Technical Field
[0001] The present invention relates to a method for producing a thread bundle consisting
of foothold silk thread obtained by allowing a bagworm to spin the foothold silk thread
onto the surface of a base material.
Background Art
[0002] The thread consisting of an insect cocoon or a hair of mammal has been used as an
animal fiber for a clothes and the like since long time ago. Especially, silk thread
from a silk moth (
Bombyx mori) larva, namely a silkworm, which is herein often referred to as "silkworm silk thread",
has excellent properties for absorption and desorption of moisture, moisture retention,
and heat retention, and also has a unique gloss and a smooth texture. Therefore, the
silkworm silk thread is valuable and expensive natural material even today.
[0003] However, there exist animal fibers in nature having properties comparable or superior
to those of silkworm silk thread. Recently, for utilizing an animal fiber having such
excellent properties as novel natural material, exploration thereof and research and
development thereon are ongoing.
[0004] A thread from a spider (herein often referred to as "spider thread") is one material
of interest. A spider thread has flexibility and elasticity and has an elastic force
up to 5 to 6 times greater than that of polystyrene, and is thus expected to be used
as a medical material for surgical suture, for example, and as a special material
for emergency ropes, protective clothes, or the like (Non-Patent Literatures 1 and
2). However, mass-production of spider threads is not feasible because mass rearing
of spiders and collecting a large amount of thread from spiders are difficult, which
also results in a problem of high production cost. An attempt to solve this problem
is ongoing by using gene recombination technology to produce a spider thread in a
host such as a silkworm or
Escherichia coli (Patent Literature 1 and Non-Patent Literature 2). However, a silkworm or
Escherichia coli for spider thread production is a recombinant and is thus allowed to be reared or
cultured only in facilities with predetermined equipment, which poses a problem of
large maintenance or management burden. Additionally, a liquid spider thread protein
expressed in
Escherichia coli needs to be converted to a fiber, which also causes a problem in that the number
of processes increases accordingly. Furthermore, another problem is that the current
spider thread spun by a recombinant silkworm is merely comprised in silkworm silk
thread at several percentages and cannot be obtained as 100% spider thread which allows
100% of the properties of spider thread to be utilized.
[0005] There exists an insect called a bagworm (alias "basket worm"). The larvae of moth
belonging to the family
Psychidae in the order
Lepidoptera is collectively referred to as a bagworm and is known to spend the whole larval stages
living with a spindle-shaped or cylindershaped nest made of pieces of leaves and twigs
assembled by thread, as shown in Figure 1A, during which the larva usually hide itself
inside the nest and move with the nest even for eating.
[0006] The silk thread spun by the bagworm (herein often referred to as "bagworm silk thread")
has recently been attracting attention as a new animal-fibrous natural material having
more excellent properties than the silkworm silk thread and the spider thread. For
example, the bagworm silk thread from the bagworm
Eumeta minuscula has an elastic modulus up to 3.5 times of that of the silkworm silk thread and up
to 2.5 times of that of the
Nephila clavata spider thread, and a very high strength (Non-Patent Literatures 1 and 2). Additionally,
the bagworm silk thread not only have a gloss and a shiny appearance comparable or
superior to those of the silkworm silk thread but also allow production of much fine,
thin and light fabric with a smooth texture compared to the silkworm silk thread because
monofiber of the bagworm silk thread has a cross-sectional area only about one-seventh
of that of the silkworm silk thread.
[0007] The bagworm is more advantageous than the silkworm and the spider also in terms of
rearing. The bagworm is phytophagous, as is the silkworm. Thus, differently from the
spider, which is carnivorous, the bagworm food is easy to procure and can be supplied
stably. Additionally, the bagworm is phytophagous similarly to but more advantageously
than the silkworm. For example, since the silkworm feeds on only raw leaves of mulberry
(species belonging to the genus
Morus, comprising, for example,
M. bombycis, M. alba, and
M. Ihou) in principle, the region for rearing and season for rearing depend on the supply
area of mulberry leaves and the season of mulberry leaf development. In contrast,
the bagworm is euryphagous, the specificity for food leaves is low, and many species
of the bagworm can feed on leaves of trees of various species. Accordingly, food leaves
for the bagworm are easily available, and the bagworm can be raised in any region.
Also, the bagworm of some species can feed on leaves of evergreen trees. Thus, differently
from mulberries, which are deciduous trees, it is possible to supply food leaves all
year round. Moreover, the bagworm is smaller in size than the silkworm and requires
a rearing space equal to or less than that required for rearing the silkworm, which
makes mass rearing easy. Thus, the cost for rearing can be reduced.
[0008] Also, the bagworm is superior to the silkworm in terms of productivity. For example,
the silkworm spins a large amount of thread only during cocooning and all larvae perform
cocooning in the same period. Thus, thread collection periods overlap and labor periods
concentrate thereon. However, the bagworms repeatedly spin silk thread for nest building
or migrating throughout larval stages. Thus, labor periods can be dispersed by artificially
adjusting the thread collection periods.
[0009] As described above, the bagworm silk thread has properties superior to those of the
silkworm silk thread and the spider thread, and also has many advantages for their
production, and thus, is expected as a very promising novel natural material.
[0010] However, the bagworm silk thread has several problems in the practical application
thereof. One of them is a problem associated with the characteristics of the bagworm
nest. Contaminants, such as pieces of leaves and twigs, are inevitably attached on
the surface of the bagworm nest. This is due to the habit of the bagworm incorporating
small pieces of twigs and leaves into the nests from the surroundings for camouflage
in the process of nest production and expansion. These contaminants need to be completely
removed for commercialization of the bagworm silk thread. In conventional method,
these contaminants are manually removed from the built nest, or are detached from
the nest after the nest is immersed in warm water for a long time to be softened.
However, the work of removing these contaminants requires enormous labor. Additionally,
complete removal of the contaminants is not possible with existing technologies, resulting
in a problem in that only low quality final products can be obtained, due to contamination
with a small amount of small pieces of leaves and the like, as well as lightbrown
staining of the bagworm silk thread with pigments from the contaminants and so on.
Decolorization treatment can be performed using a base or an acid to remove the pigments,
but can result in a marked decrease in quality such as an impaired strength of the
bagworm silk thread.
