an organic solvent may be added as appropriate. Organic solvents that can be used in this reaction are the same as those listed above.

The reaction used in the above-mentioned methods 3 and 4 to obtain (meth)acrylate (meth)acrylate (A) is an addition reaction (urethane reaction) between an isocyanate group and a hydroxyl group. In this reaction, the reaction temperature is preferably 40 to 80°C, more preferably 45 to 75°C. Further, the reaction time is preferably 2 to 30 hours, more preferably 3 to 20 hours.

A catalyst can be used for the purpose of promoting the addition reaction in Methods 3 and 4. Examples of the catalyst include organometallic compounds such as dibutyltin dilaurate, trimethyltin hydroxide, and tetra-n-butyltin, zinc octylate, tin octylate, cobalt naphthenate, tin chloride, and tin chloride. Metal salts, triethylamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene, N,N,N',N'-tetramethyl-1 , 3-butanediamine, N-ethylmorpholine, etc.; in addition to bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc., organic bismuth compounds such as dibutyl bismuth dilaurate, dioctyl bismuth dilaurate, 2-ethylhexane Bismuth acid salt, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth libis Examples include bismuth-based catalysts such as organic acid bismuth salts such as neodecanoate, bismuth disalicylate, and bismuth digallate.
Among these, dibutyltin dilaurate and 1,8-diazabicyclo[5,4,0]undecene are preferred.

The weight average molecular weight of (meth)acrylic (meth)acrylate (A) is usually 5,000
-1,000,000 or less, preferably 7,000 - 500,000 or less, more preferably 10,000 - 200,000 or less. If the weight average molecular weight is more than the above upper limit, the viscosity tends to increase and the coating suitability tends to decrease, which is not practically preferable. On the other hand, if the weight average molecular weight is less than the above-mentioned lower limit, the film forming properties of the coating film will be lowered, which is practically undesirable.

Number average molecular weight and weight average molecular weight are number average molecular weight based on standard polystyrene molecular weight conversion.
Weight average molecular weight, high performance liquid chromatograph (Waters, “ACQUITY
APC system"), column: ACQUITY APC XT 450 x 1, ACQ
UITY APC XT 200 x 1, ACQUITY APC XT 45 x 2 4
It is measured by using this series.

The content of (meth)acrylate (A) in the constituent components of the low-bacteria-adhesion active energy ray-curable composition of the present invention is the total content of the present low-bacteria-adhesion active energy ray-curable composition. It is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, even more preferably 20 parts by weight or more, and even more preferably 30 parts by weight per 100 parts by weight.
It is particularly preferable that the amount is at least 1 part by weight. If the content of (meth)acrylic (meth)acrylate (A) is at least the lower limit value, low bacterial adhesion will be improved.

<(meth)acrylic acid ester compound (B)>
Other (meth)acrylic acid ester compounds (B) can be added to the (meth)acrylic (meth)acrylate of the present invention, if necessary. Other (meth)acrylic ester compounds include (meth)acrylic ester monomers, (meth)acrylic ester oligomers, and (meth)acrylic (meth)acrylates other than (A).
Examples of the (meth)acrylic acid ester monomer include monofunctional monomers, bifunctional monomers, and trifunctional or higher functional monomers depending on the number of (meth)acryloyl groups. Examples of the (meth)acrylic acid ester oligomer include urethane (meth)acrylate, epoxy (meth)acrylate, and polyester (meth)acrylate.
One type of (meth)acrylic acid ester monomer or oligomer may be used alone, or two types of (meth)acrylic acid ester monomer or oligomer may be used alone.
You may use more than one species in combination.

Examples of monofunctional monomers include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, phenoxyethyl ( meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-
Hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono(meth)acrylate, glycidyl (
meth)acrylate, lauryl(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, tricyclodecanyl(meth)acrylate,
Dicyclopentenyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate Acrylate, dodecyl (meth)acrylate, n-stearyl (meth)acrylate, benzyl (meth)acrylate, phenol ethylene oxide modified (n=2) (meth)acrylate, nonylphenol propylene oxide modified (n=2.5) (meth) Acrylate, half (meth)acrylate of phthalic acid derivatives such as 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, furfuryl (meth)acrylate, carbitol (meth)acrylate , benzyl (meth)acrylate, butoxyethyl (meth)acrylate, allyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl acrylamide, N
-Methylol (meth)acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, and polyoxyethylene secondary alkyl ether acrylate.
One type of monofunctional monomer may be used alone, or two or more types may be used in combination.

Examples of the bifunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and dipropylene. Glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified bisphenol A type di(meth)acrylate, propylene oxide modified bisphenol A type Di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di( Examples include meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate, and isocyanuric acid ethylene oxide-modified diacrylate.
One type of bifunctional monomer may be used alone, or two or more types may be used in combination.

Examples of trifunctional or higher functional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. ) acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol hexa( meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide Examples include modified pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, and ethoxylated glycerin triacrylate.
One type of trifunctional or higher functional monomer may be used alone, or two or more types may be used in combination.

