Technical Field
[0001] The present invention relates to an aerosol cooling member.
Background Art
[0002] There has been an increasing demand for Reduced Risk Products, which do not use fire,
in place of regular cigarettes. Reduced Risk Products are generally divided into two
types. The first is a type in which a solution obtained by dissolving nicotine in
an organic solvent is heated, and the resulting aerosol or vapor is inhaled. The second
is a type in which an aerosol containing nicotine that disperses upon the heating
of tobacco leaves is inhaled. This type does not burn the tobacco leaves. Here, the
tobacco leaves may be pseudo-tobacco leaves, product obtained by processing tobacco
leaves, or a base material soaked with tobacco components. However, in Japan, nicotine
itself is designated as a pharmaceutical product, and the handling of nicotine is
regulated. For example, the sale of nicotine is prohibited, in principle. In such
cases, e-cigarettes of a type in which a solution that contains nicotine dissolved
in an organic solvent is heated and the resulting aerosol or vapor is inhaled, cannot
be sold. Further, nicotine is also designated as a pharmaceutical product in many
countries besides Japan. Note that iQOS (trade name), available from Philip Morris
International Inc., is a Reduced Risk Product (heated tobacco product (HTP)) of a
type in which a dedicated aerosol-generating article (Heatstick (trade name)) is used,
and an aerosol containing nicotine that disperses upon the heating of tobacco leaves
is inhaled.
[0003] Patent Document 1 describes, as an example of an aerosol-generating article for use
in a heated tobacco product, one having a structure in which a mouthpiece, an aerosol-cooling
element, a support element, and an aerosol-forming base material are arranged in this
order from a side close to a mouth-end, and also indicates that the aerosol-generating
article includes a cellulose acetate tow filter as the mouthpiece, a polylactic acid
sheet as the aerosol-cooling element, a hollow cellulose acetate tube as the support
element, and tobacco as the aerosol-forming base material.
[0004] With heated tobacco products, a portion of the aerosol-generating article remains
after smoking is finished. Thus, an environmental issue can arise when the remaining
used aerosol-generating article is discarded. To address this environmental issue,
as described above, a film that uses a biodegradable polylactic acid as a material
is used as an aerosol-cooling element of the aerosol-generating article used in a
heated tobacco product. Note that in typical cigarette members (cigarettes), a cooling
member is not required because the air-flow resistance of the cigarette leaf or filter
portion is high.
Citation List
Patent Document
Summary of Invention
Technical Problem
[0006] However, polylactic acid has a low degree of crystallization, and the glass transition
temperature (Tg) is also low, and thus the heat resistance of polylactic acid is poor.
In particular, polylactic acid has a property of softening and deforming at around
60°C. Thus, aerosol-generating articles that use polylactic acid in a cooling member
have poor thermal stability. Therefore, in a heated tobacco product (HTP) in which
a polylactic acid film is used as a cooling member, the film is deformed by heat while
the product is smoked, and this deformation blocks the air flow channel, and makes
smoking difficult.
[0007] In addition, an aerosol with a temperature of approximately 70°C has to be cooled
to room temperature with a cooling member, but the polylactic acid film in the current
product has insufficient endothermic performance (cooling performance), and there
is a demand for further cooling effects.
[0008] Furthermore, polylactic acid is biodegradable in certain environments, such as at
elevated temperatures of around 60°C during composting, but similar to typical general
purpose petroleum-based plastics (for example: polypropylene (PP)), polylactic acid
does not degrade for the most part in other ordinary environments (for example, in
seawater or rivers). As such, polylactic acid films are also inferior in biodegradability.
[0009] Thus, an object of the present invention is to provide an aerosol cooling member
excelling in thermal stability, endothermic properties, and biodegradability.
Solution to Problem
[0010] The present disclosure relates to an aerosol cooling member containing cellulose
acetate having a total degree of acetyl substitution of greater than 1.4 and not greater
than 2.7 as defined in claim 1. Preferred embodiments are given in claims 2 to 14
as well as in the following description.
[0011] The aerosol cooling member preferably has a glass transition temperature of 70°C
or higher.
[0012] Preferably, a marine biodegradability performance of the aerosol cooling member is
50% or greater for 180 days as measured in accordance with ASTM D6691.
[0013] With respect to the aerosol cooling member, the cellulose acetate preferably has:
τ of not less than 2.0, τ being a ratio of a sum of a degree of acetyl substitution
at a 2-position and a degree of acetyl substitution at a 3-position to a degree of
acetyl substitution at a 6-position in terms of the total degree of acetyl substitution;
and a sulfuric acid component amount of greater than 20 ppm and not greater than 400
ppm.
[0014] With respect to the aerosol cooling member, the amount of sulfuric acid component
in the cellulose acetate is preferably from 80 ppm to 380 ppm.
[0015] With respect to the aerosol cooling member, the amount of the sulfuric acid component
in the cellulose acetate is preferably from 150 ppm to 350 pm.
[0016] With respect to the aerosol cooling member, the cellulose acetate preferably has
τ of not greater than 2.5, τ being a ratio of a sum of a degree of acetyl substitution
at a 2-position and a degree of acetyl substitution at a 3-position to a degree of
acetyl substitution at a 6-position in terms of the total degree of acetyl substitution.
[0017] The aerosol cooling member may further include an additive, wherein the additive
is one or more selected from the group consisting of a material for which a pH of
a 1 wt.% aqueous solution thereof at 20°C is 8 or higher, a material that dissolves
at an amount of not less than 2 wt.% in water at 20°C, and a material having excellent
biodegradability in the ocean.
[0018] With respect to the aerosol cooling member, a content of the additive is preferably
from 4 to 40 wt.%.
[0019] With respect to the aerosol cooling member, the material for which a pH of a 1 wt.%
aqueous solution thereof at 20°C is 8 or higher is preferably magnesium oxide.
[0020] With respect to the aerosol cooling member, the material that dissolves at an amount
of not less than 2 wt.% in water at 20°C is preferably triacetin.
[0021] The aerosol cooling member may be fibrous.
[0022] The aerosol cooling member may be in a fibrous tow form having a denier per filament
of from 0.6 tex to 3.5 tex and a total denier from 1000 tex to 4500 tex.
[0023] The aerosol cooling member may be a particle.
[0024] The aerosol cooling member may be a porous structure.
[0025] The aerosol cooling member may be tubular.
[0026] The aerosol cooling member may be a film.
[0027] The aerosol cooling member preferably has an average temperature decrease rate of
water vapor of 5% or greater as measured under Conditions below:
Conditions:
[0028] A film-shaped aerosol cooling member having a length of 23.3 cm, a width of 17 mm,
and a thickness of 50 µm is inserted into a tube made of polytetrafluoroethylene and
having an inner diameter of 7 mm and a length of 17 mm, water vapor having a temperature
of approximately 70°C immediately before passing through the tube is continuously
passed through the inside of the tube at a constant flow rate 35 ml/min, and the temperature
(°C) of the water vapor immediately before passing through the tube and the temperature
(°C) of the water vapor immediately after passing through the tube are measured every
1 second for 120 seconds. An average value of the temperature decrease rate (%) of
the water vapor for 120 seconds, as calculated by formulas below, is taken as the
average temperature decrease rate of the water vapor:

Advantageous Effects of Invention
[0029] According to the present invention, an aerosol cooling member excelling in thermal
stability, endothermic properties, and biodegradability can be provided.
