U.S. patent application number 16/638857 was filed with the patent office on 2020-11-19 for antimicrobial/antiviral composition.
This patent application is currently assigned to NBC MESHTEC INC.. The applicant listed for this patent is NBC MESHTEC INC.. Invention is credited to Yoshie FUJIMORI, Shinji KURAHASHI, Nobukazu MOTOJIMA, Tsuruo NAKAYAMA, Masako TAKINO.
Application Number | 20200359633 16/638857 |
Document ID | / |
Family ID | 1000005035550 |
Filed Date | 2020-11-19 |
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United States Patent
Application |
20200359633 |
Kind Code |
A1 |
TAKINO; Masako ; et
al. |
November 19, 2020 |
ANTIMICROBIAL/ANTIVIRAL COMPOSITION
Abstract
To provide an antimicrobial/antiviral composition having an
excellent immediate effect while the content of monovalent copper
compound is low. The antimicrobial/antiviral composition includes:
a resin; an antimicrobial/antiviral agent containing monovalent
copper compound microparticles coated with a dispersant; and a
hydrophilic compound that is dispersed in the resin and is
immiscible with the resin.
Inventors: |
TAKINO; Masako; (Tokyo,
JP) ; KURAHASHI; Shinji; (Tokyo, JP) ;
FUJIMORI; Yoshie; (Tokyo, JP) ; MOTOJIMA;
Nobukazu; (Tokyo, JP) ; NAKAYAMA; Tsuruo;
(Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NBC MESHTEC INC. |
Tokyo |
|
JP |
|
|
Assignee: |
NBC MESHTEC INC.
Tokyo
JP
|
Family ID: |
1000005035550 |
Appl. No.: |
16/638857 |
Filed: |
September 3, 2018 |
PCT Filed: |
September 3, 2018 |
PCT NO: |
PCT/JP2018/032677 |
371 Date: |
February 13, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A01N 59/20 20130101;
A01N 25/10 20130101; A01N 25/26 20130101 |
International
Class: |
A01N 59/20 20060101
A01N059/20; A01N 25/10 20060101 A01N025/10; A01N 25/26 20060101
A01N025/26 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 4, 2017 |
JP |
2017-169865 |
Sep 4, 2017 |
JP |
2017-169874 |
Claims
1. An antimicrobial/antiviral composition comprising: a resin; an
antimicrobial/antiviral agent comprising monovalent copper compound
microparticles coated with a dispersant; and a hydrophilic compound
that is dispersed in the resin and is immiscible with the
resin.
2. The antimicrobial/antiviral composition according to claim 1,
wherein the dispersant is an inorganic compound.
3. The antimicrobial/antiviral composition according to claim 1,
wherein the copper compound microparticles comprise at least one of
cuprous oxide or copper iodide.
4. An antimicrobial/antiviral coating comprising the
antimicrobial/antiviral composition according to claim 1, wherein a
contribution of polar component to surface free energy of coating
film formed by drying and/or curing is 2.0% or higher and 40.0% or
lower.
5. An antimicrobial/antiviral resin member comprising the
antimicrobial/antiviral composition according to claim 1, wherein a
contribution of polar component to surface free energy of the
antimicrobial/antiviral resin member is 2.0% or higher and 40.0% or
lower.
6. The antimicrobial/antiviral resin member according to claim 5,
wherein the antimicrobial/antiviral resin member is a molding.
7. The antimicrobial/antiviral resin member according to claim 5,
wherein the antimicrobial/antiviral resin member is fiber.
8. A method of producing the antimicrobial/antiviral composition
according to claim 1, comprising steps of: mixing the resin and the
hydrophilic compound to give a mixture; and mixing the mixture and
the copper compound microparticles.
9. A method of producing the antimicrobial/antiviral resin member
according to claim 6, comprising steps of: mixing the resin, the
dispersant, and the copper compound microparticles to give a first
mixture; mixing the resin and the hydrophilic compound to give a
second mixture; and mixing the first mixture and the second
mixture.
10. The antimicrobial/antiviral composition according to claim 2,
wherein the copper compound microparticles comprise at least one of
cuprous oxide or copper iodide.
11. An antimicrobial/antiviral coating comprising the
antimicrobial/antiviral composition according to claim 2, wherein a
contribution of polar component to surface free energy of coating
film formed by drying and/or curing is 2.0% or higher and 40.0% or
lower.
12. An antimicrobial/antiviral coating comprising the
antimicrobial/antiviral composition according to claim 3, wherein a
contribution of polar component to surface free energy of coating
film formed by drying and/or curing is 2.0% or higher and 40.0% or
lower.
13. An antimicrobial/antiviral resin member comprising the
antimicrobial/antiviral composition according to claim 2, wherein a
contribution of polar component to surface free energy of the
antimicrobial/antiviral resin member is 2.0% or higher and 40.0% or
lower.
14. An antimicrobial/antiviral resin member comprising the
antimicrobial/antiviral composition according to claim 3, wherein a
contribution of polar component to surface free energy of the
antimicrobial/antiviral resin member is 2.0% or higher and 40.0% or
lower.
15. A method of producing the antimicrobial/antiviral composition
according to claim 2, comprising steps of: mixing the resin and the
hydrophilic compound to give a mixture; and mixing the mixture and
the copper compound microparticles.
16. A method of producing the antimicrobial/antiviral composition
according to claim 3, comprising steps of: mixing the resin and the
hydrophilic compound to give a mixture; and mixing the mixture and
the copper compound microparticles.
Description
TECHNICAL FIELD
[0001] The present invention relates to an antimicrobial/antiviral
composition, and an antimicrobial/antiviral coating and
antimicrobial/antiviral resin member using the composition.
BACKGROUND ART
[0002] Recently, new viral infections have increasingly become
threatening. For instance, infections caused by virus such as SARS
(severe acute respiratory syndrome), norovirus, and avian influenza
virus have prevailed. Meanwhile, Ebola hemorrhagic fever prevailed
in West Africa in 2013. According to announcement of the World
Health Organization (WHO), among 27,550 infection cases including
suspected infection 11,235 of dead cases have been reported by
2015.
[0003] In addition, norovirus and/or influenza infections in
institutions such as hospitals and nursing homes and nosocomial
infection due to drug-resistant bacteria such as MRSA have also
prevailed. As a result, urgent countermeasures against the
infections should be implemented.
[0004] In view of such a background, products should be developed
that can easily impart a potent function of inactivating viruses
and/or bacteria.
[0005] To provide a solution to the problems, the following has
been developed, including an antiviral spray agent (Patent
Literature 1) in which monovalent copper compound microparticles
are suspended in a dispersant; an antiviral coating (Patent
Literature 2) in which monovalent copper compound microparticles
are added to a binder resin; an antimicrobial composition (Patent
Literature 3) in which an antiviral agent having copper iodide
microparticles coated with a functionalization agent is added;
fiber (Patent Literature 4) in which platinum particles having an
antiviral property are fixed to a fiber surface by soaking fiber in
a platinum nano-colloid aqueous solution; and an
antimicrobial/antiviral polymer material (Patent Literature 5) in
which copper oxide and cuprous oxide are included.
CITATION LIST
Patent Literature
[0006] Patent Literature 1: JP 2010-239897 A [0007] Patent
Literature 2: JP 2010-168578 A [0008] Patent Literature 3: JP
2014-519504 A [0009] Patent Literature 4: JP 2014-122457 A [0010]
Patent Literature 5: JP 5457504 B2
SUMMARY OF INVENTION
Technical Problem
[0011] Unfortunately, the problem in the antiviral spray agent of
Patent Literature 1 is that monovalent copper compound
microparticles remain at the sprayed site after spraying and the
antiviral effect thus persists; however, once the monovalent copper
compound microparticles are removed by cleaning, the antiviral
spray agent has to be re-sprayed. The problem in the antiviral
coating of Patent Literature 2 is that although the antiviral
effect is high, this high antiviral effect is unlikely to be
exerted unless a large volume of monovalent copper compound is
dispersed and filled; on the other hand, if a large volume of
monovalent copper compound is dispersed or dissolved,
characteristics such as coating film strength and tight adhesion
deteriorate.
[0012] In addition, the problem in the antimicrobial composition of
Patent Literature 3 is that although the antimicrobial effect is
high, it takes a very long time, for example, from several hours to
a day to exert effect, and as a result of which the composition
lacks an immediate effect. In addition, long-term storage causes a
monovalent copper compound to be oxidized, thereby decreasing the
antimicrobial effect. Further, the problem in the fiber in which
platinum particles are fixed on the surface thereof according to
Patent Literature 4 is that there is an antiviral effect, but the
immediate effect of inactivating viruses in a short period of time
is poor. Furthermore, the problem in the antimicrobial/antiviral
polymer material of Patent Literature 5 is that no effect is
exerted unless antimicrobial/antiviral particles are projected from
the polymer surface. Besides, to exert the effect in a short period
of time, the number of particles to be projected has to be
increased. As a result, there is a need to increase the number of
antimicrobial/antiviral particles included in the polymer
material.
[0013] Here, to solve the above problems, it is an object of the
present invention to provide an antimicrobial/antiviral composition
having an excellent immediate effect even when the content of
monovalent copper compound is low as well as an
antimicrobial/antiviral coating and an antimicrobial/antiviral
resin member.
Solution to Problem
[0014] Specifically, the first aspect of the invention is an
antimicrobial/antiviral composition including: a resin; an
antimicrobial/antiviral agent including monovalent copper compound
microparticles coated with a dispersant; and a hydrophilic compound
that is dispersed in the resin and is immiscible with the
resin.
[0015] Meanwhile, the second aspect of the invention is the
antimicrobial/antiviral composition according to the first aspect
of the invention, wherein the dispersant is an inorganic
compound.
[0016] In addition, the third aspect of the invention is the
antimicrobial/antiviral composition according to the first or
second aspect of the invention, wherein the copper compound
microparticles include at least one of cuprous oxide or copper
iodide.
[0017] In addition, the fourth aspect of the invention is an
antimicrobial/antiviral coating including the
antimicrobial/antiviral composition according to any one of the
first to third aspects of the invention, wherein a contribution of
polar component to surface free energy of coating film formed by
drying and/or curing is 2.0% or higher and 40.0% or lower.
[0018] In addition, the fifth aspect of the invention is an
antimicrobial/antiviral resin member including the
antimicrobial/antiviral composition according to any one of the
first to third aspects of the invention, wherein a contribution of
polar component to surface free energy of the
antimicrobial/antiviral resin member is 2.0% or higher and 40.0% or
lower.
[0019] In addition, the sixth aspect of the invention is the
antimicrobial/antiviral resin member according to the fifth aspect
of the invention, wherein the antimicrobial/antiviral resin member
is a molding.
[0020] In addition, the seventh aspect of the invention is the
antimicrobial/antiviral resin member according to the fifth aspect
of the invention, wherein the antimicrobial/antiviral resin member
is fiber.
[0021] In addition, the eighth aspect of the invention is a method
of producing the antimicrobial/antiviral composition according to
any one of the first to third aspects of the invention, including
the steps of: mixing the resin and the hydrophilic compound to give
a mixture; and mixing the mixture and the copper compound
microparticles.
[0022] In addition, the ninth aspect of the invention is a method
of producing the antimicrobial/antiviral resin member according to
the sixth aspect of the invention, including the steps of: mixing
the resin and the copper compound microparticles to give a first
mixture; mixing the resin and the hydrophilic compound to give a
second mixture; and mixing the first mixture and the second
mixture.
Advantageous Effects of Invention
[0023] According to the invention, a hydrophilic compound is
dispersed in the resin of the antimicrobial/antiviral composition.
Consequently, the hydrophilic compound is dispersed in a coating
film of coating containing the antimicrobial/antiviral composition
and/or a resin of resin member containing the
antimicrobial/antiviral composition. As a result, the contribution
of polar component to surface free energy on a surface of the
coating film or the resin member is increased. Accordingly,
bacteria and/or viruses having both a hydrophilic group and a
hydrophobic group are readily spread and adsorbed on the surface of
the coating film or the resin member. This can provide a member
having an excellent immediate effect even when the concentration of
monovalent copper compound microparticles is low. In addition,
because the monovalent copper compound microparticles are coated
with a dispersant, aggregation of the copper compound
microparticles in the resin can be prevented. Thus, the copper
compound microparticles can be efficiently in contact with bacteria
and/or viruses. Further, because the hydrophilic compound present
in the resin readily adsorbs moisture content in the air, a
humidity and/or room temperature fluctuation hardly causes an
adsorbed moisture content change. This makes it possible to
continue eliciting high antimicrobial/antiviral performance.
DESCRIPTION OF EMBODIMENTS
[0024] Hereinafter, an antimicrobial/antiviral composition
according to an embodiment of the invention will be described in
detail.