[0011] The bagworm silk thread comprises a silk thread called a foothold silk thread, as
well as a nest silk thread constituting the nest. As shown in Figure 1B, this foothold
silk thread is a silk thread spun to be used as a scaffold for preventing the bagworm
from falling when the bagworm migrates. The results of the present inventors' studies
have revealed that this foothold silk thread is tougher and has excellent mechanical
properties than the nest silk thread. Additionally, the foothold silk thread has no
contaminant such as pieces of leaves and twigs, differently from the nest silk thread.
Accordingly, if the foothold thread can be collected to be utilized, it can serve
as a practical bagworm silk thread.
[0012] However, such a method still has a problem. First, foothold thread is usually spun
in the intended direction and in a zigzag pattern, as shown in Figure 2A. The bagworm
silk thread is spun in the form of a mixture of a fiber component and a paste-like
protein covering the surface thereof, and in the case of the foothold silk thread,
the foothold silk thread is fixed to the surface of a base material by the paste-like
protein (as shown by the arrowheads in the larger circle in Figure 2A) at the turnaround
points in the zigzag pattern. This fixation is very strong, and thus, a strong tension
is necessary to mechanically peel the foothold silk thread from the base material.
In many cases, such an operation also causes the foothold silk thread to be broken
around the fixed portion and to be fragmented. Furthermore, the migration of a bagworm
is generally difficult to control, and it is possible that a bagworm migrates among
the same place back and forth for number of times. As a result, the silk threads spun
in a zigzag pattern overlap and entwine one another in the form of a complicated entanglement
as shown in Figure 2B that it is even more difficult to collect the silk thread from
the base material without damaging the thread. For this reason, foothold silk thread
spun on a base material has hitherto never been utilized effectively as a natural
fiber material.
Citation List
Patent Literature
Non-Patent Literature
Summary of Invention
Technical Problem
[0015] A bagworm foothold silk thread spun on a base material is conventionally difficult
to be collected and cannot be utilized. A purpose of the present invention is to develop
and provide a method in which such a bagworm foothold silk thread can be peeled from
a base material with a weak force without being damaged and can be collected as a
thread bundle so as to be utilized.
Solution to Problem
[0016] To solve the above-mentioned problems, the present inventors have vigorously made
studies, and as a result, have succeeded in enabling a bagworm silk thread spun on
a base material to be peeled in the form of a thread bundle from the base material
without being damaged, by such a bagworm silk thread is sprayed or coated with a wetting
liquid such as ethanol, an aqueous solution, or an organic solvent and peeled with
a force of only 15% or less, compared with a negative control with such a wetting
liquid not being used. The present invention provides the followings based on the
method described above.
- (1) A method for producing a thread bundle of a bagworm silk thread(s), comprising:
wetting liquid applying process of applying a wetting liquid to the bagworm silk thread(s)
spun on the surface of a base material; and
separation process of separating the bagworm silk thread(s) from the base material,
wherein the wetting liquid presents a liquid form at least in the range of 20°C or
more and less than 30°C under the atmospheric pressure, and is a pure substance or
a mixture that does not damage, denature, or dissolve a fibroin protein which is a
fiber component of the bagworm silk thread(s).
- (2) The method according to (1), comprising a spinning process of placing a bagworm
on the surface of the base material before the wetting liquid applying process and
allowing the bagworm to spin the thread.
- (3) The method according to (2), further comprising a bagworm collection process of
collecting the bagworm together with a nest after the spinning process and before
the wetting liquid applying process.
- (4) The method according to any one of (1) to (3), comprising a washing process of
washing the separated bagworm silk thread(s).
- (5) The method according to any one of (1) to (4), comprising a degumming process
of degumming the separated bagworm silk thread(s).
- (6) The method according to any one of (1) to (5), wherein the wetting liquid is a
pure substance or a mixture that has a melting point of less than 20°C and a boiling
point of 30°C or more and 300°C or less.
- (7) The method according to any one of (1) to (6), wherein the wetting liquid is an
aqueous solution or an organic solvent.
- (8) A method for collecting a bagworm silk thread(s) spun on the surface of a base
material, comprising:
wetting liquid applying process of applying a wetting liquid to the bagworm silk thread(s)
spun on the surface of the base material; and
separation process of separating the bagworm silk thread(s) from the base material,
wherein the wetting liquid presents a liquid form at least in the range of 20°C or
more and less than 30°C under the atmospheric pressure, and is a pure substance or
a mixture that does not damage, denature, or dissolve a fibroin protein which is a
fiber component of the bagworm silk thread(s).
- (9) The method according to (8), wherein the wetting liquid is an aqueous solution
or an organic solvent.
- (10) A bagworm silk thread(s) obtainable by using the method for producing a thread
bundle according to any one of (1) to (7) or the method for collecting a bagworm silk
thread(s) according to (8) or (9).
- (11) An unwoven fabric formed of a bagworm silk thread(s) obtainable by using the
method for producing a thread bundle according to any one of (1) to (7).
Advantageous Effects of Invention
[0018] The method for producing a thread bundle of a bagworm silk thread according to the
present invention makes it possible that a bagworm foothold thread spun on the surface
of a base material, which was conventionally difficult to be collected, is collected
with a weak force without being fragmented.
Brief Description of Drawings
[0019]
[Figure 1] Figure 1A shows the appearance of a nest of a bagworm of Eumeta japonica (Eumeta japonica bagworm). Figure 1B shows the spinning behavior of a Eumeta japonica bagworm in migration. This shows how the bagworm moves while spinning a foothold
silk thread (as shown by the arrowhead) and hooks its claws onto the spun bagworm
silk thread (foothold silk thread) (as shown by the thin arrows).
[Figure 2] Figure 2A is a schematic diagram showing the spun state of the bagworm
silk thread (foothold silk thread) spun by a bagworm migrating on the surface of a
base material. As shown here, the bagworm foothold silk thread presents a ladder-like
zigzag pattern. In the figure, the black arrows indicate the direction in which the
bagworm migrates spinning the thread. Additionally, the view in the larger circle
is an enlarged view of that in the smaller circle, and the arrowheads in the larger
circle indicate a paste-like protein. The foothold silk thread is fixed on the base
material at the turnaround points of the zigzag portions corresponding to the steps
of the ladder. Figure 2B shows the state of the bagworm silk thread, which is a thread
spun on a plastic plate by the Eumeta japonica bagworm. This shows how the bagworm silk threads spun in a zigzag pattern are entangled
complicatedly.
[Figure 3] Figure 3 shows a process flow diagram of a method for producing a thread
bundle of a bagworm silk thread according to the present invention.