In addition, other (meth)acrylic acid ester monomers include Michael adducts of acrylic acid and 2-acryloyloxyethyldicarboxylic acid monoesters.
Michael adducts of acrylic acid include acrylic acid dimer, methacrylic acid dimer,
Examples include acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, and methacrylic acid tetramer.
Examples of the 2-acryloyloxyethyldicarboxylic acid monoester include 2-acryloyloxyethylsuccinic acid monoester, 2-methacryloyloxyethylsuccinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, and 2-methacryloyloxyethyl phthalate. Examples include acid monoester, 2-acryloyloxyethylhexahydrophthalic acid monoester, and 2-methacryloyloxyethylhexahydrophthalic acid monoester. Furthermore, other oligoester acrylates may also be mentioned.

When a compound further having an oxyalkylene structure is used among these (meth)acrylic acid ester compounds (B), further improvement in the bacterial adhesion performance can be expected.

The content of the (meth)acrylic acid ester compound (B) in the constituent components of the low-bacteria-adhesive active energy ray-curable composition of the present invention is 100% of the total component of the present low-bacteria-adhesive active energy ray-curable composition. It is preferably 0 to 95 parts by weight, more preferably 0 to 90 parts by weight, even more preferably 0 to 80 parts by weight, and even more preferably 0 to 7 parts by weight.
Particularly preferred is 0 parts by weight. If the content of the (meth)acrylic acid ester compound (B) is more than the upper limit, the low bacterial adhesion may be reduced.

<Photopolymerization initiator (C)>
When a coating film is obtained by irradiation with ultraviolet rays, the present low-bacteria-adhesive active energy ray-curable composition preferably contains a photopolymerization initiator (C). However, when electron beam irradiation is performed, the present low-bacteria-adhesive active energy ray-curable composition can be cured even without the photopolymerization initiator (C).
The photopolymerization initiator (C) is not particularly limited as long as it generates radicals by the action of light. For example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylenephenyl)-2- Hydroxy-2-
Methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-
2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1
-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin,
Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2
-Methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4',4''-
Diethylisophthalophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanth Lenquinone, 4-(2
-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone and the like.
Among these, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin isopropyl ether, 4-(2-hydroxyethoxy)-phenyl (
2-hydroxy-2-propyl)ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one are preferably used.
One type of photopolymerization initiator (C) may be used alone, or two or more types may be used in combination.

Furthermore, an auxiliary agent for the photopolymerization initiator (C) may be used in combination. Examples of auxiliary agents for the photopolymerization initiator (C) include triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone,
2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-
2-ethylhexyl dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4
-Diisopropylthioxanthone and the like.
One type of auxiliary agent for the photopolymerization initiator (C) may be used alone, or two or more types may be used in combination.

The content of the photopolymerization initiator (C) in the constituent components of the low-bacteria-adhering active energy ray-curable composition of the present invention is based on 100 parts by weight of the total components of the present low-bacteria-adhesive active energy ray-curable composition. It is preferably 0 to 15 parts by weight, more preferably 0 to 10 parts by weight, even more preferably 0 to 5 parts by weight. If the content of the photopolymerization initiator (C) is below the lower limit, curability in ultraviolet curing will be insufficient, and if it is above the upper limit, the coating film may become brittle.

<Other ingredients>
Other ingredients include antibacterial agents, fungicides, antivirals, antiallergens, thermoplastic resins, polymerization inhibitors, ultraviolet absorbers, thermal polymerization initiators, chain transfer agents, crosslinking agents, bluing agents, and enhancers. Stickers, dyes and pigments, oils, plasticizers, waxes, desiccants, dispersants, wetting agents, emulsifiers, gelling agents,
Stabilizers, antifoaming agents, leveling agents, thixotropic agents, antioxidants, flame retardants, antistatic agents, fillers, reinforcing agents, matting agents, various fillers and the like can be mentioned.
One type of other components may be used alone, or two or more types may be used in combination.

Examples of antibacterial agents of organic compounds include 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride, tetradecyldimethylbenzylammonium chloride, 1-hexadecylpyridinium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, N -Polyoxyethylene-N,N
, N-trimethylammonium chloride, cetyltrimethylammonium chloride, octadecyltrimethylammonium chloride, didecyldimethylammonium chloride, benzalkonium chloride, behenyltrimethylammonium chloride, benzethonium chloride, 4,4'-(tetramethylene dicarbonyldiamino)bis( 1-decylpyridinium bromide), N,N'-hexamethylenebis(4-carbamoyl-1-decylpyridinium salt), 4,4'-(p-phthalamide)bis(1-octylpyridinium bromide), 3,3' - Quaternary ammonium salt compounds such as (m-phthalamide) bis(1-octylpyridinium iodide); Monohydric phenol compounds such as 5-chloro-2-(2,4-dichlorophenoxy)phenol; 2-( Pyridine compounds such as 3,5-dimethylpyrazolyl)-4-hydroxy-6-phenylpyridine; Alcohol compounds such as 2-(hydroxymethylamino)ethanol and 2-(hydroxymethylamino)-2-methylpropanol; Tetra Examples include phosphonium salt compounds such as decyltrimethylphosphonium chloride and didecyldimethylphosphonium chloride; chlorohexidine gluconate compounds, and the like.