Description of Embodiments
[Aerosol cooling member]
[0030] An aerosol cooling member according to an embodiment of the present disclosure contains
cellulose acetate having a total degree of acetyl substitution of greater than 1.4
and not greater than 2.7.
[0031] In the present disclosure, "aerosol" refers to a colloidal dispersion system in which
a solid or liquid is dispersed in a gas, and includes smoke (a state in which a group
of microparticles (less than approximately 10 µm) is suspended in a gas).
[0032] The total degree of acetyl substitution of the cellulose acetate contained in the
aerosol cooling member according to an embodiment of the present disclosure is greater
than 1.4 and not greater than 2.7, preferably not greater than 2.6, more preferably
not greater than 2.5, and even more preferably not greater than 2.2. Such a total
degree of acetyl substitution is preferable because at such level, the equilibrium
moisture ratio is high and endothermic performance (cooling performance) is excellent.
The total degree of acetyl substitution may be not less than 1.6, and is preferably
not less than 1.8. When the total degree of acetyl substitution of the cellulose acetate
is too high, the biodegradability of the aerosol cooling member in seawater is inferior,
and when the total degree of acetyl substitution is too low, the moldability of the
aerosol cooling member is poor.
[0033] The total degree of acetyl substitution is a sum of each degree of acetyl substitution
at the 2-, 3-, and 6-positions of the glucose ring of the cellulose acetate as measured
below.
[0034] Each degree of acetyl substitution at the 2-, 3-, and 6-positions of the glucose
ring of the cellulose acetate can be measured by NMR in accordance with the Tezuka
method (
Tezuka, Carbohydr. Res. 273, 83 (1995)). That is, the free hydroxyl group of a cellulose acetate sample is propionylated
with propionic anhydride in pyridine. The resulting sample is dissolved in deuterated
chloroform, and the 13C-NMR spectrum is measured. The carbon signals of the acetyl
group appear in the region from 169 ppm to 171 ppm in the order of position 2-, 3-,
and 6- from the high magnetic field; and the carbonyl carbon signals of the propionyl
group appear in the region from 172 ppm to 174 ppm in the same order. Each degree
of acetyl substitution at the 2-, 3-, and 6-positions of the glucose ring in the original
cellulose acetate can be determined from the presence ratio of the acetyl group and
the propionyl group at respective positions (in other words, the area ratio of each
signal). The degree of acetyl substitution can also be analyzed by
1H-NMR in addition to
13C-NMR
[0035] The ratio τ, which is the sum of the degree of acetyl substitution at the 2-position
and the degree of acetyl substitution at the 3-position to the degree of acetyl substitution
at the 6-position in the total degree of acetyl substitution, is preferably 2.0 or
greater. Also, τ may be 2.1 or greater, 2.2 or greater, or 2.3 or greater. The upper
limit is not particularly limited, but τ may be not greater than 2.5. The aerosol
cooling member exhibits more excellent biodegradability in seawater when τ of the
cellulose acetate is 2.0 or greater.
[0036] An amount of a sulfuric acid component in the cellulose acetate of the aerosol cooling
member according to an embodiment of the present disclosure preferably exceeds 20
ppm and is not greater than 400, is more preferably from 50 ppm to 380 ppm, is even
more preferably from 80 ppm to 380 ppm, is particularly preferably from 100 ppm to
350 ppm, and is most preferably from 150 ppm to 350 ppm. When the amount of the sulfuric
acid component is within the above range, the aerosol cooling member exhibits more
excellent biodegradability in seawater. As the amount of the sulfuric acid component
increases, the biodegradability in seawater increases. In addition, production of
the cellulose acetate becomes difficult when the amount of the sulfuric acid component
is too high.
[0037] The amount of the sulfuric acid component is the amount calculated in terms of the
SO
42- of a sulfurous acid gas sublimated from dried cellulose acetate.
[0038] The glass transition temperature of the aerosol cooling member according to an embodiment
of the present disclosure is preferably 70°C or higher, more preferably 90°C or higher,
and even more preferably 110°C or higher. Furthermore, the glass transition temperature
may be 190°C or lower, 170°C or lower, or 150°C or lower.
[0039] The glass transition temperature can be measured using a differential scanning calorimeter
(DSC).
[0040] In the aerosol cooling member according to an embodiment of the present disclosure,
the marine biodegradability performance is, for 180 days, preferably 50% or greater,
more preferably 60% or greater, even more preferably 70% or greater, particularly
preferably 80% or greater, and most preferably 90% or greater, as measured in accordance
with ASTM D6691. As the value indicated by "%" increases, the biodegradability in
a marine environment becomes more superior.
[0041] The equilibrium moisture ratio of the aerosol cooling member according to an embodiment
of the present disclosure is preferably 1 wt.% or higher, more preferably 2 wt.% or
higher, and even more preferably at 4 wt.% or higher. Additionally, the equilibrium
moisture ratio may be 10 wt.% or less. A larger value of the equilibrium moisture
ratio indicates more superior endothermic performance (cooling performance).
[0042] The equilibrium moisture ratio in the present disclosure is a value that is obtained
by leaving the aerosol cooling member standing at a temperature of 23°C and a relative
humidity of 60 RH% for 6 hours or longer to thereby humidify the aerosol cooling member,
and subsequently vacuum drying the aerosol cooling member for three full days at a
temperature of 40°C, determining the weights immediately after humidification and
immediately after drying, and using the weights thereof to calculate the equilibrium
moisture ratio using the following formula. Equilibrium Moisture Ratio (wt.%) = (Weight
immediately after humidification - weight immediately after drying)/(weight immediately
after drying) × 100
[0043] The aerosol cooling member according to an embodiment of the present disclosure may
contain an optional component in addition to the cellulose acetate. Examples of the
optional component include additives and materials that are highly safe in a marine
environment.
[0044] Examples of the additive include one or more additives selected from the group consisting
of a material for which a pH of a 1 wt.% aqueous solution thereof at 20°C is 8 or
higher, a material that dissolves at an amount of not less than 2 wt.% in water at
20°C, and a material with excellent biodegradability in the ocean.
(Material for which the pH of a 1 wt.% aqueous solution thereof at 20°C is 8 or higher)
[0045] The material for which the pH of a 1 wt.% aqueous solution thereof at 20°C is 8 or
higher can be also referred to as a basic additive. The pH of the 1 wt.% aqueous solution
of the basic additive at 20°C is preferably 8.5 or higher, and more preferably from
8.5 to 11.
[0046] The pH of the 1 wt.% aqueous solution at 20°C is measured according to a standard
procedure, and for example, can be measured with a glass pH electrode.
[0047] In the present disclosure, the "1 wt.% aqueous solution at 20°C" does not require
that all the solute be dissolved in water. An aqueous solution typically refers to
a liquid in which a solute is dissolved in water (H
2O), that is, a solution in which the solvent is water. The water molecule is a polar
molecule, and thus the material that becomes the solute in the aqueous solution is
believed to be an ionic crystal or a polar molecular material. However, in the present
disclosure, the term"aqueous solution" includes a suspension. That is, the aqueous
solution includes a slurry and a colloidal solution, which are disperse systems in
which solid particles are dispersed in a liquid. In addition, the "1 wt.% aqueous
solution at 20°C" in the present disclosure includes those aqueous solutions for which,
when 1 wt.% of the basic additive is added to water, a portion of the basic additive
dissolves and forms an aqueous solution, and a remaining portion of the basic additive
forms a suspension.