[Figure 4] Figure 4 is the graphs showing the results of a peeling tension evaluation
test performed in Example 1. In the graphs, (A), (B), and (C) show the test results
of a negative control with no wetting liquid applied thereto, a sample with water
applied thereto, and a sample with ethanol (99.5%) applied thereto respectively.
Description of Embodiments
1. Method for Producing Thread Bundle of Bagworm Silk Thread
1-1. Concept
[0020] The first aspect of the present invention is a method for producing a thread bundle
of a bagworm silk thread. The production method according to the present invention
is a method in which a thread bundle consisting of an intended bagworm silk thread
is obtained by applying a wetting liquid to a bagworm silk thread spun on the surface
of a base material and then separating the bagworm silk thread from the base material.
The method according to the present invention makes it possible that a foothold silk
thread, which has excellent properties but is difficult to collect without being physically
damaged and thus, has never been utilized, is efficiently collected without being
damaged.
1-2. Definition of Terms
[0021] The following terms frequently used herein are defined as described below.
[0022] The term "bagworm" collectively refers to a moth larva belonging to the family
Psychidae in the order
Lepidoptera, as described above. Moths belonging to the family
Psychidae are distributed worldwide and the larva (bagworm) of any species of the moth spends
the whole larval stages living in a nest covered with natural materials, such as pieces
of leaves and twigs, which are assembled by silk threads spun by the larva itself.
Additionally, any species of bagworm has the habit of spinning a foothold silk thread
which functions as a scaffold in the intended direction of migration to prevent the
bagworm from falling when the bagworm migrates. Accordingly, the species, instar,
and gender of bagworms used herein are not limited, as long as that the bagworm is
a larva of a moth species belonging to the family
Psychidae and that the species has the habit as described above. For example, the family
Psychidae comprises the genera
Acanthopsyche, Anatolopsyche, Bacotia, Bambalina, Canephora, Chalioides, Dahlica,
Diplodoma, Eumeta, Eumasia, Kozhantshikovia, Mahasena, Nipponopsyche, Paranarychia,
Proutia, Psyche, Pteroma, Siederia, Striglocyrbasia, Taleporia, Theriodopteryx, Trigonodoma, etc., and the bagworm used herein may be a species belonging to any genus. Additionally,
the instar of the larva may be any instar between the first instar and the last instar.
However, a larger bagworm is preferable to obtain a large mass of the bagworm silk
thread. For example, among larvae of the same species, a larva in the last instar
is more preferable, and a female larva is more preferable than a male larva because
the female grows larger than the male. Furthermore, among the family
Psychidae, a large species is more preferable. For example,
Eumeta japonica and
Eumeta minuscula, which are large species, are suitable as species used in the present invention.
[0023] A bagworm to be used in a method for producing according to the present invention
is preferably, but is not limited to, a bagworm keeping a nest. "Keeping a nest" refers
to the state in which the bagworm has a nest therewith. As described above, the bagworm
lives with its own nest, and exposes only part thereof out of the nest even during
eating and moving, as shown in Figure 1B, and in principle, the bagworm never exposes
its whole body out of the nest throughout the whole larval stage. When the bagworm
is artificially separated from the nest and wholly exposed to the outside, the bagworm
thus made naked generally minimizes its movement and promptly starts rebuilding a
nest for self-protection and to keep itself warm. Accordingly, the reason why a bagworm
keeping a nest is suitable is not to make prioritize the behavior of spinning a nest
silk thread but rather to make actively spin a foothold silk thread, which is a purpose
of the present invention.
[0024] The term "silk thread" as used herein refers to a thread derived from an insect and
made of proteins, which is spun by the insect in a larval or adult stage for the purpose
of nest building, migrating, anchoring, cocooning, prey capture, and the like. When
the term "silk thread" is simply recited herein, it refers to a general silk thread
from an unspecified insect. In case of indicating a silk thread from a particular
insect species, the name of the organism is placed before the term "silk thread,"
as a "silkworm silk thread" or a "bagworm silk thread."
[0025] The term "bagworm silk thread" as used herein refers to a silk thread spun by a bagworm.
The "bagworm silk thread" herein encompasses a monofiber, spun fiber, and fiber assembly.
The term "monofiber", which is also referred to as monofilament, is the smallest filament
unit constituting fiber components. The monofiber contains a fibroin protein as a
main component. The bagworm silk thread and the silkworm silk thread in natural states
are spun in the form of bifilament in which two monofibers are joined together by
a sericin protein, a gummy material. This bifilament is referred to as a "spun fiber".
The bagworm nest and the silkworm cocoon are constituted with spun fiber(s). Also,
a fiber bundle formed by assembling plural spun fibers is referred to as a "fiber
assembly (or multifilament)". In general, this fiber assembly corresponds to a raw
silk thread. Furthermore, silk thread obtained by treatment of raw silk thread with
an enzyme and a basic chemical such as soap, lye, sodium carbonate, and urea to remove
sericin protein is called degummed silk thread.
[0026] The bagworm silk thread includes two kinds of the silk thread: foothold silk thread
and nest silk thread. As described above, the "foothold silk thread" refers to a silk
thread spun by a bagworm for the purpose of its migration, which has a function as
a foothold (scaffold) for preventing it from falling from a branch, a leaf, or the
like. On the other hand, the "nest silk thread" refers to a bagworm silk thread spun
for forming a nest, which is spun to assemble pieces of leaves and twigs or to make
an internal wall of a nest so that its accommodation space becomes a comfortable environment.
A foothold silk thread is intended as a bagworm silk thread in the present invention
in view of the purpose. Thus, the expression "bagworm silk thread" herein refers to
a foothold silk thread unless otherwise specified.
[0027] As used herein, a "thread bundle" refers to a silk thread aggregate consisting of
a bagworm foothold silk thread(s) alone. A bagworm nest is an aggregate of a bagworm
silk thread(s), but usually is a mixture of contaminants of small pieces of twigs,
leaves, and the like, and is consisting of a nest silk thread(s). Therefore, it is
not the thread bundle according to the present invention. The thread bundle herein
is, but is not limited, an aggregate of a foothold silk thread(s) with no contaminant
intruded produced through some artificial process. Examples of such thread bundles
comprise a thread bundle which a bagworm placed on a base material is allowed to spin.
