JP2020028813A - Bacterial cell low adhesion article and method for dealing with bacterial cell adhesion - Google Patents

Abstract

To provide a bacterial cell low adhesion article in which bacteria are hard to adhere and in addition the material selectivity is wide, and a method for dealing with bacterial cell adhesion.SOLUTION: Provided is a bacterial cell low adhesion article 10 having on the surface thereof a fine relief structure that has a cycle smaller than 5 times of the size of bacterial cell, and in which the surface on the side of the fine relief structure is water-repellent or hydrophilic, and the fine relief structure is made of a cured product of a curable resin composition and the fine relief structure is a structure obtained by transferring from a mold having the fine relief structure.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an article having low bacterial cell adhesion and a method for preventing bacterial cell adhesion.

BACKGROUND ART Conventionally, it has been known that bacterial bodies are unlikely to adhere to the surface of an article formed from a superhydrophilic material.
For example, Patent Document 1 discloses an antibacterial material composed of a superhydrophilic material such as a polymer or copolymer of 2-methacryloyloxyethylphosphorylcholine.

JP 2003-180801 A

  However, there were material limitations to make the surface superhydrophilic.

  SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a low-adherent cell article having a low cell adhesion and a wide material selectivity, and a method for preventing cell adhesion.

The present invention has the following aspects.
[1] The surface has a fine concavo-convex structure having a period smaller than 5 times the size of the bacterial cell,
The surface of the fine uneven structure side is water-repellent,
The fine uneven structure is made of a cured product of a curable resin composition,
In addition, the article having low bacterial cell adhesion, wherein the fine uneven structure is a structure obtained by transferring from a mold having the fine uneven structure.
[2] having a fine uneven structure on the surface with a period smaller than 5 times the size of the cells,
The surface of the fine uneven structure side is hydrophilic,
The fine uneven structure is made of a cured product of a curable resin composition,
In addition, the article having low bacterial cell adhesion, wherein the fine uneven structure is a structure obtained by transferring from a mold having the fine uneven structure.
[3] The low bacterial cell adhesion article according to [2], wherein the fine uneven structure is formed of a cured product of a composition containing a hydrophilic monofunctional monomer.
[4] The hydrophilic monofunctional monomer contains at least one selected from the group consisting of (meth) acrylamide derivatives, monofunctional amides, and monofunctional (meth) acrylates having a polyethylene glycol chain in an ester group. 3] The article having low bacterial cell adhesion according to 3).
[5] The article with low bacterial cell adhesion according to any one of [1] to [4], wherein the cycle is equal to or smaller than the size of the bacterial cell.
[6] The low bacterial cell adhesion article according to any one of [1] to [5], wherein the period is 50 nm or more and 4 μm or less.
[7] A method for preventing microbial cell adhesion, in which the low-adherent microbial cell article according to any one of [1] to [6] is provided at a location where the microbial cell adhesion is to be reduced.

  ADVANTAGE OF THE INVENTION According to this invention, a microbial cell adhesion | attachment article with which a microbial cell is hard to adhere | attach and a material selection is wide, and a microbial cell adhesion countermeasure method can be provided.

It is sectional drawing which shows an example of the low bacterial cell adhesion article of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a block diagram which shows an example of the manufacturing apparatus of the low bacterial cell adhesion article of this invention. It is sectional drawing which shows the manufacturing process of the mold which has anodized alumina on the surface. It is sectional drawing which shows other examples of the low cell adhesion | attachment article of this invention. It is a transmission electron microscope image of the surface of low bacterial cell adhesion article A3. It is a transmission electron microscope image of the surface of the low-adherent bacterial cell article A4. It is a transmission electron microscope image of the surface of low bacterial cell adhesion article A5. It is a transmission electron microscope image of the surface of the flat film z after performing the cell adhesion test 6. It is a transmission electron microscope image of the surface of the flat film e after performing the cell adhesion test 6. It is a transmission electron microscope image of the surface of the low cell adhesion article E1 after performing the cell adhesion test 6. It is a transmission electron microscope image of the surface of the low cell adhesion article E7 after performing the cell adhesion test 6. It is a transmission electron microscope image of the surface of the flat film z after performing the cell adhesion test 7. It is a transmission electron microscope image of the surface of the flat film e after performing the cell adhesion test 7. It is a transmission electron microscope image of the surface of the low cell adhesion article E1 after performing the cell adhesion test 7. It is a transmission electron microscope image of the surface of the low-adherence-of-cells article E7 after performing the cell adhesion test 7.

In the present specification, “(meth) acrylate” is a generic term for acrylate and methacrylate, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, and “(meth) acrylonitrile” is acrylonitrile and methacrylonitrile. "(Meth) acrylamide" is a generic term for acrylamide and methacrylamide, and "(meth) acryloxy" is a generic term for acryloxy and methacryloxy.
In the present specification, “active energy rays” means visible rays, ultraviolet rays, electron beams, plasma, heat rays (such as infrared rays), and the like.
In FIGS. 1 to 4, the dimensional ratio is different from the actual one for convenience of explanation. In FIG. 4, the same components as those in FIG. 1 are denoted by the same reference numerals, and description thereof will be omitted.

Further, in the present specification, the term "cells" means bacteria, yeast, filamentous fungi, and the like. Bacteria include Escherichia coli, Pseudomonas aeruginosa, Streptococcus, Staphylococcus, and the like. Yeasts include Saccharomyces, Schizosaccharomyces, Cryptococcus, Candida, and the like.
The shape of the bacterial cell is not particularly limited, and includes a sphere, an ellipse, and other shapes other than those. Examples of the cells having other shapes include mycelium-shaped cells, and cells having flagella and cilia. For example, Streptococcus and Staphylococcus are spherical cells. Escherichia coli and Pseudomonas aeruginosa are oval cells, but may have flagella and / or cilia. Saccharomyces are spherical or elliptical cells. Candida is a spherical and mycelial cell.

The present invention is effective for cells having a size of 10 μm or less, but is particularly effective for cells having a size of preferably 50 nm or more and 4 μm or less, more preferably 80 nm or more and 2 μm or less. The shape is particularly effective for spherical and elliptical cells.
The size of the cells in this specification is defined as follows. That is, when the cells are spherical, the size of the cells is the diameter of the cells. When the cells are oval or mycelial, the size of the cells is the minor axis of the cells. If the cells have flagella or cilia, their length is not considered.

`` Bacterial low adhesion product ''
An article with low bacterial cell adhesion is one in which a fine uneven structure having a period smaller than 5 times the size of the bacterial body is formed on the surface of the article body, and it is difficult for the bacterial body to stay on the surface even when the bacterial body comes into contact with the article ( (It is difficult to adhere). Hereinafter, the fact that the cells are difficult to adhere is also referred to as “bacteriorepellency”.
Examples of the article main body include films and various molded articles (for example, members that make up a portion touched by human hands, such as door knobs, doors, and straps). The material of the article body is not particularly limited, and examples thereof include resin, metal, and glass.
Hereinafter, the present invention will be described by taking, as an example, an article having a low microbial adherence in which a fine uneven structure is formed on the surface of a film-shaped article main body.

  FIG. 1 is a cross-sectional view showing an example of the low-adherent bacterial cell article of the present invention. The low-adherent-bacteria article 10 of this example is a cured resin layer having on its surface a base film 12 as an article body and a fine uneven structure formed on the surface of the base film 12 and composed of a plurality of convex portions 14. 16 in the form of a film.

<Base film>
Examples of the material of the base film 12 include acrylic resin, polycarbonate, styrene resin, polyester, cellulose resin (such as triacetyl cellulose), polyolefin, alicyclic polyolefin, vinyl chloride resin, polyamide, polyurethane, and glass. No. The substrate is not limited to a film, and may be a sheet, an injection molded product, or the like.

<Curing resin layer>
The cured resin layer 16 is a film made of a cured product of an active energy ray-curable resin composition described later, and has a fine uneven structure composed of a plurality of convex portions 14 on the surface.

  The method for forming the fine concavo-convex structure is not particularly limited, and examples thereof include a method of directly forming a molded article, a method of transferring from a mold having a fine concavo-convex structure, and the like. In the case of the transfer method, the fine concavo-convex structure is preferably formed by transferring a plurality of pores of anodized alumina described later. The concavo-convex structure formed by transferring a plurality of pores of anodized alumina can be formed at low cost and can have a large area.

Since the low bacterial cell adhesion article 10 has the cured resin layer 16 having a fine uneven structure on the surface, the contact area when the bacterial cells come into contact is smaller than when the bacterial cells come into contact with the flat surface. Therefore, it is difficult for bacteria to adhere.
In addition, the period of the fine uneven structure, that is, the average interval P between the adjacent convex portions 14 is smaller than five times the size of the cells (that is, the period P <(the size of the cells × 5)). Satisfy the relationship.). If the period of the fine uneven structure is smaller than 5 times the size of the microbial cells, it is difficult for the microbial cells to enter the concave portions existing between the convex portions 14 of the fine uneven structure, and it is difficult for the microbial cells to stay in the concave portions. Therefore, a sufficient bactericidal effect can be obtained.

The period of the fine uneven structure is preferably 2.5 times or less the size of the cells, and is not more than the size of the cells (that is, the relationship of “period ≦ the size of the cells” is satisfied). It is more preferable that the size is smaller than the size of the cells (that is, the relationship of “period <size of the cells” is satisfied), more preferably 50 nm or more and 4 μm or less, and particularly preferably 50 nm or more and 2 μm or less. . When the period of the fine concavo-convex structure is 50 nm or more and 4 μm or less, particularly 50 nm or more and 2 μm or less, a germicidal effect superior to a smooth surface can be obtained.
The period of the fine concavo-convex structure was measured at 50 points between the adjacent convex portions 14 (distance from the center of the convex portion 14 to the center of the adjacent convex portion 14) by electron microscope observation, and these values were averaged. Things.

The height H of the projection 14 is preferably from 10 to 50,000 nm, more preferably from 10 to 10,000 nm.
The height H of the projections 14 was measured by measuring the distance between the top of the projections 14 and the bottom of the recess existing between the projections 50 by electron microscope observation, and these values were averaged. Things.

  The aspect ratio (H / P) of the projection 14 is preferably 0.05 to 100, more preferably 0.1 to 5, and particularly preferably 0.25 to 3. The aspect ratio of the projection 14 is 0.05 or more. If it is, the bactericidal effect will be more easily exhibited. When the aspect ratio of the convex portion 14 is 5 or less, the scratch resistance of the convex portion 14 becomes good.

  Examples of the shape of the convex portion 14 include a substantially conical shape, a pyramid shape, a bell shape, a cylindrical shape, a line and space, and the like. In particular, a shape such as a conical shape or a pyramid shape in which the cross-sectional area of the convex portion in the direction orthogonal to the height direction continuously increases from the top to the depth direction is preferable.