[0025] An antimicrobial/antiviral composition according to an
embodiment of the invention includes: a resin as a main ingredient;
an antimicrobial/antiviral agent containing monovalent copper
compound microparticles coated with a dispersant (hereinafter, also
simply referred to as copper compound microparticles); and a
hydrophilic compound that is dispersed in the resin and is
immiscible with the resin.
[0026] First, ingredients included in the antimicrobial/antiviral
composition according to this embodiment are described. Examples of
the hydrophilic compound contained in the antimicrobial/antiviral
composition of this embodiment include: water-soluble synthetic
polymers such as polyvinyl alcohol (PVA), polyvinylpyrrolidone
(PVP), polyethylene oxide (PEO), hydroxypropyl cellulose (HPC),
polyethylene glycol (PEG), polyacrylamide (PAAM), polyacrylic acid
(PAA), sodium polyacrylate, polyethyleneimine; and carboxymethyl
starch, dialdehyde starch, alginate, polystyrene sulfonate,
carboxymethyl cellulose (CMC), polysaccharides, a
polyoxyethylene-polyoxypropylene copolymer, poly-N-alkyl
acrylamide, hydroxyethyl cellulose, poly-N-isopropyl acrylamide
(PNIAAm), chondroitin sulfate, dextran sulfate, dermatan sulfate, a
methyl vinyl ether-maleic anhydride copolymer, an ethylene-vinyl
acetate copolymer, and an acrylamide-acrylate copolymer such as a
dimethylacrylamide-glycidyl methacrylate copolymer.
[0027] The hydrophilic compound is characterized in that the
hydrophilic compound is immiscible with the below-described resin
as a main ingredient of the antimicrobial/antiviral composition and
is formed as an independent discontinuous phase in, for instance, a
spherical sea-island form, a lamellar form, or a cylindrical form.
The discontinuous phase of hydrophilic compound is intermixed in
the resin as a main ingredient of the antimicrobial/antiviral
composition of this embodiment and a phase-separated structure is
formed. When the antimicrobial/antiviral composition is applied to
a coating, the above makes the surface of a coating film
hydrophilic after the coating is dried or cured. Alternatively,
when the antimicrobial/antiviral composition is applied to a resin
member, the above makes the surface of the resin member
hydrophilic. These results are characterized in that as described
below, how well viruses and/or microbial cells spread on the above
surface is enhanced and the antimicrobial/antiviral effect is thus
improved.
[0028] Here, the phase separation in this embodiment is
illustrated. In the case of this embodiment, after the resin and
the hydrophilic compound are mixed, discontinuous phases (small
domains) caused by hydrophilic compound assembly are
micro-dispersed in the hydrophobic resin. The hydrophilic compound
and the resin are macroscopically uniform but the phase separation
occurs microscopically. The size of each discontinuous phase
composed of the hydrophilic compound is said to be typically 1
.mu.m or less. In this embodiment, regardless of whether the
hydrophilic compound is in a discontinuous phase (small domain) or
a continuous phase in which the discontinuous phases are fused to
one another, the hydrophilic compound can be used as long as the
hydrophilic compound is present and immiscible with the resin.
[0029] Meanwhile, a user can optionally select a resin as a main
ingredient of the antimicrobial/antiviral composition of this
embodiment if the resin is immiscible with the above hydrophilic
compound. Specific examples of this resin will be illustrated in
the description of an antimicrobial/antiviral coating and/or an
antimicrobial/antiviral resin member using the
antimicrobial/antiviral composition.
[0030] The antimicrobial/antiviral composition of this embodiment
is characterized by further including monovalent copper compound
microparticles as an antimicrobial/antiviral agent that is a
substance capable of inactivating either microbial cells (e.g.,
fungi, bacteria) or viruses or the both. Specific examples of the
monovalent copper compound that can be preferably used include
cuprous oxide and a copper halide (in particular, copper iodide)
from the viewpoints of temporal stability and effect
sustainability. The shape of the antimicrobial/antiviral agent is
not particularly limited and examples can include a powder form, a
paste form, a liquid form, and a microparticle form.
[0031] The particle size of the antimicrobial/antiviral agent
(copper compound microparticles) is not particularly limited and
can be optionally set by a person skilled in the art. Here, it is
preferable that the average particle size is 1 nm or larger and
less than 1 .mu.m. This is because if the average particle size is
less than 1 nm, the substance is unstable; and if the average
particle size is 1 .mu.m or larger, the antimicrobial/antiviral
effect is lower than the case of less than 1 .mu.m and stability of
the antimicrobial/antiviral composition during storage
deteriorates. Note that the average particle size herein refers to
a volume-average particle size. The volume-average particle size
can be measured on the basis of, for instance, a laser Doppler
method (dynamic/electrophoretic light scattering). The measuring
device is not particularly limited and a .zeta.-potential/particle
size-measuring system (manufactured by OTSUKA ELECTRONICS Co.,
LTD.), for instance, may be used.
[0032] Further, the antimicrobial/antiviral agent in this
embodiment is characterized in that the surface of copper compound
microparticle is coated with a dispersant so as to prevent
aggregation of the antimicrobial/antiviral agent. As the
dispersant, an organic compound such as a polymer-based dispersant,
a surfactant, or a plasticizer or an inorganic compound such as a
metal soap may be used, if appropriate. In this embodiment, an
inorganic compound is preferably used because the inorganic
compound can increase contact with bacteria and/or viruses and the
antimicrobial/antiviral effect is thus readily exploited. For
instance, the .zeta.-potential of inorganic compound such as
zirconia, aluminum oxide, or titanium oxide is a positive potential
at pH 7. Meanwhile, viruses, in general, possess a negative
potential. Accordingly, by coating copper compound microparticles
with the inorganic compound microparticles, contact between the
antimicrobial/antiviral agent and viruses can be increased, readily
resulting in expression of the antiviral effect. Further, when the
copper compound microparticles are coated with the inorganic
compound, the copper compound microparticles are unlikely to be
oxidized, so that the antimicrobial/antiviral effect can persist.
The "coat" herein refers to the presence of a dispersant on at
least a part of a surface of each copper compound
microparticle.
[0033] A metal soap as the dispersant is a microparticle, excels in
dispersion in a resin, and imparts adequate smoothness to the
resin. For the metal soap, a fatty acid such as stearic acid, oleic
acid, ricinoleic acid, octylic acid, and lauric acid; and a metal
such as lithium, magnesium, calcium, barium, and zinc are used.
[0034] Examples of the inorganic compound include, in addition to
the metal soap, a metal hydroxide, a metal oxide, and a metal
peroxide. Examples of the metal hydroxide include aluminum
hydroxide, zirconium hydroxide, zinc hydroxide, and iron hydroxide.
Examples of the metal oxide include magnesium oxide, barium oxide,
calcium oxide, aluminum oxide, tin oxide, titanium oxide, zinc
oxide, zirconium oxide, iron oxide, and tungsten oxide. Examples of
the metal peroxide include barium peroxide, titanium peroxide, and
calcium peroxide. Note that these inorganic compounds may be used
singly or may be in combination of two or more kinds. The sizes of
inorganic compound microparticles are not particularly limited and
the average particle size is preferably 1.0 nm or larger and 300 nm
or less.
[0035] The virus inactivation mechanism by the monovalent copper
compound is not necessarily clear at the moment. However, it seems
that when a monovalent copper compound comes into contact with
water content in the air or in droplets, a monovalent copper ion is
eluted; the eluted monovalent copper ion comes into contact with a
virus to release an electron; at that time, the generated reactive
species give the virus some damage to inactivate the virus.
[0036] Regardless of the kind of genome and/or the presence or
absence of envelope, various viruses are listed for the viruses
capable of being inactivated by the antimicrobial/antiviral
composition of this embodiment. Examples of the viruses include
rhinovirus, poliovirus, foot-and-mouth disease virus, rotavirus,
norovirus, enterovirus, hepatovirus, astrovirus, sapovirus,
hepatitis E virus, influenza virus A, B or C, parainfluenza virus,
mumps virus (mumps), measles virus, human metapneumovirus, RS
virus, nipahvirus, hendravirus, yellow fever virus, dengue virus,
Japan encephalitis virus, West Nile virus, hepatitis B or C virus,
eastern and western equine encephalitis virus, Onyong-nyong virus,
rubella virus, Lassa virus, Junin virus, Machupo virus, Guanarito
virus, Sabia virus, Crimean-Congo hemorrhagic fever virus, sandfly
fever/hantavirus, hantavirus, Sin Nombre virus, rabies virus, Ebola
virus, Marburg virus, bat lyssavirus, human T cell leukemia virus,
human immunodeficiency virus, human coronavirus, SARS coronavirus,
human parvovirus, polyoma virus, human papilloma virus, adenovirus,
herpes virus, varicella-zoster virus, EB virus, cytomegalovirus,
smallpox virus, monkeypox virus, cowpox virus, molluscipoxvirus
virus, parapox virus, and zika virus.
[0037] In addition, microbial cells capable of being inactivated by
the antimicrobial/antiviral composition according to this
embodiment are not particularly limited and various bacteria can be
listed regardless of gram-positive or -negative, aerobic, or
anaerobic characteristics and so on. Examples include Escherichia
coli, Staphylococcus aureus, Staphylococcus epidermidis,
Streptococcus, Streptococcus pneumoniae, Haemophilus influenzae,
Haemophilus pertussis, Salmonella enteritidis, Klebsiella
pneumoniae, Pseudomonas aeruginosa, Vibrio, Salmonella enterica,
Vibrio cholerae, Shigella dysenteriae, Bacillus anthracis,
Mycobacterium tuberculosis, Clostridium botulinum, Clostridium
tetani, and Streptococcus.
[0038] Next, an example of a method of producing the
antimicrobial/antiviral composition according to this embodiment
will be specifically described.
[0039] First, a resin, which is a main ingredient of the
above-described antimicrobial/antiviral composition, is mixed with
a hydrophilic compound. For the mixing procedure, it is possible to
use a mixer, a homogenizer, a bead mill, a ball mill, a three-roll
mill, or another instrument. Depending on the purpose, the
antimicrobial/antiviral composition of this embodiment may be
optionally blended with an additional additive(s) (e.g., a flame
retardant, a flame retardant aid, a stabilizer, a UV absorber, a
plasticizer, and/or a lubricant), a pigment, a filler, and/or
another ingredient.
[0040] Next, the copper compound microparticles used in this
embodiment are ground to particles in nano-order by using, for
instance, a jet mill, a hammer mill, a ball mill, a vibration mill,
or a bead mill. The grinding procedure is not particularly limited
and both dry and wet processes may be utilized. At this time, an
inorganic compound for coating the copper compound microparticles
is added. After the inorganic compound is added, the copper
compound microparticles and the inorganic compound are in contact
with each other and are crushed. Then, the inorganic compound with
a smaller particle size occurs. At the same time, electrostatic
attraction causes the inorganic compound to be attached to the
surface of each copper compound microparticle. Then, an
antimicrobial/antiviral agent is obtained in which the copper
compound microparticles are coated with the inorganic compound.
This antimicrobial/antiviral agent and a mixture of a resin and a
hydrophilic compound are mixed to yield an antimicrobial/antiviral
composition.
[0041] The procedure for coating the surface of each copper
compound microparticle with a metal hydroxide, a metal oxide, or a
metal peroxide as the inorganic compound may include: dispersing
copper compound microparticles in an aqueous solution containing
such a dissolved metal compound so as to chemically adsorb the
metal compound on the surface of each copper compound
microparticle; or dispersing copper compound microparticles in a
solvent containing a dispersed metal compound so as to precipitate
the metal compound on the surface of each copper compound
microparticle.
[0042] Examples of another procedure include a mechanochemical
procedure. This procedure is a process for embedding child
particles into mother particles by applying strong pressure to core
mother particles (in this embodiment, copper compound
microparticles) and child particles (in this embodiment, an
inorganic compound) covering the mother particles by using a
rolling ball mill, a high-speed rotary grinder, a high-speed flow
impact grinder, a medium-agitating mill, or a mechanical fusion
device. When this procedure is used, it is preferable that the
copper compound microparticles, which are mother particles, should
be beforehand ground to a desired particle size by the above
process.
[0043] Examples of an apparatus allowing for preparation of the
mother particles and the child particles include: a rotary blade
type such as a super mixer from KAWATA MFG. CO., LTD.; and a shaker
type such as a paint shaker from ASADA IRON WORKS. CO., LTD., a
Hybridization System (registered trademark) manufactured by NARA
MACHINERY CO., LTD., a Mechanofusion (registered trademark) from
Hosokawa Micron Group, or a medium flow dryer. However, the
apparatus is not particularly limited to these devices. The devices
allowing for both grinding and coating of child particles may be
used, including an automated mortar, a high-speed rotary grinder, a
high-speed flow impact grinder, or a rolling ball mill. In this
case, it is unnecessary to beforehand crush copper compound
microparticles which are mother particles.