[0048] The solid particles may be colloidal particles (for example, approximately 100 nm
or less), or may be particles larger than colloidal particles. A suspension of colloidal
particles is referred to as a colloidal solution, and a suspension of particles larger
than colloidal particles may be referred to simply as suspension. Unlike a colloidal
solution, a suspension of particles larger than the colloidal particles settles to
a steady state over time. The solid particles larger than colloidal particles can
be seen under a microscope and may subside over time when placed in a quiet location.
[0049] When the basic additive in the aqueous solution is an inorganic material that is
ionized in the aqueous solution, the surface of the inorganic material adsorbs and
charges ions by the effect of the surface charge of the particles and affects the
ion distribution in the vicinity of the surface. This effect causes a distribution
of ions around the surface of the basic additive called an electric double layer,
the distribution different from that in the solution (solvent) outside the vicinity
of the particle interface. The electric double layer is formed of a fixed layer in
which ions are strongly adsorbed on the particle surface and a diffusion layer that
exists away from the fixed layer. Also when the basic additive of the present disclosure
is not dissolved in water, the pH of the dispersion medium changes because of the
surface charge of the basic additive as described above.
[0050] Examples of the material (basic additive) for which the pH of a 1 wt.% aqueous solution
thereof at 20°C is 8 or higher include oxides, hydroxides, carbonates, acetates, ammonium
salts, aluminates, silicates, or metasilicates of alkaline earth metals or alkali
metals; ZnO; and basic Al
2O
3.
[0051] The basic additive is preferably one or more selected from the group consisting of
oxides, hydroxides, carbonates, ammonium salts, aluminates, silicates, or metasilicates
of alkaline earth metals or alkali metals; ZnO; and basic Al
2O
3.
[0052] The basic additive is more preferably one or more selected from the group consisting
of oxides, hydroxides, aluminates, silicates, or metasilicates of alkaline earth metals
or alkali metals; ZnO; and basic Al
2O
3.
[0053] The basic additive is even more preferably one or more selected from the group consisting
of oxides, aluminates, silicates, or metasilicates of alkaline earth metals or alkali
metals; ZnO; and basic Al
2O
3.
[0054] The basic additive is still even more preferably one or more selected from the group
consisting of oxides, aluminates, silicates, and metasilicates of alkaline earth metals
or alkali metals.
[0055] The basic additive is particularly preferably an oxide of an alkaline earth metal.
Magnesium oxide (MgO) is one of the most preferred basic additives.
[0056] An example of the metasilicates of alkaline earth metals or alkali metals is magnesium
aluminometasilicate, which is represented by the general formula Al
2O
3•MgO•2SiO
2•xH
2O (where x represents the number of waters of crystallization, and 1 ≤ x ≤ 10). Magnesium
aluminometasilicate itself is well known, and a commercially available product can
also be used. For example, magnesium aluminometasilicate of the Japanese Pharmaceutical
Codex can be suitably used. Magnesium metasilicate aluminate is marketed under the
trade designation of Neusilin (trade name) as an antacid.
[0057] The basic additive according to an embodiment of the present disclosure need not
necessarily be water soluble, and may have a solubility from 10
-7 to 70 g per 100 mL of water at 20°C. The basic additive according to an embodiment
of the present disclosure preferably has a solubility of not less than 10
-6 g per 100 mL of water at 20°C, more preferably has a solubility of not less than
10
-5 g per 100 mL of water at 20°C, and even more preferably has a solubility of not less
than 10
-4 g per 100 mL of water at 20°C. In addition, the basic additive preferably has a solubility
of not greater than 10 g per 100 mL of water at 20°C, more preferably has a solubility
of not greater than 1 g per 100 mL of water at 20°C, and even more preferably has
a solubility of not greater than 0.1 g per 100 mL of water at 20°C.
[0058] Examples of the additive having a solubility in water of about 10
-4 g/100 mL (20°C) include MgO, ZnO, and Mg(OH)
2. An example of the additive having a solubility in water of about 10
-2 g/100 mL (20°C) is MgCO
3. Examples of the additive having a solubility in water of about 0.1 g/100 mL (20°C)
include CaO and Ca(OH)
2.
(Material dissolving at not less than 2 wt.% in water at 20°C)
[0059] The material dissolving at not less than 2 wt.% in water at 20°C may be either a
high molecular weight material or a low molecular weight material as long as the material
is water soluble.
[0060] Examples of the high molecular weight material include hydrophilic polymers, and
examples of the high molecular weight material include polysaccharides and plasticizers
for cellulose acetate. Examples of the polysaccharides include oligosaccharides (powdered
oligosaccharides), reduced starch syrup, and cluster dextrin. Examples of oligosaccharides
include starch sugars (starch saccharification products), galactooligosaccharides,
coupling sugars, fructooligosaccharides, xylooligosaccharides, soybean oligosaccharides,
chitin oligosaccharides, and chitosan oligosaccharides, and these components can be
used alone or in a combination of two or more.
[0061] The material dissolving at not less than 2 wt.% in water at 20°C described above
preferably contains a plasticizer for cellulose acetate.
(Plasticizer for cellulose acetate)
[0063] In addition, as the plasticizer, a glycerin ester plasticizer can be used. As the
glycerin ester plasticizer, a lower fatty acid ester of glycerin, in other words,
an ester compound of glycerin and a fatty acid having from 2 to 4 carbons can be used.
A fatty acid having 2 carbons is acetic acid, a fatty acid having 3 carbons is propionic
acid, and a fatty acid having 4 carbons is butyl acid. The glycerin ester plasticizer
may be an ester in which all three hydroxyl groups of glycerin are esterified with
the same fatty acids, an ester in which two hydroxyl groups are esterified with the
same fatty acids, or an ester in which all three hydroxyl groups of glycerin are esterified
with different fatty acids.
[0064] Glycerin ester plasticizers are non-toxic and easily biodegraded, and thus have a
small environmental load. In addition, the addition of a glycerin ester plasticizer
to the cellulose acetate can lower the glass transition temperature of the resulting
aerosol cooling member. Thus, this can also impart excellent thermoformability to
the raw material.
[0065] When the fatty acid is acetic acid, examples of the glycerin ester plasticizer include
triacetin, in which three hydroxyl groups of glycerin are esterified with acetic acid,
and diacetin, in which two hydroxyl groups are esterified with acetic acid.
[0066] Among the glycerin ester plasticizers described above, triacetin (glycerol trisacetate),
in which all three hydroxyl groups of glycerin are esterified with acetic acid (in
other words, acetylated), is preferred. Triacetin is a component recognized as safe
for humans even when ingested. Triacetin is also easily biodegraded, and thus has
a small environmental load. In addition, the biodegradability of an aerosol cooling
member obtained by adding triacetin to the cellulose acetate is improved compared
to a case in which cellulose acetate is used alone. Furthermore, the addition of triacetin
to the cellulose acetate can efficiently lower the glass transition temperature. Thus,
this can impart excellent thermoformability to the raw material.
[0067] Triacetin is preferably pure in terms of chemical structure and high in purity. In
addition, for example, a plasticizer containing not less than 80 wt.% or not less
than 90 wt.% of triacetin with the remaining being monoacetin and/or diacetin may
be used.
(Material with excellent biodegradability in the ocean)
[0068] The addition of a material with excellent biodegradability in the ocean can promote
biodegradability of the aerosol cooling member. Examples of the material with excellent
biodegradability in the ocean include compounds with excellent biodegradability in
the ocean. Examples of such compounds include polyhydroxyalkanoates such as poly[hydroxybutyrate-co-hydroxyhexanoate]
(PHBH), polyhydroxybutyrate, and thermoplastic starch resins (including acetylated
starch).