Without limitation, the state of the thread bundle may be, for example, a sheet-like
state such as an unwoven fabric in which one or more bagworm silk threads are entwined
complicatedly, or may be an assembled state in which one or more bagworm silk threads
are reelably held together.
[0028] A "wetting liquid" refers to a pure substance or a mixture which presents a liquid
form at least in the range of 20°C or more and less than 30°C under the atmospheric
pressure, and does not damage, denature, or dissolve a fibroin protein which is a
fiber component of the bagworm silk thread. Accordingly, a pure substance which is
in a state other than a liquid state in the above-mentioned temperature range, and
a substance in a liquid state which denatures a protein including a strongly acid
solvent, a strongly basic solvent, a mixture such as a solution containing protease,
or the like are not suitable as a wetting liquid in the present invention.
[0029] A "pure substance" refers to a chemical substance having certain properties, and
examples thereof comprise a simple substance consisting of a single element, and a
compound consisting of a plurality of elements. A pure substance in the present invention
usually corresponds, but is not limited, to a compound.
[0030] A "mixture" refers to a substance formed by mixing a plurality of pure substances.
A mixture corresponds to, for example, a solution.
[0031] A wetting liquid may be consisting of any pure substance or a mixture as long as
the wetting liquid satisfies the above-mentioned requirements. Examples thereof comprise,
but are not limited to, compounds having a melting point (Melting Point: MP) of less
than 20°C and a boiling point (Boiling Point: BP) of 30°C or more and 300°C or less
under normal temperature (25°C) and normal pressure (100 kPa). A compound having such
properties often has the properties as a "solvent" which can dissolve another compound
as a solute.
[0032] Specific of a compound for wetting liquids are as mentioned below, but a wetting
liquid herein is not limited to the examples below.
[0033] A wetting liquid may be a liquid consisting of a polar molecule (polar solvent).
Examples thereof comprise: protic polar solvents such as water (MP: 0°C; BP: 100°C),
methanol (MP: -96°C; BP: 64.7°C), ethanol (MP: -117°C; BP: 78.3°C), 1-propanol (MP:
-127°C; BP: 97.2°C), 1-butanol (MP: -90°C; BP: 118°C), glycerin (MP: 17.8°C; BP: 290°C),
formic acid (MP: 8.3°C; BP: 100.8°C), acetic acid (MP: 15°C; BP: 118°C), and butyric
acid (MP: -7.9°C; BP: 164°C); and aprotic polar solvents such as DMSO (MP: 18.5°C;
BP: 189°C), acetonitrile (MP: -48°C; BP: 81.6°C), acetone (MP: -94°C; BP: 56°C), dimethylformamide
(MP: -61°C; BP: 153°C), dimethylsulfoxide (MP: 19°C; BP: 189°C), tetrahydrofuran (MP:
-108°C; BP: 66°C), and 1,1,1,3,3,3-hexafluoro-2-propanol (MP:-3.3°C; BP:58.2°C). Other
examples comprise an ionic liquid. Here, the values in the parenthesis following each
compound indicate a melting point (MP) and a boiling point (BP) under normal temperature
and normal pressure (the same applies hereinafter).
[0034] A wetting liquid may also be a nonpolar liquid consisting of a nonpolar molecule
(nonpolar liquid: nonpolar solvent). Examples thereof comprise an oil and many organic
solvents (low polarity organic solvents) excluding some. An oil is a compound in a
liquid state under normal temperature and normal pressure, and examples thereof comprise
a fatty acid represented by the general formula: R-COOH (wherein R is a C
4-8 alkyl group). Specific examples of nonpolar liquids comprise: fatty acids such as
valeric acid (valerianic acid: MP: - 34.5°C; BP: 186°C), caproic acid (hexanoic acid:
MP: -3°C; BP: 205°C), enanthic acid (heptylic acid, heptanoic acid: MP: -7.5°C; BP:
223°C), caprylic acid (octanoic acid: MP: 16.7°C; BP: 239.7°C), pelargonic acid (nonanoic
acid: MP 11°C; BP: 247°C), palmitoleic acid (hexadecenoic acid: MP: -0.1°C; BP: 230°C),
linoleic acid (octadecadienoic acid: MP: -5°C; BP: 229°C), linolenic acid (octadecatrienoic
acid: MP: -11°C; BP: 278°C), and arachidonic acid (eicosatetraenoic acid: MP: -49°C;
BP: 169°C); hexane (MP: -95.3°C; BP: 68.7°C); toluene (MP: -95°C; BP: 110.6°C); chloroform
(MP: -63.5°C; BP: 61°C); dichloromethane (MP: -95°C; BP: 39.8°C); 1,2-dichloroethane
(MP: -35.7°C; BP: 83.4°C); trichloroethylene (MP: -86.4°C; BP: 87°C); acetone (MP:
-94°C; BP: 56°C); diethyl ether (MP: -116°C; BP: 34.6°C); xylene (MP: -25°C; BP: 137°C);
carbon tetrachloride (MP: -23°C; BP: 76.7°C); methyl acetate (MP: - 98°C; BP: 57°C);
and ethyl acetate (MP: -84°C; BP: 77°C).
[0035] Additionally, in cases where a wetting liquid herein is a mixture, specific examples
thereof comprise a solution. Examples of such solutions comprise, but are not limited
to: a solution consisting of a polar liquid or nonpolar liquid in which one or more
different solutes are dissolved; a colloidal solution or sol in which a colloid is
dispersed in a liquid which is a dispersion medium; two or more different liquids
(for example, a liquid mixture or the like consisting of different polar liquids);
or a combination thereof. Examples of polar solutions comprise: an aqueous solution
in which a solute is dissolved in water; and a solution mixture of solvents such as
of ethanol and water. Solute in the aqueous solution is not limited. Examples thereof
comprise, but are not limited to, a salt, a sugar, and a surfactant. A preferable
salt is, but is not limited to, a salt having high solubility. Examples thereof comprise
sodium chloride salt, potassium chloride salt, sodium carbonate salt, and sodium hydrogencarbonate
salt. The solute concentration of the solution is not particularly limited. For example,
it may be equal to solubility. Solute concentration for the solution mixture is also
not limited in particular. For example, a liquid mixture of ethanol and water may
be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 99.5% ethanol.
[0036] As mentioned above, a pure substance or mixture constituting a wetting liquid is
not limited to any type. Considering the easiness of handling (including waste liquid
disposal), safety, and purchasing cost, water (including warm water and hot water),
an aqueous solution, ethanol, and a liquid mixture thereof are preferable; and an
aqueous solution and ethanol are particularly preferable.