[0044] Next, an antimicrobial/antiviral coating using the
antimicrobial/antiviral composition of this embodiment will be
described in detail.
[0045] The antimicrobial/antiviral coating of an embodiment of the
invention includes the above-mentioned antimicrobial/antiviral
composition. Then, the antimicrobial/antiviral coating of this
embodiment is characterized in that in a dried and/or cured state
(i.e., in a coating film state), the contribution (hereinafter,
referred to as polar contribution R.gamma.p) of polar component
.gamma.sp to surface free energy .gamma.s is 2.0% or higher and
40.0% or lower.
[0046] Now, the polar contribution R.gamma.p of coating film when
the antimicrobial/antiviral coating of this embodiment is in a
dried and/or cured state will be illustrated.
[0047] The surface free energy .gamma.s refers to surplus energy of
a molecule (or an atom) present on a solid surface or liquid
surface when compared to that of a molecule (or an atom) present
inside the solid or liquid. The surface free energy .gamma.s is
defined by the following Formula (1); and the polar contribution
R.gamma.p is defined by the following Formula (2). In the following
Formula (1), .gamma.sp is the polar component in the surface free
energy .gamma.s and .gamma.sd is the non-polar component in the
surface free energy .gamma.s. In addition, the surface free energy
.gamma.s, the non-polar component .gamma.sd, and the polar
component .gamma.sp are values when the antimicrobial/antiviral
coating of this embodiment is in a dried and/or cured state.
[ Expression 1 ] .gamma. s = .gamma. sd + .gamma. sp ( 1 ) R
.gamma. p = .gamma. sp .gamma. s .times. 100 ( 2 ) ##EQU00001##
[0048] When the surface free energy .gamma.s is measured, a surface
of coating film, which is subject to measurement, in a dried and/or
cured state is coated with a measurement liquid (each of water or
diiodomethane is used) to measure the contact angle (.theta.) of
each measurement liquid. The value obtained for the contact angle
and the following Formula (3) are used to calculate the polar
component .gamma.sp and the non-polar component .gamma.sd.
[ Expression 2 ] ( 1 + cos .theta. ) .times. .gamma. L 4 = (
.gamma. sd + .gamma. Ld ) .gamma. sd + .gamma. Ld + ( .gamma. sp
.times. .gamma. Lp ) .gamma. sp + .gamma. Lp ( 3 ) ##EQU00002##
.theta.: Contact angle of measurement liquid on a surface of
coating film in a dried and/or cured state .gamma.L: Surface
tension of measurement liquid (water or diiodomethane) .gamma.Ld:
Non-polar component of surface free energy of measurement liquid
(water or diiodomethane) .gamma.Lp: Polar component of surface free
energy of measurement liquid (water or diiodomethane) .gamma.sd:
Non-polar component of surface free energy of coating film in a
dried and/or cured state .gamma.sp: Polar component of surface free
energy of coating film in a dried and/or cured state
[0049] Regarding the two measurement liquids (water and
diiodomethane), the surface tension .gamma.L, the non-polar
component .gamma.Ld, and the polar component .gamma.Lp may be
measured beforehand. When simultaneous equations, in which the
contact angles 8 of the two measurement liquids are each assigned
in the above Formula (3), are solved, the polar component .gamma.sp
and the non-polar component .gamma.sd can be calculated. When the
resulting non-polar component .gamma.sd and polar component
.gamma.sp are assigned to the above Formula (1), the surface free
energy .gamma.s can be calculated. Then, this surface free energy
.gamma.s and the polar component .gamma.sp may be assigned to the
above Formula (2) to calculate the polar contribution
R.gamma.p.
[0050] The surface free energy .gamma.s may be comparable. Even in
this case, as the polar contribution R.gamma.p increases, the
antimicrobial/antiviral effect becomes higher. The rationale is not
necessarily clear at the moment. However, it seems that as the
polar contribution R.gamma.p increases, microbial cells and/or
viruses attached to the coating film surface spread more readily.
This causes the antimicrobial/antiviral agent to easily contact the
microbial cells and the viruses, thereby enhancing the
antimicrobial/antiviral effect.
[0051] In addition, a material to be coated with the
antimicrobial/antiviral coating of this embodiment may have a high
intrinsic polar contribution R.gamma.p. Even in this case, the
antimicrobial/antiviral effect is not increased unless the
hydrophilic compound is included. The rationale is unclear, but it
seems that if the hydrophilic compound is not included, microbial
cells and viruses are unlikely to spread on the coating film
surface and are thus not readily in contact with the
antimicrobial/antiviral agent.
[0052] The polar contribution R.gamma.p of coating film in a dried
and/or cured state may be adjusted by how much the hydrophilic
compound is added. In order to increase the antimicrobial effect
and the antiviral effect, it is preferable that the polar
contribution R.gamma.p of a coating film is 2.0% or higher and
40.0% or lower. More preferably, the polar contribution R.gamma.p
is 5% or higher and 30% or lower.
[0053] When the polar contribution R.gamma.p is less than 2.0%, the
antimicrobial effect and the antiviral effect are insufficient
compared to the case where the polar contribution R.gamma.p is 2.0%
or higher. To improve the antimicrobial effect and the antiviral
effect, it is more preferable that the polar contribution R.gamma.p
is 5% or higher. Meanwhile, when the polar contribution R.gamma.p
exceeds 40%, the antimicrobial effect and the antiviral effect are
not much elevated compared to the case where the polar contribution
R.gamma.p is 40% or lower. Because of the above, it is preferable
that the polar contribution R.gamma.p is 40% or lower.
[0054] Note that the dried state of an antimicrobial/antiviral
coating herein means a state in which when the
antimicrobial/antiviral coating is subjected to drying treatment
and so on, the antimicrobial/antiviral coating residual content is
substantially in a solid state. In addition, the cured state of an
antimicrobial/antiviral coating means a state in which when the
antimicrobial/antiviral coating is coated/dried, etc., to form a
coating film, dust, etc., may be attached to the surface thereof;
and even in this case, the dust, etc., is not incorporated into the
coating film. The attached dust, etc., may be easily removed by
blowing the air. Further, the cured state of an
antimicrobial/antiviral coating herein indicates a state of at
least a surface of a coating film and does not necessarily means
that the inside of the coating film is completely cured.
[0055] Meanwhile, a user can optionally select a resin as a base of
the antimicrobial/antiviral coating of this embodiment if the resin
is immiscible with the above-mentioned hydrophilic compound.
Specific examples used include thermoplastic resins, thermosetting
resins, and radiation curable resins that can be cured by
irradiation with an electron beam and/or UV light, etc. These
resins may be in combination of two or more kinds.
[0056] Examples of the thermoplastic resins include: olefin-based
resins such as polyethylene, polypropylene, chlorinated
polyethylene; polystyrene resin, polyvinyl acetate resin,
polyurethane resin, polyester resin; copolymers containing acrylic
acid, acrylic acid ester, methacrylic acid, or methacrylic acid
ester as a backbone; acrylic styrene resin, fluorine-based resin;
cellulose-based resins such as nitrocellulose and ethyl cellulose;
drying oil such as castor oil, linseed oil, or Tung oil; and
natural resins such as shellac and copal. In addition, examples of
the thermosetting resins include phenol resin, epoxy resin,
melamine resin, urea resin, unsaturated polyester resin, acrylic
silicone resin, alkyd resin, polyurethane resin, thermosetting
acrylic resin, and thermosetting polyimide resin.
[0057] Further, the radiation (e.g., an electron beam or UV light)
curable resins are monomers, oligomers, or polymers. From the
viewpoints of being capable of increasing the post-cure crosslink
density, enhancing the effect of improving the surface hardness,
and enhancing the effect of improving the transparency, preferable
examples include multifunctional (meth)acrylate compounds such as
multifunctional (meth)acrylate monomers, multifunctional
(meth)acrylate oligomers, or multifunctional (meth)acrylate
polymers. In addition, a photopolymerization initiator may be added
depending on the needs. Examples of the photopolymerization
initiator include anthraquinone, acetophenone, isopropyl benzoin
ether, isobutyl benzoin ether, ethylanthraquinone, carbazole,
xanthone, 4-chlorobenzophenone, o-benzoyl methylbenzoate,
2,4-diethylthioxantone, 2-chlorothioxanthone,
2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylamino benzoic acid
isoamyl ester, p-dimethylamino benzoic acid ethyl ester,
2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl
ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one,
1-hydroxycyclohexyl phenyl ketone,
2-benzyl-2-dimethylamino-1(4-morpholinophenyl)-butanone-1,
bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, methylbenzyl
formate, fluorenone, benzophenone, benzaldehyde, fluorene,
triphenylamine, Michler's ketone, 3-methylacetophenone,
2-methyl-1-1[4-(methylthio)phenyl]-2-morpholino-propane-1-one,
2,4,6-trimethylbenzoyl diphenylphosphine oxide, and
bis-(2,6-dimethylbenzoyl)2,4,4-trimethylpentylphosphine oxide.
[0058] The antimicrobial/antiviral coating of this embodiment may
be used to coat each different target member to give the
antimicrobial/antiviral performance.
[0059] Examples of the target member include fiber structures,
films, and sheets. Examples of the fiber structures capable of
having a coating film include woven fabrics and nonwoven fabrics.
Specific application examples of them include masks, filters for
air conditioners, filters for air cleaners, filters for vacuum
cleaners, filters for ventilators, vehicle filters, air
conditioning filters, clothing, protective clothing, bedding,
window screen nets, and henhouse nets. Each fiber structure may
include a polymer material (e.g., polyester, polyethylene,
polypropylene, polyvinyl chloride, polyethylene terephthalate,
polybutylene terephthalate, polytetramethylene terephthalate,
nylon, acryl, polytetrafluoroethylene, polyvinyl alcohol, Kevlar,
polyacrylic acid, polymethyl methacrylate, rayon, Cupra, Tencel,
polynosic, acetate, triacetate, cotton, hemp, wool, silk, bamboo)
and/or fiber containing a metal (e.g., aluminum, iron, stainless
steel, brass, copper, tungsten, titanium).
[0060] Examples of materials for the films include those containing
a resin such as polyester, polyethylene, polypropylene, polyamide,
polyvinyl chloride, polyvinylidene fluoride, polyvinyl alcohol,
polyvinyl acetate, polyimide, polyamide imide,
polytetrafluoroethylene, or an ethylene tetrafluoride-ethylene
copolymer.
[0061] Examples of the sheets include polymer-made sheets (e.g.,
polycarbonate resin sheets, film vinyl chloride sheets, fluorine
resin sheets, polyethylene sheets, silicone resin sheets, nylon
sheets, ABS sheets, urethane sheets) or sheets containing a metal
(e.g., titanium, aluminum, stainless steel, magnesium, brass).
[0062] Specific application examples of the films and/or sheets
include wallpapers and windows, ceilings, vehicle seats, doors,
window shades, chairs, sofas, floor materials, facilities in which
microbial cells and/or viruses are involved, train/vehicle interior
materials, interior materials for buildings such as hospitals,
agricultural materials, or roller shutters. They are applicable to
various fields.
[0063] Further, the antimicrobial/antiviral coating of this
embodiment may be directly applied to a panel, a construction
decorative material, an interior material, a writing instrument, a
handrail, a strap, a phone, a toy, or a molding such as a door
handle to form a film (coating film). Examples of the polymer-made
molding include moldings formed by using ABS, polycarbonate, nylon,
polypropylene, polystyrene, polyacetal, polyester, or the like. In
addition, examples of the metal molding include moldings formed by
using aluminum, zinc, magnesium, brass, stainless steel, titanium,
or the like. The surface of the metal molding may have a metal thin
film, a coating, or a printing, etc., prefabricated by
electroplating or electroless plating.
[0064] Next, an example of a method of producing the
antimicrobial/antiviral coating according to this embodiment will
be specifically described.
[0065] Like the method of producing the above-described
antimicrobial/antiviral composition, a mixture obtained by mixing a
resin and a hydrophilic compound and a ground
antimicrobial/antiviral agent (copper compound microparticles
coated by a dispersant) are prepared. Then, they are mixed to yield
an antimicrobial/antiviral coating of this embodiment. Depending on
the purpose, the antimicrobial/antiviral coating may be optionally
blended with an additional additive(s) (e.g., a flame retardant, a
flame retardant aid, a stabilizer, a UV absorber, a plasticizer,
and/or a lubricant), a pigment, a filler, and/or another
ingredient.
[0066] The following details an antimicrobial/antiviral resin
member using the antimicrobial/antiviral composition of the above
embodiment.