[0069] The process of biodegradation of the cellulose acetate contained in the aerosol cooling
member according to an embodiment of the present disclosure is as follows. The mechanism
of biodegradation of cellulose acetate is commonly believed to be a mechanism in which
once each acetyl group of the cellulose acetate is hydrolyzed, the resulting cellulose
acetate with a reduced degree of substitution undergoes degradation by an action of
a cellulose-degrading enzyme (e.g., β-glucosidase; EC 3.2.1.21). β-glucosidase (EC
3.2.1.21) is an enzyme that catalyzes the hydrolysis of β-glycosidic linkages in sugars
and is also called β-D-glucoside glucohydrolase and amygdalase. The β-glycosidic linkage
constituting the polymer chain of cellulose acetate is hydrolyzed, and the resulting
monosaccharides and low molecular weight polysaccharides then undergo degradation
through metabolism by common microorganisms. Thus, to promote biodegradability, promoting
the detachment of acetyl groups is effective.
[0070] The ocean is weakly basic, and this basicity also leads to deacetylation of cellulose
acetate. As a result of examinations, it was found that deacetylation (hydrolysis)
under basic conditions is faster at the 2- and 3-positions in the glucose ring than
at the 6-position. Thus, for example, for cellulose acetates with the same total degree
of substitution, it was found that a cellulose acetate with higher degree of substitution
at the 2- and 3-positions than at the 6-position results in a faster rate of decrease
in the total degree of substitution and leads to faster biodegradation. In addition,
it was found that when the amount of the sulfuric acid component in the cellulose
acetate at that time is from greater than 20 ppm to 400 ppm or less, more excellent
biodegradability is achieved. When the amount of the sulfuric acid component is in
excess, there is a concern that degradation may occur when used as a product that
is immersed in the ocean. These effects are considered to exhibit the same tendency
in any total degree of substitution, when compared among the cellulose acetates having
the same total degree of substitution. However, the cellulose acetate with a total
degree of acetyl substitution of not greater than 2.7 has an excellent level of biodegradability.
[0071] When a material for which the pH of a 1 wt.% aqueous solution thereof at 20°C is
8 or higher is contained, the degradation mechanism of the aerosol cooling member
according to an embodiment of the present disclosure is as follows. Although this
mechanism is a speculation, it is thought that a material (basic additive) for which
the pH of a 1 wt.% aqueous solution thereof at 20°C is 8 or higher promotes hydrolysis
(deacetylation) of the cellulose acetate in weakly basic seawater. This deacetylation
effect due to the basic material is remarkable in a cellulose acetate having more
acetyl groups at the 2- and 3-positions than at the 6-position, and is more remarkable
in a cellulose acetate having a large amount of sulfuric acid components. It is thought
that as a result, the degree of substitution of the cellulose acetate constituting
the aerosol cooling member is reduced, and this can then contribute to improved biodegradability.
These properties are preferably exhibited immediately upon contact with seawater,
without being exhibited during use of the aerosol cooling member as a product. Thus,
the basic material is dispersed as solid particles in the aerosol cooling member,
the particle diameter of the basic material is preferably as fine as possible, and
the specific surface area is preferably large.
[0072] In addition, the aerosol cooling member according to an embodiment of the present
disclosure can contain a material that dissolves at an amount of not less than 2 wt.%
in water at 20°C. Such a material can dissolve in seawater when the aerosol cooling
member is immersed in seawater. In addition, such as material escapes from the aerosol
cooling member and thereby forms structural gaps in a molded article configured by
the aerosol cooling member. This allows microorganisms to easily enter the gaps and
increases the surface area of the molded article configured by a composition of cellulose
acetate. As a result, such a material can contribute to improved biodegradability.
Examples of the material include triacetin and diacetin. Triacetin and diacetin also
act as plasticizers for the cellulose acetate and thus can contribute to improving
thermoformability.
[0073] The content of the additive in the aerosol cooling member, in terms of the total
content, is preferably not greater than 40 wt.%, more preferably not greater than
30 wt.%, and even more preferably not greater than 20 wt.%. In addition, the content
of the additive is preferably not less than 4 wt.%, more preferably not less than
5 wt.%, and even more preferably not less than 10 wt.%.
[0074] The content of the basic additive (material for which the pH of a 1 wt.% aqueous
solution thereof at 20°C is 8 or higher) in the aerosol cooling member is preferably
from 1 to 30 wt.%, more preferably from 2 to 20 wt.%, even more preferably from 3
to 15 wt.%, and particularly preferably from 4 to 10 wt.%. An excess amount of the
basic additive could cause problems in areas such as moldability including difficulty
in molding the aerosol cooling member.
[0075] The content of the water-soluble additive (material dissolving at not less than 2
wt.% in water at 20°C) in the aerosol cooling member is preferably from 5 to 30 wt.%,
more preferably from 7.5 to 28 wt.%, and even more preferably from 10 to 25 wt.%.
An excess amount of the water-soluble additive reduces the strength of the aerosol
cooling member.
[0076] The content of the material excelling in biodegradability in the ocean with respect
to the aerosol cooling member is preferably from 5 to 40 wt.%.
[0077] The aerosol cooling member according to an embodiment of the present disclosure can
be used in a mixture with another material to improve biodegradability of the mixture
as a whole.
[0078] Although the basic material is added to the aerosol cooling member, the effect from
the addition of the basic material may not be obtained in a case in which the composition
contains, for example, an acidic material, undergoes a neutralization reaction when
immersed in water, and becomes neutral to acidic.
[0079] Thus, when the aerosol cooling member according to an embodiment of the present disclosure
is mixed with water to obtain a slurry, the pH of the slurry at 20°C is preferably
from 7 to 13, and is more preferably from 8 to 12.
[0080] The biodegradation of the cellulose acetate of the present disclosure is thought
to occur as follows. Namely, acetyl groups are first detached, the degree of acetyl
substitution is reduced and approaches that of cellulose, and the cellulose acetate
is degraded by the action of microorganisms. Thus, the additive is preferably an additive
promoting the degradation of the cellulose acetate.
[0081] The shape of the aerosol cooling member according to an embodiment of the present
disclosure is not particularly limited, and for example, may be fibrous, film-shaped,
particle-shaped, a porous structure, or tubular. The fibers may also form the shape
of a fiber tow.
[0082] Fibrous means a shape with a fiber diameter of not greater than 0.2 mm and an aspect
ratio of greater than 50.
[0083] Examples of the fiber tow shaped aerosol cooling member include a fiber tow shape
having a denier per filament from 0.6 tex to 3.5 tex and a total denier from 1000
tex to 4500 tex. When the denier per filament and total denier are within the above
ranges, the balance between the cooling effect and the air permeability of the aerosol
is favorable, and thus such ranges are preferable. If the denier per filament is too
small, the air-flow resistance may be too high, and the smoke flavor components in
the aerosol may be excessively adsorbed.
[0084] "Particle-shaped" refers to a shape in which the particle diameter is 5 mm or less
and the aspect ratio is from 0.1 to 50.
[0085] When the aerosol cooling member is particle-shaped, the upper limit of the particle
diameter may be, for example, 3.35 mm, 3.0 mm, 2.5 mm, 2.0 mm, or 1.5 mm. The lower
limit of the particle diameter may be, for example, 0.18 mm, 0.20 mm, 0.30 mm, 0.40
mm, or 0.50 mm.