Examples of bacteria targeted by antibacterial agents include Staphylococcus aureu.
Staphylococcus spp. (including methicillin-resistant Staphylococcus aureus), Streptococcus spp. including Streptococcus pyogenes
Bacillus genus, including Bacillus occus, Enterococcus, Peptostreptococcus, Bacillus subtilis, Clost
Clostridium spp. including R. tetani, Mycobac.
Mycobacterium spp. including terium tuberculosis, Actinomyces spp., Nocardia spp., Streptomyces spp., Ps.
Pseudomonas genus, including Eudomonas aeruginosa,
Escherichia coli including Escherichia coli (including pathogenic Escherichia coli)
Chia genus, Salmonella genus including Salmonella typhi, Vibrio genus including Vibrio cholerae, Shigellad.
Shigella genus including Ysenteriae, Enterobacterc
Enterobacter spp., including Loacae, Klebsiellapne
Klebsiella genus including Umoniae, Serratiamarces
Serratia genus including Cens, Haemophilus influenzae
Haemophilus spp., including Alcaligenes faeca
Alcaligenes including lis, Legionella pneumo
Leonella genus including phila, Campylobacter jeju
Campylobacter genus including Ni, Bacteroidesfragi
Bacteroides genus including lis, Neisseria gonorrh
Neisseria spp. including oeae, Treponema pallidum
Examples include bacteria of the genus Treponema, including .

Some antibacterial agents also exhibit antifungal properties, and some antifungal agents also exhibit antibacterial properties. In this specification, the two are described separately for convenience, but it may be difficult to strictly distinguish them. Furthermore, antibacterial and antifungal properties often result in deodorizing and antiseptic properties as well. Antibacterial agents and fungicides are sometimes called storage improvers and preservatives.

Examples of antiviral agents include thiosulfate silver salt, hydroxytyrosol, glutaral, hexachlorophene, and chlorohexidine.
Viruses targeted by antiviral agents usually include membraned viruses such as AIDS virus, measles virus, herpes simplex virus, and influenza virus; and membraneless viruses such as poliovirus.

Examples of the anti-allergen agent include polyphenol compounds such as polyphenol, polycresol, and polymethoxyphenol; polyvinylphenol compounds; polybisphenol A compounds; lignophenol compounds; tannic acid; polytyrosine, and the like.
Allergens targeted by anti-allergen agents include those that cause allergic diseases such as atopic dermatitis, bronchial asthma, and allergic rhinitis. Examples include mite allergen, cedar pollen allergen, and allergen substances generated from these allergens.

<Application>
The active energy ray-curable composition with low bacterial adhesion can be used as a coating composition containing the active energy ray-curable composition with low bacterial adhesion. Also,
Such a coating composition is cured by irradiation with active energy rays to form a cured coating film.

<Organic solvent>
When preparing the coating agent composition of the present invention, it is preferable to include an organic solvent. The organic solvent is not particularly limited, and can be appropriately selected in consideration of the types of components contained in the curable composition. Specific examples of organic solvents that can be used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone (MIBK), and cyclohexanone; diethyl ether and isopropyl ether. , tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether (PGM), anisole, phenethole, etc.; ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol dimethyl ether; Ester solvents such as acetate; amide solvents such as dimethylformamide, diethylformamide, N-methylpyrrolidone;
Examples include cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; and halogen solvents such as dichloromethane and chloroform.

[Method for manufacturing laminate]
The coating composition of the present invention can be applied to any desired substrate. Examples of substrates to which the coating agent of the present invention is applied include polyolefin resins, polyester resins, polycarbonate resins, acrylic resins, acrylonitrile butadiene styrene copolymer (ABS), polystyrene resins, and polyurethane resins. Plastic base materials such as resins and their molded products (films, sheets, cups, etc.), composite base materials thereof, composite base materials of the above materials mixed with glass fiber and inorganic materials, metals (aluminum, copper, etc.) ,iron,
SUS, zinc, magnesium, alloys thereof, etc. (including metal films such as metal vapor deposited films), glass, etc. A primer layer may be provided on these base materials if necessary.

Examples of methods for applying the coating composition of the present invention include wet coating methods such as spraying, showering, dipping, rolling, spinning, screen printing, and inkjet printing. Can be applied to materials.

In addition, the coating agent of the present invention can be prepared by using the above-mentioned organic solvent and having a solid content concentration of usually 3 to 6.
It is preferable to dilute it to 0% by weight, preferably 5 to 40% by weight, and then apply.