[0067] The antimicrobial/antiviral resin member according to an
embodiment of the invention includes the above-mentioned
antimicrobial/antiviral composition. Then, the
antimicrobial/antiviral resin member of this embodiment is
characterized in that the contribution (hereinafter, referred to as
polar contribution R.gamma.p) of polar component .gamma.sp to
surface free energy .gamma.s of the resin member is 2.0% or higher
and 40.0% or lower.
[0068] The polar contribution R.gamma.p of the
antimicrobial/antiviral resin member of this embodiment is defined
by the above Formulas (1) to (3) as described regarding the
above-mentioned antimicrobial/antiviral coating. To obtain the
antimicrobial/antiviral resin member, a solvent may be removed and
dried by heating and reheating and/or irradiation with infrared
light, UV light, an electron beam, a .gamma. ray, or the like may
cause curing. Because of this, in the above Formulas (1) and (2),
the surface free energy .gamma.s, the non-polar component
.gamma.sd, and the polar component .gamma.sp are values when the
antimicrobial/antiviral resin member of this embodiment is in a
dried and/or cured state. In addition, in the above Formula (3), a
surface of the antimicrobial/antiviral resin member is used instead
of the coating film surface.
[0069] Like the polar contribution R.gamma.p of coating film of the
antimicrobial/antiviral coating, when the polar contribution
R.gamma.p is less than 2.0%, the antimicrobial/antiviral effect is
insufficient when compared to the case where the polar contribution
R.gamma.p is 2.0% or higher. Meanwhile, when the polar contribution
R.gamma.p exceeds 40.0%, the antimicrobial/antiviral effect is not
much elevated compared to the case where the polar contribution
R.gamma.p is 40.0% or lower. Because of the above, it is preferable
that the polar contribution R.gamma.p is 40.0% or lower. The polar
contribution R.gamma.p of the antimicrobial/antiviral resin member
is preferably 5.0% or higher and 30.0% or lower and more preferably
10.0% or higher and 20.0% or lower. To improve the
antimicrobial/antiviral effect, the polar contribution R.gamma.p is
preferably 5.0% or higher and more preferably 10.0% or higher.
[0070] The content of the hydrophilic compound in the
antimicrobial/antiviral resin member of this embodiment is not
particularly limited and can be set by those skilled in the art, if
appropriate. The content is preferably 0.01 mass % or higher and
50.0 mass % or lower with respect to 100 mass % of the
antimicrobial/antiviral resin member. When the content of the
hydrophilic compound is less than 0.01 mass %, the polar
contribution R.gamma.p of the antimicrobial/antiviral resin member
cannot be adequately increased when compared to the case where the
content of the hydrophilic compound is 0.01 mass % or higher. In
addition, when the content of the hydrophilic compound exceeds 50.0
mass %, the strength of the antimicrobial/antiviral resin member is
lower than that of the case where the content of the hydrophilic
compound is 50.0 mass % or lower. Further, when the content of the
hydrophilic compound is 0.01 mass % or higher and 50.0 mass % or
lower and the content of the hydrophilic compound is larger than
the content of the antimicrobial/antiviral agent, the strength of
the antimicrobial/antiviral resin member may be decreased. Thus, it
is preferable that the content of the hydrophilic compound is below
the content of the antimicrobial/antiviral agent.
[0071] The base resin for the antimicrobial/antiviral resin member
is not particularly limited as long as the resin is immiscible with
the above-stated hydrophilic compound. Examples include:
thermoplastic resins such as polyester resin, polyethylene resin,
polypropylene resin, polystyrene resin, ABS resin, AS resin, EVA
resin, polymethylpentene resin, polyvinyl chloride resin,
polyvinylidene chloride resin, methyl polyacrylate resin, polyvinyl
acetate resin, polyamide resin, polyimide resin, polycarbonate
resin, polyethylene terephthalate resin, polytetramethylene
terephthalate resin, polybutylene terephthalate resin, polyacetal
resin, polyacrylate resin, polysulfone resin, nylon resin, acrylic
resin, polyvinylidene fluoride resin, polyethylene
tetrafluoroethylene resin, polytetrafluoroethylene resin, polyvinyl
alcohol resin, Kevlar (registered trademark), and polymethyl
methacrylate resin; silicone resins; styrene-based elastomers such
as polystyrene elastomers; olefin-based elastomers such as
polyethylene elastomers or polypropylene elastomers;
polyurethane-based elastomers such as polyurethane elastomers;
thermoplastic elastomers such as vinyl chloride-based elastomers,
polyester-based elastomers, or nylon-based elastomers; and rayon,
Cupra (registered trademark), Tencel (registered trademark),
polynosic, acetate, and triacetate. These resins may be in
combination of two or more kinds.
[0072] Regarding the hydrophilic compound in the
antimicrobial/antiviral composition when used for the
antimicrobial/antiviral resin member of this embodiment, a liquid
hydrophilic compound may be used. In this case, foaming, etc., may
occur. Thus, it is preferable to use a solid hydrophilic
compound.
[0073] Further, the antimicrobial/antiviral resin member of this
embodiment may contain the above-stated antimicrobial/antiviral
composition. As long as the purpose of the invention of the present
application can be achieved, an additional ingredient(s) may be
included and the shape thereof is also not limited.
[0074] For instance, the antimicrobial/antiviral resin member of
this embodiment may be a molded product and may be shaped like a
sheet, a film, fiber, a cloth, a mesh (net structure), a honeycomb,
a nonwoven fabric, or the like. When the antimicrobial/antiviral
resin member is fibrous, nano-fiber (fiber with an average fiber
diameter of 5 nm or larger and less than 1 .mu.m) may be allowed.
Note that the average fiber diameter refers to the average of the
fiber diameters of plural nano-fibers. The fiber diameter of
nano-fiber may be measured, using a microscope, by examining a
nano-fiber image. Specifically, multiple nano-fibers are observed
with an electron microscope, etc., and some of the nano-fibers are
selected at random in the resulting observed image. Then, image
processing software is used to measure the fiber diameter of each
nano-fiber and the average of the respective fiber diameters can be
calculated.
[0075] Next, an example of a method of producing the
antimicrobial/antiviral resin member of this embodiment is
specifically described.
[0076] A first master batch pellet (first mixture), which is a
resin pellet containing the antimicrobial/antiviral agent, is
prepared and a second master batch pellet (second mixture), which
is obtained by mixing a hydrophilic compound and a base resin
pellet at a prescribed weight ratio, is prepared. Next, the first
master batch pellet and the second master batch pellet are melted
and kneaded. Then, the kneaded material is formed as a
predetermined shape to obtain an antimicrobial/antiviral resin
member of this embodiment. The first master batch pellet and the
second master batch pellet are separately prepared and are then
melted and kneaded. This makes it possible to avoid contact between
the antimicrobial/antiviral agent and the hydrophilic compound in
the antimicrobial/antiviral resin member.
[0077] For instance, the first master batch pellet is prepared as
follows. First, ground copper compound microparticles and a
dispersant are mixed. After the surface of each copper compound
microparticle is coated with the dispersant to produce an
antimicrobial/antiviral agent, this antimicrobial/antiviral agent
and a resin pellet are mixed. Then, a kneading extruder is used to
disperse the antimicrobial/antiviral agent in the resin pellet.
Alternatively, ground copper compound microparticles and a
dispersant are mixed with a resin pellet. Next, a kneading extruder
is used and the dispersant is so attracted to the surrounding of
the copper compound microparticles during kneading. As a result,
the copper compound microparticles are coated with the dispersant
to produce an antimicrobial/antiviral agent. This
antimicrobial/antiviral agent is also dispersed in the resin
pellet. After the kneaded material is cooled, a pelletizer is used
to finely cut the antimicrobial/antiviral agent-containing resin.
In this way, the first master batch pellet containing the
antimicrobial/antiviral agent is obtained. Note that the proportion
(concentration) of the antimicrobial/antiviral agent at the time of
manufacture of the first master batch pellet may be set by those
skilled in the art, if appropriate.
[0078] For instance, the second master batch pellet is prepared as
follows. First, a hydrophilic compound and a resin pellet are mixed
at a prescribed weight ratio to yield a mixture. Here, as the resin
pellet, the same material as the resin pellet used during
manufacture of the first master batch pellet is used. The resulting
mixture is melted and kneaded to yield the second master batch
pellet.
[0079] A molding machine is used to mold a material obtained by
melting and kneading the first and second master batch pellets.
Then, it is possible to obtain an antimicrobial/antiviral resin
member in which the antimicrobial/antiviral agent and the
hydrophilic compound are dispersed in the base resin.
[0080] In addition, when manufactured as a molded product, the
antimicrobial/antiviral resin member according to this embodiment
can be molded by a process such as injection molding or blow
molding.
[0081] Note that examples of the antimicrobial/antiviral resin
member according to this embodiment include, in addition to the
molded product, a sheet-shaped, a film-shaped, a fiber-shaped, a
cloth-shaped, a meshed (net structure), a honeycomb-shaped, or a
nonwoven fabric-shaped form, etc. The antimicrobial/antiviral resin
member can be manufactured in various forms (e.g., a shape,
dimension) fit for their usage. When the antimicrobial/antiviral
resin member is manufactured like a sheet or film, a T-die process,
an inflation process, or the like may be used for the formation. In
addition, when the antimicrobial/antiviral resin member is
manufactured like fiber, melt spinning, etc., may be used for the
formation. Further, when the antimicrobial/antiviral resin member
is manufactured like a nonwoven fabric, it can be manufactured by
an existing manufacturing process such as spun-bonding.
[0082] In addition, the antimicrobial/antiviral resin member
according to this embodiment may contain, as an additive(s), for
instance, a plasticizer, a desiccant, a curing agent, an
antiskinning agent, a leveling agent, an anti-sagging agent, an
antifungal, a UV absorber, a heat ray absorber, a lubricant, a
surfactant, a thickener, a viscosity modifier, a stabilizer, and/or
a drying modifier. These additives may be used singly or may be
used in combination of two or more kinds. Further, other antiviral
composition, antimicrobial composition, antifungal composition,
anti-allergen composition, catalyst, antireflection material,
and/or material having heat shield characteristics may be added and
used.
[0083] The antimicrobial/antiviral resin member of this embodiment
is applicable to: fibers; agricultural materials such as house
films, tunnel house films; moldings such as trays used in plant
factories; panels; construction decorative materials; interior
materials; writing instruments; handrails; straps; phones; toys;
door handles; stationery such as clear folders or label tapes;
sheets; shrinking materials that are contracted when heated;
construction decorative materials (e.g., chairs, sofas, exterior
wall materials, sashes, doors, window shades, ceiling plates, floor
plates, windows); interior materials (e.g., wallpapers, carpets,
resin tiles); interior materials for trains or vehicles; clothing;
innerwear; socks; gloves; shoe covers; footwear such as shoes;
bedding materials (e.g., pajamas, mats, sheets, pillows,
pillowcases, blankets, towelkets, futons, futon covers); caps;
handkerchiefs; towels; rugs; curtains; filters for air cleaners,
air conditioners, ventilators, vacuum cleaners, fans, or the like;
various water surface-contacting members (e.g., fishing nets such
as fish preserve or fixed nets; filters for water treatment;
filters for drinking water; filters for ballast water treatment;
in-pipe lining materials; film-shaped members attached, using a
bonding agent or adhesive, to surfaces of seashore structures;
members bonded, like sheets, to surfaces of ships such as fishing
boats or tankers; sheet-shaped members on the inner walls of water
intake ports of power plants; pre-filters for water intake ports;
inner surfaces of water intake ports; plate coolers; drain pipes;
water supply pipes); or fiber structure products (e.g., insect
screens, screen printing meshes). Thus, the antimicrobial/antiviral
resin member according to this embodiment is a useful member that
makes it possible to provide a variety of excellent products in
various field.
[0084] An example of a method of producing fiber as the
antimicrobial/antiviral resin member will be specifically
described.
[0085] A first master batch pellet, which is a resin pellet
containing the antimicrobial/antiviral agent, is prepared and a
second master batch pellet, which is obtained by mixing a
hydrophilic compound and a resin pellet at a prescribed weight
ratio, is prepared. Next, the first master batch pellet and the
second master batch pellet are mixed, melted, and kneaded to
produce a spinning raw material. Then, the resulting spinning raw
material may be subjected to a melt spinning step to obtain fiber
in this embodiment. The melt spinning process is not limited to a
specific process and a known process may be used. The spinning
temperature may be optionally selected from a temperature range fit
for fiber material if the range is set such that discharge from a
spinneret is possible while the resin viscosity is appropriately
low, neither resin deterioration nor thermal decomposition occurs,
the spinning step is not markedly unstabilized, and fiber with high
strength can be obtained by subsequent stretching processing.
