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JP2006116807

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This translation is machine-generated. It cannot be guaranteed that it is intelligible, accurate,
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DESCRIPTION JP2006116807
The present invention provides an acoustic material having excellent acoustic characteristics that
can be substituted for wood. SOLUTION: A lignin having a bisarylpropane unit in which a carbon
atom at an ortho position and / or a para position with respect to a phenolic hydroxyl group of a
phenol compound is bonded to a carbon material at a C1 position of an arylpropane unit of lignin
The phenol derivative of is complexed to make an acoustic material. By doing this, an acoustic
material having excellent acoustic characteristics can be obtained. [Selected figure] None
Acoustic material and method of manufacturing the same
[0001]
The present invention relates to an acoustic material, an acoustic device, and a method of
manufacturing the acoustic material.
[0002]
Conventionally, for example, wood has been used as an acoustic material such as a sound board
of a musical instrument, and a fiber material such as pulp has been used as an acoustic material
such as a diaphragm of a speaker.
Furthermore, in recent years, as an alternative material to those mentioned above, addition of
resin to wood which has been subjected to heat treatment to wood, composite material of
urethane foam and fiber material, and wood material has been tried (patent documents 1, 2, 3) .
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JP 2003-145510 JP JP 2001-306062 JP JP 2001-225302 JP
[0003]
Soundboards used for musical instruments and the like are required to have severe acoustic
characteristics, such as limited wood species depending on the type of musical instrument. Also,
higher performance is being sought for diaphragms in speakers and the like. In addition, sound
insulation and sound absorption require different acoustic characteristics. Thus, acoustic
materials are required to have different acoustic characteristics in a wide range. However, wood
can satisfy these various acoustic characteristics depending on the tree species and the like. On
the other hand, natural wood is not uniform because of its natural nature and is susceptible to
the influence of humidity and the like, and sometimes has difficulties in processing and storage.
[0004]
Therefore, it is an object of the present invention to provide an acoustic material having excellent
acoustic characteristics that can be substituted for wood. Another object of the present invention
is to provide an acoustic material which is easy to process in shape. Furthermore, in the present
invention, it is another object to provide an acoustic material capable of adjusting acoustic
characteristics. Furthermore, another object of the present invention is to provide a method of
producing an acoustic material, and still another object is to provide a composition for acoustic
material.
[0005]
The present inventors have found that a material in which a phenolic derivative of lignin derived
from lignin by a phenolic compound and a cellulosic material are complexed has excellent
acoustic properties, and completed the present invention. That is, according to the present
invention, the following means are provided.
[0006]
According to one aspect of the present invention, there is provided an acoustic material,
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comprising: a cellulose-based material containing a cellulose-based material consisting of
cellulose and / or hemicellulose; d) (a) having a 1,1-bisarylpropane unit in which a carbon atom
at an ortho position and / or a para position to a phenolic hydroxyl group of a phenol compound
is bonded to a carbon atom at the C1 position of an arylpropane unit of lignin A phenol
derivative of lignin, (b) introduction of a lignin derivative of (a) into the 1,1-bisarylpropane unit
of a coumaran derivative of a phenol compound, (c) a phenolic hydroxyl group of a lignin
derivative of (a) Of the crosslinkable derivative (d) (c) having a crosslinkable reactive group at the
ortho position and / or para position of An acoustic material is provided, comprising: one or
more lignin derivatives selected from the group consisting of cross-linked products in which the
crosslinkable reactive groups of the sex derivatives are cross-linked. In this embodiment, the
lignin derivative is preferably the lignophenol derivative of (a), and the cellulose-based material is
preferably any one of the aggregate, the entangled body and the dense body thereof. It is an
aspect. Furthermore, it is also a preferred embodiment that the cellulose-based material is a sheet
or a molded product having a three-dimensional shape other than a sheet.
[0007]
In these acoustic materials, the lignin derivative may be contained substantially uniformly in the
whole of the acoustic material, or may be contained mainly on the surface side of the acoustic
material. Moreover, any one of the above-mentioned acoustic materials is a preferable aspect that
it is a sound board or a vibration material, and it is also a preferable aspect that it is a sound
absorbing material.
[0008]
Further, according to another aspect of the present invention, there is provided an instrument
comprising at least a portion of any of the above-mentioned acoustic materials, and further
comprising, at least in part, the acoustic materials described in any of the above. An acoustic
member for a speaker is provided.