The drying conditions when diluting with the organic solvent mentioned above can be adjusted arbitrarily depending on the heat resistance temperature of the base material, the type of diluting organic solvent, the thickness of the coating film, etc. The temperature is usually 40 to 120°C, preferably 50 to 100°C, and the drying time is usually 10 seconds to 20 minutes, preferably 30 seconds to 10 minutes.

Active energy rays that can be used to cure the coating composition of the present invention include, for example, far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays, γ-rays, and electron beams. , proton beams, neutron beams, etc. Ultraviolet irradiation is advantageous in terms of curing speed, availability of irradiation equipment, cost, etc.
Examples of light sources for ultraviolet irradiation include chemical lamps, xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. The irradiation energy is not particularly limited, but it is usually sufficient to irradiate at about 50 to 3,000 mJ/cm2, preferably 100 to 1,000 mJ/cm2. After irradiation with ultraviolet rays, heating may be performed as necessary to ensure complete curing.

When curing by electron beam irradiation, various electron beam irradiation devices can be used. The irradiation dose (Mrad) of the electron beam is usually 0.5 to 20 Mrad, and preferably 1 to 15 Mrad from the viewpoint of curability, flexibility of the cured product, and prevention of damage to the base material. After electron beam irradiation, heating may be performed as necessary to ensure complete curing.

The thickness of the cured layer after curing of the coating composition of the present invention is preferably thicker from the viewpoint of low bacterial adhesion, pencil hardness, and scratch resistance of the resulting laminate, and from the viewpoint of crack resistance and weight reduction. It is preferable that it be thinner. The thickness of the cured layer after curing is preferably 0.5 μm or more,
More preferably 1 μm or more, still more preferably 2 μm or more, particularly preferably 3 μm or more.
On the other hand, it is preferably 150 μm or less, more preferably 100 μm or less, and still more preferably 75 μm or less.

The coating composition of the present invention can be applied to the surfaces of articles that may be touched by humans, from industrial products to daily necessities in medical settings, food factories, clothing manufacturing factories, schools, stations, banks, convenience stores, various public facilities, etc. It is suitably used as a protective layer. The surface protective layer can be provided on the surface of the article as a cured coating film, which is a cured product obtained by curing the present low-bacteria-adhesive active energy ray-curable composition.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. In addition, in the following description, "department"
, "%" means "parts by mass" and "% by mass", respectively, unless otherwise specified.

[Manufacturing example]
(Production of (meth)acrylic (meth)acrylate (A-1))
In a reactor equipped with a stirrer, a reflux condenser, and a thermometer, 40 parts of methoxypolyethylene glycol methacrylate ("Blenmar PME400" manufactured by NOF Corporation), 40 parts of methyl methacrylate (MMA), and 2-hydroxyethyl methacrylate (2- HEMA) 20 copies,
After charging 144 parts of ethyl acetate and starting stirring, the system was purged with nitrogen and the temperature was raised to 55°C. After adding 0.8 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (Fuji Film Wako Pure Chemical Industries, Ltd. "V-65") and 7.3 parts of ethyl acetate, the system After raising the temperature to 65°C and stirring for 3 hours, 0.4 part of V-65 and 7 parts of ethyl acetate were added and the mixture was heated to 65°C.
The mixture was stirred for 3 hours. After raising the temperature of the system to 78°C and stirring for 2 hours, 0.52 parts by weight of p-methoxyphenol and 8 parts of ethyl acetate were added. After replacing the inside of the system with a mixed gas of 7% oxygen/93% nitrogen and further cooling the inside of the system to 40°C, 0.01 part of dibutyltin dilaurate and 2-isocyanatoethyl acrylate (“Karens AOI” manufactured by Showa Denko) were added. After adding 21.3 parts of ethyl acetate and 19 parts of ethyl acetate, the temperature inside the system was raised to 50°C. After stirring at 50° C. for 6 hours, disappearance of the isocyanate group was confirmed, and a solution of compound (A-1) having a (meth)acryloyl group and a polyoxyalkylene structure in the side chain was obtained. The composition of the reaction solution was A-1/ethyl acetate = 40/60 (
weight ratio). Further, the acryloyl group concentration of A-1 was 1.23 mmol/g.