[0086] In the melt spinning step, spinning raw material is
discharged from a spinneret; the discharged fibrous spinning raw
material is cooled and solidified to yield fiber. Specifically, the
discharged spinning raw material is cooled to a solidification
temperature or lower and solidified in a medium such as the air,
water, or glycerol. In the case of water-cooling-type cooling,
while heated to about 60.degree. C. and then gradually cooled,
fiber does not move at the time of injection into a water tank and
can then pass through the water tank. Thus, stability during the
cooling is excellent. In the case of air-cooling, the air
temperature and the wind speed may be arbitrarily set. However, to
suppress the molecular orientation, it is desirable that the wind
speed should be low and the temperature is not too low. If the
degree of molecular orientation at the cooling time point is high,
fiber is not readily stretched when a heating/stretching step is
carried out as the next step. Consequently, the
antimicrobial/antiviral effect may be unlikely to be obtained.
[0087] Then, the solidified fiber is wound. The winding rate may be
set to a given rate. In this regard, however, when the winding rate
is lower than the free-fall rate of molten unstretched yarn,
uniform unstretched yarn is not necessarily obtained, leading to a
decrease in stretchability. Note that when a heating/stretching
step is carried out as the next step, the solidified yarn is not
necessarily wound and may be subjected, as it is, to the
heating/stretching step.
[0088] Next, the heating/stretching step is described. The
heating/stretching step is a step of heating and stretching fiber
(unstretched yarn) wound in the spinning step. The
heating/stretching step may include multiple stretching steps. When
the heating/stretching step includes multiple stretching steps, the
stretch factors in the respective stretching steps are multiplied
to give a total stretch factor. Note that when the
heating/stretching step includes a single stretching step, the
stretch factor in this single stretching step is a total stretch
factor.
[0089] The fiber in this embodiment may be heated and stretched to
express much better antimicrobial/antiviral performance and thus
can efficiently inactivate bacteria and/or viruses attached to the
fiber surface, etc. When the fiber is a monofilament, in
particular, the heating and stretching can cause the
antimicrobial/antiviral effect to increase. The mechanism of
markedly increasing the antimicrobial/antiviral effect by heating
and stretching is not necessarily clear at the moment. However, the
following rationale may be considered. A surface layer portion of
fiber in a molten state during the spinning step is directly cooled
and solidified once the cooling begins. Then, the
antimicrobial/antiviral agent, which is present in a portion (inner
layer portion) inside of the fiber relative to the surface layer
portion, is structured such that the agent is not readily in
contact with water content outside the fiber. In contrast, the
inner layer portion is cooled via the surface layer portion and
solidified. Accordingly, the cooling speed of the inner layer
portion is lower than the cooling speed of the surface layer
portion. This may cause the fiber structure of the surface layer
portion to be different from the fiber structure of the inner layer
portion. When heating and stretching are carried out under such a
state, the stretching is conducted under a heating condition at a
glass transition point or higher. This causes the fiber structure
of the surface layer portion to be a fiber structure in which the
antimicrobial/antiviral agent and water content outside the fiber
easily come into contact. On top of that, the heating and
stretching make the fiber structure of the surface layer portion
close to the fiber structure of the inner layer portion. This seems
to impart some effect on the surface charges and/or DNA of bacteria
and/or viruses, thereby inactivating them.
[0090] The stretching process is not particularly limited and a
known stretching process such as hot roll drawing, hot plate
drawing, tubular stretching, stretch-blowing, or laser stretching
may be optionally adopted. When hot roll drawing is used for the
heating and stretching, the rotational speeds of hot rolls, which
are combined in multiple stages, are changed. Accordingly,
unstretched yarn can be stretched at a high factor.
[0091] The stretch factor may be optionally selected depending on
the fineness of material to be stretched, and the total stretch
factor is set usually to 3.0 or higher and 7.0 or less and
preferably 4.0 or higher and 6.0 or less. When the stretch factor
is 3.0 or higher and 7.0 or less, the molecule is more oriented to
give stronger fiber. When the stretch factor is less than 3.0, the
antimicrobial/antiviral effect is lower than that in the case of
the stretch factor of 3.0 or higher and the resulting fiber
strength is lowered. In addition, when the stretch factor exceeds
7.0, the stretching tension becomes extremely high. This may
frequently cause yarn rapture, leading to a decrease in yarn
productivity.
[0092] Not that the fiber in the antimicrobial/antiviral resin
member according to this embodiment may have a core-sheath
structure. In this case, the core, for instance, may be formed
using a regular resin (antimicrobial/antiviral agent-free resin)
and the sheath may be formed using a resin containing the
antimicrobial/antiviral agent and/or a hydrophilic compound. This
not only can improve the fiber strength, but also provides an
advantage such that the content of the antimicrobial/antiviral
agent may be decreased. A resin for the core and a resin for the
sheath may be the same or different resins.
[0093] The shape of cross-section perpendicular to the longitudinal
direction of the fiber in the core-sheath structure is not
particularly limited, and the cross-sectional shape is preferably
circular and the core and the sheath are preferably shaped like
concentric circles. The ratio of the area of the core to the area
of the sheath in the cross-section perpendicular to the
longitudinal direction of the fiber is not particularly limited and
may be set by a user, if appropriate.
[0094] In addition, the fiber in the antimicrobial/antiviral resin
member according to this embodiment may contain, as an additive(s),
for instance, a plasticizer, a desiccant, a curing agent, an
antiskinning agent, a leveling agent, an anti-sagging agent, an
antifungal, a UV absorber, a heat ray absorber, a lubricant, a
surfactant, a thickener, a viscosity modifier, a stabilizer, and/or
a drying modifier. These additives may be used singly or may be
used in combination of two or more kinds. Further, other antiviral
composition, antimicrobial composition, antifungal composition,
anti-allergen composition, catalyst, antireflection material,
and/or material having heat shield characteristics may be added and
used.
[0095] The fiber in the antimicrobial/antiviral resin member
according to this embodiment may be used for woven fabrics, knitted
fabrics, nonwoven fabrics, paper materials such as mixed papers,
and so on. Then, this fiber can be used for various products
including: sheet-shaped products (e.g., clothing, bedding, bedding
materials, masks, handkerchiefs, towels, rugs, curtains, exterior
wall materials, construction decorative materials, interior
materials); filters for air cleaners, air conditioners,
ventilators, vacuum cleaners, fans, air-conditioning, or vehicles;
fishing nets such as fish preserve or fixed nets; filters for water
treatment; filters for drinking water; filters for ballast water
treatment; protective clothing; protection nets; insect screens; or
henhouse nets. The fiber in this embodiment is therefore a useful
material that makes it possible to provide a variety of excellent
products in various fields.
[0096] Hereinafter, the invention is specifically described by
referring to Examples. However, the invention is not restricted to
just these Examples.
Examples 1 to 3
[0097] First, 40.0 g of commercially available copper iodide (I)
powder (manufactured by Wako Pure Chemical Corporation), which is
monovalent copper compound microparticles, and 60.0 g of zirconium
oxide particles (manufactured by NIHON DENKO, Inc.), which are
inorganic compound microparticles, were pre-dispersed in 900.0 g of
methanol. Next, the mixture was crushed and dispersed with a bead
mill to prepare a slurry of copper iodide particles coated with
zirconium oxide having an average particle size of 140 nm. Note
that the average particle size herein refers to a volume-average
particle size.
[0098] Then, polyvinylpyrrolidone (PVP) and an olefin-based resin
were provided and mixed in a toluene solvent. After the mixture was
dispersed using a ball mill, the above-described copper iodide
particles coated with zirconium oxide were added and further
dispersed to produce an antimicrobial/antiviral coating. In
Examples 1 to 3, the mass % of each raw material included in the
antimicrobial/antiviral coating is as designated in the following
Table 1.
[0099] Each resulting antimicrobial/antiviral coating was applied
onto a polypropylene sheet (with a thickness of 200 .mu.m) by using
a bar coater (#20) and then dried to obtain a sheet painted with
the antimicrobial/antiviral coating. At that time, the thickness of
the coating film was 2 .mu.m.
Example 4
[0100] A sheet painted with an antimicrobial/antiviral coating was
obtained under the same conditions as for Example 1 except that
polyethylene glycol (PEG) was used instead of polyvinylpyrrolidone.
The mass % of each raw material included in the
antimicrobial/antiviral coating was as designated in the following
Table 1.
Example 5
[0101] A sheet painted with an antimicrobial/antiviral coating was
obtained under the same conditions as for Example 1 except that a
urethane-based resin was used instead of the olefin-based resin.
The mass % of each raw material included in the
antimicrobial/antiviral coating was as designated in the following
Table 1.
Example 6
[0102] A sheet painted with an antimicrobial/antiviral coating was
obtained under the same conditions as for Example 5 except that
polyethylene glycol was used instead of polyvinylpyrrolidone. The
mass % of each raw material included in the antimicrobial/antiviral
coating was as designated in the following Table 1.
Example 7
[0103] A sheet painted with an antimicrobial/antiviral coating was
obtained under the same conditions as for Example 1 except that an
acryl-based resin was used instead of the olefin-based resin. The
mass % of each raw material included in the antimicrobial/antiviral
coating was as designated in the following Table 1.
Example 8
[0104] First, 40.0 g of commercially available cuprous oxide powder
(manufactured by Wako Pure Chemical Corporation), which is
monovalent copper compound microparticles, and 60.0 g of zirconium
oxide particles (manufactured by NIHON DENKO, Inc.), which are
inorganic compound microparticles, were pre-dispersed in 900.0 g of
methanol. Next, the mixture was crushed and dispersed with a bead
mill to prepare a slurry of cuprous oxide particles coated with
zirconium oxide having an average particle size of 140 nm. Note
that the average particle size herein refers to a volume-average
particle size.
[0105] Then, polyvinylpyrrolidone and an olefin-based resin were
provided and mixed in a toluene solvent. After the mixture was
dispersed using a ball mill, the above-described cuprous oxide
particles coated with zirconium oxide were added and further
dispersed to produce an antimicrobial/antiviral coating. The mass %
of each raw material included in the antimicrobial/antiviral
coating was as designated in the following Table 1.
[0106] The resulting antimicrobial/antiviral coating was applied
onto a polypropylene sheet (with a thickness of 200 .mu.m) by using
a bar coater (#20) and then dried to obtain a sheet painted with
the antimicrobial/antiviral coating. At that time, the thickness of
the coating film was 2 .mu.m.
Example 9
[0107] A sheet painted with an antimicrobial/antiviral coating was
obtained under the same conditions as for Example 8 except that a
urethane-based resin was used instead of the olefin-based resin.
The mass % of each raw material included in the
antimicrobial/antiviral coating was as designated in the following
Table 1.
Example 10
[0108] A sheet painted with an antimicrobial/antiviral coating was
obtained under the same conditions as for Example 8 except that an
acryl-based resin was used instead of the olefin-based resin and
polyethylene glycol was used instead of polyvinylpyrrolidone. The
mass % of each raw material included in the antimicrobial/antiviral
coating was as designated in the following Table 1.
Comparative Example 1
[0109] A just olefin-based resin was a material, mixed in a toluene
solvent, and dispersed with a ball mill to produce a coating. The
mass % of the olefin-based resin is 100 mass % as designated in the
following Table 2.
[0110] The resulting coating was applied onto a polypropylene sheet
(with a thickness of 200 .mu.m) by using a bar coater (#20) and
then dried to obtain a sheet painted with the coating. At that
time, the thickness of the coating film was 2 .mu.m.
Comparative Example 2
[0111] A sheet painted with a coating was obtained under the same
conditions as for Example 1 except that the mixing and dispersion
were carried out while copper iodide particles coated with
zirconium oxide were not included. The mass % of each raw material
included in this coating was as designated in the following Table
2.
Comparative Example 3
[0112] A sheet painted with a coating was obtained under the same
conditions as for Example 1 except that the mixing and dispersion
were carried out while polyvinylpyrrolidone was not included. The
mass % of each raw material included in this coating was as
designated in the following Table 2.
Comparative Example 4
[0113] A sheet painted with a coating was obtained under the same
conditions as for Example 5 except that the mixing and dispersion
were carried out while copper iodide particles coated with
zirconium oxide were not included. The mass % of each raw material
included in this coating was as designated in the following Table
2.
Comparative Example 5
[0114] A sheet painted with a coating was obtained under the same
conditions as for Example 5 except that the mixing and dispersion
were carried out while polyvinylpyrrolidone was not included. The
mass % of each raw material included in this coating was as
designated in the following Table 2.
Comparative Example 6
[0115] A sheet painted with a coating was obtained under the same
conditions as for Example 10 except that the mixing and dispersion
were carried out while cuprous oxide coated with zirconium oxide
were not included. The mass % of each raw material included in this
coating was as designated in the following Table 2.