The water content of the surface on the side of the fine uneven structure (that is, the material of the fine uneven structure) is preferably 100% or less, more preferably 50% or less. When the water content of the surface on the side of the fine unevenness is 100% or less, a change in volume between saturated water content and drying can be suppressed, and cracks and the like of the product can be suppressed. The water content of the surface on the side of the fine uneven structure is preferably 10% or more.
The moisture content of the surface on the side of the fine uneven structure can be adjusted by the crosslinking density and the material of the material of the fine uneven structure. For example, when a hydrophilic monofunctional monomer is added to a material having a fine uneven structure, or when the crosslink density of the material is reduced, the water content tends to increase.
The moisture content of the surface on the side of the fine uneven structure was determined by forming a test film using the material having the fine uneven structure, and then weighing the test film in pure water at 25 ° C. for 2 weeks or more, The weight change rate is calculated from the weight (dry weight) of the test film after standing for two weeks in a room at a temperature of 25 ° C. and a humidity of 50% RH. The moisture content can also be determined by peeling the cured resin layer 16 from the base film 12 and using the peeled cured resin layer 16 instead of a test film. In addition to this method, the moisture content can also be obtained by performing a humidity control method or a dynamic water vapor adsorption / desorption measurement.

<Manufacturing method for low-adherent bacterial cells>
The article 10 with low adherence of cells shown in FIG. 1 is produced, for example, using the production apparatus shown in FIG. 2 as follows.
A surface of a roll-shaped mold 20 on the surface of which anodized alumina having a plurality of pores (not shown) is formed, and a strip-shaped base film that moves along the surface of the mold 20 in synchronization with the rotation of the mold 20 The active energy ray-curable resin composition 24 is supplied from the tank 22 to the gap between the active energy ray curable resin composition 24 and the surface of the resin composition 12.

  The base film 12 and the active energy ray-curable resin composition 24 are nipped between the mold 20 and a nip roll 28 whose nip pressure is adjusted by a pneumatic cylinder 26, and the active energy ray-curable resin composition 24 is The resin is uniformly distributed between the base film 12 and the mold 20 and is filled in the pores of the mold 20.

With the active energy ray-curable resin composition 24 sandwiched between the mold 20 and the base film 12, the active energy ray irradiation device 30 installed below the mold 20 is used to form the base film 12 side By irradiating the active energy ray-curable resin composition 24 with an active energy ray to cure the active energy ray-curable resin composition 24, a plurality of convexes on the surface of the mold 20 are transferred. A cured resin layer 16 having a concave-convex structure made up of portions (not shown) on the surface is formed.
By peeling the base film 12 on which the cured resin layer 16 is formed on the surface by the peeling roll 32, the article 10 with low bacterial cell adhesion is obtained.

As the active energy ray irradiation device 30, a high-pressure mercury lamp, a metal halide lamp, a fusion UV or the like is preferable. The integrated light quantity is preferably from 100 to 10000 mJ / cm ² .

(mold)
The mold 20 is not particularly limited, and includes a mold having an uneven structure by lithography or laser processing, a mold having anodized alumina on its surface, and the like. Is preferred on the surface. The mold having anodized alumina on the surface can have a large area and is easy to manufacture.

  Anodized alumina is a porous oxide film (alumite) of aluminum and has a plurality of pores on the surface.

A mold having anodized alumina on the surface can be manufactured, for example, through the following steps (a) to (f). Although the regularity of the arrangement of the pores is slightly reduced, the steps (a) and (b) are not performed, and the steps (a) and (b) are performed from the step (c) or only the step (a). , (F) may be performed, and steps (c) and (d) may be performed.
(A) a step of forming an oxide film by anodizing an aluminum substrate in an electrolytic solution;
(B) a step of removing an oxide film and forming a pore generation point of anodic oxidation;
(C) a step of anodizing the aluminum base again in the electrolytic solution to form an oxide film having pores at the pore generation points.
(D) a step of enlarging the pore diameter.
(E) After the step (d), a step of anodizing again in the electrolytic solution.
(F) a step of repeatedly performing the steps (d) and (e).

Step (a):
As shown in FIG. 3, when an aluminum substrate 34 is anodized, an oxide film 38 having pores 36 is formed. The regularity of pores formed by anodic oxidation is extremely low in the initial stage, but the regularity of pores is improved by performing anodic oxidation for a long time. The treatment time (anodizing time) is preferably 5 minutes or more, and more preferably 15 minutes or more. However, if the anodic oxidation is performed for a long time, the regularity of the pores is improved, but the pores tend to be relatively deep. Therefore, the treatment in the step (b) is performed to form regular pores. Used as an origin. If only regular pores are to be formed without expecting regularity, the treatment time until a desired pore depth is reached may be set as appropriate.
The purity of aluminum is preferably 99% or more, more preferably 99.5% or more, and particularly preferably 99.8% or more. If the purity of aluminum is low, the regularity of pores obtained by anodic oxidation may decrease.
Examples of the electrolytic solution include sulfuric acid, oxalic acid aqueous solution, and phosphoric acid aqueous solution.

Step (b):
As shown in FIG. 3, the regularity of the pores can be improved by removing the oxide film 38 once and setting it as the pore generation point 40 of the anodic oxidation.

  As a method of removing the oxide film, a method of dissolving the aluminum oxide film in a solution that selectively dissolves the aluminum oxide film without dissolving the aluminum film can be used. Examples of such a solution include a chromic acid / phosphoric acid mixed solution.

Step (c):
As shown in FIG. 3, when the aluminum substrate 34 from which the oxide film has been removed is again anodized, an oxide film 38 having columnar pores 36 is formed.
Examples of the electrolyte include those similar to those in step (a).

Step (d):
As shown in FIG. 3, a process of enlarging the diameter of the pores 36 (hereinafter, referred to as a pore diameter enlarging process) is performed. The pore diameter enlargement process is a process of increasing the diameter of pores obtained by anodic oxidation by immersion in a solution that dissolves an oxide film. Examples of such a solution include a phosphoric acid aqueous solution of about 5% by mass.

Step (e):
As shown in FIG. 3, when anodic oxidation is performed again, cylindrical pores 36 having a small diameter and extending downward from the bottom of the cylindrical pores 36 are further formed.
Examples of the electrolyte include those similar to those in step (a).

Step (f):
As shown in FIG. 3, when the pore diameter enlarging treatment in the step (d) and the anodic oxidation in the step (e) are repeated, the pores 36 have a shape whose diameter continuously decreases from the opening in the depth direction. The mold 20 on which the anodized alumina (porous aluminum oxide film (alumite)) is formed is obtained. The end preferably ends in step (d).

  The surface of the anodized alumina may be treated with a release agent so as to facilitate separation from the cured resin layer 16. Examples of the treatment method include a method of coating a silicone resin or a fluorine-containing polymer, a method of depositing a fluorine-containing compound, and a method of coating a fluorine-containing silane compound.

  Examples of the shape of the pore 36 include a substantially conical shape, a pyramid shape, a bell shape, a column shape, a line and space, and the like.

  The average distance between the pores 36 is smaller than 5 times the size of the cells. The average distance between the pores 36 is preferably 2.5 times or less the size of the cells, more preferably not more than the size of the cells, and is preferably smaller than the size of the cells. It is more preferably 10 nm or more and 10 μm or less, further preferably 50 nm or more and 4 μm or less, and particularly preferably 50 nm or more and 2 μm or less. When the average interval between the pores 36 is 50 nm or more and 4 μm or less, particularly 50 nm or more and 2 μm or less, a better bacteriostatic effect than a smooth surface can be obtained.

(Active energy ray-curable resin composition)
The active energy ray-curable resin composition contains a polymerizable compound and a polymerization initiator.
Examples of the polymerizable compound include monomers, oligomers, and reactive polymers having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule.
The active energy ray-curable resin composition may include a non-reactive polymer and an active energy ray sol-gel reactive composition.

Monomers having a radical polymerizable bond include monofunctional monomers and polyfunctional monomers.
Monofunctional monomers include 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, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acryle , Allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) (Meth) acrylate derivatives such as acrylate and methoxypolyethylene glycol acrylate; (meth) acrylic acid; (meth) acrylonitrile; styrene derivatives such as styrene and α-methylstyrene; (meth) acrylamide; N, N-dimethyl (meth) Acrylamide, N, N-diethyl (meth) acrylamide, N-dimethylaminoethyl (meth) acrylamide, N-isopropylacrylamide, acryloylmorpholine, dimethylaminopropyl (meth) acrylamide, etc. (Meth) acrylamide derivatives; monofunctional amides such as N-vinylformamide, N-vinylacetamide, N-vinylisobutylamide, and N-vinylacylamide monomers.
These may be used alone or in combination of two or more.

As polyfunctional monomers, ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, polybutylene glycol di ( (Meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- ( 3- (me ) Acryloxy-2-hydroxypropoxy) phenyl) propane, 1,2-bis (3- (meth) acryloxy-2-hydroxypropoxy) ethane, 1,4-bis (3- (meth) acryloxy-2-hydroxypropoxy) Butane, dimethylol tricyclodecane di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, divinylbenzene, Bifunctional monomers such as methylenebisacrylamide; pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-modified tri ( T) trifunctional monomers such as acrylate, trimethylolpropane propylene oxide-modified triacrylate, trimethylolpropane ethylene oxide-modified triacrylate, and isocyanuric acid ethylene oxide-modified tri (meth) acrylate; a condensation reaction mixture of succinic acid / trimethylolethane / acrylic acid Di- or higher-functional monomers such as dipentaeristol hexa (meth) acrylate, dipenta-eristol penta (meth) acrylate, ditrimethylolpropanetetraacrylate, tetramethylolmethanetetra (meth) acrylate; bifunctional or higher urethane acrylate, Bifunctional or higher functional polyester acrylate and the like can be mentioned.
These may be used alone or in combination of two or more.

  Examples of the monomer having a cationic polymerizable bond include a monomer having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group, and the like, and a monomer having an epoxy group is particularly preferable.

  As the oligomer or the reactive polymer, unsaturated polyesters such as a condensate of an unsaturated dicarboxylic acid and a polyhydric alcohol; polyester (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, epoxy (meth) Acrylates, urethane (meth) acrylates, cationic polymerization type epoxy compounds, homopolymers or copolymers of the above-mentioned monomers having a radical polymerizable bond in the side chain, and the like can be given.

Examples of the non-reactive polymer include an acrylic resin, a styrene resin, a polyurethane, a cellulose resin, polyvinyl butyral, polyester, and a thermoplastic elastomer.
Examples of the active energy ray sol-gel reactive composition include an alkoxysilane compound and an alkyl silicate compound.

Examples of the alkoxysilane compound include a compound represented by the following formula (1).
R ¹¹ _x Si (OR ¹² ) _y (1)
Here, R ¹¹ and R ¹² each represent an alkyl group having 1 to 10 carbon atoms, and x and y represent integers satisfying the relationship of x + y = 4.

  Examples of the alkoxysilane compound include tetramethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, methyltriethoxysilane, Examples include methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, trimethylpropoxysilane, trimethylbutoxysilane, and the like.

Examples of the alkyl silicate compound include a compound represented by the following formula (2).
R ²¹ O [Si (OR ²³ ) (OR ²⁴ ) O] _z R ²² (2)
Here, R ^{21 to} R ²⁴ each represent an alkyl group having 1 to 5 carbon atoms, and z represents an integer of 3 to 20.

  Examples of the alkyl silicate compound include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, n-pentyl silicate, acetyl silicate and the like.

When a photocuring reaction is used, examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl, benzophenone, p-methoxybenzophenone, and 2,2-diethoxy. Acetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropane- Carbonyl compounds such as 1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyl Diethoxyphosphine oxide and the like.
These may be used alone or in combination of two or more.

When an electron beam curing reaction is used, examples of the polymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone, and tert- Thioxanthones such as butylanthraquinone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone and 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl Dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-mo Acetophenones such as holinophenyl) -butanone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)- Acylphosphine oxides such as 2,4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; methylbenzoyl formate, 1,7-bisacridinyl heptane, 9-phenyl Acridine and the like.
These may be used alone or in combination of two or more.