(Production of (meth)acrylic (meth)acrylate (A-2))
In a reactor equipped with a stirrer, a reflux condenser, and a thermometer, 60 parts of methoxypolyethylene glycol methacrylate ("Blenmar PME400" manufactured by NOF Corporation), 20 parts of MMA, 2
- Charge 20 parts of HEMA and 144 parts of ethyl acetate, and after starting stirring, replace the system with nitrogen.
The temperature was raised to ℃. After adding 0.8 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (Fuji Film Wako Pure Chemical Industries, Ltd. "V-65") and 7.3 parts of ethyl acetate,
After raising the temperature of the system to 65°C and stirring for 3 hours, 0.4 parts of V-65 and 7 parts of ethyl acetate were further added, and the mixture was stirred at 65°C for 3 hours. After raising the temperature of the system to 78°C and stirring for 2 hours, p
- 0.52 parts by weight of methoxyphenol and 8 parts of ethyl acetate were added. 7% oxygen in the system/93
After purging the system with a mixed gas of 0% nitrogen and further cooling the system to 40°C, dibutyltin dilaurate was added.
01 parts, 2-isocyanatoethyl acrylate (“Karens AOI” manufactured by Showa Denko) 21 parts
．． After adding 3 parts of ethyl acetate and 19 parts of ethyl acetate, the temperature inside the system was raised to 50°C. After stirring at 50° C. for 6 hours, disappearance of the isocyanate group was confirmed, and a solution of compound (A-1) having a (meth)acryloyl group and a polyoxyalkylene structure in the side chain was obtained. The composition of the reaction solution was A-2/ethyl acetate = 40/60 (weight ratio). In addition, the acryloyl group concentration of A-2 is 1.22
It was mmol/g.

(Production of (meth)acrylic (meth)acrylate (A-3))
(Meth)acrylic (meth)acrylate (A-1) except that methoxypolyethylene glycol methacrylate ("Blenmar PME400" manufactured by NOF Corporation) was changed to methoxypolyethylene glycol methacrylate ("Blenmar PME1000" manufactured by NOF Corporation), Synthesis was carried out in a similar manner to obtain a solution of compound (A-3) having a (meth)acryloyl group and a polyoxyalkylene structure in the side chain. The composition of the reaction solution is A-3/ethyl acetate = 40/
60 (weight ratio). In addition, the acryloyl group concentration of A-3 is 1.22 mmol/g
Met.

(Production of (meth)acrylic (meth)acrylate (A-4))
In a reactor equipped with a stirrer, a reflux condenser, and a thermometer, 40 parts of polypropylene glycol methacrylate ("Blemmer PP1000" manufactured by NOF Corporation) and methyl methacrylate (
MMA), 20 parts of 2-hydroxyethyl methacrylate (2-HEMA), and 144 parts of ethyl acetate were charged, and after starting stirring, the system was purged with nitrogen and the temperature was raised to 55°C. here, 2
, 0.8 parts of 2'-azobis(2,4-dimethylvaleronitrile) (Fuji Film Wako Pure Chemical Industries, Ltd. "V-65") and 7.3 parts of ethyl acetate, the system was heated to 65°C. The temperature is raised to
After stirring for 3 hours, 0.4 part of V-65 and 7 parts of ethyl acetate were further added, and the mixture was stirred at 65°C for 3 hours. After raising the temperature of the system to 78°C and stirring for 2 hours, 0.0% of p-methoxyphenol was added.
52 parts by weight and 8 parts of ethyl acetate were added. After replacing the inside of the system with a mixed gas of 7% oxygen/93% nitrogen and further cooling the inside of the system to 40°C, 0.01 part of dibutyltin dilaurate and 2-isocyanatoethyl acrylate (“Karens AOI” manufactured by Showa Denko) were added. 26.3 parts of ethyl acetate, 26 parts of ethyl acetate
After adding 50% of the mixture, the temperature inside the system was raised to 50°C. After stirring at 50° C. for 6 hours, disappearance of the isocyanate group was confirmed, and a solution of compound (A-4) having a (meth)acryloyl group and a polyoxyalkylene structure in the side chain was obtained. The composition of the reaction solution was A-4/ethyl acetate = 40/60 (weight ratio). Further, the acryloyl group concentration of A-4 was 1.45 mmol/g.

(Production of (meth)acrylic (meth)acrylate (A-5))
A reactor equipped with a stirrer, a reflux condenser, and a thermometer was charged with 40 parts of polypropylene glycol methacrylate ("Blenmar PP1000" manufactured by NOF Corporation), 60 parts of MMA, and 144 parts of ethyl acetate, and after the stirring started, the system was purged with nitrogen. The mixture was replaced and the temperature was raised to 55°C. Here, 2,
2'-Azobis(2,4-dimethylvaleronitrile) (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
After adding 0.8 parts of ethyl acetate and 7.3 parts of ethyl acetate, the temperature of the system was raised to 65°C, and
After stirring for an hour, 0.4 part of V-65 and 7 parts of ethyl acetate were further added, and the mixture was stirred at 65°C for 3 hours. After raising the temperature of the system to 78°C and stirring for 2 hours, 0.5 p-methoxyphenol was added.
2 parts by weight and 10 parts of ethyl acetate were added. After replacing the inside of the system with a mixed gas of 7% oxygen/93% nitrogen and further cooling the inside of the system to 40°C, 0.01 part of dibutyltin dilaurate and 2-isocyanatoethyl acrylate (“Karens AOI” manufactured by Showa Denko) were added. After adding 5.0 parts of ethyl acetate and 26 parts of ethyl acetate, the temperature inside the system was raised to 50°C. After stirring at 50° C. for 6 hours, disappearance of the isocyanate group was confirmed, and a solution of compound (A-5) having a (meth)acryloyl group and a polyoxyalkylene structure in the side chain was obtained. The composition of the reaction solution is A-5/ethyl acetate = 40/60 (weight ratio)
Met. The acryloyl group concentration of A-5 was 0.33 mmol/g.