Comparative Example 7
[0116] A sheet painted with a coating was obtained under the same
conditions as for Example 10 except that the mixing and dispersion
were carried out while polyethylene glycol was not included. The
mass % of each raw material included in this coating was as
designated in the following Table 2.
[0117] Here, the following Tables 1 and 2 list the respective
components of the antimicrobial/antiviral coatings of Examples 1 to
10 and Comparative Examples 1 to 7 described.
TABLE-US-00001 TABLE 1 Hydrophilic Resin Compound Monovalent Copper
Compound Kind Mass % Kind Mass % Kind Mass % Example 1 Olefin 98
PVP 1 Copper Iodide* 1 Example 2 Olefin 96 PVP 1 Copper Iodide* 3
Example 3 Olefin 89 PVP 10 Copper Iodide* 1 Example 4 Olefin 90 PEG
5 Copper Iodide* 5 Example 5 Urethane 94 PVP 3 Copper Iodide* 3
Example 6 Urethane 92 PEG 5 Copper Iodide* 3 Example 7 Acrylic 92
PVP 5 Copper Iodide* 3 Example 8 Olefin 92 PVP 5 Cuprous Oxide* 3
Example 9 Urethane 92 PVP 3 Cuprous Oxide* 5 Example 10 Acrylic 85
PEG 5 Cuprous Oxide* 10 *Dispersant in Examples 1 to 10: Zirconium
Oxide
TABLE-US-00002 TABLE 2 Hydrophilic Monovalent Copper Resin Compound
Compound Kind Mass % Kind Mass % Kind Mass % Comparative Olefin 100
-- -- -- -- Example 1 Comparative Olefin 90 PVP 10 -- -- Example 2
Comparative Olefin 95 -- -- Copper 5 Example 3 Iodide* Comparative
Urethane 95 PVP 5 -- -- Example 4 Comparative Urethane 95 -- --
Copper 5 Example 5 Iodide* Comparative Acrylic 95 PEG 5 -- --
Example 6 Comparative Acrylic 90 -- -- Cuprous 10 Example 7 Oxide*
*Dispersant in Examples 3, 5, and 7: Zirconium Oxide
[0118] (Antiviral Performance Evaluation Protocol)
[0119] When virus inactivation performance of each sheet painted
with an antimicrobial/antiviral coating was measured, influenza
virus (influenza A/Kitakyushu/159/93(H3N2)) cultured using MDCK
cells was used.
[0120] Each sheet (50 mm.times.50 mm) painted with the
antimicrobial/antiviral coating of each one of Examples 1 to 10 and
Comparative Examples 1 to 7 was placed on a plastic dish. Next, 100
.mu.L of virus liquid diluted with PBS was added dropwise thereto
and reacted at 25.degree. C. for 15 min. At that time, an upper
surface of the sheet test product was covered with a PET film (40
mm.times.40 mm) such that the area of contact between the virus
liquid and the sheet test product was made constant. Then, testing
was conducted. After 10-min reaction, 900 .mu.L of SCDLP broth was
added so as to stop the reaction. Then, the virus was purged by
pipetting. Subsequently, MEM diluent was used to dilute each
post-reaction virus liquid to from 10.sup.-1 to 10.sup.-5 (10-fold
serial dilution) to prepare sample solutions. Then, 100 .mu.L of
each sample solution was seeded onto MDCK cells cultured on a dish.
The cells seeded with the sample solution were allowed to stand for
60 min in an incubator at 34.degree. C. and 5% CO.sub.2. After the
virus was adsorbed on the cells, 0.7% agar broth was overlaid and
the virus was cultured for 48 h in the incubator at 34.degree. C.
and 5% CO.sub.2. After the culturing, formalin fixation and
methylene blue staining were conducted and the number of plaques
formed was counted to calculate a viral infectivity titer (PFU/0.1
mL, Log 10) (PFU: plaque-forming units).
[0121] (Antimicrobial Performance Evaluation Protocol)
When antimicrobial performance of each sheet painted with an
antimicrobial/antiviral coating was measured, E. coli cultured in
NB broth was used.
[0122] Each sheet (50 mm.times.50 mm) painted with the
antimicrobial/antiviral coating of each one of Examples 1 to 10 and
Comparative Examples 1 to 7 was placed on a plastic dish. Next, 100
.mu.L of microbial cell liquid, which was diluted with 1/500 NB
broth until the cell count reached 2.5.times.10.sup.5 to
10.times.10.sup.6, was added dropwise thereto and reacted at
35.degree. C. for 10 min. At that time, an upper surface of the
sheet test product was covered with a PET film (40 mm.times.40 mm)
such that the area of contact between the microbial cell liquid and
the sheet test product was made constant. Then, testing was
conducted. After 15-min reaction, 4 mL of SCDLP broth was added so
as to stop the reaction. Then, the microbial cells were purged by
pipetting. Subsequently, SCDLP broth was used to dilute each
post-reaction microbial cell liquid to from 10.sup.-1 to 10.sup.-5
(10-fold serial dilution) to prepare sample solutions. Then, 1 mL
of each sample solution was pipetted onto a dish and 1.5% agar
broth was added and mixed therewith. The inverted dish was placed
in an incubator at 37.degree. C. and the microbial cells were
cultured for 24 to 48 h. After that, the number of colonies was
counted to calculate the viable cell count of the microbial cells
(CFU/0.1 mL, Log 10) (CFU: colony-forming units).
[0123] (Procedure for Measuring Surface Free Energy)
Each sheet painted with the antimicrobial/antiviral coating of each
one of Examples 1 to 10 and Comparative Examples 1 to 7 was used to
measure the contact angle of each measurement liquid (water or
diiodomethane was used) by using a contact angle meter (a
solid/liquid interface analyzer DropMaster300, manufactured by
Kyowa Interface Science, Inc.). Each measurement result was used to
calculate a polar component .gamma.sp and a non-polar component
.gamma.sd by using the above Formula (3) and to calculate the
surface free energy .gamma.s of each coating film by using the
above Formula (1). In addition, the above Formula (2) was used to
calculate a polar contribution R.gamma.p.
[0124] Here, Tables 3 and 4 collectively provide the respective
measurement results of the sheets painted with the
antimicrobial/antiviral coatings of Examples 1 to 10 and
Comparative Examples 1 to 7 described.
TABLE-US-00003 TABLE 3 Antiviral Antimicrobial Performance
Performance Infectivity Viable Cell Surface Free Polar Titer Count
Energy Contribution PFU/0.1 mL, CFU/0.1 mL, .gamma.s R.gamma.p
Log10 Log10 [mJ/m.sup.2] [%] Example 1 2.1 1.7 39.5 9.6 Example 2
1.6 1.2 39.0 8.9 Example 3 <1.3 <1.0 39.9 17.6 Example 4
<1.3 <1.0 39.6 12.5 Example 5 <1.3 <1.0 40.4 25.7
Example 6 <1.3 <1.0 40.0 24.5 Example 7 <1.3 <1.0 40.2
26.1 Example 8 2.5 2.4 38.7 17.0 Example 9 2.6 2.8 40.4 24.0
Example 10 <1.3 <1.0 39.4 24.6 Control 5.8 5.6 -- --
TABLE-US-00004 TABLE 4 Antiviral Antimicrobial Performance
Performance Infectivity Viable Cell Surface Free Polar Titer Count
Energy Contribution PFU/0.1 mL, CFU/0.1 mL, .gamma.s R.gamma.p
Log10 Log10 [mJ/m.sup.2] [%] Comparative 5.8 5.7 38.6 5.7 Example 1
Comparative 5.7 5.4 38.8 17.4 Example 2 Comparative 4.4 4.1 38.8
6.0 Example 3 Comparative 5.7 5.7 40.5 26.0 Example 4 Comparative
4.1 4.6 39.2 20.7 Example 5 Comparative 4.3 4.7 40.0 24.3 Example 6
Comparative 4.9 4.1 39.1 22.6 Example 7 Control 5.8 5.6 -- --
[0125] The above results demonstrated potent
antimicrobial/antiviral performance regardless of short sensitized
time of 10 min in all the Examples 1 to 10. However, in Comparative
Examples 1 to 7, the antimicrobial/antiviral performance was not
found. In view of the above, when an antimicrobial/antiviral
coating of the invention is used, the antimicrobial/antiviral
effects can be easily imparted to various products.
Example 11
[0126] The coating prepared using the procedure in Example 3 was
that in Example 11.
Comparative Example 8
[0127] The coating in Comparative Example 8 was a coating adjusted
using the same procedure as in Example 3 except that zirconium
oxide particles (manufactured by NIHON DENKO, Inc.), which are
inorganic compound microparticles, were not used, that is, copper
iodide particles not coated with zirconium oxide particles were
used.
[0128] (Storage Stability Assessment)
[0129] An accelerated test was carried out such that the samples of
Example 11 and Comparative Example 8 were left for 3 months under
conditions at a temperature of 50.degree. C. and a humidity of 90%.
Then, a color change (color difference .DELTA.E) between before and
after the test was determined with a color-difference meter. Table
5 shows the results.
TABLE-US-00005 TABLE 5 Color Difference (.DELTA.E) Example 11 0.8
Comparative Example 8 5.3
[0130] The results of Table 5 demonstrated that the coating of
Comparative Example 8, in which copper iodide not coated with
zirconium oxide was used, had a larger color change than that of
Example 11, in which copper iodide coated with zirconium oxide was
used. It is postulated that a change from a monovalent copper
compound to a divalent copper compound was suppressed by coating
the surface of copper iodide with zirconium oxide.
[0131] (Antimicrobial/Antiviral Performance Evaluation
Protocol)
[0132] Each coating of Example 11 or Comparative Example 8 was
applied onto a polypropylene sheet and dried in the same procedure
as in Example 3. The antimicrobial/antiviral performance of each
resulting sheet was evaluated by the above-described evaluation
protocol. The results are shown in Table 6.
TABLE-US-00006 TABLE 6 Antiviral Performance Antimicrobial
Performance Infectivity Titer Viable Cell Count PFU/0.1 mL, Log10
CFU/0.1 mL, Log10 Example 11 <1.3 <1.0 Comparative 3.4 4.1
Example 8 Control 5.8 5.6
[0133] The results of Table 6 indicate that Comparative Example 8,
in which the color change was large, exhibited low effectiveness in
both antiviral performance and antimicrobial performance; by
contrast, Example 11, in which the color change was small,
maintained both antiviral performance and antimicrobial
performance.
To Produce Injection-Molded Member as Antimicrobial/Antiviral Resin
Member
Example 12
[0134] A dry grinder Nano Jetmizer NJ-100B (manufactured by Aishin
Nano Technologies CO., LTD.) was used to grind commercially
available copper (I) iodide powder (manufactured by NIHON KAGAKU
SANGYO CO., LTD.) to an average particle size of 150 nm to yield
copper iodide particles. The resulting copper iodide particles and
a metal soap, which is a dispersant to prevent aggregation of the
copper iodide particles, were mixed.
[0135] A polyethylene (PE) resin pellet (manufactured by Asahi
Kasei Chemicals Corporation), as a base resin, was added, such that
the content of the copper iodide particles mixed with the
dispersant was 40 mass % with respect to the whole master batch
pellet, to prepare a mixture. The resulting mixture was fed to a
twin-screw melt kneader to obtain a first master batch pellet.
[0136] A polyethylene resin pellet (manufactured by Asahi Kasei
Chemicals Corporation), as a base resin, was added, such that the
content of polyethylene glycol (with a molecular weight of 20,000)
was 20 mass % with respect to the whole master batch pellet, to
prepare a mixture. The resulting mixture was fed to a twin-screw
melt kneader to obtain a second master batch pellet.
[0137] A polyethylene resin pellet, the first master batch pellet,
and the second master batch pellet were mixed so as to have 5 mass
% of copper iodide and 3 mass % of polyethylene glycol (with a
molecular weight of 20,000) with respect to the whole
injection-molded member. An injection molding machine was used to
perform injection molding, and an injection-molded member, as an
antimicrobial/antiviral resin member, was then obtained.
Example 13
[0138] A polypropylene (PP) resin pellet as a base resin was added,
such that the content of the copper iodide particles mixed with the
dispersant (metal soap) was 40 mass % with respect to the whole
master batch pellet, to prepare a mixture. The resulting mixture
was fed to a twin-screw melt kneader to obtain a master batch
pellet.
[0139] An injection-molded member as an antimicrobial/antiviral
resin member was obtained under the same conditions as for Example
12 except that the polypropylene (PP) resin pellet, the master
batch pellet, and polyethylene glycol were mixed so as to have 5
mass % of copper iodide and 5 mass % of polyethylene glycol with
respect to the whole injection-molded member.
Example 14
[0140] An injection-molded member as an antimicrobial/antiviral
resin member was obtained under the same conditions as for Example
13 except that polyvinylpyrrolidone (with a molecular weight of
10,000) was used instead of polyethylene glycol used in Example
13.