[0037] As used herein, a "base material" refers to a base for collecting a bagworm silk
thread. A bagworm placed on the surface of this base material is allowed to migrate,
thus spinning a bagworm silk thread on the surface.
[0038] A material constituting a base material is not limited as long as it can fix a bagworm
silk thread on its surface with a paste-like protein. Examples thereof comprise glass
(comprising enamel), metal, a synthetic resin (comprising a thermoplastic resin, a
thermosetting resin, and a synthetic rubber), ceramic, paper, a piece of plant (comprising,
for example, a piece of wood), or a piece of animal (comprising, for example, a piece
of bone, seashell, and sponge). However, a base material which is dissolved by a wetting
liquid used or causes a reaction such as an oxidation-reduction reaction with a wetting
liquid does not fit with the spirit of the present invention in which a bagworm silk
thread spun on a base material is collected. Accordingly, a material constituting
a base material is desirably a material insoluble in and nonreactive with a wetting
liquid used in the present invention. Being "insoluble in a wetting liquid" refers
to the property of not being dissolved in a wetting liquid used in the present invention.
Additionally, being "nonreactive with a wetting liquid" refers to the property of
causing no chemical reaction with a wetting liquid used in the present invention.
Accordingly, the material of a base material in the present invention can be vary
depending on the type of the wetting liquid used. For example, with a wetting liquid
such as water or an aqueous solution, a synthetic resin can be used, such as polyethylene,
polypropylene, polystyrene, vinyl acetate, cellulose acetate, acrylic resin, or polycarbonate,
but with a wetting liquid such as a low polarity organic solvent, those having solubility
therein cannot be used, such as polystyrene, vinyl acetate, cellulose acetate, acrylic
resin, polycarbonate, or the like. Glass, ceramic, polypropylene, or the like, which
is readily available and relatively inexpensive and has low reactivity, is suitable
as the material of a base material.
[0039] The thickness of a base material used in this process is not limited. The thickness
can suitably be determined considering the production cost and rigidity of the base
material, the easiness of processing in the subsequent processes, and the like. For
example, it is preferable that an average thickness of the base material is 0.5 mm
or more, 0.6 mm or more, 0.7 mm or more, 0.8 mm or more, 0.9 mm or more, 1.0 mm or
more, 1.2 mm or more, or 1.5 mm or more, and in addition, may be 3.0 mm or less, 2.8
mm or less, 2.5 mm or less, 2.2 mm or less, or 2.0 mm or less. In cases where the
base material is consisting of a thin film having an average thickness of less than
0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.5 mm, the base material itself does not have
enough rigidity to retain a given shape, and thus, the base material may be placed
on a suitable support.
[0040] As used herein, a "support" refers to a member on the surface of which a base material
is placed so that rigidity and/or a shape is given to the base material. The support
is an optional constituent to be used in the method according to the present invention,
and can be used if necessary. The material of the support is not particularly limited
as long as it has enough rigidity to retain a given shape. Examples thereof comprise
glass, metal, plastic, synthetic rubber or ceramic, or paper, a piece of plant or
a piece of animal.
[0041] The shape and size of a base material used in this process are not limited. For example,
the shape may be a sheet-like or plate-like planar shape, or may be a three-dimensional
shape, and is preferably a planar shape, considering the easiness of separating the
base material from the bagworm silk thread. Additionally, the surface condition of
base material is preferably, but is not limited to, smooth surface from which bagworm
silk thread can be easily separated rather than that which is rough surface to which
the thread can be strongly fixed. The size of the base material can be that which
is selected as necessary, and in view of the fact that the foothold silk thread is
a bagworm silk thread spun during migration, the lower limit is preferably a size
equal to or greater than the size of the bagworm and the body length of the bagworm.
For example, the long axis or the major axis can be 1 cm or more, 2 cm or more, 3
cm or more, 4 cm or more, or 5 cm or more. Additionally, the size of the base material
is not limited to any upper limit, but in cases where the long axis or the major axis
is 10 cm or more, 15 cm or more, 20 cm or more, 25 cm or more, or 30 cm or more, it
is more preferable to allow a plurality of bagworms to spin threads.
1-3. Method
[0042] The process flow diagram of this aspect is shown in Figure 3. As shown in this Figure,
the method according to the present aspect comprises: a wetting liquid applying process
(S0103) and a separation process (S0104) as essential processes; and a spinning process
(S0101), a bagworm collection process (S0102), a washing process (S0105), and a degumming
process (S0106) as optional processes. Each of the processes will be described below
in flow order.
1-3-1. Spinning process
[0043] The "spinning process" (S0101) is a process of placing a bagworm on the surface of
a base material or placing a bagworm together with a base material and allowing the
bagworm to spin a thread. This process is an optional process in the present invention.
This process is performed before the wetting liquid applying process mentioned below.
[0044] "Placing a bagworm on the surface of a base material" refers to positioning both
of them such that the bagworm can touch the surface of the base material. For example,
the bagworm may be directly placed on the arranged base material, or be placed so
that the bagworm can migrate to reach the base material. Specific examples of the
latter option comprise a case in which a bagworm is placed on the bottom of a lidless
wide-mouthed plastic container, and then, a base material is used as a lid for the
container. The bagworm prefers a higher position and accordingly migrates along the
inner sidewall of the wide-mouthed plastic container to reach the undersurface of
the base material corresponding to the ceiling of the container, followed by spinning
a foothold silk thread while migrating on the base material. The arrangement of the
base material on which a bagworm silk thread is spun is not particularly limited.
As mentioned above, the base material may be arranged on the ceiling of a container,
or may be arranged on the wall thereof. It is convenient to arrange the base material
on a portion other than the bottom as such because feces defecated by a bagworm fall
on the bottom and the surface being spun on is not contaminated by the feces.
[0045] In this regard, the species and the number of the bagworm to be placed are not limited.
For example, one bagworm or a plurality of bagworms may be placed at one time per
base material onto which the bagworm silk thread is to be spun. Additionally, the
species or age of the bagworm to be placed are not limited. In cases where a plurality
of bagworms are placed, the individuals may be of the same species and the same age,
or may be a mixture of bagworms of different species or different ages.