[Comparative manufacturing example]
(Production of (meth)acrylic (meth)acrylate (A'-1))
60 parts of MMA, 2-HEMA4 were added to a reactor equipped with a stirrer, a reflux condenser, and a thermometer.
After starting stirring, the system was purged with nitrogen and the temperature was raised to 55°C. After adding 0.8 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (Fuji Film Wako Pure Chemical Industries, Ltd. "V-65") and 7.3 parts of ethyl acetate, the system 65℃ inside
After stirring for 3 hours, 0.4 part of V-65 and 4 parts of ethyl acetate were added, and the mixture was stirred at 65°C for 3 hours. After raising the temperature of the system to 78°C and stirring for 2 hours, 0.52 parts by weight of p-methoxyphenol and 4 parts of ethyl acetate were added. After replacing the inside of the system with a mixed gas of 7% oxygen/93% nitrogen and further cooling the inside of the system to 40°C, 0.01 part of dibutyltin dilaurate, 2-
After adding 42.6 parts of isocyanatoethyl acrylate ("Karens AOI" manufactured by Showa Denko) and 57 parts of ethyl acetate, the temperature inside the system was raised to 50°C. After stirring at 50° C. for 6 hours, disappearance of the isocyanate group was confirmed, and a solution of compound (A'-1) having no polyoxyalkylene structure in the side chain and having a (meth)acryloyl group was obtained. The composition of the reaction solution is B-5/ethyl acetate=
The weight ratio was 40/60. The acryloyl group concentration of A'-1 is 2.09 mmol/
It was g.

(Production of (meth)acrylic (meth)acrylate (A'-2))
98 parts by weight of glycidyl methacrylate (GMA), 1 part by weight of MMA, 1 part by weight of ethyl acrylate (EA), mercaptopropyltrimethoxysilane (KBM8 manufactured by Shin-Etsu Chemical Co., Ltd.)
03'') 1.9 parts by weight, propylene glycol monomethyl ether (PGM) 157.3
Parts by weight were charged, and after starting stirring, the system was purged with nitrogen and the temperature was raised to 55°C. Here, 2,2'
- After adding 1 part by weight of azobis(2,4-dimethylvaleronitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd.), the temperature in the system was raised to 65 ° C., and after stirring for 3 hours, V-65 to 0
．． 5 parts by weight were added and stirred at 65°C for 3 hours. After raising the temperature of the system to 100°C and stirring for 30 minutes, 0.45 parts by weight of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) and PGM138.
1 part by weight was added, and the temperature inside the system was again raised to 100°C. Next, triparatolylphosphine (
After adding 3.1 parts by weight (manufactured by Hokuko Chemical Industries), 50.7 parts by weight of acrylic acid was added, and 110 parts by weight was added.
The temperature was raised to .degree. C. and stirred for 6 hours to obtain a solution of compound A'-2 having no polyoxyalkylene structure in the side chain and having a (meth)acryloyl group. The composition of the reaction solution is A'-2/PGM=30
/70 (weight ratio). The acryloyl group concentration of A'-2 was 4.41 mmol/g.

(Production of (meth)acrylic polymer (a-2))
In a reactor equipped with a stirrer, a reflux condenser, and a thermometer, 60 parts of methoxypolyethylene glycol methacrylate ("Blenmar PME400" manufactured by NOF Corporation), 20 parts of MMA, 2
- Charge 20 parts of HEMA and 144 parts of ethyl acetate, and after starting stirring, replace the system with nitrogen.
The temperature was raised to ℃. After adding 0.8 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (Fuji Film Wako Pure Chemical Industries, Ltd. "V-65") and 7.3 parts of ethyl acetate,
After raising the temperature of the system to 65°C and stirring for 3 hours, 0.4 parts of V-65 and 7 parts of ethyl acetate were further added, and the mixture was stirred at 65°C for 3 hours. The temperature of the system was raised to 78° C., stirred for 2 hours, and then cooled to obtain a solution of compound (a-2) having no (meth)acryloyl group in the side chain and having a polyoxyalkylene structure. The composition of the reaction solution is a-2/ethyl acetate = 40/60 (weight ratio)
Met. The acryloyl group concentration of a-2 was 0 mmol/g.

(Production of (meth)acrylic polymer (a-3))
(Meth)acrylic polymer (a-2) was the same except that methoxypolyethylene glycol methacrylate ("Blenmar PME400" manufactured by NOF Corporation) was changed to methoxypolyethylene glycol methacrylate ("Blenmar PME1000" manufactured by NOF Corporation). A solution of compound (a-3) having no (meth)acryloyl group in the side chain and having a polyoxyalkylene structure was obtained. The composition of the reaction solution was a-3/ethyl acetate = 40/60 (weight ratio). The acryloyl group concentration of a-3 was 0 mmol/g.