Example 15
[0141] An ABS resin pellet as a base resin was added, such that the
content of copper iodide particles ground with the dispersant was
30 mass % with respect to the whole master batch pellet, to prepare
a mixture. The resulting mixture was fed to a twin-screw melt
kneader to obtain a master batch pellet.
[0142] The ABS resin pellet, the master batch pellet, and
polyvinylpyrrolidone were mixed so as to have 5 mass % of copper
iodide and 3 mass % of polyvinylpyrrolidone (with a molecular
weight of 10,000) with respect to the whole injection-molded
member. An injection molding machine was used to perform injection
molding, and an injection-molded member, as an
antimicrobial/antiviral resin member, was then obtained.
Example 16
[0143] An injection-molded member as an antimicrobial/antiviral
resin member was obtained under the same conditions as for Example
15 except that the ABS resin pellet, the master batch pellet, and
polyvinylpyrrolidone were mixed so as to have 5 mass % of copper
iodide and 5 mass % of polyvinylpyrrolidone (with a molecular
weight of 10,000) with respect to the whole injection-molded
member.
Example 17
[0144] The surface of polypropylene (PP) resin pellet was coated,
using a Henschel mixer (registered trademark), with a slurry (40
mass %) of copper iodide particles coated with zirconium oxide
having an average particle size of 140 nm as used in Example 1.
Next, the coated polypropylene resin pellet was fed to a twin-screw
melt kneader to yield a first master batch pellet.
[0145] A polypropylene (PP) resin was added, such that the content
of polyethylene glycol (with a molecular weight of 20,000) was 20
mass % with respect to the whole master batch pellet, to prepare a
mixture. The resulting mixture was fed to a twin-screw melt kneader
to obtain a second master batch pellet.
[0146] A polypropylene (PP) resin pellet, the first master batch
pellet, and the second master batch pellet were mixed so as to have
5 mass % of copper iodide and 5 mass % of polyethylene glycol (with
a molecular weight of 20,000) with respect to the whole
injection-molded member. An injection molding machine was used to
perform injection molding, and an injection-molded member as an
antimicrobial/antiviral resin member was then obtained.
Comparative Example 9
[0147] A just polypropylene resin pellet was a material and an
injection molding machine was used to obtain an injection-molded
member.
Comparative Example 10
[0148] An injection-molded member was obtained under the same
conditions as for Example 13 except that the polypropylene resin
pellet and the master batch pellet were mixed such that
polyethylene glycol was not include and the content of copper
iodide was 5 mass % with respect to the whole injection-molded
member.
Comparative Example 11
[0149] An injection-molded member was obtained under the same
conditions as for Example 13 except that the polypropylene resin
pellet and polyethylene glycol were mixed such that copper iodide
and the dispersant (metal soap) were not included and the content
of polyethylene glycol was 10 mass % with respect to the whole
injection-molded member.
Comparative Example 12
[0150] A just ABS resin pellet was a material and an injection
molding machine was used to obtain an injection-molded member.
Comparative Example 13
[0151] An injection-molded member was obtained under the same
conditions as for Example 15 except that the ABS resin pellet and
the master batch pellet were mixed such that polyvinylpyrrolidone
was not include and the content of copper iodide was 5 mass % with
respect to the whole injection-molded member.
Comparative Example 14
[0152] An injection-molded member was obtained under the same
conditions as for Example 15 except that the ABS resin pellet and
polyvinylpyrrolidone were mixed such that copper iodide and the
dispersant (metal soap) were not include and the content of
polyvinylpyrrolidone was 10 mass % with respect to the whole
injection-molded member.
[0153] The following Table 7 lists the components of the
injection-molded members of Examples 12 to 17 and Comparative
Examples 9 to 14 described.
TABLE-US-00007 TABLE 7 Monovalent Copper Compound Hydrophilic
Compound Resin Kind Mass % Kind Mass % Example 12 PE Copper 5
Polyethylene Glycol 3 Iodide* Example 13 PP Copper 5 Polyethylene
Glycol 5 Iodide* Example 14 PP Copper 5 Polyvinylpyrrolidone 5
Iodide* Example 15 ABS Copper 5 Polyvinylpyrrolidone 3 Iodide*
Example 16 ABS Copper 5 Polyvinylpyrrolidone 5 Iodide* Example 17
PP Copper 5 Polyethylene Glycol 5 Iodide* Comparative PP -- -- --
-- Example 9 Comparative PP Copper 5 -- -- Example 10 Iodide*
Comparative PP -- -- Polyethylene Glycol 10 Example 11 Comparative
ABS -- -- -- -- Example 12 Comparative ABS Copper 5 -- -- Example
13 Iodide* Comparative ABS -- -- Polyvinylpyrrolidone 10 Example 14
*Dispersant in Examples 12 to 16 and Comparative Examples 10 and
13: Metal Soap *Dispersant in Example 17: Zirconium Oxide
To Produce Sheet-Shaped Member as Antimicrobial/Antiviral Resin
Member
Example 18
[0154] By using a dry grinder Nano Jetmizer (NJ-100B, manufactured
by Aishin Nano Technologies CO., LTD.), commercially available
copper (I) iodide powder (manufactured by NIHON KAGAKU SANGYO CO.,
LTD.) was ground to an average particle size of 150 nm to obtain
copper iodide particles. The resulting copper iodide particles and
a metal soap, which is a dispersant to prevent aggregation of the
copper iodide particles, were mixed.
[0155] A polyethylene resin pellet (manufactured by Asahi Kasei
Chemicals Corporation) as a base resin was added, such that the
content of the resulting copper iodide particles was 40 mass % with
respect to the whole master batch pellet, to prepare a mixture. The
resulting mixture was fed to a twin-screw melt kneader to obtain a
master batch pellet.
[0156] A polyethylene resin pellet, the master batch pellet, and
polyethylene glycol were mixed so as to have 5 mass % of copper
iodide and 1 mass % of polyethylene glycol (with a molecular weight
of 20,000) with respect to the whole sheet-shaped member. A T-die
extruder was used to obtain a sheet-shaped member as an
antimicrobial/antiviral resin member with a thickness of 100
.mu.m.
Example 19
[0157] A sheet-shaped member as an antimicrobial/antiviral resin
member was obtained under the same conditions as for Example 18
except that the polyethylene resin pellet, the master batch pellet,
and polyethylene glycol were mixed so as to have 5 mass % of copper
iodide and 5 mass % of polyethylene glycol with respect to the
whole sheet-shaped member.
Example 20
[0158] A polypropylene resin pellet, as a base resin, was added,
such that the content of copper iodide particles was 40 mass % with
respect to the whole master batch pellet, to prepare a mixture. The
resulting mixture was fed to a twin-screw melt kneader to obtain a
master batch pellet. An antimicrobial/antiviral sheet-shaped member
was obtained under the same conditions as for Example 18 except
that the polypropylene resin pellet, the master batch pellet, and
polyethylene glycol were mixed so as to have 5 mass % of copper
iodide and 5 mass % of polyethylene glycol with respect to the
whole sheet-shaped member.
Comparative Example 15
[0159] A just polyethylene resin pellet was a material and a T-die
extruder was used to obtain a sheet-shaped member with a thickness
of 100 .mu.m.
Comparative Example 16
[0160] A sheet-shaped member was obtained under the same conditions
as for Example 18 except that the polyethylene resin pellet and the
master batch pellet were mixed such that polyethylene glycol was
not include and the content of copper iodide was 5 mass % with
respect to the whole sheet-shaped member.
Comparative Example 17
[0161] A sheet-shaped member was obtained under the same conditions
as for Example 18 except that the polyethylene resin pellet and
polyethylene glycol were mixed such that copper iodide and the
dispersant (metal soap) were not included and the content of
polyethylene glycol was 5 mass % with respect to the whole
sheet-shaped member.
Comparative Example 18
[0162] A sheet-shaped member was obtained under the same conditions
as for Example 18 except that the polyethylene resin pellet and
polyvinylpyrrolidone were mixed such that copper iodide and the
dispersant (metal soap) were not included and the content of
polyvinylpyrrolidone instead of polyethylene glycol was 5 mass %
with respect to the whole sheet-shaped member.
[0163] The following Table 8 lists the components of the
sheet-shaped members of Examples 18 to 20 and Comparative Examples
15 to 18 described.
TABLE-US-00008 TABLE 8 Monovalent Copper Compound Hydrophilic
Compound Resin Kind Mass % Kind Mass % Example 18 PE Copper 5
Polyethylene Glycol 1 Iodide* Example 19 PE Copper 5 Polyethylene
Glycol 5 Iodide* Example 20 PP Copper 5 Polyethylene Glycol 5
Iodide* Comparative PE -- -- -- -- Example 15 Comparative PE Copper
5 -- -- Example 16 Iodide* Comparative PE -- -- Polyethylene Glycol
5 Example 17 Comparative PE -- -- Polyvinylpyrrolidone 5 Example 18
*Dispersant in Examples 18 to 20 and Comparative Example 16: Metal
Soap
[0164] (Antiviral Performance Evaluation Protocol)
[0165] When virus inactivation performance of an injection-molded
member or a sheet-shaped member was measured, influenza virus
(influenza A/Kitakyushu/159/93(H3N2)) cultured using MDCK cells was
used as an enveloped virus. As a non-enveloped virus, feline
calicivirus, which has been typically and frequently used as a
virus alternative for norovirus, was used.
[0166] (Injection-Molded Member and Sheet-Shaped Member)
[0167] Injection-molded members of Examples 12 to 17 and
Comparative Examples 9 to 14 or sheet-shaped members (50
mm.times.50 mm) of Examples 18 to 20 and Comparative Examples 15 to
18 were each placed on a plastic dish. Next, 100 .mu.L of virus
liquid diluted with PBS was added dropwise thereto and reacted at
25.degree. C. for 15 min. At that time, an upper surface of the
sheet test product was covered with a PET film (40 mm.times.40 mm)
such that the area of contact between the virus liquid and the
sheet test product was made constant. Then, testing was conducted.
After 15-min reaction, 900 .mu.L of SCDLP broth was added so as to
stop the reaction. Then, the virus was purged by pipetting.
Subsequently, MEM diluent was used to dilute each post-reaction
virus liquid to from 10.sup.-1 to 10.sup.-5 (10-fold serial
dilution) to prepare sample solutions. Then, 100 .mu.L of each
sample solution was seeded onto MDCK cells cultured on a dish. The
cells seeded with the sample solution were allowed to stand for 60
min in an incubator at 34.degree. C. and 5% CO.sub.2. After the
virus was adsorbed on the cells, 0.7% agar broth was overlaid and
the virus was cultured for 48 h in the incubator at 34.degree. C.
and 5% CO.sub.2. After the culturing, formalin fixation and
methylene blue staining were conducted and the number of plaques
formed was counted to calculate a viral infectivity titer (PFU/0.1
mL, Log 10) (PFU: plaque-forming units).
[0168] (Antimicrobial Performance Evaluation Protocol)
[0169] When antimicrobial performance of each injection-molded
member or each sheet-shaped member was measured, Staphylococcus
aureus cultured in NB broth was used as gram-positive bacteria. As
gram-negative bacteria, E. coli cultured in NB broth was used.
[0170] (Injection-Molded Member and Sheet-Shaped Member)
[0171] Injection-molded members of Examples 12 to 17 and
Comparative Examples 9 to 14 or sheet-shaped members (50
mm.times.50 mm) of Examples 18 to 20 and Comparative Examples 15 to
18 were each placed on a plastic dish. Next, 100 .mu.L of microbial
cell liquid, which was diluted with 1/500 NB broth until the
microbial cell count reached 2.5.times.10.sup.5 to
10.times.10.sup.6, was added dropwise thereto and reacted at
35.degree. C. for 60 min. At that time, an upper surface of the
sheet test product was covered with a PET film (40 mm.times.40 mm)
such that the area of contact between the microbial cell liquid and
the sheet test product was made constant. Then, testing was
conducted. After 60-min reaction, 4 mL of SCDLP broth was added so
as to stop the reaction. Then, the microbial cells were purged by
pipetting. Subsequently, SCDLP broth was used to dilute each
post-reaction microbial cell liquid to from 10.sup.-1 to 10.sup.-5
(10-fold serial dilution) to prepare sample solutions. Then, 1 mL
of each sample solution was pipetted onto a dish and 1.5% agar
broth was added and mixed therewith. The inverted dish was placed
in an incubator at 37.degree. C. and the microbial cells were
cultured for 24 to 48 h. After that, the number of colonies was
counted to calculate the viable cell count of the microbial cells
(CFU/0.1 mL, Log 10) (CFU: colony-forming units).