[0086] Furthermore, the particle diameter is defined as the minimum value of the mesh size
of a sieve through which the aerosol cooling member can pass, from among test sieves
conforming to JIS Z 8801.
[0087] When the aerosol cooling member is in the form of particles, a proportion of particles
having a particle diameter of not greater than 2 mm is preferably 50 wt.% or less.
This is due to excellent biodegradability of such particles.
[0088] The proportion (wt.%) of particles having a particle diameter of not greater than
2 mm can be determined using a sieve specified in JIS Z 8801. That is, the proportion
thereof can be determined by attaching a receiving pan and a sieve having mesh openings
of 2 mm to a RO-TAP sieve shaker (available from Sieve Factory Iida Co., Ltd., tapping:
156 times/min, rolling: 290 times/min), oscillating 100 g of a sample for 5 minutes,
and then calculating the proportion of the weight of the particles in the receiving
pan relative to the total weight (100 g of the sample).
[0089] When the aerosol cooling member is in the form of particles, each particle may have
one or a plurality of faces, and each face may be in a shape selected from any of
circular, triangular, quadrilateral, pentagonal, and hexagonal shapes. In addition,
each side length may be set to a value in a range from 0.18 mm to 3.35 mm, or in a
range from 0.18 mm to less than 3.00 mm. Note that a particle shape having a plurality
of faces is referred to as a polyhedral shape.
[0090] When the aerosol cooling member is in the form of particles, each particle may be
formed in a cylindrical (including ellipsoid) shape. In addition, each side length
may be set to a value in a range from 0.18 mm to 3.35 mm, or in a range from 0.18
mm to less than 3.00 mm.
[0091] The side length refers to a linear distance between adjacent vertices at the projected
plane when viewed from a certain angle, or the intersecting line distance between
faces. In addition, the polyhedrons, cylinders, and elliptical cylinders mentioned
here also include shapes having some shape error that may occur during production,
for example.
[0092] "Porous structure" refers to a porous structure having a continuous porosity of not
less than 50%.
[0093] "Tubular" refers to a structure that forms a hollow tube shape. The tubular shape
may be a hollow shape having substantially the same cross-section along the axial
direction of the member, or may have a circular, elliptical, rectangular, or polygonal
cross-sectional shape. Tubular refers to an elongated shape for which the shape is
maintained at the outer side, a hollow cavity is present in the inside, and at least
a portion of the cavity is opened to the outside. Note that it is not necessary for
both ends to be penetrated, and the tubular form is not required to be penetrating
in all cross sections.
[0094] "Film-shaped" refers to a shape in the form of a thin film with a thickness of 200
µm or less.
[0095] When the aerosol cooling member is formed in the shape of a film, the air-flow resistance
(air-flow resistance per unit weight) measured under the following conditions may
be 1 mmWG/g or greater, 5 mmWG/g or greater, 10 mmWG/g or grater, 30 mmWG/g or greater,
or 40 mmWG/g or greater. The air-flow resistance may also be 1500 mmWG g or less,
1000 mmWG/g or less, 500 mmWG/g or less, 100 mmWG/g or less, or 50 mmWG/g or less.
[0096] A film-shaped aerosol cooling member having a length of 23.3 cm, a width of 17 mm,
and a thickness of 50 µm is inserted into a polytetrafluoroethylene tube having an
inner diameter of 7 mm and a length of 17 mm. The tube containing the aerosol cooling
member is then inserted into a sample holder of an air-flow resistance measuring instrument
(available from OTIC KATO KOGYOSHO TOKYO), and the air-flow resistance (mmWG) may
be measured.
[0097] When the aerosol cooling member has a film shape, the average temperature decrease
rate of the water vapor measured under the following conditions is preferably 5% or
higher, more preferably 8% or higher, and even more preferably 10% or higher.
[0098] A film-shaped aerosol cooling member having a length of 23.3 cm, a width of 17 mm,
and a thickness of 50 µm is inserted into a tube made of polytetrafluoroethylene and
having an inner diameter of 7 mm and a length of 17 mm, water vapor having a temperature
of approximately 70°C immediately before passing through the tube is continuously
passed through the inside of the tube at a constant flow rate 35 ml/min, and the temperature
(°C) of the water vapor immediately before passing through the tube and the temperature
(°C) of the water vapor immediately after passing through the tube are measured every
1 second for 120 seconds. An average value of the temperature decrease rate (%) of
the water vapor over the period of 120 seconds, calculated by the following formula,
is taken as the average temperature decrease rate of the water vapor.
[0099] Temperature Decrease Rate (%) of Water Vapor = [(Temperature (°C) of water vapor
immediately before passing through tube) - (Temperature (°C) of water vapor immediately
after passing through tube)]/(Temperature (°C) of water vapor immediately before passing
through tube) × 100
[0100] When the aerosol cooling member is in the shape of a film, the thickness of the film
is preferably not greater than 100 µm, more preferably not greater than 80 µm, and
even more preferably not greater than 60 µm. This is because the thickness does not
have a significant impact on the cooling effect, but has a negative effect of increasing
the air-flow resistance.
[Aerosol cooling member production method]
[0101] The method for producing the aerosol cooling member according to an embodiment of
the present disclosure is not particularly limited, and examples include the following
methods. A method that includes mixing cellulose acetate with a solvent such as acetone,
and removing the solvent (when the aerosol cooling member is molded into a fibrous
form, specific examples of the method thereof include a method of molding cellulose
acetate dissolved in a solvent, as exemplified by dry spinning), and a melt molding
method (for example, extrusion molding) in which cellulose acetate is heated and melted
with an additive. Either method may further include thermoforming into a desired shape.
[0102] Methods that can be used to include an additive include, for example, a method of
mixing the cellulose acetate and the additive in advance prior to mixing with the
solvent or prior to melt molding, and forming a mixture of cellulose and the additive,
a method of mixing an additive into a solution obtained by mixing cellulose acetate
with a solvent, and a method of mixing cellulose acetate and an additive in parallel
with mixing with a solvent or melt molding.
(Method for producing cellulose acetate)
[0103] The method for producing the cellulose acetate used as a raw material of the aerosol
cooling member is not particularly limited, and examples include the following method.
A production method including (a) producing a cellulose acetate dope by allowing a
cellulose and acetic anhydride to react in the presence of an acid catalyst and an
acetic acid solvent, (b) hydrolyzing the produced cellulose acetate to achieve a total
degree of acetyl substitution of greater than 1.4 and not greater than 2.7, and (c)
precipitating the hydrolyzed cellulose acetate with a precipitant.
[0104] A case in which a molding step is included to mold the aerosol cooling member according
to an embodiment of the present disclosure into a desired shape is described.
[0105] In the case of molding into a fibrous form, the molding method is not particularly
limited, and examples thereof include methods such as a known dry spinning method
using a spinning solution containing a spinning solution and a cellulose acetate according
to an embodiment of the present disclosure. Examples of the spinning solution include
acetone.
[0106] In addition, in a case in which the aerosol cooling member is molded into a fiber
tow shape, the molding method is not particularly limited, and examples thereof include
known methods in which monofilaments of a quantity of around from 100 to 1000000,
from 500 to 50000, or from 1000 to 10000 are bundled (converged).