[0046] The period of time for this process is not particularly limited. The process period
depends on species and age of the bagworm, and the number of individuals to be used,
but in any case, the process may usually be continued until a necessary amount of
thread is spun on a base material. For example, when one last instar bagworm of
Eumeta japonica is used to spin a thread onto a circular base material having a diameter of 9 cm,
the bagworm is allowed to spin for 1 day or more, 2 days or more, 3 days or more,
4 days or more, 5 days or more, 6 days or more, or 7 days or more. As described above,
the bagworm foothold silk thread is spun while the bagworm migrates, and thus, the
amount of the obtained silk thread is in proportion to the migration distance of the
bagworm in principle. Therefore, by using a plurality of bagworms to spin, time of
the spinning process is shorter than that by using a single bagworm to spin. In addition,
the bagworm is not allowed to eat food while spinning, and thus, the bagworm often
stops spinning in this process. In such a case, the bagworm may be exchanged for a
new one to continuously maintain the spinning process.
[0047] It is recommended that the temperature and humidity in this process be constant or
with little change so that the amount of thread spun by a bagworm per unit time can
be larger. It is preferable that the temperature is around 20°C, for example, ranges
from 15°C to 25°C, or from 18°C to 22°C, and that the humidity is around 50%, for
example, ranges from 40% to 65%, or from 45% to 60%. There is no limit about light
and dark period during this process, and it may have only a light period, or may have
cyclical light and dark periods. For example, the cycle may be such that, in 24 hours,
the light period is 6 hours to 18 hours, 7 hours to 17 hours, 8 hours to 16 hours,
9 hours to 15 hours, 10 hours to 14 hours, 11 hours to 13 hours, or 12 hours, and
the rest is the dark period.
1-3-2. Bagworm collection process
[0048] The "bagworm collection process" (S0102) is a process of collecting the bagworm used
in the spinning process together with the nest, and is an optional process in the
present invention. A purpose of this process is to separate the bagworm no longer
required from the base material and collect it after the spinning process.
[0049] After the spinning process, the spun foothold silk thread and the bagworm which has
spun the thread coexist on the base material. In principle, however, the bagworm is
not needed in the subsequent wetting liquid applying process. In addition, when the
liquid to be used is applied to a bagworm in the wetting liquid applying process,
it is possible that the bagworm silk thread is stained with an undesirable color by
the bodily fluid of the bagworm and the extract from dead leaves and the like used
for the nest. Thus, this process is an optional process, but is preferably performed
after the spinning process.
[0050] The method for collecting a bagworm from the base material is not limited. Any method
for separating a bagworm from the base material can be utilized. For example, the
bagworm in contact with the base material may be peeled away together with the nest.
However, for purposes of the present invention, it is preferred that the damage to
the bagworm silk thread is as low as possible. For example, the bagworm may be induced
to spontaneously leave the base material. Specific examples of such a method comprise
a method in which, utilizing the feature of the bagworm, which migrates to a higher
place, the container is turned upside down so that the position of the base material
can be changed from the ceiling to the bottom. After the bagworm migrates to the inner
sidewall of the container, the base material can be collected. Another method is heating
of the base material. The bagworm spontaneously leaves the base material to escape
from high temperature, and thus, the base material can be collected after the migration.
The heating temperature may be ordinary temperature or more and the temperature without
the damage of the bagworm silk thread and melting the base material. For example,
the temperature may be 30°C or more, 33°C or more, 35°C or more, 38°C or more, 40°C
or more, 42°C or more, 45°C or more, 48°C or more, or 50°C or more, and 80°C or less,
75°C or less, 70°C or less, 65°C or less, 60°C or less, or 55°C or less.
[0051] Incidentally, the collected bagworm can be fed and then reused in the method for
producing according to the present invention.
1-3-3. Wetting liquid applying process
[0052] The "wetting liquid applying process" (S0103) is a process of applying a wetting
liquid to a bagworm silk thread spun on the surface of a base material, and is the
most important essential process in the present invention.
[0053] The method for applying wetting liquid is not limited. Any method can be used as
long as by which the bagworm silk thread on the surface of a base material is sufficiently
wetted with a wetting liquid. For example, the method comprises a method for spraying,
splashing, or spreading a wetting liquid onto the surface of a base material having
a bagworm silk thread spun thereon, and a method for immersing a base material having
a bagworm silk thread spun thereon in a wetting liquid.
[0054] After the wetting liquid is applied, it is preferably retained for a predetermined
time. This is in order to ensure the time for the wetting liquid to sufficiently permeate
between the base material and the bagworm silk threads. The length of the "predetermined
time" herein is not limited in particular. The time depends on the amount of a wetting
liquid to be applied and the applying method, and usually may be from 1 second to
1 hour, from 1 minute to 40 minutes, from 2 minutes to 30 minutes, from 3 minutes
to 20 minutes, from 4 minutes to 15 minutes, or from 5 minutes to 10 minutes, after
the application.
[0055] The temperature of a wetting liquid used in this process is not limited in particular
as long as the temperature does not damage, denature, or dissolve the bagworm silk
thread. The temperature is usually be in the range of room temperature, for example,
from 1°C to 35°C, from 5°C to 32°C, from 10°C to 30°C, from 12°C to 27°C, from 15°C
to 25°C, or from 18°C to 20°C, when the wetting liquid has a melting point of less
than 1°C and a boiling point of more than 35°C. In general, however, a wetting liquid
has higher reactivity at a higher temperature, and thus, it is preferable in this
process that the temperature of the wetting liquid is higher. For example, if the
wetting liquid is an aqueous solution, the liquid temperature under the atmospheric
pressure is preferably 35°C or more, 38°C or more, 40°C or more, 42°C or more, 45°C
or more, 48°C or more, 50°C or more, 52°C or more, 55°C or more, 58°C or more, 60°C
or more, 62°C or more, 65°C or more, 68°C or more, 70°C or more, 72°C or more, 75°C
or more, 78°C or more, 80°C or more, 82°C or more, 85°C or more, 88°C or more, 90°C
or more, 92°C or more, 95°C or more, or 98°C or more. Incidentally, the wetting liquid
can be heated before and/or during this process.
1-3-4. Separation process
[0056] The "separation process" (S0104) is a process of separating a bagworm silk thread
spun on the surface of the base material from a base material after the wetting liquid
applying process. It is an essential process in the present invention. The method
for separating a bagworm silk thread from the base material is not limited. The wetting
liquid applying process decreases the bonding force between the base material and
the bagworm silk thread, and thus, both can be separated with a relatively weak tension.