[0172] (Procedure for Measuring Surface Free Energy)
[0173] A contact angle meter (a solid/liquid interface analyzer
DropMaster300, manufactured by Kyowa Interface Science, Inc.) was
used to measure the contact angle of each measurement liquid (water
or diiodomethane was used) on a surface of each one of the
injection-molded members of Examples 12 to 17 and Comparative
Examples 9 to 14 or the sheet-shaped members of Examples 18 to 20
and Comparative Examples 15 to 18. These measurement results were
used to calculate a polar component .gamma.sp and a non-polar
component .gamma.sd by using the above Formula (3) and to calculate
the surface free energy .gamma.s of each injection-molded member or
each sheet-shaped member by using the above Formula (1). In
addition, the above Formula (2) was used to calculate a polar
contribution R.gamma.p.
[0174] Here, Table 9 collectively provides the measurement results
of the antimicrobial/antiviral resin members that are the
injection-molded members of Examples 12 to 17 and Comparative
Examples 9 to 14 described.
TABLE-US-00009 TABLE 9 Antiviral Antimicrobial Performance
Performance Surface Polar Infectivity Viable Cell Free Contri-
Titer Count Energy bution 15-min 60-min .gamma.s R.gamma.p Resin
sensitized sensitized [mJ/m.sup.2] [%] Example 12 PE 1.8 1.8 34.7
9.6 Example 13 PP <1.3 1.2 34.5 13.6 Example 14 PP <1.3
<1.0 34.9 14.6 Example 15 ABS 2.2 1.6 34.8 7.8 Example 16 ABS
<1.3 <1.0 34.6 11.8 Example 17 PP 1.5 1.6 34.7 13.3
Comparative PP 5.7 5.4 35.1 7.4 Example 9 Comparative PP 4.8 4.8
35.1 7.4 Example 10 Comparative PP 5.5 5.2 34.4 18.0 Example 11
Comparative ABS 5.7 5.4 34.8 0.0 Example 12 Comparative ABS 4.9 5.0
34.8 0.1 Example 13 Comparative ABS 5.7 5.2 34.4 17.8 Example 14
Control 5.8 5.4
[0175] As can be seen from the results of the injection-molded
members in the above Table 9, in Examples 12 to 17 where an
antimicrobial/antiviral agent, a hydrophilic compound, and a
dispersant were included in a base resin and the polar contribution
R.gamma.p was 2.0% or higher, the viral infectivity titer is more
significantly lowered and the viable microbial cell count is also
more significantly decreased than those of Comparative Examples 9
to 14.
[0176] The following Table 10 collectively provides the measurement
results of the antimicrobial/antiviral resin members that are the
sheet-shaped members of Examples 18 to 20 and Comparative Examples
15 to 18.
TABLE-US-00010 TABLE 10 Antiviral Antimicrobial Performance
Performance Surface Polar Infectivity Viable Cell Free Contri-
Titer Count Energy bution 15-min 60-min .gamma.s R.gamma.p Resin
sensitized sensitized [mJ/m.sup.2] [%] Example 18 PE 1.8 <1.0
34.7 8.6 Example 19 PE <1.3 <1.0 34.7 13.8 Example 20 PE 1.8
<1.0 34.8 8.0 Comparative PE 5.5 5.4 35.0 5.8 Example 15
Comparative PE 4.3 4.6 35.1 5.7 Example 16 Comparative PE 5.6 5.4
34.7 13.5 Example 17 Comparative PE 5.4 5.4 34.7 12.6 Example 18
Control 5.8 5.4
[0177] As can be seen from the results of the sheet-shaped members
of the above Table 10, in Examples 18 to 20 where an
antimicrobial/antiviral agent (copper compound microparticles
coated with a dispersant) and a hydrophilic compound were included
in a base resin, the viral infectivity titer is more significantly
lowered and the viable microbial cell count is also more
significantly decreased than those of Comparative Examples 15 to
18.
[0178] The above has demonstrated that the antimicrobial and/or
antiviral effects can be exerted regardless of the kind of base
resin. In addition, it has been verified from the above Tables 9
and 10 that the antimicrobial/antiviral resin members of the
invention can elicit the antimicrobial and/or antiviral effects
regardless of their form.
To Produce Fiber as Antimicrobial/Antiviral Resin Member
Example 21
[0179] By using a dry grinder Nano Jetmizer (NJ-100B, manufactured
by Aishin Nano Technologies CO., LTD.), commercially available
copper (I) iodide powder (manufactured by NIHON KAGAKU SANGYO CO.,
LTD.) was ground to an average particle size of 150 nm to obtain
copper iodide microparticles. The resulting copper iodide particles
and a metal soap, which is a dispersant to prevent aggregation of
the copper iodide particles, were mixed.
[0180] A polypropylene resin pellet (manufactured by Asahi Kasei
Chemicals Corporation), as a base resin, was added thereto so as to
have 40 mass % of the resulting copper iodide. The resulting
mixture was fed to a twin-screw melt kneader to obtain a copper
iodide master batch pellet.
[0181] Commercially available polyethylene glycol (manufactured by
SANYO CHEMICAL, LTD.) was added at a content of 30 mass % to a
polypropylene resin pellet (manufactured by Asahi Kasei Chemicals
Corporation) as a base resin. The resulting mixture was fed to a
twin-screw melt kneader to obtain a polyethylene glycol master
batch pellet.
[0182] A polypropylene resin pellet, the copper iodide master batch
pellet, and the polyethylene glycol master batch pellet were mixed
using a tumbler so as to have 1 mass % of copper iodide and 3 mass
% of polyethylene glycol. Next, melt spinning was carried out to
obtain monofilament fiber, which was an antimicrobial/antiviral
resin member with a fineness of 300 D.
Example 22
[0183] Regarding a copper iodide master batch pellet and a
polyethylene glycol master batch pellet, those prepared in Example
21 were used.
[0184] A polypropylene resin pellet, the copper iodide master batch
pellet, and the polyethylene glycol master batch pellet were mixed
using a tumbler so as to have 1 mass % of copper iodide and 3 mass
% of polyethylene glycol in its sheath. Next, a polypropylene resin
pellet was used as its core. Then, melt spinning was carried out to
obtain monofilament fiber that had a core-sheath structure and was
an antimicrobial/antiviral resin member having a core-sheath area
ratio of 7/3 and a fineness of 300 D.
Comparative Example 19
[0185] Regarding a copper iodide master batch pellet, the one
prepared in Example 21 was used.
[0186] A polypropylene resin pellet and the copper iodide master
batch pellet were mixed using a tumbler so as to have 1 mass % of
copper iodide. Next, melt spinning was carried out to obtain
monofilament fiber with a fineness of 300 D.
[0187] The following Table 11 lists the components of the fibers of
Examples 21 to 22 and Comparative Example 19 described.
TABLE-US-00011 TABLE 11 Monovalent Copper Compound Hydrophilic
Compound Resin Kind Mass % Kind Mass % Example 21 PP Copper 1
Polyethylene 3 Iodide* Glycol Example 22 PP Copper 1 Polyethylene 3
Iodide* Glycol Comparative PP Copper 1 -- -- Example 19 Iodide*
*Dispersant in Examples 21 and 22 and Comparative Example 19: Metal
Soap
[0188] (Antiviral Performance Evaluation Protocol)
[0189] When virus inactivation performance of monofilament fiber
was measured, influenza virus (influenza A/Kitakyushu/159/93(H3N2))
cultured using MDCK cells was used as an enveloped virus. As a
non-enveloped virus, feline calicivirus, which has been typically
and frequently used as a virus alternative for norovirus, was
used.
[0190] Monofilament fiber, which was an antimicrobial/antiviral
resin member of each of Example 21 or 22 or Comparative Example 19,
was wound around the middle of a glass plate (50 mm.times.100 mm)
as a single layer with a width of 60 mm without any gap. The glass
plate, around which the monofilament fiber was wound, was placed in
a plastic container. Then, 200 .mu.L of virus liquid diluted with
sterile water was added dropwise and was reacted therewith at
25.degree. C. for 15 min. At that time, an upper surface of the
monofilament fiber test product was covered with a PET film (40
mm.times.40 mm) such that the area of contact between the virus
liquid and the monofilament fiber test product was made constant.
Then, testing was conducted. After 15-min reaction, 20 mL of SCDLP
broth was added so as to stop the reaction. Then, the virus was
purged by pipetting. Subsequently, MEM diluent was used to dilute
each post-reaction virus liquid to from 10.sup.-2 to 10.sup.-5
(10-fold serial dilution) to prepare sample solutions. Then, 100
.mu.L of each sample solution was seeded onto MDCK cells cultured
on a dish. The cells seeded with the sample solution were allowed
to stand for 60 min in an incubator at 34.degree. C. and 5%
CO.sub.2. After the virus was adsorbed on the cells, 0.7% agar
broth was overlaid and the virus was cultured for 48 h in the
incubator at 34.degree. C. and 5% CO.sub.2. After the culturing,
formalin fixation and methylene blue staining were conducted and
the number of plaques formed was counted to calculate a viral
infectivity titer (PFU/0.1 mL, Log 10) (PFU: plaque-forming
units).
[0191] (Antimicrobial Performance Evaluation Protocol)
[0192] When antimicrobial performance of each monofilament fiber as
an antimicrobial/antiviral resin member was measured,
Staphylococcus aureus cultured using NB broth was used as
gram-positive bacteria. As gram-negative bacteria, E. coli cultured
using NB broth was used.
[0193] Monofilament fiber, which was an antimicrobial/antiviral
resin member of each of Example 21 or 22 or Comparative Example 19,
was wound around the middle of a glass plate (50 mm.times.100 mm)
as a single layer with a width of 60 mm without any gap. The glass
plate, around which the monofilament fiber was wound, was placed in
a plastic container. Then, 100 .mu.L of microbial cell liquid
diluted with sterile water was added dropwise and was reacted
therewith at 35.degree. C. for 15 min. At that time, an upper
surface of the monofilament fiber test product was covered with a
PET film (40 mm.times.40 mm) such that the area of contact between
the microbial cell liquid and the monofilament fiber test product
was made constant. Then, testing was conducted. After 15-min
reaction, 20 mL of SCDLP broth was added so as to stop the
reaction. Then, the microbial cells were purged by pipetting.
Subsequently, SCDLP broth was used to dilute each post-reaction
microbial cell liquid to from 10.sup.-1 to 10.sup.-5 (10-fold
serial dilution) to prepare sample solutions. Then, 1 mL of each
sample solution was pipetted onto a dish and 1.5% agar broth was
added and mixed therewith. The inverted dish was allowed to stand
in an incubator at 37.degree. C. and the microbial cells were
cultured for 24 to 48 h. After that, the number of colonies was
counted to calculate the viable cell count of the microbial cells
(CFU/0.1 mL, Log 10) (CFU: colony-forming units).
[0194] (Surface Free Energy)
[0195] A contact angle meter (an automated micro-contact meter
MCA-3, manufactured by Kyowa Interface Science, Inc.) was used to
measure the contact angle of each measurement liquid (water or
diiodomethane was used) on a surface of the monofilament fiber of
Example 21 or 22 or Comparative Example 19. These measurement
results were used to calculate a polar component .gamma.sp and a
non-polar component .gamma.sd by using the above Formula (3) and to
calculate the surface free energy .gamma.s of each monofilament
fiber by using the above Formula (1). In addition, the above
Formula (2) was used to calculate a polar contribution
R.gamma.p.
[0196] Here, the following Table 12 collectively provides the
measurement results regarding the monofilament fibers of Examples
21 to 22 and Comparative Example 19 described.
TABLE-US-00012 TABLE 12 Antiviral Antimicrobial Surface Polar
Performance Performance Free Contri- Infectivity Titer Viable Cell
Count Energy bution (PFU/0.1 mL, (CFU/0.1 mL, .gamma.s R.gamma.p
Log10) Log10) [mJ/m.sup.2] [%] Example 21 <2.3 <1.3 34.5 9.5
Example 22 <2.3 <1.3 34.7 9.6 Comparative 5.7 2.2 35.1 7.4
Example 19 Control 6.2 6.0 -- --
[0197] It was found that Examples 21 and 22, where a compound with
a polar group (polyethylene glycol) was added, elicited potent
antimicrobial performance and antiviral performance. In contrast to
this result, the result of Comparative Example 19 free of a
compound with a polar group was inferior both in antimicrobial
performance and antiviral performance. The above results have
confirmed that it is possible to provide potent
antimicrobial/antiviral products by using monofilament fiber as an
antimicrobial/antiviral resin member of the invention.
[0198] In conclusion, it has been demonstrated that any
antimicrobial/antiviral composition, which is included in an
antimicrobial/antiviral coating and/or an antimicrobial/antiviral
resin member, according to the invention elicits antimicrobial
and/or antiviral performance.
* * * * *