  When utilizing a thermosetting reaction, as the thermal polymerization initiator, for example, methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyoctoate, organic peroxides such as tert-butylperoxybenzoate and lauroyl peroxide; azo compounds such as azobisisobutyronitrile; N, N-dimethylaniline and N, N-dimethyl-p- Redox polymerization initiators in which an amine such as toluidine is combined are exemplified.

The active energy ray-curable resin composition may contain an antistatic agent, a release agent, an additive such as a fluorine compound for improving antifouling properties, fine particles, and a small amount of a solvent, if necessary.
From the viewpoint of sustained release, the effect can be obtained even if the cured product of the active energy ray-curable resin composition is hydrophobic or hydrophilic.

(Hydrophilic material)
In the case of imparting hydrophilicity to the surface of the microcellular low-adhesive article on the side of the fine unevenness structure, an active energy ray-curable resin composition capable of forming a hydrophilic material is a polyfunctional (meth) having four or more functional groups. It is preferable to use a composition (hydrophilic material) containing an acrylate, a bifunctional or higher hydrophilic (meth) acrylate, preferably a monofunctional monomer.
If the surface of the microcellular low-adhesive article on the side of the fine uneven structure is hydrophilic, that is, if the fine uneven structure is formed of a hydrophilic material, excellent microbial repellency can be exhibited for a long time. In addition, excellent lyophobicity can be exhibited not only for low-concentration cells but also for high-concentration cells.
Here, “hydrophilic” means that the water contact angle of the surface on the side of the fine unevenness structure of the article with low bacterial cell adhesion is 90 ° or less. The water contact angle is a value calculated by the θ / 2 method by dropping 1 μL of ion-exchanged water onto the surface of the article with low bacterial cell adhesion on the side of the fine uneven structure.

In particular, if the water contact angle of the smooth surface obtained by curing the active energy ray-curable resin composition is 60 ° or less, the surface of the fine uneven structure obtained using this active energy ray-curable resin composition is hydrophilic. It tends to be more effective, and the effect of low adherence of cells such as water droplets and water tends to be higher.
The water contact angle on the surface of the microcellular low-adhesive article on the side of the fine unevenness structure is preferably 60 ° or less from the viewpoint that more excellent bacterio-repellency can be maintained.
Here, the smooth surface means that the arithmetic average roughness Ra is 10 nm or less based on the standard of JIS B 0601: 1994.

Examples of the tetrafunctional or higher polyfunctional (meth) acrylate include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, condensation reaction mixture of succinic acid / trimethylolethane / acrylic acid in a molar ratio of 1: 2: 4, urethane acrylates (manufactured by Daicel Psytech Co., Ltd .: EBECRYL220, EBECRYL1290, EBECRYL1290K, EBECRYL5129, EBECRYL8210) EBECRYL8301, KRM8200), polyether acrylates (manufactured by Daicel Psytech: EBEC) YL81), modified epoxy acrylates (manufactured by Daicel-Cytec Co., Ltd.: EBECRYL3416), polyester acrylates (manufactured by Daicel-Cytec: EBECRYL450, EBECRYL657, EBECRYL800, EBECRYL810, EBECRYL811, EBECRYL812, EBECRYL1830, EBECRYL845, EBECRYL846, EBECRYL1870) and the like include Can be These may be used alone or in combination of two or more.
As the polyfunctional (meth) acrylate having four or more functional groups, a polyfunctional (meth) acrylate having five or more functional groups is more preferable.

As a bifunctional or more hydrophilic (meth) acrylate, long chain polyethylene such as Aronix M-240, Aronix M260 (manufactured by Toagosei Co., Ltd.), NK ester AT-20E, NK ester ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.) Examples include a polyfunctional acrylate having a glycol, polyethylene glycol di (meth) acrylate, and the like. These may be used alone or in combination of two or more.
In polyethylene glycol di (meth) acrylate, the total of the average repeating units of the polyethylene glycol chain present in one molecule is preferably from 6 to 40, more preferably from 9 to 30, and particularly preferably from 12 to 20. When the average repeating unit of the polyethylene glycol chain is 6 or more, the hydrophilicity becomes sufficient and the antifouling property is improved. When the average repeating unit of the polyethylene glycol chain is 40 or less, the compatibility with the polyfunctional (meth) acrylate having 4 or more functional groups becomes good, and the active energy ray-curable resin composition is hardly separated.

As the monofunctional monomer, a hydrophilic monofunctional monomer is preferable.
Examples of hydrophilic monofunctional monomers include monofunctional monomers having a polyethylene glycol chain in an ester group such as M-20G, M-90G, M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.), MPE400A, and MPE550A (manufactured by Osaka Organic Chemical Co., Ltd.). (Meth) acrylate (that is, ethylene oxide-modified (meth) acrylate); monofunctional (meth) acrylate having a hydroxyl group in an ester group such as hydroxyalkyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide (Meth) acrylamide derivatives such as N, N-N-diethyl (meth) acrylamide, N-dimethylaminoethyl (meth) acrylamide, N-isopropylacrylamide, acryloylmorpholine, and dimethylaminopropyl (meth) acrylamide; Monofunctional amides such as amide, N-vinylacetamide, N-vinylisobutyramide, and N-vinylacylamide monomers; cationic monomers such as methacrylamidopropyltrimethylammonium methyl sulfate and methacryloyloxyethyltrimethylammonium methyl sulfate; No.
Further, as the monofunctional monomer, a viscosity modifier such as vinylpyrrolidone, an adhesion improver such as acryloyl isocyanate for improving the adhesion to the substrate, or the like may be used.

  The monofunctional monomer may be blended in the active energy ray-curable resin composition as a low-polymerized polymer obtained by (co) polymerizing one or more kinds. Examples of the polymer having a low polymerization degree include 40/60 of monofunctional (meth) acrylates having a polyethylene glycol chain in an ester group such as M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.) and methacrylamidopropyltrimethylammonium methyl sulfate. Copolymer oligomers (MG polymer, manufactured by MRC Unitech) and the like.

  The content of the monofunctional monomer is preferably from 5 to 75% by mass, more preferably from 10 to 50% by mass, based on 100% by mass of the active energy ray-curable resin composition. When the content of the monofunctional monomer is 5% by mass or more, the effect of hydrophilicity is more easily obtained, and when it is 75% by mass or less, the tackiness of the surface on the side of the fine uneven structure is suppressed.

(Hydrophobic material)
When imparting water repellency to the surface of the microcellular low-adhesive article on the side of the fine uneven structure, the active energy ray-curable resin composition capable of forming a hydrophobic material contains a fluorine-containing compound or a silicone-based compound. It is preferable to use a composition (hydrophobic material).
If the surface of the micro-rough structure of the low-adherent microbial article is water-repellent, that is, if the micro-rough structure is formed of a hydrophobic material, excellent microbial repellency against low-concentration microbial cells is obtained. Can demonstrate.
Here, the term "water repellency" means that the water contact angle of the surface on the side of the fine unevenness structure of the low-adherent microbial article is more than 90 °.

  In particular, when the water contact angle of the smooth surface obtained by curing the active energy ray-curable resin composition exceeds 60 °, the surface of the fine uneven structure obtained using the active energy ray-curable resin composition is repellent. It tends to be water-based, and the effect of low adherence of bacterial cells contained in water droplets under dry conditions tends to be higher.

Fluorine-containing compounds:
As the fluorine-containing compound, a compound having a fluoroalkyl group represented by the following formula (3) is preferable.
− (CF ₂ ) _n −X (3)
However, X represents a fluorine atom or a hydrogen atom, n represents an integer of 1 or more, preferably 1 to 20, more preferably 3 to 10, and particularly preferably 4 to 8.

  Examples of the fluorine-containing compound include a fluorine-containing monomer, a fluorine-containing silane compound, a fluorine-containing surfactant, and a fluorine-containing polymer.

Examples of the fluorine-containing monomer include a fluoroalkyl group-substituted vinyl monomer and a fluoroalkyl group-substituted ring-opening polymerizable monomer.
Examples of the fluoroalkyl-substituted vinyl monomer include fluoroalkyl-substituted (meth) acrylate, fluoroalkyl-substituted (meth) acrylamide, fluoroalkyl-substituted vinyl ether, and fluoroalkyl-substituted styrene.

  Examples of the fluoroalkyl-substituted ring-opening polymerizable monomer include a fluoroalkyl-substituted epoxy compound, a fluoroalkyl-substituted oxetane compound, and a fluoroalkyl-substituted oxazoline compound.

As the fluorine-containing monomer, a fluoroalkyl group-substituted (meth) acrylate is preferable, and a compound represented by the following formula (4) is particularly preferable.
^{_{CH 2 = C (R 41)}} C (O) O- (CH 2) m - (CF 2) n -X ··· (4)
However, R ⁴¹ represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a fluorine atom, m represents an integer of 1 to 6, preferably 1 to 3, more preferably 1 or 2, and n Represents an integer of 1 to 20, preferably 3 to 10, and more preferably 4 to 8.

As the fluorine-containing silane compound, a fluoroalkyl group-substituted silane compound is preferable, and a compound represented by the following formula (5) is particularly preferable.
(R ^f ) _a R ⁵¹ _b SiY _c (5)

R ^f represents a C 1 to C 20 fluorine-substituted alkyl group which may contain one or more ether bonds or ester bonds. Examples of R ^f include a 3,3,3-trifluoropropyl group, a tridecafluoro-1,1,2,2-tetrahydrooctyl group, a 3-trifluoromethoxypropyl group, and a 3-trifluoroacetoxypropyl group. Can be

R ⁵¹ represents an alkyl group having 1 to 10 carbon atoms. Examples of ^R51 include a methyl group, an ethyl group, a cyclohexyl group, and the like.

Y represents a hydroxyl group or a hydrolyzable group.
Examples of the hydrolyzable group include an alkoxy group, a halogen atom, and R ⁵² C (O) O (where R ⁵² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an iso-propyloxy group, a butoxy group, an iso-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group, and a heptyloxy group. Group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group and the like.
Examples of the halogen atom include Cl, Br, and I.
Examples of R ⁵² C (O) O include CH ₃ C (O) O and C ₂ H ₅ C (O) O.

  a, b, and c are integers satisfying a + b + c = 4 and satisfying a ≧ 1 and c ≧ 1, and are preferably a = 1, b = 0, and c = 3.

  Examples of the fluorine-containing silane coupling agent include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriacetoxysilane, dimethyl-3,3,3-trifluoropropylmethoxysilane, Decafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane and the like can be mentioned.

  Examples of the fluorine-containing surfactant include a fluoroalkyl group-containing anionic surfactant and a fluoroalkyl group-containing cationic surfactant.

Examples of the fluoroalkyl group-containing anionic surfactant include a fluoroalkyl carboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, and 3- [omega-fluoroalkyl (C ₆ -C ₁₁ ) oxy. ] -1-alkyl _(C 3 _{~C 4)} sulfonate, sodium 3- [omega - fluoroalkanoyl _{(C 6 ~C} 8) -N- ethylamino] -1-sodium sulfonic acid, fluoroalkyl _{(C 11} ~ C ₂₀₎ carboxylic acids and metal salts thereof, perfluoroalkyl carboxylic acids _(C 7 _{~C 13)} or metal salts thereof, perfluoroalkyl _(C 4 _{~C 12)} sulfonic acids and metal salts thereof, diethanol perfluorooctane sulfonic acid Ami , N-propyl-N- (2-hydroxy Chill) perfluorooctane sulfonamide, perfluoroalkyl _(C 6 _{-C 10)} sulfonamide propyl trimethyl ammonium salts, perfluoroalkyl _{(C 6} -C 10)-N-ethylsulfonyl glycine salts, monoperfluoroalkyl _{(C 6} To C ₁₆ ) ethyl phosphate and the like.