For example, the method comprises a method of holding a bagworm silk thread with the
end and ripping off or peeling from a base material, a method for jetting air or liquid
with high pressure into the bonding surface between a base material and the bagworm
silk thread so that the bagworm silk thread can be peeled away, a method for sucking
a bagworm silk thread and peeling away from a fixed base material, a method for immersing
a base material in liquid and separating both with a liquid pressure or the like from
the liquid flow caused by shaking the base material, by stirring the liquid, or the
like. If a liquid is used in this process, the liquid is preferably, but is not limited
to, the wetting liquid used in the wetting liquid applying process. In particular,
water is suitable. This process makes it possible to obtain a bagworm foothold silk
thread spun on the surface of a base material, which was difficult to be collected
with a conventional method without damaging the thread.
1-3-5. Washing process
[0057] The "washing process" (S0105) is a process of washing the bagworm silk thread separated
in the separation process. This process is an optional process and may be performed
if necessary.
[0058] The wetting liquid used in the wetting liquid applying process remains on the surface
of the bagworm silk thread obtained from the separation process. If the wetting liquid
used is a solution or a low polarity organic solvent, and is dried and stuck to the
surface of a bagworm silk thread, the bagworm silk thread can be deteriorated or discolored
over time. Therefore, it is preferable that the wetting liquid used is completely
removed by washing in this process. By this process, part of the feces or the like
attached to the bagworm silk thread can be removed simultaneously even when they are
present.
[0059] A washing solution used for washing in this process is not limited. If the wetting
liquid used is a polar liquid, an aqueous solution, or a colloidal solution, a liquid
suitable as a washing solution is water (comprising warm water). If the wetting liquid
used is a nonpolar liquid such as a low polarity organic solvent, another highly volatile
solvent with high affinity to the low polarity organic solvent is suitable as a washing
solution. For example, when toluene or benzene is used in the wetting liquid applying
process, other xylene or ethanol can be used as a washing solution.
[0060] The washing method is not limited as long as the wetting liquid used in the wetting
liquid applying process can be removed from the bagworm silk thread. The bagworm silk
thread may be sprayed with the washing solution or immersed in the washing solution.
[0061] The number of washes is not limited. The wash can be performed once or plural times.
The term "plural times" as used herein refers to, for example, 2 to 20 times, 2 to
15 times, 2 to 10 times, 2 to 7 times, 2 to 5 times, 2 to 4 times, or 2 to 3 times.
In general, the wash is preferably performed plural times. If the wash is performed
plural times, the washing solution to be used at each time may be the same or different.
Also, the washing methods may be the same or different. After the wash, the thread
may be left to be naturally dried, or the washing solution may be separated and removed
by centrifugation using a dehydrator or the like.
1-3-6. Scouring process
[0062] The "degumming process" (S0106) is a process of degumming a thread bundle consisting
of a bagworm foothold silk thread produced in this process. This process is an optional
process and may be performed if necessary.
[0063] The term "degumming" refers to removing a sericin-like gummy substance (paste-like
protein) from the bagworm silk thread to obtain a fibroin fiber.
[0064] A method for degumming a bagworm silk thread is not limited in particular as long
as a gummy substance can be removed without weakening the strength of the fiber component
of the silk thread. For example, any degumming method for a silkworm silk thread can
be applied. In a method for degumming a silkworm silk thread, 0.01 mol/L to 0.1 mol/L,
0.03 to 0.08 mol/L, or 0.04 to 0.06 mol/L of sodium carbonate solution is used as
a degumming solution, and the solution can be used in the same manner also in the
degumming process in the present method. The obtained bagworm silk thread may be boiled
in the sodium carbonate solution, a degumming solution, for 1 second to 1 hour, 5
seconds to 30 minutes, 10 seconds to 15 minutes, 20 seconds to 10 minutes, or 30 seconds
to 5 minutes.
[0065] It is convenient to use a degumming solution such as a sodium carbonate solution
as a wetting liquid used in the wetting liquid applying process, since the same degumming
solution is subsequently used in the degumming process, and a washing process before
the degumming process is not necessary. After being treated in this process, the silk
thread may be washed in the same manner as in the washing process.
[0066] After the degumming process, the collected bagworm silk thread may be dried. The
drying method is not limited in particular as long as the amount of the wetting liquid,
washing solution, or degumming solution remaining on the bagworm silk thread can be
reduced without denaturing or deteriorating the foothold silk thread. For example,
the method comprises a natural drying method (comprising sun drying) in which the
thread is exposed to external air to vaporize the wetting liquid, washing solution,
or degumming solution, an air drying method in which a blowing device or the like
is used to blow the thread with warm air or cold air; a dehumidification drying method
in which a dehumidifying agent is placed together in a hermetically sealed space for
a given period of time, a heat drying method in which the wetting liquid, washing
solution, or degumming solution is evaporated and dried by heating; a decompression
drying method in which evaporation is performed by degasification with a vacuum pump
or the like in a container; or combinations thereof.
2. Bagworm Silk Thread and Unwoven Fabric constituted therewith
2-1. Overview
[0067] The second aspect of the present invention is a foothold silk thread of a bagworm
silk thread and an unwoven fabric constituted therewith. A bagworm silk thread and
an unwoven fabric according to the present invention are obtained using the method
for producing a thread bundle according to the first aspect.
2-2. Constitution
[0068] A thread bundle obtained by the method according to the first aspect is often in
the form of an unwoven fabric in which the bagworm silk threads are superposed one
on another lengthwise and crosswise on the surface of a base material when the thread
bundle is spun on the surface of the base material without any control of the movement
of the bagworm. Accordingly, the bagworm silk thread peeled from the surface of a
base material in the method for producing a thread bundle according to the first aspect
can itself be utilized as an unwoven fabric. Furthermore, the foothold silk thread
obtained by the method according to the first aspect can be made into an unwoven fabric
by an existing method for producing an unwoven fabric. Without limitation, a spun
lace method or a needle-punching method can be utilized as an existing method for
producing an unwoven fabric.
[0069] Alternatively, when the bagworm silk thread is peeled from the surface of a base
material with generating a correct end or when the thread is reeled from the correct
end pulled off from the state of a peeled unwoven fabric, the thread can be obtained
as a long bagworm silk thread.