(Production of urethane (meth)acrylate composition (B-1))
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet,
6.6 parts by mass of isophorone diisocyanate, 94 parts by mass of a mixture of dipentaerythritol and dipentaerythritol hexaacrylate with a hydroxyl value of 50 mgKOH/g, and 0.6 parts by mass of 2,6-di-tert-butylcresol as a polymerization inhibitor. ,
0.05 parts by mass of dibutyltin dilaurate was added as a reaction catalyst, and the reaction was carried out at 60°C.
The reaction was terminated when the remaining isocyanate groups reached 0.3%, and the acryloyl group concentration was 9.
A 3 mmol/g urethane acrylate composition (B-1) was obtained.
The mass average molecular weight of the obtained urethane (meth)acrylate composition (B-1) was 1.6.
The viscosity at 0.00 and 60° C. was 1,500 mPa·s.

(Production of urethane (meth)acrylate composition (B-2))
In a four-neck flask equipped with a thermometer, stirrer, and water-cooled condenser, 99.3 parts by mass of isophorone diisocyanate, 1.5 parts by mass of 2,6-di-tert-butylcresol, and 0.1 part by mass of dibutyltin dilaurylate. A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 51
．． 0mgKOH/g) was reacted at 60°C for 2 hours.
After the start of the reaction, when the remaining isocyanate groups reached 2.2%, polyethylene glycol (number average molecular weight 993.1, number of moles of ethylene oxide added 22, hydroxyl value 113) was added.
310.7 parts by mass of mgKOH/g) was added dropwise at 55°C and reacted at 60°C for 4 hours. The reaction was terminated when the remaining isocyanate group reached 0.1%, and the acryloyl group concentration was 5.9.
A resin composition (B-2) containing mmol/g of urethane (meth)acrylate was obtained.
The weight average molecular weight of the obtained urethane (meth)acrylate composition (B-2) was 3.7.
The viscosity at 0.00 and 60° C. was 1,100 mPa·s.

<Raw materials>
The following raw materials were prepared as (meth)acrylic esters (B) other than B-1 and B-2.
B-3: Ethoxylated dipentaerythritol polyacrylate, product name: NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
B-4: Polyether-modified polydimethylsiloxane with acrylic group, product name: BY
K-UV3500 (manufactured by BYK)
B-5: Primary particle diameter 10 nm to 15 nm surface modified with (meth)acryloyloxy group
m silica particles, MEK dispersion with a solid content of 46% by mass, product name: MEK-AC-2140Z
(Manufactured by Nissan Chemical Co., Ltd.)
As the photopolymerization initiator (C-1), 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone (manufactured by IGM Resins, “Omnira
d-2959''), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by IGM Resins, ``
Omnirad-907"), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins, "Omnirad-907"), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins, "Omnirad-907") as a photopolymerization initiator (C-3).
rad-TPO") was prepared.

<Example 1-1>
4 parts by mass of a photopolymerization initiator (C-1) is mixed with 100 parts by mass of a resin composition containing (meth)acrylate (meth)acrylate (A-1), so that the mixture has a resin content of 40%. The mixture was diluted with 50 parts/50 parts of methyl ethyl ketone/propylene glycol monomethyl ether to prepare an active energy ray-curable composition. The obtained active energy ray-curable composition was coated onto a 125 μm thick PET film provided with an easily adhesive layer using a bar coater so that the film thickness after drying was 5 μm, and then heated at 80° C. for 1 minute. Dry. After that, using one 80W high-pressure mercury lamp, the illumination intensity was 150mW/cm2, and the cumulative irradiation amount was 400mJ/cm.
A cured coating film was obtained by irradiating ultraviolet rays under the conditions of 2. The cured coating film was evaluated as follows. The results are shown in Table 1.

(Hard coat (HC) property)
Scratches were checked by scratching the cured paint film with a fingernail.
〇: No scratches with nails △: Scratches with nails ×: Tackiness remains, no HC property

(Low bacterial adhesion)
Staphylococcus aureus (NBRC12732) and Escherichia coli (NBRC3972) were cultured in advance at 37°C overnight, and then cultured in phosphate buffered saline (
(pH 7.0) to prepare a diluted culture solution. A 3 cm square test piece was cut out from the cured coating and was pasted on the inside of a TPP cell culture flask, 100 mL of diluted culture solution was added, and various bacteria were allowed to adhere to the test piece by allowing it to stand at 37°C for 1 hour. After attachment, the diluted culture solution was removed by suction, and the inside of the flask was washed three times with 100 mL of phosphate buffered saline (pH 7.0). After removing the droplets remaining in the flask, wipe the inner wall of the flask with an ATP measurement kit (Kikkoman Lucipak A3 Surface) with a cotton swab tip moistened with ion-exchanged water to measure the luminescence amount (Relative Light Unit; RLU). ) was used to measure the amount of attached bacterial cells.
<Escherichia coli>
S: RLU is less than 100.
A: RLU is 100 or more and less than 500.
B: RLU is 500 or more and less than 1,000.
C: RLU is 1,000 or more and less than 5,000.
D: RLU is 5,000 or more.
<Staphylococcus aureus>
S: RLU is less than 1,000.
A: RLU is 1,000 or more and less than 5,000.
B: RLU is 5,000 or more and less than 10,000.
C: RLU is 10,000 or more and less than 50,000.
D: RLU is 50,000 or more.