Examples of the fluoroalkyl group-containing cationic surfactant include aliphatic quaternary such as aliphatic primary, secondary and tertiary amine acids containing fluoroalkyl group and perfluoroalkyl (C ₆ -C ₁₀ ) sulfonamidopropyltrimethylammonium salt. Ammonium salt, benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

  Examples of the fluorine-containing polymer include a polymer of a fluoroalkyl group-containing monomer, a copolymer of a fluoroalkyl group-containing monomer and a poly (oxyalkylene) group-containing monomer, and a copolymer of a fluoroalkyl group-containing monomer and a crosslinking reactive group-containing monomer. Polymers. The fluorine-containing polymer may be a copolymer with another copolymerizable monomer.

As the fluorine-containing polymer, a copolymer of a fluoroalkyl group-containing monomer and a poly (oxyalkylene) group-containing monomer is preferable.
As the poly (oxyalkylene) group, a group represented by the following formula (6) is preferable.
− (OR ⁶¹ ) _p − (6)
Here, R ⁶¹ represents an alkylene group having 2 to 4 carbon atoms, and p represents an integer of 2 or more.
The _{^{R 61, -CH 2 CH 2 -}} , - CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 -, - CH (CH 3) CH (CH 3) - , and the like.

The poly (oxyalkylene) group may be composed of the same oxyalkylene unit (OR ⁶¹ ) or may be composed of two or more oxyalkylene units (OR ⁶¹ ). The sequence of two or more types of oxyalkylene units (OR ⁶¹ ) may be blocks or random.

Silicone compounds:
Examples of the silicone-based compound include (meth) acrylic acid-modified silicone, silicone resin, and silicone-based silane coupling agent.
Examples of the (meth) acrylic acid-modified silicone include silicone (di) (meth) acrylates such as X-22-1602 (manufactured by Shin-Etsu Chemical Co., Ltd.).

<Effects>
The article with low bacterial cell adhesion of the present invention described above has a fine uneven structure having a cycle smaller than five times the size of the bacterial cell on the surface, and thus the bacterial cell is less likely to adhere. In addition, the article with low bacterial cell adhesion according to the present invention exhibits bacterio-repellency due to its surface structure. Therefore, the type of the article is not limited as long as it can form a fine uneven structure. Therefore, the low bacterial cell adhesion article of the present invention has a wider material selectivity as compared with the case where a superhydrophilic material is used to exhibit germicidal properties.

  The details of the mechanism by which the low cell-adherent article exhibits bacterial repellency are unknown at this time, but since the protrusions are formed on the surface with a narrow pitch whose cycle is less than the size of the cells, It is thought that the contact area between the film and the film becomes small, and the bacteria repellency is exhibited.

<How to use>
It is expected that the article with low bacterial cell adhesion of the present invention will be widely used in places where it is desired to reduce bacterial cell adhesion. For example, in the case where the article with low bacterial cell adhesion is in the form of a film as shown in FIG. 1, a portion where the bacterial cell adhesion is to be reduced (for example, movement of a door knob, a door, a strap, a handrail, a child seat, an automobile, a train, a ship, an airplane, etc.) The adhesion of bacterial cells can be suppressed only by sticking the low bacterial cell adhesion article of the present invention to the interior material of the body, the inner wall of the water tank, and the like. In addition, the film-shaped microbial cell low-adhesive article is also referred to as a “bacteriorepellent film”.
In addition, the low bacterial cell adhesion article of the present invention can be used for medical equipment. For example, the articles with low bacterial cell adhesion of the present invention can be used for artificial organs, catheters, stents, syringes, and their packaging materials, building materials and equipment in medical facilities (toilet peripheral products, operating room interiors, operating tables, wallpapers, floors, (A bed frame, a desk, or the like), or the article with low bacterial cell adhesion of the present invention can be used. Thus, the use of the low-adherent microbial article of the present invention in a medical device makes it difficult for microbial cells to adhere to the article, which is expected to be effective in preventing hospital-acquired infections in medical facilities and reducing the risk of infectious diseases. Can be

<Other forms>
The low-bacteria-based article of the present invention is not limited to the low-bacteria-based article 10 in the illustrated example.
For example, the fine uneven structure is formed on the surface of the cured resin layer 16 in the illustrated example, but may be formed directly on the surface of the base film 12 without providing the cured resin layer 16.
However, it is preferable that the uneven structure is formed on the surface of the cured resin layer 16 from the viewpoint that the uneven structure can be efficiently formed using the roll-shaped mold 20.

  Further, the shape of the projection is not limited to the projection 14 (projection) as in the illustrated example, and may be a projection extending in a certain direction.

  In addition, the article with low bacterial cell adhesion is not limited to the article obtained by the above-described manufacturing method, and may be formed by a known method (nanoimprinting, cutting, etching, resin phase separation, dew condensation during the wet film forming process). It may be manufactured by forming a fine uneven structure on the surface of the substrate film by a method using self-assembly of aligned water droplets).

  Further, in the above-described manufacturing method, a fine uneven structure is formed using a mold having anodized alumina on the surface. However, the mold is not limited to the above-described one, and for example, a mold having a diffraction grating formed on the surface. Alternatively, a mold having a fine uneven structure layer made of metal on the surface may be used.

The mold having the diffraction grating formed on the surface is manufactured as follows.
First, a cutting process is performed on the surface of the metal base material so as to have a desired pitch (period) and a cutting depth (first cutting process). Next, the metal substrate is rotated by 90 degrees, and a cutting process is performed so as to have a desired pitch (period) and a cutting depth (second cutting process). If the conditions of the first cutting process and the second cutting process are the same, a mold having a square lattice formed on the surface can be obtained.
By using the thus obtained mold, for example, as shown in FIG. 4, a fine uneven structure composed of a base film 12 and a diffraction grating-shaped convex portion 14 formed on the surface of the base film 12 is obtained. The low-adherence-of-bacteria article 10 having the cured resin layer 16 on the surface is obtained.

  Examples of the mold having a fine uneven structure layer made of metal on the surface include a mold described in WO2012 / 043828.

  In addition, when the article body is various molded articles (for example, a member such as a doorknob, a door, a strap, etc., which constitutes a portion that can be touched by a human hand), a fine uneven structure is formed directly on the surface of the article body, and It is good also as an article with low bacterial cell adhesion.

`` Countermeasures for bacterial cell adhesion ''
The method for preventing bacterial cell adhesion according to the first aspect of the present invention is characterized in that a micro uneven structure having a period smaller than five times the size of the bacterial cells is formed in a portion where the bacterial cells are to be reduced.
As a method of forming a fine uneven structure at a place where it is desired to reduce the attachment of bacterial cells, for example, the above-described method of forming a fine uneven structure directly on the surface of the article body is exemplified.

Further, the method for preventing bacterial cell adhesion according to the second aspect of the present invention is characterized in that the low bacterial cell-adherent article of the present invention is provided at a position where the bacterial cell adhesion is to be reduced.
As a method of providing the low cell adhesion article of the present invention at a place where the adhesion of bacteria is to be reduced, for example, a film-like low cell adhesion article 10 as shown in FIG. For example. If the part to which the low-bacteria-adhering article is adhered has a three-dimensional shape, a base material having a shape corresponding to the three-dimensional shape is used in advance, and the low-bacterially-adhering article is manufactured by a manufacturing method such as the above-described transfer method using a mold. May be manufactured, and this may be attached to a predetermined portion of the object.

  According to the method for preventing microbial cell adhesion of the present invention, a micro uneven structure having a cycle smaller than 5 times the size of the microbial cells is formed at a place where the microbial cell adhesion is to be reduced, or the low microbial cell adhesion of the present invention. Since the sexual article is provided, it is possible to suppress the adherence of bacterial cells to the location. In addition, in the method for preventing bacterial cell adhesion of the present invention, since the micro-rough structure provides bacterio-repellency, the material is not limited as long as the material can form the micro-rough structure. Therefore, the method for preventing bacterial cell adhesion of the present invention has a wider range of material selectivity as compared to the case where a superhydrophilic material is used to exhibit bacterio-repellency.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

"Test 1"
<Manufacture of mold>
(Manufacture of mold A)
An aluminum plate having a purity of 99.99% was mirror polished by feather cloth polishing and electrolytic polishing in a perchloric acid / ethanol mixed solution (1/4 volume ratio).
Step (a):
The aluminum plate was anodized in a 0.3 M oxalic acid aqueous solution at a direct current of 40 V and a temperature of 16 ° C. for 30 minutes.
Step (b):
The aluminum plate on which the oxide film was formed was immersed in a 6% by mass phosphoric acid / 1.8% by mass chromic acid mixed aqueous solution for 6 hours to remove part or all of the oxide film.
Step (c):
This aluminum plate was anodized in a 0.3 M oxalic acid aqueous solution at a direct current of 40 V and a temperature of 16 ° C. for 30 seconds.
Step (d):
The aluminum plate on which the oxide film was formed was immersed in 5% by mass of phosphoric acid at 32 ° C. for 8 minutes to perform a pore diameter enlargement treatment.
Step (e):
The steps (c) and (d) were repeated a total of 5 times to obtain anodized porous alumina having a substantially conical pore with a period of 100 nm and a depth of 180 nm.

The obtained anodized porous alumina was washed with deionized water, and the water content on the surface was removed by air blow, and this was coated with a surface antifouling coating agent (manufactured by Daikin, "Optool DSX") at a solid content of 0.1 mass. %, And immersed in a solution diluted with a diluent ("HD-ZV", manufactured by Harves Co., Ltd.) for 10 minutes, air-dried for 20 hours, and released to obtain a mold A.
The pores of the obtained mold A were measured by the following method. As a result, the average interval (period) between adjacent pores was 100 nm, and the average depth of the pores was 180 nm. ) Was formed on the surface.

Measurement of mold pores;
A part of the anodized alumina was shaved, platinum was vapor-deposited on the cross section for one minute, and a field emission scanning electron microscope (manufactured by JEOL Ltd., “JSM-7400F”) was used under the conditions of an acceleration voltage of 3.00 kV. The cross section was observed, and the distance between the pores and the depth of the pores were measured. Each measurement was performed for each of 50 points, and the average value was obtained.

<Preparation of active energy ray-curable resin composition>
(Preparation of active energy ray-curable resin composition a)
20 parts by mass of dipentaerythritol hexaacrylate, 70 parts by mass of bifunctional or more hydrophilic (meth) acrylate (manufactured by Toagosei Co., Ltd., “Aronix M-260”, average repeating unit of polyethylene glycol chain is 13), and hydroxyethyl 10 parts by mass of acrylate and 1.5 parts by mass of 1-hydroxycyclohexyl phenyl ketone (“IRGACURE (registered trademark) 184”, manufactured by BASF Japan) were mixed to obtain an active energy ray-curable resin composition a.
The obtained active energy ray-curable resin composition a is a hydrophilic material.