[0107] In a case in which the aerosol cooling member is molded into the form of particles,
the molding method is not particularly limited, and an example includes a method of,
first, preparing the cellulose acetate (and additives such as a plasticizer as necessary)
through dry or wet pre-mixing using a mixer such as a tumbler mixer, a Henschel mixer,
a ribbon mixer, or a kneader, then melt-kneading the material in an extruder such
as a single or twin screw extruder, extruding the melt-kneaded product into the form
of strands, and cutting the strands to prepare the aerosol cooling member in the form
of pellets.
[0108] The specific method for forming a porous structure with a foamed body, or a three-dimensional
molded article such as one with a tubular or hollow cylindrical form from a pellet-shaped
aerosol molded article through melt extrusion molding is not particularly limited,
and for example, injection molding, extrusion molding, vacuum molding, profile molding,
foam molding, injection pressing, press molding, blow molding, gas injection molding
can be used.
[0109] In the case of molding into a film shape, examples of the molding method include
known melt film formation methods using cellulose acetate according to an embodiment
of the present disclosure, and known solvent casting film formation methods using
a solution of cellulose acetate according to an embodiment of the present disclosure.
Examples
[0110] Hereinafter, the present invention will be specifically described with reference
to examples, but the technical scope of the present invention is not limited by these
examples.
[0111] Each physical property of the Examples and Comparative Examples described below were
evaluated by the following methods.
<Degrees of acetyl substitution at 2-, 3-, and 6-positions and total degree of acetyl
substitution>
[0112] The degrees of acetyl substitution at the 2-, 3-, and 6-positions of the glucose
ring of the cellulose acetate were each measured according to the method of Tezuka
(
Tezuka, Carbohydr. Res. 273, 83 (1995)) as described above by propionylating the free hydroxyl group of a cellulose acetate
sample using propionic anhydride in pyridine, dissolving the resulting sample in deuterated
chloroform, and measuring the
13C-NMR spectrum. Then, the degrees of acetyl substitution at the 2-, 3-, and 6-positions
(DS2, DS3, and DS6) were determined from surface area ratios of respective carbon
signals of the acetyl groups appearing in the order of the 2-, 3-, and 6-positions
from the high magnetic field in the region from 169 ppm to 171 ppm. The total degree
of acetyl substitution is the sum of the degrees of acetyl substitution at the 2-,
3-, and 6-positions. In addition, the sum of the degree of acetyl substitution at
the 2-position and the degree of acetyl substitution at the 3-position (DS2 + 3) and
the ratio τ of the sum of the degree of acetyl substitution at the 2-position and
the degree of acetyl substitution at the 3-position to the degree of acetyl substitution
at the 6-position were calculated.
<Sulfuric acid component amount>
[0113] Dried cellulose acetate was burned in an electric furnace at 1300°C, sublimated sulfurous
acid gas was trapped in a 10% hydrogen peroxide solution and titrated with a normal
aqueous solution of sodium hydroxide, and the amount of the sulfuric acid component
was measured in terms of SO
42-. The amount of the sulfuric acid component amount was expressed in units of ppm as
the amount of sulfuric acid component in 1 g of the cellulose acetate in an absolute
dry state.
<Slurry pH>
[0114] First, 2.0 g of a dried sample in the form of a fine powder was accurately weighed,
80 mL of boiled distilled water was added thereto and stirred. The mixture was then
sealed and allowed to stand for one night, after which the mixture was further stirred,
and the sample was precipitated. About 10 mL of the supernatant was taken as the sample
liquid, and the pH was measured with a calibrated pH meter. The pH of the boiled distilled
water was also measured as a blank, and the hydrogen ion concentration [H
+]
s of the sample liquid and the hydrogen ion concentration [H
+]
b of the blank liquid (where s represents the sample and b represents the blank) were
each calculated by the formula [H
+] = 10
-(pH) (where pH represents the measured pH value).
[0115] When [H
+]
s ≥ [H
+]
b, the slurry pH was calculated by the following formula.

[0116] When [H
+]
s < [H
+]
b, the hydroxyl group ion concentrations [OH
-]
s of the sample liquid and [OH
-]
b of the blank liquid were each calculated by the formula [OH
-] = 10
-14/[H
+], and the slurry pH was then calculated by the following formula.

<Thermal stability 1 (glass transition temperature (Tg))>
[0117] The glass transition temperature (Tg) was measured under the following measurement
conditions using a differential scanning calorimeter (DSC-Q2000, available from TA
Instruments Inc.).
Measurement Conditions:
[0118] Atmosphere: nitrogen
Temperature range: 30°C to 280°C
Rate of temperature increase: 10°C/min
<Thermal stability 2 (rate of increase in air-flow resistance)>
[0119] A film-shaped sample having a length of 23.3 cm, a width of 17 mm, and a thickness
of 50 µm was inserted into a polytetrafluoroethylene tube having an inner diameter
of 7 mm and a length of 17 mm. The tube containing the sample was then inserted into
a sample holder of an air-flow resistance measuring instrument (available from OTIC
KATO KOGYOSHO TOKYO), and the air-flow resistance (mmWG) was measured.
[0120] Subsequently, water vapor at a temperature of approximately 70°C immediately prior
to passing through the tube in which the sample was inserted was then continuously
passed through the tube at a constant flow rate of 35 ml/min for 120 seconds. The
tube containing the sample and through which was passed this water vapor was inserted
into the sample holder of the air-flow resistance measuring instrument, and the air-flow
resistance (mmWG) was measured once again.
[0121] The percentage (%) of increase in the air-flow resistance after the passage of the
water vapor relative to the air-flow resistance prior to the passage of the water
vapor was calculated. The measurements were performed five times (n = 5), and the
percentage of increase in the air-flow resistance was determined as the average value
of the five measurements.
<Endothermic property 1 (equilibrium moisture ratio)>
[0122] A film-shaped sample having a length of 23.3 cm, a width of 17 mm, and a thickness
of 50 µm was left standing at a temperature of 23°C and a relative humidity of 60
RH% for 6 hours or longer to thereby humidify the sample, after which the sample was
vacuum dried for three full days at a temperature of 40°C, and the weight immediately
after humidification and the weight immediately after drying were determined. The
equilibrium moisture ratio was calculated using the following formula: Equilibrium
Moisture Ratio (wt.%) = (Weight immediately after humidification - weight immediately
after drying)/(weight immediately after drying) × 100
<Endothermic property 2 (rate of temperature decrease of water vapor)>
[0123] A film-shaped sample having a length of 23.3 cm, a width of 17 mm, and a thickness
of 50 µm was inserted into a tube made of polytetrafluoroethylene and having an inner
diameter of 7 mm and a length of 17 mm, water vapor having a temperature of approximately
70°C immediately before passing through the tube was continuously passed through the
inside of the tube at a constant flow rate 35 ml/min, and the temperature (°C) of
the water vapor immediately before passing through the tube and the temperature (°C)
of the water vapor after passing through the tube were measured every 1 second for
120 seconds. The average value of the temperature decrease rate (%) of the water vapor
over the period of 120 seconds, calculated by the following formula, was taken as
the average temperature decrease rate of the water vapor.

[0124] For a case in which water vapor was similarly passed through a tube in which a sample
was not inserted, the temperature (°C) of the water vapor immediately prior to passing
through the tube and the temperature (°C) of the water vapor immediately after passing
through the tube were determined in advance as blank values. For the case in which
water vapor was passed through the tube in which the sample was inserted, the temperature
(°C) of the water vapor immediately prior to passing through the tube and the temperature
(°C) of the water vapor immediately after passing through the tube were values from
which the respective temperatures of the blanks were subtracted.