Examples
<Example 1>
(Purpose)
[0070] A peeling tension evaluation test verifies that the method for producing a thread
bundle according to the present invention can easily collect a bagworm silk thread
(foothold silk thread) spun on a base material, which was difficult to be collected
with a conventional method.
(Material)
[0071] As a bagworm, a last instar larva of
Eumeta japonica (
Eumeta japonica bagworm) collected at an orchard in Tsukuba, Ibaraki, Japan was used. Additionally,
an acrylic plate, which was approximately 30 cm
2, was used as a base material.
(Method)
[0072] A sufficient amount of food leaves was fed to a bagworm used in each of the Examples
until the day before that spinning process was performed.
[0073] The bagworm was allowed to spin a thread on the surface of an acrylic plate as a
base material by placing the bagworm on the acrylic plate erected vertically and by
allowing the bagworm to climb along the wall surface of the acrylic plate.
[0074] After a bagworm silk thread was sufficiently spun on the surface of the acrylic plate,
water (pure water), aqueous solutions of 30%, 50%, and 70% ethanol, and 99.5% ethanol,
a few drops each, were dripped on the site for evaluation using a syringe. A negative
control was a bagworm silk thread having no wetting liquid applied thereto (a wetting
liquid-unapplied sample).
[0075] Next, the peeling tension evaluation test used in the present Example is described.
As shown in Figure 2A, the bagworm foothold silk thread presents a ladder-like zigzag
pattern. This foothold silk thread is fixed to the surface of a base material at the
turnaround points (referred to as "fixed points") in a zigzag portion (herein referred
to as a "zigzag block") corresponding to the steps of a ladder shown in the broken
line ellipse in Figure 2A. When the foothold silk thread is being peeled away, the
tension exhibits a peak at a fixed point in each zigzag block because the largest
force is needed at the fixed point, but once being peeled, the tension is relaxed
down to the initial value of zero because the foothold silk thread is not fixed to
the base material to the next fixed point. At this next fixed point, a large tension
is needed in the same manner when the thread is peeled away, but the tension becomes
the initial value immediately after the peeling. When the foothold silk thread is
being peeled away, this cycle is repeated between every zigzag block. In the peeling
tension evaluation test, one end of a bagworm foothold silk thread spun on the surface
of a base material is fixed to a load cell of a tensile tester, and then, the bagworm
silk thread is peeled off at a constant speed, with variations in the tension being
continuously recorded, thus the process of releasing the adhesion at the fixed points
to sequentially unbend the zigzag foothold thread into a linear form can be measured
as the relationship between a peeled length (pulled off distance) and a tension.
[0076] Each wetting liquid was applied to a bagworm silk thread and the sufficient wetting
of which was verified, and then, one end of the bagworm silk thread on each acrylic
plate was pulled off and fixed to the load cell of the tensile tester. The fixed bagworm
silk thread was peeled off at a constant speed (100 µm/sec), with variations in the
tension being continuously recorded on the load cell. This measurement was made using
a tensile tester (a small tabletop tester, EZ Test, from Shimadzu Corporation).
[0077] In this Example, the total of peak areas per zigzag block obtained in the peeling
test was divided by the peeled length to calculate a peeling energy per unit peeled
length. In order to minimize the influence of differences between bagworm individuals
used in the spinning process on the adhesive force, the result obtained from when
each wetting liquid was used was normalized with the peeling energy of a negative
control (wetting liquid unapplied sample), in which a foothold silk thread is spun
by the same bagworm individual, and was evaluated and compared in percentage (%) assuming
that the peeling energy for the negative control was 100.
(Result)
[0078] The results are shown in Figure 4 and Table 1.
[Table 1]
| |
H2O |
EtOH Concentration |
|
| 30% |
50% |
70% |
99.5% |
| Relative value (%) |
29 |
11 |
7 |
10 |
6 |
[0079] In Figure 4, the horizontal axis indicates the peeled length (mm), and the vertical
axis indicates the peel tension (N). As shown in Figure 4(A), the negative control
required a relatively strong peeling tension of 0.003 to 0.004 N at each fixed point
per zigzag block. In contrast, in the case where water was applied, the peeling tension
was approximately 0.001 N, showing a decrease to approximately 1/4 of that for the
negative control, as shown in Figure 4(B). Furthermore, when ethanol (99.5%) was applied,
it was revealed, as shown in Figure 4(C), that the peeling tension was 0.0001 to 0.0002
N, showing a dramatic decrease to approximately 1/20 to 1/40 of that for the negative
control.
[0080] As shown in Table 1, the peeling energy was decreased to approximately 30% of that
for the negative control when water was applied to a base material and a bagworm silk
thread. When ethanol (99.5%) was applied, the peeling energy was decreased to 6% of
that for the negative control, exhibiting a more marked effect than water. This effect
of ethanol was also maintained at various concentrations when an aqueous ethanol solution,
a solution mixture of ethanol and water, was used. At any of the concentrations, the
effect was verified as higher than that of water.
<Example 2>
(Purpose)
[0081] A peeling tension evaluation test verifies that the method for producing a thread
bundle according to the present invention can be used with the other wetting liquid
other than water and ethanol.
(Method)
[0082] The basic procedures and basic operation were performed as in Example 1. The wetting
liquids used here were: methanol (MeOH) as a polarity monovalent alcohol; 1,1,1,3,3,3-hexafluoro-2-propanol
(HFIP) as a polarity halogen-containing organic solvent; dimethylsulfoxide (DMSO)
as a polarity sulfur-containing organic solvent; carbon tetrachloride as a low polarity
halogen-containing organic solvent; glycerin as a polarity trivalent alcohol; furthermore,
an aqueous solution of sodium chloride having a concentration of 0.05 M (NaCl aq);
and an aqueous solution of 0.05 M sodium carbonate (Na
2CO3 aq) widely used in a degumming process for a silkworm silk thread.
(Result)
[0083] The results are shown Table 2.
[Table 2]
| |
MeOH |
HFIP |
DMSO |
Carbon Tetrachloride |
Glycerin |
0.05M Na2CO3 |
0.05M NaCl |
| Relative value (%) |
11 |
13 |
13 |
6 |
14 |
6 |
11 |
[0084] As shown in Table 2, with any wetting liquid, the peeling energy was decreased to
15% or less of that for the negative control. Additionally, a high effect was verified
with any of the liquids, showing that half or less of the peeling energy for the water-applied
sample was sufficient.
[0085] All publications, patents, and patent applications cited herein should be incorporated
herein by reference in their entirety.