(Preparation of active energy ray-curable resin composition b)
85 parts by mass of ethoxylated pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., "NK Ester ATM-4E"), 8 parts by mass of cetyl acrylate (manufactured by NOF CORPORATION, "Blemmer CA"), and 7 parts by mass of methyl acrylate 0.5 parts by mass of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (“DAROCURE TPO”, manufactured by BASF Japan) and an internal release agent (“MOLD WITH INT AM-121”, manufactured by AXEL) And 0.1 part by mass to obtain an active energy ray-curable resin composition b.
The obtained active energy ray-curable resin composition b is a hydrophobic material.

<Manufacture of low bacterial cell adhesion products>
(Manufacture of low adherence article A1)
The active energy ray-curable resin composition a was applied to the surface of the mold A on the side of the fine uneven structure, and an 80 μm-thick triacetyl cellulose (TAC) film was covered thereon.
Using an ultraviolet irradiator (fusion lamp D bulb), irradiating ultraviolet rays through the film at an integrated light amount of 1000 mJ / cm ² to cure the active energy ray-curable resin composition a, and then separating from the mold A, A low-adhesion article A1 having a 10 μm-thick cured resin layer formed on the surface and having a fine concavo-convex structure composed of a plurality of truncated cone-shaped convex portions on the surface was obtained.
As a result of measuring the protruding portions of the obtained low-adherent bacterial article A1 by the following method, the average interval (period) between adjacent protruding portions was 100 nm, the height of the protruding portions was 180 nm, and the Had a bottom width of 160 nm. In addition, when the water contact angle of the low-bacteria article A1 was measured by the following method, it was 27 °, and the surface of the low-bacteria article A1 on the side of the fine unevenness structure was hydrophilic.

Measurement of convexities of the cured resin layer;
Platinum was vapor-deposited on the fractured surface of the cured resin layer for 10 minutes, the cross-section was observed in the same manner as the pores of the mold, and the distance between the convex portions and the height of the convex portions were measured. Each measurement was performed for each of 50 points, and the average value was obtained.

Measurement of water contact angle;
1 μL of ion-exchanged water was dropped onto the surface of the article with low bacterial cell adhesion on the side of the fine unevenness structure, and the water contact angle was calculated by the θ / 2 method using an automatic contact angle measuring device (manufactured by KRUSS).

(Manufacture of article B1 with low bacterial cell adhesion)
The active energy ray-curable resin composition b is applied to the surface of the mold A on the side of the fine unevenness, and a 125 μm-thick polyethylene terephthalate (PET) film (“Diafoil T910E125”, manufactured by Mitsubishi Plastics, Inc.) is coated thereon. Except for the above, a low-bacteria article B1 was obtained in the same manner as the low-bacteria article A1.
The average interval between adjacent protrusions was 100 nm, the height of the protrusions was 180 nm, and the width of the bottom of the protrusions was 160 nm. Further, the water contact angle was 120 °, and the surface on the side of the fine unevenness structure of the low-adherent bacterial cell article B1 was water-repellent.

<Manufacture of flat film>
(Production of flat film a)
The active energy ray-curable resin composition a was applied to a mirror-finished aluminum base material having no fine irregularities on the surface, and a 125-μm-thick PET film was placed on the active energy-ray-curable resin composition.
Using an ultraviolet irradiator (fusion lamp D bulb), the active energy ray-curable resin composition a is irradiated with ultraviolet light through the film at an integrated light amount of 1000 mJ / cm ² , and then separated from the mirror-finished aluminum base material. Then, a flat film a having a cured resin layer having a thickness of 10 μm and having no fine unevenness structure on the surface was formed on the surface.
The water contact angle of the surface of the flat film a on the cured resin layer side was 54 °, and the surface of the flat film a on the cured resin layer side was hydrophilic.

(Production of flat film b)
A flat film b was obtained in the same manner as the flat film a, except that the active energy ray-curable resin composition b was applied to a mirror-finished aluminum base material having no fine uneven structure on the surface.
The water contact angle of the surface of the flat film b on the cured resin layer side was 95 °, and the surface of the flat film b on the cured resin layer side was water-repellent.

(Flat film z)
A polyethylene film having no uneven structure on the surface was used as the flat film z.

<Example 1>
Each of the low-bacteria-cell-adherent article A1, the low-bacteria-cell-adhesive article B1, the flat film b, and the flat film z was used as a test piece, and a microbial cell adhesion test 1 was performed as follows. Table 1 shows the results.

Cell adhesion test 1;
Three test pieces (1 cm × 1 cm) were immersed in bacteria-containing water containing 1 × 10 ⁵ cfu / ml of S. mutans for 1 hour, and then washed with deionized water. Then, moisture on the surface was removed by air blow and dried. A transmission electron microscope (10 surfaces) at any 10 places on the surface of each test piece after drying (the surface on the cured resin layer side in the case of the low bacterial cell adhesion product A1, the low bacterial cell adhesion product B1, and the flat film b). (Magnification: 2000 times), the number of bacteria within the range visible with a transmission electron microscope was counted, and the average value and standard deviation (SD) were determined. Further, the obtained average value and SD were converted per 1 mm ² of the test piece.
In addition, the shape of the mutans bacteria is substantially spherical, and the size (diameter) is about 1 μm.

<Example 2>
A cell adhesion test 1 was performed in the same manner as in Example 1 except that bacteria-containing water containing 1 × 10 ⁵ cfu / ml of S. aureus was used. Table 2 shows the results.
The shape of Staphylococcus aureus is almost spherical, and its size (diameter) is about 1 μm.

<Example 3>
A cell adhesion test 1 was performed in the same manner as in Example 1 except that water containing bacteria containing 1 × 10 ⁵ cfu / ml of C. albicans was used. Table 3 shows the results.
Candida bacteria are spherical and hyphal cells, and their size is 6 to 7 μm.

<Example 4>
Cell adhesion test 1 was performed in the same manner as in Example 1 except that bacteria-containing water containing 1 × 10 ⁵ cfu / ml of P. aeruginosa was used. Table 4 shows the results.
Pseudomonas aeruginosa is a cell having flagella and cilia, and has a size of 0.5 to 1 μm.

  As is clear from Tables 1 to 4, when immersed for a short time in low-concentration bacterial-cell-containing water, the bacterial-cell-low-adherence article A1 and the bacterial-cell-low-adhesion article B1 show the bacterial cells as compared to the flat film z. Was difficult to adhere. Moreover, the low-bacteria-cell-adherent article A1 and the low-bacteria-cell-adherence article B1 have a repellency equal to or higher than that of the flat film b. It showed excellent bactericidal properties.

<Example 5>
A bacterial cell adhesion test 1 was performed in the same manner as in Example 1 except that the immersion time was changed to 8 hours. Table 5 shows the results.

<Example 6>
Bacterial cell adhesion test 1 was performed in the same manner as in Example 1 except that bacteria-containing water containing 1 × 10 ⁵ cfu / ml of Staphylococcus aureus was used and the immersion time was changed to 8 hours. Table 6 shows the results.

<Example 7>
Bacterial cell adhesion test 1 was performed in the same manner as in Example 1 except that bacterium-containing water containing 1 × 10 ⁵ cfu / ml of Candida was used and the immersion time was changed to 8 hours. Table 7 shows the results.

<Example 8>
Bacterial cell adhesion test 1 was performed in the same manner as in Example 1 except that bacteria-containing water containing 1 × 10 ⁵ cfu / ml of Pseudomonas aeruginosa was used and the immersion time was changed to 8 hours. Table 8 shows the results.

  As is clear from Tables 5 to 8, when immersed in low-concentration bacterial-cell-containing water for a long time, the bacterial-cell-low-adhesive article A1 was harder for bacterial cells to adhere to than the flat film z. In addition, the low-cellular-body-adherent article A1 has a bactericidal property equal to or higher than that of the flat film b, and particularly, has a better bactericidal property against spherical cells than the flat film b. . From these results, it was shown that when the surface on the side of the fine unevenness structure of the low-adherent microbial structure article was hydrophilic, the bacteria repellency could be exhibited for a long time.

<Example 9>
A cell adhesion test 1 was performed in the same manner as in Example 1 except that bacteria-containing water containing 1 × 10 ⁷ cfu / ml of mutans was used. Table 9 shows the results.

<Example 10>
A bacterial cell adhesion test 1 was performed in the same manner as in Example 1 except that bacterial-containing water containing 1 × 10 ⁷ cfu / ml of Staphylococcus aureus was used. Table 10 shows the results.

<Example 11>
A bacterial cell adhesion test 1 was performed in the same manner as in Example 1 except that bacterial-containing water containing 1 × 10 ⁷ cfu / ml of Candida was used. Table 11 shows the results.

<Example 12>
A bacterial cell adhesion test 1 was performed in the same manner as in Example 1 except that bacterial-containing water containing 1 × 10 ⁷ cfu / ml of Pseudomonas aeruginosa was used. Table 12 shows the results.

  As is clear from Tables 9 to 12, when immersed in high-concentration bacterial-cell-containing water for a short time, the bacterial-cell-low-adherence article A1 is less likely to adhere bacterial cells than the flat film b and the flat film z. Was. Therefore, it was shown that if the surface on the side of the fine unevenness structure of the article with low bacterial cell adhesion is hydrophilic, excellent bacterial repellency can be exhibited even with a high concentration of bacterial cells.

<Example 13>
Each of the low-adherent-cell-adherence article A1, the low-adherent-cell-adherent article B1, the flat film a, the flat film b, and the flat film z was used as a test piece, and a cell adhesion test 2 was performed as follows. Table 13 shows the results.

Cell adhesion test 2;
For each test piece, three pieces were inclined at 45 degrees, and the surface of each test piece (in the case of the low bacterial cell adhesion article A1, the low bacterial cell adhesion article B1, the flat film a, and the flat film b, 100 μl of bacteria-containing water containing 1 × 10 ⁷ cfu / ml of Staphylococcus aureus 209P strain (S. aureus 209P) was dropped on the surface of the cured resin layer). After repeating this operation five times, the surface of the test piece on which the bacterium-containing water was dropped was observed with a transmission electron microscope (magnification: 2000) at any ten positions, and the bacteria within a range visible with the transmission electron microscope were observed. The numbers were counted and the mean and standard deviation (SD) were determined. Further, the obtained average value and SD were converted per 1 mm ² of the test piece.
The Staphylococcus aureus 209P strain is substantially spherical in shape, and its size (diameter) is 0.8 μm.

<Example 14>
A bacterial cell adhesion test 2 was performed in the same manner as in Example 13, except that bacterial-containing water containing 1 × 10 ⁷ cfu / ml of Escherichia coli K12 (E. coli K12) was used. Table 14 shows the results.
The E. coli K12 strain has a substantially elliptical shape, and its size (short diameter) is 0.5 μm.

  As is clear from Tables 13 and 14, when high-concentration bacterial-cell-containing water is dropped, the low-bacteria-adherent article A1 and the low-bacteria-adherent article B1 have a flat film a, a flat film b, and a flat film. Bactericidal properties were superior to film z.