<Biodegradability (marine biodegradability performance)>
[0125] Biodegradability was evaluated using a method for evaluating biodegradability by
immersion in seawater. First, a film was produced by a typical solvent casting method.
From 10 to 15 parts by weight of the sample were dissolved in from 85 to 90 parts
by weight of acetone, a predetermined amount of MgO was further added, and a dope
was prepared. The dope was allowed to flow on a glass plate and casted with a bar
coater. The dope was dried at 40°C for 30 minutes, and an obtained film was peeled
from the glass plate and further dried at 80°C for 30 minutes, and a film for evaluation
with a thickness of 30 µm was obtained.
[0126] The film (10 cm × 10 cm × 30 µm) produced by the method described above was shredded
with a liquid nitrogen freeze grinder (S6770 FREEZER/MILL, available from Spex Sampleprep,
LLC of Metuchen, New Jersey, USA) and inserted into a stainless steel container, and
the biodegradability (marine biodegradability performance) was determined by a method
according to ASTM D6691. The biodegradability was specifically determined as follows.
[0127] The amount of carbon dioxide discharged from each sample was measured at 90 days
and 180 days after the start of the biodegradability test. As indicated in the formula
below, the percentage of the amount of carbon dioxide discharged from each sample
relative to the theoretical amount of biochemical discharge of carbon dioxide in complete
degradation based on the chemical composition was calculated as the biodegradation
degree (%). The biodegradation degree (%) of each sample at 90 days and 180 days after
starting the biodegradation test was converted to a relative value with respect to
a case in which the biodegradation degree of cellulose was considered to be 100. This
converted value was defined as the marine biodegradability performance (%).

[0128] Amount of carbon dioxide as a blank: The amount of carbon dioxide discharged when
the biodegradation test was similarly implemented using a stainless steel container
not containing a sample.
Examples 1 to 8
[0129] Cellulose (hardwood pulp) in the form of a sheet was processed with a disc refiner
into a cotton-like form. Next, 32.71 parts by weight of acetic acid was sprayed onto
100 parts by weight of the cotton-like cellulose (water content percentage of 8.0
wt.%), and the mixture was well stirred and then left standing at a temperature of
24°C for 60 minutes (activating step). Next, 358.51 parts by weight of acetic acid,
214.99 parts by weight of acetic anhydride, and A parts by weight of sulfuric acid
were mixed with the activated cellulose. The mixture was maintained at 15°C for 20
minutes, after which the temperature of the reaction system was increased to 45°C
at a rate of temperature increase of 0.3 1°C/min and then maintained at 45°C for 70
minutes, and the cellulose was acetylated, and cellulose triacetate was produced.
Then, 0.28 parts by weight of acetic acid, 89.55 parts by weight of water, and 13.60
parts by weight of magnesium acetate were added, and the acetylation reaction was
stopped. The sulfuric acid amount A was appropriately adjusted in a range from 0.1
to 15 parts by weight, and the sulfuric acid amount of the cellulose acetate to be
synthesized was adjusted. To the resulting reaction mixture, 0.06 parts by weight
of acetic acid, B parts by weight of water, and 2.90 parts by weight of magnesium
acetate were added, and an aging reaction was performed at 85°C for C minutes. The
amount of water B to be added to the aging reaction was adjusted in a range of from
1 to 50 parts by weight, and the degrees of substitutions at the 2-, 3-, and 6-positions
were adjusted. The aging reaction time C was adjusted in a range from 5 to 120 minutes,
and the degree of substitution of the cellulose acetate to be synthesized was adjusted.
Cellulose acetate was thus obtained. The evaluation results of each physical property
are shown in Table 1.
Example 9
[0130] An amount of 9.5 parts by weight of the cellulose acetate having a degree of substitution
of 2.46 and synthesized in Example 1 was heated at 110°C for 2 hours and dried, after
which the cellulose acetate was added to 90 parts by weight of acetone, stirred at
25°C for 6 hours, and dissolved. To this mixed solution, 0.5 parts by weight of a
powder of magnesium aluminometasilicate, which is a basic additive, was added as an
additive, the mixture was further stirred at 25°C for 6 hours, and a dope was thereby
prepared.
[0131] The prepared dope was allowed to flow onto a glass plate and casted with a bar coater,
and then dried at 40°C for 30 minutes. Next, the obtained film was peeled off from
the glass plate and dried at 80°C for another 30 minutes, and a film having a thickness
of 30 µm was obtained. Biodegradability was evaluated by the method described above
using this film as an evaluation film. The evaluation results of each physical property
are shown in Table 1.
Example 10
[0132] A dope was prepared in the same manner as in Example 9 with the exception that 0.4
parts by weight of magnesium oxide were used as the basic additive, and the amount
of the cellulose acetate was changed to 9.6 parts by weight. After the dope was prepared,
each of the physical properties was evaluated in the same manner as in Example 9.
The results are shown in Table 1.
Example 11
[0133] A dope was prepared in the same manner as in Example 9 with the exception that as
an additive, in addition to the basic additive, 2.5 parts by weight of triacetin,
which is a water-soluble additive, was used, and the amount of the cellulose acetate
was changed to 7.5 parts by weight. After the dope was prepared, each of the physical
properties was evaluated in the same manner as in Example 9. The results are shown
in Table 1.
Example 12
[0134] A dope was prepared in the same manner as in Example 9 with the exception that as
additives, 0.5 parts by weight of magnesium oxide, which is a basic additive, and
2.0 parts by weight of triacetin, which is a water-soluble additive, were used, and
the amount of the cellulose acetate was changed to 7.5 parts by weight. After the
dope was prepared, each of the physical properties was evaluated in the same manner
as in Example 9. The results are shown in Table 1.
Example 13
[0135] A dope was prepared in the same manner as in Example 9 with the exception that as
the cellulose acetate, 7.5 parts by weight of the cellulose acetate synthesized in
Example 5 with a substitution degree of 2.45 was used, and as an additive, in addition
to the basic additive, 2.5 parts by weight of triacetin, which is a water-soluble
additive, was used. The dope was allowed to flow onto a glass plate, and was then
casted with a bar coater and dried at 40°C for 30 minutes. Next, the obtained film
was peeled off from the glass plate, dried at 80°C for another 30 minutes, and a film
having length of 23.3 cm, a width of 17 mm, and a thickness of 30 µm was obtained.
The physical properties were evaluated by the method described above using this film
as an evaluation film. The results are shown in Tables 1 and 2.
Example 14
[0136] A dope was prepared in the same manner as in Example 9 with the exception that as
the cellulose acetate, 7.5 parts by weight of the cellulose acetate synthesized in
Example 8 with a substitution degree of 2.20 was used, and as an additive, in addition
to the basic additive, 2.5 parts by weight of triacetin, which is a water-soluble
additive, was used. After the dope was prepared, a film was obtained in the same manner
as in Example 13. The physical properties were evaluated by the method described above
using this film as an evaluation film. The results are shown in Table 1.
Comparative Example 1
[0137] Polylactic acid was melt kneaded at a temperature from 170 to 190°C using a twin
screw kneader, and a film was obtained using a T-die mold of a laboratory plastomil.
The evaluation results of each physical property are shown in Table 1 and Table 2.