<Examples 1-2 to 1-5>
Instead of (meth)acrylic (meth)acrylate (A-1), the acrylics listed in Table 1 (
An active energy ray-curable composition was prepared and a cured coating film was obtained in the same manner as in Example 1-1, except that each of the meth)acrylates (A-2 to A-5) was used. The obtained cured coating film was evaluated in the same manner as in Example 1-1.

<Examples 1-6 to 1-12>
(meth)acrylic (meth)acrylate (A-2) and (meth)acrylic acid ester (B)
An active energy ray-curable composition was prepared in the same manner as in Example 1-1, except that B-1 to B-6) were blended in the proportions shown in Table 1, and a cured coating film was obtained. The obtained cured coating film was evaluated in the same manner as in Example 1-1.

<Examples 1-13 to 1-14>
In Example 1-1, photopolymerization initiators (C-2, C
An active energy ray-curable composition was prepared in the same manner as in Example 1-1, except that 3) was blended in the amount shown in Table 1, and a cured coating film was obtained. Regarding the obtained cured coating film, Example 1-
Evaluation was made in the same manner as in 1.

<Comparative Examples 1-1 to 1-2>
Without using a resin composition containing (meth)acrylate (meth)acrylate (A-1),
An active energy ray-curable composition was prepared in the same manner as in Example 1-1 except that resin compositions containing (meth)acrylate (A'-1) and (A'-2) were used. was prepared. The obtained cured coating film was evaluated in the same manner as in Example 1-1. The results are shown in Table 1.

<Example 2-1>
Table 2 shows the evaluation results of the cured coating film obtained in Example 1-2 before and after the ethanol wiping test.

<Example 2-2>
An active energy ray-curable composition was prepared in the same manner as in Example 2-1, except that the cured coating film obtained in Example 1-3 was used instead of the cured coating film obtained in Example 1-2. was prepared to obtain a cured coating film. The obtained cured coating film was evaluated in the same manner as in Example 2-1. The evaluation results are shown in Table 2.

<Comparative Examples 2-1, 2-2>
Example 1-1 except that (meth)acrylic polymers (a-2) and (a-3) listed in Table 2 were used instead of (meth)acrylate (A-1), respectively. In the same manner as above, an active energy ray-curable composition was prepared, and a cured coating film was obtained. The obtained cured coating film was evaluated in the same manner as in Example 2-1. The evaluation results are shown in Table 2. In addition, Comparative Example 2-1
Samples 2-2 were sticky and could not be tested before wiping with ethanol.

As shown in the results of Examples 1-1 to 1-14 and Examples 2-1 to 2-2 described above, an active energy ray-curable composition containing (meth)acrylate (meth)acrylate (A) It was confirmed that a cured coating film with excellent low bacterial adhesion and ethanol wiping resistance could be obtained.
Further, according to the active energy ray-curable compositions of Examples 1-1 to 1-14, cured coating films with excellent hard coat properties were obtained.
On the other hand, Comparative Examples 1-1 and 1-2 are active energy ray-curable compositions containing (meth)acrylate (meth)acrylate that does not have an oxyalkylene structure in the molecule, so they have low bacterial adhesion. It wasn't great.
In addition, Comparative Examples 2-1 and 2-2 are active energy ray-curable compositions containing (meth)acrylate that has an oxyalkylene structure but does not have a (meth)acryloyl group, so after wiping with ethanol, It was not excellent in low bacterial adhesion.

Claims (6)

Contains (meth)acrylic (meth)acrylate (A) whose polyoxyalkylene structure has a repeating number of 2 or more,
1. A low-bacteria-adhesive active energy ray-curable composition, characterized in that the amount of luminescence of Escherichia coli is 1,000 or less and the amount of luminescence of Staphylococcus aureus is 50,000 or less when measuring ATP. The polyoxyalkylene structure is a polyoxymethylene structure, a polyoxyethylene structure,
The low-bacteria-adhesive active energy ray-curable composition according to claim 1, which has at least one member selected from the group consisting of a polyoxypropylene structure and a polyoxytetramethylene structure. The low-bacteria-adhesive active energy ray-curable composition according to claim 1, further comprising a (meth)acrylic acid ester compound (B) in addition to the (meth)acrylate (A). The low bacterial adhesion active energy ray-curable composition according to claim 1, further comprising a photopolymerization initiator (C). A cured coating film of the low bacterial adhesion active energy ray-curable composition according to any one of claims 1 to 4. A laminate having the cured coating film according to claim 5 on at least one surface of a base material.