"Test 2"
<Manufacture of mold>
(Manufacture of mold B)
A STAVAX flat plate (length 200 mm, width 200 mm, thickness 20 mm) was prepared as a work material. Hard copper plating having a thickness of 100 μm was applied to the surface of the flat plate. The Vickers hardness of the hard copper plating was 220 Hv.
Next, the flat plate was mounted on an ultra-precision flat plate processing machine, and the surface on the hard copper plating side was mirror-finished.
Next, the flat surface of the flat plate is cut by a single crystal diamond tool (blade thickness: 1 μm) at a cutting depth of 0.4 μm and a pitch of 2 μm, so that the flat surface has a pitch (period). A groove (recess) having a thickness of 2 μm, a depth of 0.4 μm, and a width of 1 μm was formed.
Then, the flat plate is rotated by 90 degrees and cut in the same manner as in the above-described cutting process, thereby forming a square lattice-shaped groove (recess) having a pitch (period) of 2 μm, a depth of 0.4 μm, and a width of 1 μm on the surface. ) Was obtained (mold B).

(Manufacture of mold C)
Undercoating on a glass substrate (Eagle XG, Corning, 5 cm long, 5 cm wide, 0.7 mm thick) that has been washed with a UV lamp (manufactured by MD Excimer, wavelength 172 nm). Polyethylene glycol diacrylate ("A-200", manufactured by Shin-Nakamura Chemical Co., Ltd.) as a layer-forming composition was spin-coated (at 500 rpm, 3 μm in thickness) and heated on a hot plate at 60 ° C. for 10 minutes. Then, the composition was irradiated with ultraviolet rays (integrated light amount: 1000 mJ / cm ² ) to cure the composition for forming an undercoat layer, thereby forming an undercoat layer on a glass substrate.
Then, on the undercoat layer, indium tin oxide (ITO) was laminated to a thickness of 20 nm using an RF sputtering apparatus (manufactured by Sanyu Electronics Co., Ltd., "SVC-700RF") to form a thin metal layer having a fine uneven structure on the surface. . This is designated as mold C.

(Manufacture of mold D)
Mold D was obtained in the same manner as for mold C, except that polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “A-1000”) was used as the composition for forming the undercoat layer.

(Manufacture of mold E)
Mold E was obtained in the same manner as for mold C, except that polybutylene glycol diacrylate ("PBOM2000", manufactured by Mitsubishi Rayon Co., Ltd.) was used as the composition for forming the undercoat layer.

<Manufacture of low bacterial cell adhesion products>
(Manufacture of low adherence article A2)
The active energy ray-curable resin composition a of Test 1 was applied to the surface of the mold B on the side of the fine uneven structure, and a 125 μm-thick PET film (“Diafoil T910E125” manufactured by Mitsubishi Plastics, Inc.) was applied thereon. Was.
Using an ultraviolet irradiator (fusion lamp D bulb), irradiating ultraviolet rays through the film at an integrated light quantity of 1000 mJ / cm ² to cure the active energy ray-curable resin composition a, and then separating from the mold B, A microbial cell having a 10 μm-thick cured resin layer formed on the surface with a fine uneven structure formed of a square lattice-shaped protrusion having a pitch (period) of 2 μm, a height of 0.4 μm, and a width of 1 μm on the surface. A low-adhesion article A2 was obtained.
The water contact angle of the low bacterial cell adhesion article A2 was measured in the same manner as in Test 1, and was found to be 82 °. The surface of the microcellular low adhesion article A2 on the side of the fine unevenness structure was hydrophilic.

(Manufacture of low adherence article A3)
Except for using the mold C in place of the mold B, an article A3 having a low cell adhesion was obtained in the same manner as the article A2 having a low cell adhesion.
FIG. 5 shows an image (50 μm × 50 μm) of the surface on the cured resin layer side of the obtained low-adherent bacterial article A3 taken with a transmission electron microscope (2,000-fold magnification). As shown in FIG. 5, very fine wrinkles (fine irregularities) were formed on the surface of the low-adherent microbial article A3 so that they could not be measured.
The water contact angle of the low-adherent microbial article A3 measured in the same manner as in Test 1 was 41 °, and the surface of the low-adherent microbial article A3 on the side of the fine uneven structure was hydrophilic.

(Manufacture of low adherence article A4)
Except for using mold D instead of mold B, an article A4 having low cell adhesion was obtained in the same manner as article A2 having low cell adhesion.
FIG. 6 shows an image (50 μm × 50 μm) obtained by photographing the surface on the cured resin layer side of the obtained low-adherent bacterial article A4 with a transmission electron microscope (2,000-fold magnification). As shown in FIG. 6, a wrinkle (fine uneven structure) having a period (wrinkle width) of 1100 nm and a height of 110 nm was formed on the surface of the low-adherent microbial article A4.
Further, the water contact angle of the low-adherent microbial article A4 was measured in the same manner as in Test 1, which was 53 °, and the surface of the low-adherent microbial article A4 on the side of the fine unevenness structure was hydrophilic.

(Manufacture of low adherence article A5)
Except for using the mold E in place of the mold B, an article A5 with low cell adhesion was obtained in the same manner as the article A2 with low cell adhesion.
FIG. 7 shows an image (50 μm × 50 μm) of the surface on the cured resin layer side of the obtained low-adherent bacterial cell article A5 taken with a transmission electron microscope (2,000-fold magnification). As shown in FIG. 7, wrinkles (fine uneven structure) having a period (wrinkle width) of 2500 nm and a height of 225 nm were formed on the surface of the low-adherent microbial article A5.
Further, the water contact angle of the low-adherent microbial article A5 measured in the same manner as in Test 1 was 55 °, and the surface on the side of the fine unevenness structure of the low-adherent microbial article A5 was hydrophilic.

<Example 15>
Each of the test pieces was prepared using the low cell adhesion products A2 to A5 and the flat film z of Test 1 as follows, and a cell adhesion test 3 was performed as follows. Table 15 shows the results.

Cell adhesion test 3;
For each test piece, three of them were inclined at 45 degrees, and the surface of each test piece (the surface on the hardened resin layer side in the case of the low-adherent bacterial cells A2 to A5) was applied to the Staphylococcus aureus 209P strain (S Aureus 209P) was added dropwise at 100 μl of bacteria-containing water containing 1 × 10 ⁷ cfu / ml. After repeating this operation five times, the surface of the test piece on which the bacterium-containing water was dropped was observed with a transmission electron microscope (magnification: 2000) at any ten positions, and the bacteria within a range visible with the transmission electron microscope were observed. The numbers were counted and the mean and standard deviation (SD) were determined. Further, the obtained average value and SD were converted per 1 mm ² of the test piece.

<Example 16>
A bacterial cell adhesion test 3 was performed in the same manner as in Example 15, except that bacteria-containing water containing 1 × 10 ⁷ cfu / ml of Escherichia coli K12 (E. coli K12) was used. Table 16 shows the results.

  As is clear from Tables 15 and 16, when the high-concentration bacterial-cell-containing water was dropped, the bacterial-cell-low-adherence articles A2 to A5 were more excellent in bacterial repellency than the flat film z.

"Test 3"
<Manufacture of mold>
(Manufacture of mold F)
An aluminum plate having a purity of 99.99% was mirror polished by feather cloth polishing and electrolytic polishing in a perchloric acid / ethanol mixed solution (1/4 volume ratio).
Step (a):
This aluminum plate was anodized in a 0.4 M phosphoric acid aqueous solution under the conditions of DC 100 V and a temperature of 15 ° C. for 45 to 60 minutes.
Step (b):
The aluminum plate on which the oxide film was formed was immersed in a 6% by mass phosphoric acid / 1.8% by mass chromic acid mixed aqueous solution for 6 hours to remove part or all of the oxide film.
Step (c):
This aluminum plate was anodized in a 0.2 M phosphoric acid aqueous solution under the conditions of DC 100 V and a temperature of 15 ° C. for 7 to 24 seconds.
Step (d):
The aluminum plate on which the oxide film was formed was immersed in 5% by mass of phosphoric acid at 31.5 ° C. for 19 minutes to perform a pore diameter enlargement treatment.
Step (e):
The steps (c) and (d) were repeated a total of five times to obtain anodically oxidized porous alumina having a period of 300 nm and a depth of 300 nm and substantially conical pores.

The obtained anodized porous alumina was subjected to a mold release treatment in the same manner as in mold A, to obtain mold F.
The pores of the obtained mold F were measured in the same manner as the mold A. As a result, the average interval (period) between adjacent pores was 300 nm and the average depth of the pores was 300 nm. A fine uneven structure consisting of (pores) was formed on the surface.

(Mold G)
A mold G was formed with a concave-convex pitch of 2 μm, a height of 0.5 μm, and a die-shaped pillar portion (“Trial Mold DTM2-3” manufactured by Kyodo International).

(Of mold H)
A mold H was obtained in the same manner as the mold A, except that the anodic oxidation time in the step (c) was changed to 21 seconds.
As a result of measuring the pores of the obtained mold H in the same manner as in the mold A, a substantially conical tapered concave portion (average interval (period) between adjacent pores of 100 nm and average pore depth of 50 nm) was obtained. A fine uneven structure consisting of (pores) was formed on the surface.

(Mold I)
A mold I was formed with a concave-convex pitch of 1 μm, a height of 0.5 μm, and a die-shaped pillar portion (“Trial Mold DTM2-3” manufactured by Kyodo International).

(Mold J)
A mold J was formed with a concave / convex pitch of 1 μm, a height of 2 μm, and a die-shaped pillar portion (“Trial Mold DTM2-3” manufactured by Kyodo International).

(Mold K)
The mold pitch was 2 μm, the height was 2 μm, and the mold-shaped pillar portion (“Trial mold DTM2-3” manufactured by Kyodo International) was used as mold K.

(Mold L)
A mold L was formed with a concave / convex pitch of 4 μm, a height of 0.5 μm, and a die-shaped pillar portion (“Trial Mold DTM2-3” manufactured by Kyodo International).

(Mold M)
A mold M was formed with a concave-convex pitch of 4 μm, a height of 1 μm, and a die-shaped pillar portion (“Trial Mold DTM2-1” manufactured by Kyodo International).

(Mold N)
A mold N was formed with an uneven pitch of 2 μm, a height of 0.5 μm, and a mold shape line and space (L / S) portion (“Trial Mold DTM2-3” manufactured by Kyodo International).

(Mold O)
A mold O was formed with an uneven pitch of 4 μm, a height of 1 μm, and a mold line and space (L / S) portion (“Trial Mold DTM2-1” manufactured by Kyodo International).

<Preparation of active energy ray-curable resin composition>
(Preparation of active energy ray-curable resin composition c)
25 parts by mass of dipentaerythritol hexaacrylate (“A-DPH”, manufactured by Shin-Nakamura Chemical Co., Ltd.), 25 parts by mass of ditrimethylolpropanetetraacrylate (“AD-TMP”, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethylene oxide-modified diamine 25 parts by mass of pentaerythritol hexaacrylate (“DPEA-12”, manufactured by Nippon Kayaku Co., Ltd.), 25 parts by mass of methoxypolyethylene glycol acrylate (“MPE400A”, manufactured by Osaka Organic Chemical Co., Ltd.) as a hydrophilic monofunctional monomer, 1- 1.5 parts by mass of hydroxycyclohexyl phenyl ketone (“IRGACURE (registered trademark) 184”, manufactured by BASF Japan), and 0.5 parts by mass of Moldwith (“INT-120MC”, manufactured by Tomoe Industries) as a release agent Was mixed to obtain an active energy ray-curable resin composition c.
The obtained active energy ray-curable resin composition c is a hydrophilic material.