Comparative Example 2
[0138] Cellulose (cotton linter pulp) in the form of a sheet and having an α-cellulose content
of 97 wt.% was processed with a disc refiner into a cotton-like form. Acetic acid
at a proportion indicated was sprayed onto 100 parts by weight of the cotton-like
cellulose (water content percentage of 8.0 wt.%), and the mixture was stirred well
and then left standing at a temperature of 24°C for 60 minutes (first activating step).
Furthermore, 30.24 parts of acetic acid containing 0.94 parts of sulfuric acid was
added to the cellulose that had been subjected to the first activating step, and the
mixture was allowed to stand at 24°C for 45 minutes (second activating step). In addition,
417.85 parts of acetic acid, 282.98 parts of acetic anhydride, and 8.72 parts of sulfuric
acid were mixed into the activated cellulose that had been subjected to the second
activating step. The mixture was then maintained at a temperature of not higher than
15°C for 20 minutes, after which the temperature of the reaction system was increased
to 35°C at a rate of temperature increase of 0.3 1°C/min and then maintained at 35°C
for 80 minutes, and the material was acetylated. Furthermore, 0.15 parts by weight
of acetic acid, 22.98 parts by weight of water, and 7.30 parts by weight of magnesium
acetate were mixed and maintained at a temperature of 61°C for 95 minutes, after which
7.48 parts by weight of magnesium acetate, 20.94 parts by weight of acetic acid, and
21.44 parts of water were added, and the aging reaction was stopped. The reaction
bath was charged into a dilute acetic acid under stirring, and the product was precipitated
and immersed in a dilute aqueous solution of calcium hydroxide, and then separated
by filtration and dried, and cellulose acetate was obtained.
[0139] An amount of 7.5 parts by weight of the obtained cellulose acetate with a degree
of substitution of 2.81 was heated at 110°C for 2 hours and dried, after which the
cellulose acetate was added to 90 parts by weight of acetone, stirred at 25°C for
6 hours, and dissolved. To this mixed solution, 2.5 parts by weight of triacetin,
which is a water-soluble additive, was added as an additive, the mixture was further
stirred at 25°C for 6 hours, and a dope was thereby prepared. After the dope was prepared,
a film was obtained in the same manner as in Example 13. The physical properties were
each evaluated using this film as an evaluation film. The results are shown in Table
1.
[Table 1]
| |
Cellulose Acetate |
Additive |
Slurry pH |
Thermal Stability |
Endothermic Properties |
Biodegradability |
| Total degree of acetyl substitution |
DS6 |
DS2+3 |
τ |
Sulfuric acid component amount (ppm) |
Type |
Content (wt.%) |
Glass transition temperature (Tg) (°C) |
Rate of increase air-flow resistance [%] |
Equilibrium moisture amount (%) |
Average temperature reduction rate of water vapor (%) |
Marine biodegradability performance [%] |
| 0 days |
90 days |
180 days |
| Example 1 |
2.46 |
0.74 |
1.72 |
2.32 |
30 |
- |
- |
5.8 |
- |
- |
- |
- |
0 |
27 |
70 |
| Example 2 |
2.48 |
0.79 |
1.69 |
2.13 |
50 |
- |
- |
5.8 |
- |
- |
- |
- |
0 |
26 |
69 |
| Example 3 |
2.46 |
0.74 |
1.72 |
2.32 |
140 |
- |
- |
5.6 |
- |
- |
- |
|
0 |
27 |
67 |
| Example 4 |
2.45 |
0.73 |
1.72 |
2.35 |
180 |
- |
- |
3.7 |
- |
- |
- |
- |
0 |
28 |
70 |
| Example 5 |
2.45 |
0.73 |
1.72 |
2.35 |
350 |
- |
- |
5.5 |
190 |
- |
- |
- |
0 |
29 |
69 |
| Example 6 |
2.44 |
0.75 |
1.69 |
2.25 |
200 |
- |
- |
5.6 |
- |
- |
- |
- |
0 |
31 |
73 |
| Example 7 |
2.42 |
0.78 |
1.64 |
2.10 |
380 |
- |
- |
5.5 |
- |
- |
- |
- |
0 |
33 |
76 |
| Example 8 |
2.20 |
0.67 |
1.53 |
2.28 |
150 |
- |
- |
5.4 |
- |
- |
- |
- |
0 |
64 |
91 |
| Example 9 |
2.46 |
0.74 |
1.72 |
2.32 |
140 |
Mg aluminometasilicate |
5 |
8.5 |
- |
- |
- |
- |
0 |
37 |
76 |
| Example 10 |
2.49 |
0.74 |
1.72 |
2.32 |
140 |
MgO |
4 |
9.5 |
- |
- |
- |
- |
0 |
79 |
98 |
| Example 11 |
2.46 |
0.74 |
1.72 |
2.32 |
140 |
Triacetin |
25 |
5.6 |
- |
- |
- |
- |
0 |
33 |
84 |
| Example 12 |
2.46 |
0.74 |
1.72 |
2.32 |
140 |
MgO + triacetin |
MgO 5 Triacetin 20 |
1.0 |
- |
- |
- |
- |
0 |
95 |
99 |
| Example 13 |
2.45 |
0.73 |
1.72 |
2.35 |
350 |
Triacetin |
25 |
- |
125 |
2.50 |
5.2 |
10.2 |
- |
- |
- |
| Example 14 |
2.20 |
0.67 |
1.53 |
2.28 |
150 |
Triacetin |
25 |
- |
144 |
- |
6.1 |
12.2 |
- |
- |
- |
| Comparative Example 1 |
- |
- |
- |
- |
- |
- |
- |
- |
60 |
20.00 |
0.3 |
4.3 |
- |
- |
- |
| Comparative Example 2 |
2.81 |
0.90 |
1.91 |
2.12 |
200 |
Triacetin |
25 |
- |
- |
- |
1.0 |
8.4 |
- |
- |
- |
[Table 2]
| |
n |
Air-flow Resistance (mmWG) |
Air-flow Resistance Increase Rate (%) |
| Prior to water vapor passage |
After water vapor passage |
| Example 13 |
1 |
7 |
7 |
0.00 |
| 2 |
8 |
7 |
12.50 |
| 3 |
4 |
4 |
0.00 |
| 4 |
6 |
6 |
0.00 |
| 5 |
6 |
6 |
0.00 |
| |
Average |
2.50 |
| Comparative Example 1 |
1 |
4 |
3 |
25.00 |
| 2 |
4 |
4 |
0.00 |
| 3 |
4 |
3 |
25.00 |
| 4 |
4 |
3 |
25.00 |
| 5 |
4 |
3 |
25.00 |
| |
Average |
20.00 |
[0140] The polylactic acid of Comparative Example 1 exhibited poor biodegradability, as
it is so known, and was also inferior in thermal stability and endothermic properties
as shown in Table 1. Furthermore, in the case of Comparative Example 2 in which cellulose
acetate having a high total degree of acetyl substitution was included, the aerosol
cooling member had a low equilibrium moisture ratio and a low average temperature
decrease rate for the water vapor, and was thus inferior in endothermic properties.
On the other hand, the aerosol cooling members of the examples exhibited excellent
thermal stability, endothermic properties, and biodegradability (in particular, biodegradability
in seawater). By using the aerosol cooling member of the examples as a cooling member
for a smoking tool, the flow channel is less likely to be obstructed because deformation
due to heat from the aerosol generated from the smoking tool does not easily occur,
and thus a cooling member with an excellent aerosol cooling effect can be provided,
and the environmental load can be reduced even when the smoking tool is discarded
in the environment.