(Preparation of active energy ray-curable resin composition d)
An active energy ray-curable resin composition d was obtained in the same manner as in the active energy ray-curable resin composition c except that the hydrophilic monofunctional monomer was changed to N-vinylformamide (manufactured by Mitsubishi Rayon Co., Ltd., "NVF"). Was.
The obtained active energy ray-curable resin composition d is a hydrophilic material.

(Preparation of active energy ray-curable resin composition e)
An active energy ray-curable resin composition was prepared in the same manner as the active energy ray-curable resin composition c except that the hydrophilic monofunctional monomer was changed to N, N-dimethylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd., “DMAA”). e was obtained.
The obtained active energy ray-curable resin composition e is a hydrophilic material.

(Preparation of active energy ray-curable resin composition f)
Except that the hydrophilic monofunctional monomer was changed to polyethylene glycol # 600 diacrylate (“A600” manufactured by Shin-Nakamura Chemical Co., Ltd.), which is a hydrophilic bifunctional monomer, in the same manner as in the active energy ray-curable resin composition c, An active energy ray-curable resin composition f was obtained.
The obtained active energy ray-curable resin composition f is a hydrophilic material.

(Preparation of active energy ray-curable resin composition g)
In a glass flask, 117.6 g (0.7 mol) of hexamethylene diisocyanate as a diisocyanate compound, 151.2 g (0.3 mol) of an isocyanurate-type trimer of hexamethylene diisocyanate, and 2% as a hydroxyl group-containing (meth) acrylate 128.7 g (0.99 mol) of hydroxypropyl acrylate and 693 g (1.54 mol) of pentaerythritol triacrylate, 22.1 g of di-n-butyltin dilaurate as a catalyst, and 0.55 g of hydroquinone monomethyl ether as a polymerization inhibitor , The mixture was heated to 75 ° C, and the stirring was continued while maintaining the temperature at 75 ° C. The reaction was continued until the concentration of the residual isocyanate compound in the flask became 0.1 mol / L or less. An acrylate was obtained.
35 parts by mass of the obtained urethane polyfunctional acrylate, 20 parts by mass of polybutylene glycol dimethacrylate (manufactured by Mitsubishi Rayon Co., Ltd., "Acryester PBOM"), and ethylene oxide-modified bisphenol A dimethacrylate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; New Frontier BPEM-10 "), 40 parts by mass of phenoxyethyl acrylate (Daiichi Kogyo Seiyaku Co., Ltd.," New Frontier PHE ") and 1-hydroxycyclohexyl phenyl ketone (BASF Japan, Irgacure (registered) (Trademark) 184)) and 1.2 parts by mass of the mixture to obtain an active energy ray-curable resin composition g.
The obtained active energy ray-curable resin composition g is a hydrophobic material.

<Manufacture of flat film>
(Production of flat film c)
A flat film c was obtained in the same manner as the flat film a, except that the active energy ray-curable resin composition c was applied to a mirror-finished aluminum base material having no fine uneven structure on the surface.
The water contact angle of the surface of the flat film c on the cured resin layer side was 45.4 °, and the surface of the flat film c on the cured resin layer side was hydrophilic. Table 17 shows the results.
The arithmetic average roughness Ra of the surface of the flat film c on the cured resin layer side was measured based on JIS B 0601: 1994, and was found to be 1 nm.

(Production of flat film d)
A flat film d was obtained in the same manner as the flat film a, except that the active energy ray-curable resin composition d was applied to a mirror-finished aluminum base material having no fine uneven structure on the surface.
The water contact angle of the surface of the flat film d on the cured resin layer side was 49.7 °, and the surface of the flat film d on the cured resin layer side was hydrophilic. Table 17 shows the results.
The arithmetic average roughness Ra of the surface of the flat film d on the cured resin layer side was measured based on JIS B 0601: 1994, and was 2 nm.

(Production of flat film e)
A flat film e was obtained in the same manner as the flat film a, except that the active energy ray-curable resin composition e was applied to a mirror-finished aluminum substrate having no fine uneven structure on the surface.
The water contact angle of the surface of the flat film e on the cured resin layer side was 43.8 °, and the surface of the flat film e on the cured resin layer side was hydrophilic. Table 17 shows the results.
Further, the arithmetic average roughness Ra of the surface of the flat film e on the cured resin layer side was measured based on the standard of JIS B0601: 1994, and the result was 1 nm.

(Production of flat film f)
A flat film f was obtained in the same manner as the flat film a, except that the active energy ray-curable resin composition f was applied to a mirror-finished aluminum substrate having no fine uneven structure on the surface.
The water contact angle of the surface of the flat film f on the cured resin layer side was 40.4 °, and the surface of the flat film f on the cured resin layer side was hydrophilic. Table 17 shows the results.
Further, the arithmetic average roughness Ra of the surface of the flat film f on the side of the cured resin layer was measured based on the standard of JIS B0601: 1994, and was found to be 1 nm.

(Production of flat film g)
A flat film g was obtained in the same manner as the flat film a, except that the active energy ray-curable resin composition g was applied to a mirror-finished aluminum base material having no fine uneven structure on the surface.
The water contact angle of the surface of the flat film g on the cured resin layer side was 66.8 °, and the surface of the flat film g on the cured resin layer side was water-repellent. Table 17 shows the results.
The arithmetic average roughness Ra of the surface of the flat film g on the cured resin layer side was measured based on JIS B 0601: 1994, and was 2 nm.

<Manufacture of low bacterial cell adhesion products>
(Manufacture of low adherence article C1)
The active energy ray-curable resin composition c was applied to the surface of the mold F on the side of the fine unevenness, and a 188 μm-thick PET film (“A4100”, manufactured by Toyobo Co., Ltd.) was placed thereon.
Using an ultraviolet irradiator (fusion lamp D bulb), ultraviolet rays are irradiated through the film at an integrated light amount of 1000 mJ / cm ² to cure the active energy ray-curable resin composition c, and then separated from the mold F, A low bacterial cell adhesion article C1 having a 15 μm-thick cured resin layer formed on the surface and having a fine concavo-convex structure composed of a plurality of protrusions on the surface was obtained.
As a result of measuring the protruding portions of the obtained low-adhesion product C1 in the same manner as the low-adhesion product A1, the average interval (period) between adjacent protruding portions was 300 nm, and the height of the protruding portions was measured. Was 300 nm.

(Manufacture of article D1 with low cell adhesion)
Except that the active energy ray-curable resin composition d was applied to the surface of the mold F on the side of the fine unevenness structure, a 12 μm-thick low-adherent bacterial article D1 was obtained in the same manner as the low-adherent bacterial article C1. Was.

(Manufacture of low adherence article E1)
Except that the active energy ray-curable resin composition e was applied to the surface of the mold F on the side of the fine unevenness structure, a 10 μm-thick low-adherent cell article E1 was obtained in the same manner as the low-adherent cell article C1. Was.

(Manufacture of article F1 with low cell adhesion)
Except that the active energy ray-curable resin composition f was applied to the surface of the mold F on the side of the fine unevenness structure, a 13 μm-thick low-bacteria article F1 having a thickness of 13 μm was obtained in the same manner as the low-bacteria article C1. Was.

(Manufacture of low adherence article G1)
Except that the active energy ray-curable resin composition g was applied to the surface of the mold F on the side of the fine unevenness structure, a 12 μm-thick low-adherent cell article G1 was obtained in the same manner as the low-adherent cell article C1. Was.

(Manufacture of article B2 with low cell adhesion)
Except that the active energy ray-curable resin composition c was applied to the surface of the mold G on the side of the fine uneven structure, the thickness was 12 μm having a hole-shaped fine uneven structure on the surface in the same manner as in the low-adherent bacterial article C1. , A low-adherent bacterial cell article C2 having a cured resin layer formed on the surface thereof was obtained.
As a result of measuring the concave portions of the obtained low-adherent bacterial cell article C2 by the following method, the average interval (period) between adjacent concave portions was 2 μm, and the depth of the concave portions was 500 nm.

Measurement of concave portions of the cured resin layer;
Platinum was vapor-deposited on the fractured surface of the cured resin layer for 10 minutes, the cross-section was observed in the same manner as the pores of the mold, and the distance between the concave portions and the depth of the concave portions were measured. Each measurement was performed for each of 50 points, and the average value was obtained.

(Manufacture of low adherence article D2)
Except for applying the active energy ray-curable resin composition d to the surface of the mold G on the side of the fine unevenness structure, a 12 μm-thick low-adherent cell article D2 was obtained in the same manner as the low-adherent cell article C1. Was.

(Manufacture of low adherence article E2)
Except that the active energy ray-curable resin composition e was applied to the surface of the mold G on the side of the fine uneven structure, a 15 μm-thick low-adherent cell article E2 was obtained in the same manner as the low-adherent cell article C1. Was.

(Manufacture of low adherence article F2)
Except that the active energy ray-curable resin composition f was applied to the surface of the mold G on the side of the fine uneven structure, a 13 μm-thick microbial cell low-adhesive article F2 was obtained in the same manner as the microbial cell low-adhesive article C1. Was.

(Production of article G2 with low bacterial cell adhesion)
Except that the active energy ray-curable resin composition g was applied to the surface of the mold G on the side of the fine unevenness structure, a 10 μm-thick low-adherent cell article G2 was obtained in the same manner as the low-adherent cell article C1. Was.

(Manufacture of low adherence article E3)
Except that the active energy ray-curable resin composition e was applied to the surface of the mold H on the side of the fine uneven structure, the thickness was 12 μm having a pillar-shaped fine uneven structure on the surface in the same manner as the low-adherent-bacteria article C1. A cured product layer E3 having a cured resin layer formed on the surface thereof was obtained.
As a result of measuring the protrusions of the obtained low-adhesion article E3 in the same manner as the low-adhesion article A1, the average interval (period) between adjacent protrusions was 100 nm, and the height of the protrusions was 100 nm. Was 50 nm.

(Manufacture of article E4 with low cell adhesion)
Except that the active energy ray-curable resin composition e was applied to the surface of the mold A on the side of the fine uneven structure, the thickness was 11 μm having a pillar-shaped fine uneven structure on the surface in the same manner as the low-adherent-bacteria article C1. A cured product layer E4 having a cured resin layer formed on the surface was obtained.
As a result of measuring the protrusions of the obtained low-adhesion article E4 in the same manner as the low-adhesion article A1, the average interval (period) between adjacent protrusions was 100 nm, and the height of the protrusions was 100 nm. Was 180 nm.

(Production of low adherence article E5)
Except that the active energy ray-curable resin composition e was applied to the surface of the mold I on the side of the fine unevenness structure, the thickness was 13 μm having a hole-shaped fine unevenness surface on the surface in the same manner as in the low-adherent bacterial cell article C1. A cured product layer E5 having a cured resin layer formed on the surface thereof was obtained.
As a result of measuring the concave portions of the obtained low-adhesion article E5 in the same manner as the low-adhesion article C2, the average interval (period) between adjacent depressions was 1000 nm, and the depth of the depression was 500 nm. there were.

(Manufacture of low adherence article E6)
Except that the active energy ray-curable resin composition e was applied to the surface of the mold J on the side of the fine uneven structure, the thickness was 10 μm having a hole-shaped fine uneven structure on the surface in the same manner as the low-adherent bacterial article C1. A cured product layer E6 having a cured resin layer formed on the surface thereof was obtained.
As a result of measuring the concave portions of the obtained low-adhesion product E6 in the same manner as the low-adhesion product C2, the average interval (period) between adjacent depressions was 1000 nm, and the depth of the depression was 2000 nm. there were.

(Manufacture of low adherence article E7)
Except that the active energy ray-curable resin composition e was applied to the surface of the mold K on the side of the fine uneven structure, the thickness was 12 μm having a hole-shaped fine uneven structure on the surface in the same manner as the low-adherent-bacteria article C1. The cured microbial cell E7 having a cured resin layer formed on the surface thereof was obtained.
As a result of measuring the concave portions of the obtained low-adhesive cell article E7 in the same manner as in the low-adherent cell article C2, the average interval (period) between adjacent concave sections was 2000 nm, and the depth of the concave section was 2000 nm. there were.

(Manufacture of article E8 with low cell adhesion)
Except that the active energy ray-curable resin composition e was applied to the surface of the mold L on the side of the fine uneven structure, the thickness was 12 μm having a hole-shaped fine uneven structure on the surface in the same manner as the low-adherent-bacteria article C1. To obtain a low-adhesion article E8 having a cured resin layer formed on the surface thereof.
As a result of measuring the concave portions of the obtained low-adhesion product E8 in the same manner as in the low-adhesion product C2, the average interval (period) between adjacent depressions was 4000 nm, and the depth of the depression was 500 nm. there were.

(Manufacture of low adherence article E9)
Except that the active energy ray-curable resin composition e was applied to the surface of the mold M on the side of the fine uneven structure, the thickness was 11 μm having a hole-shaped fine uneven structure on the surface in the same manner as the low-adherent-bacteria article C1. A cured product layer E9 having a cured resin layer formed on the surface thereof was obtained.
As a result of measuring the concave portions of the obtained low-adhesive article E9 in the same manner as in the low-adherent cell article C2, the average interval (period) between adjacent concave portions was 4000 nm, and the depth of the concave portion was 1000 nm. there were.

(Manufacture of low adherence article E10)
Except for applying the active energy ray-curable resin composition e to the surface of the mold N on the side of the fine uneven structure, the fine uneven structure having a line and space (L / S) shape was formed in the same manner as the low-adherent-bacteria article C1. Was obtained on the surface of which a cured resin layer having a thickness of 10 μm and having a surface was formed with a low bacterial cell adhesion.
The average distance (period) between adjacent convex portions was 2000 nm, and the height of the convex portions was measured. Was 500 nm.

(Manufacture of low adherence article E11)
Except for applying the active energy ray-curable resin composition e to the surface of the mold O on the side of the fine uneven structure, the fine uneven structure having a line and space (L / S) shape was formed in the same manner as the low-adherent-bacteria article C1. Was obtained on the surface of which a cured resin layer having a thickness of 10 μm and having a surface was formed with low bacterial cell adhesion.
As a result of measuring the protruding portion of the obtained low-adhesion product E11 in the same manner as the low-adhesion product A1, the average interval (period) between adjacent protruding portions was 4000 nm, and the height of the protruding portion was measured. Was 1000 nm.

As is clear from Table 17, the flat films c to f had a water contact angle of 50 ° or less, and the surfaces were hydrophilic. The surfaces of the microcellular low-adherence articles C1 to F1 and C2 to F2 using the same type of active energy ray-curable resin composition as those of the flat films c to f were also hydrophilic.
On the other hand, the flat film g had a water contact angle of 66.8 ° and the surface was water repellent. Surfaces of the microbacteria-low-adherence articles G1 and G2 using the same type of active energy ray-curable resin composition as the flat film g also had water repellency on the side of the fine uneven structure.

<Example 17>
The cell adhesion tests 4 and 5 were performed using the low cell adhesion products C1 to G1, C2 to G2, the flat films c to g, and the flat film z as test pieces as follows. The results are shown in Table 18.

Cell adhesion test 4;
Three test pieces (0.5 mm × 0.5 mm) were immersed in bacteria-containing water containing 1 × 10 ⁷ cfu / ml of S. aureus for 1 hour, and then deionized. After washing with water, moisture on the surface was removed by air blow and dried. Transmission electron microscopy (at any 10 locations on the surface of each test piece after drying (the surface on the cured resin layer side in the case of the low bacterial cell adhesion products C1 to G1 and C2 to G2 and the flat films c to g)) (Magnification: 2000 times), and the number of bacteria within the range visible with a transmission electron microscope was counted. The results are shown in Table 18.
In addition, the number of bacteria in the low-cellular-adhesive articles C1 to G1, C2 to G2, and the flat films c to g is divided by the number of cells in the flat film z, and a value obtained by multiplying by 100 is expressed as a “low bacterial cell adhesion rate”. No.18.
In addition, the number of bacteria of the low-cellular-adherence articles C1 to G1 and C2 to G2 was determined by using the same type of active energy ray-curable resin composition as that of the low-cellular-adhesion articles. The value obtained by dividing by the number of bacteria and multiplying by 100 was described in Table 18 as "low bacterial cell adhesion rate due to unevenness".

Cell adhesion test 5;
The test was performed in the same manner as in the bacterial cell adhesion test 4, except that bacterial-containing water containing 1 × 10 ⁷ cfu / ml of Escherichia coli (E. coli K12) was used. The results are shown in Table 18.

As is evident from Table 18, the articles with low bacterial cell adhesion C1 to G1 and C2 to G2 were less likely to adhere bacterial cells than the flat film z, and had an effect of reducing bacterial cell adhesion.
In particular, the low-adherence-adherent articles C1 to G1 obtained from the mold F had a high effect of reducing the adherence of bacterial cells to both Staphylococcus aureus and Escherichia coli.
In addition, low bacterial cell adhesion products C1 to F1 and C2 to F2 using an active energy ray-curable resin composition containing a hydrophilic monofunctional monomer have a low bacterial cell adhesion ratio of 3% or less in Escherichia coli and bacteria due to unevenness. The low body adhesion rate was able to be suppressed to 20% or less, and a more excellent effect of reducing the adhesion of bacterial cells was obtained.

<Example 18>
The microbial cell adhesion tests 6 and 7 were carried out as follows using each of the low bacterial cell adhesion products E1 to E11, the flat film e, and the flat film z as test pieces. The results are shown in Table 19.

Bacterial cell adhesion test 6;
The test was performed in the same manner as in the bacterial cell adhesion test 4, except that bacterial-containing water containing 1 × 10 ⁶ cfu / ml of S. aureus was used. The results are shown in Table 19.
FIG. 8 shows an image obtained by photographing the surface of the flat film z after the test with a transmission electron microscope (2,000-fold magnification). FIG. 8 shows the surface of the flat film e after the test on the cured resin layer side with a transmission electron microscope (2000-magnification). 9), and FIG. 10 shows an image of the surface of the cured cell layer side of the cell-adherent article E1 after the test taken with a transmission electron microscope (2,000-fold magnification). FIG. 11 shows images of the surface of the body-adhesive article E7 on the cured resin layer side taken with a transmission electron microscope (2,000-fold magnification).

Cell adhesion test 7;
The test was performed in the same manner as in the bacterial cell adhesion test 4, except that bacteria-containing water containing 1 × 10 ⁶ cfu / ml of Escherichia coli (E. coli K12) was used. The results are shown in Table 19.
FIG. 12 shows an image obtained by photographing the surface of the flat film z after the test with a transmission electron microscope (magnification: 2000 times). FIG. 12 shows the surface of the flat film e on the cured resin layer side after the test with a transmission electron microscope (magnification: 2000 magnification). 13), and FIG. 14 shows an image of the surface on the cured resin layer side of the bacterial cell-adherent article E1 after the test taken with a transmission electron microscope (2,000-fold magnification). FIG. 15 shows images of the surface of the body-adhesive article E7 on the cured resin layer side taken by a transmission electron microscope (2,000-fold magnification).

As is clear from Table 19, the cells E1 to E11 having a low cell adhesion were less likely to adhere to the cells than the flat film z, and had an effect of reducing the adhesion of the cells.
In particular, the low-cellular-adhesive articles E1 to 7 and 10 having a fine uneven structure having a period of 2 μm or less on the surface have a high adhesion-reducing effect on both Staphylococcus aureus and Escherichia coli, and have a low cell-adhering rate of 4%. Hereinafter, the low cell adhesion rate due to the irregularities could be suppressed to 30% or less, and a more excellent effect of reducing the cell adhesion was obtained.
Further, as can be seen from the transmission electron microscope images of FIGS. 10, 11, 14, and 15, the low-cellular-adherence articles E1 and E7 have a greater effect of reducing the adherence of the cells in both Staphylococcus aureus and Escherichia coli. It was high, the low cell adhesion rate was 2% or less, and the low cell adhesion rate due to irregularities could be suppressed to 10% or less, and the effect of low cell adhesion due to the shape of the fine uneven structure was easily obtained. Further, in the shape of the fine uneven structure, the low-adhesion articles E2 and E7 have a higher effect of reducing the adhesion of cells than the low-adhesion article E10. The article E7 having a low bacterial cell adhesion had a higher effect of reducing the adherence of the bacterial cells, and the shape of the two-dimensional lattice having a high aspect ratio was more suitable than the article E2 having a hydrophobic property.

INDUSTRIAL APPLICABILITY The article with low bacterial cell adhesion according to the present invention is useful as a bacterial-repellent member such as a bacterial-repellent film and the like, in which bacterial cells are unlikely to adhere and the material has a wide selectivity.
ADVANTAGEOUS EFFECTS OF THE INVENTION The method of the present invention for preventing cell adhesion can suppress the adhesion of cells to locations where cell adhesion is desired to be reduced.

REFERENCE SIGNS LIST 10 Low bacterial cell adhesion article 12 Base film 14 Convex part 16 Cured resin layer 20 Mold 22 Tank 24 Active energy ray curable resin composition 26 Pneumatic cylinder 28 Nip roll 30 Active energy ray irradiation device 32 Peeling roll 34 Aluminum base material 36 Pore 38 Oxide film 40 Pore generation point H Height P Average interval

Claims (7)

The surface has a fine uneven structure with a cycle smaller than 5 times the size of the cells,
The surface of the fine uneven structure side is water-repellent,
The fine uneven structure is made of a cured product of a curable resin composition,
In addition, the article having low bacterial cell adhesion, wherein the fine uneven structure is a structure obtained by transferring from a mold having the fine uneven structure. The surface has a fine uneven structure with a cycle smaller than 5 times the size of the cells,
The surface of the fine uneven structure side is hydrophilic,
The fine uneven structure is made of a cured product of a curable resin composition,
In addition, the article having low bacterial cell adhesion, wherein the fine uneven structure is a structure obtained by transferring from a mold having the fine uneven structure.   The article with low bacterial cell adhesion according to claim 2, wherein the fine uneven structure comprises a cured product of a composition containing a hydrophilic monofunctional monomer.   4. The method according to claim 3, wherein the hydrophilic monofunctional monomer includes at least one selected from the group consisting of a (meth) acrylamide derivative, a monofunctional amide, and a monofunctional (meth) acrylate having a polyethylene glycol chain in an ester group. The low bacterial cell adhesion article according to the above.   The article with low bacterial cell adhesion according to any one of claims 1 to 4, wherein the cycle is equal to or less than the size of the bacterial cell.   The low bacterial cell adhesion article according to any one of claims 1 to 5, wherein the cycle is 50 nm or more and 4 µm or less. A method for preventing bacterial cell adhesion, comprising providing the article with low bacterial cell adhesion according to any one of claims 1 to 6 at a location where the adherence of bacterial cells is desired to be reduced.