[0009]
Furthermore, according to another aspect of the present invention, there is provided a
composition for acoustic material, which comprises the following (a) to (c): (a) a phenolic
compound at the carbon atom C1 of the arylpropane unit of lignin A phenol derivative of lignin
having a 1,1-bisarylpropane unit in which a carbon atom in ortho and / or para position is
bonded to a phenolic hydroxyl group of A coumaran derivative obtained by coumaranizing a
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phenol compound introduced into a bisarylpropane unit, and a crosslinkable derivative having a
crosslinkable reactive group at the ortho position and / or para position of the phenolic hydroxyl
group of the lignin derivative of (c) (a) A composition is provided which contains one or more
lignin derivatives selected from the group.
The composition preferably contains a phenolic compound, preferably contains cellulose and / or
hemicellulose, and further preferably contains an acid.
[0010]
Furthermore, according to another aspect of the present invention, there is provided a
composition for forming an acoustic material, comprising a cellulose-based material, and the
following (a) to (c): (a) C1 of arylpropane unit of lignin A phenolic derivative of lignin having a
1,1-bisarylpropane unit in which a carbon atom in the ortho position and / or a para position is
bonded to a carbon atom in the position to a phenolic hydroxyl group of the phenol compound; A
coumaran derivative obtained by coumaranizing a phenol compound introduced into the 1,1bisarylpropane unit of the derivative, (c) a crosslinkable reactive group at the ortho position and
/ or para position of the phenolic hydroxyl group of the lignin derivative of (a) A composition
comprising one or more lignin derivatives selected from the group consisting of crosslinkable
derivatives having Provided.
[0011]
Furthermore, according to another aspect of the present invention, there is provided a method of
producing an acoustic material, comprising the steps of (a) to (c): (a) lignin, to a cellulose-based
material containing cellulose and / or hemicellulose. A phenol derivative of lignin having a 1,1bisarylpropane unit in which a carbon atom in an ortho and / or para position to a phenolic
hydroxyl group of a phenol compound is bonded to a carbon atom at the C1 position of an
arylpropane unit of B) a coumaran derivative obtained by coumaranizing a phenol compound
introduced into the 1,1-bisarylpropane unit of the lignin derivative of (a), (c) the ortho position of
the phenolic hydroxyl group of the lignin derivative of (a) and / or para 1 or 2 types selected
from the group consisting of crosslinkable derivatives having a crosslinkable reactive group at
the position A method for producing an acoustic material is provided, which comprises the steps
of supplying the above lignin derivative and complexing the lignin derivative with the cellulosebased material.
In this production method, the cellulose-based material used in the compounding step is
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preferably a sheet or a molded body having a three-dimensional shape other than a sheet, and
the non-dispersed cellulose-based material and It is also preferable to be a step of complexing
with a lignin derivative and imparting these predetermined shapes.
[0012]
The acoustic material of the present invention contains a cellulose-based material and a lignin
derivative complexed to the cellulose-based material. The lignin derivative is a lignin derivative
having a 1,1-bisarylpropane unit in which a carbon atom at an ortho position and / or a para
position to a phenolic hydroxyl group of a phenol compound is bonded to a carbon atom at the
C1 position of the arylpropane unit of lignin. Derivatives of phenol (hereinafter also referred to
as lignophenol derivatives. And, further, acyl derivatives, carbonyl derivatives, coumaran
derivatives, and crosslinkable derivatives of this lignophenol derivative. The acoustic material of
the present invention is not only compositionally similar to the typical lignocellulosic material
wood, but also has excellent acoustic characteristics and also has acoustic characteristics similar
to wood. Conventionally, the acoustic properties of wood are said to be derived from its physical
structure, that is, a large anisotropic structure comprising porous and elongated cell walls
extending in the trunk direction, but a lignin derivative derived from natural lignin Even if it was
complexed with a cellulose-based material, it was beyond the expectation of the person skilled in
the art to develop acoustic properties similar to wood and to exhibit superior acoustic properties.
Since the present acoustic material is thus composed of a cellulose-based material and a lignin
derivative, it is excellent in processability, and it is also easy to adjust acoustic characteristics by
preparation of its composition and selection of a substrate.
[0013]
Hereinafter, the acoustic material of the present invention will be described with respect to
various forms of the present invention, and a method of producing the acoustic material, a
composition for the acoustic material, a speaker device provided with the acoustic material, a
musical instrument, and the like will be described.
[0014]
(Cellulose-Based Material) A cellulose-based material which is a component of the acoustic
material of the present invention, and a cellulose-based material containing cellulose and / or
hemicellulose are contained.
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The cellulose-based material is not particularly limited, and fiber materials, powder materials,
amorphous materials and the like obtained from lignocellulose-based materials as trees, grasses
or wastes can be mentioned. In addition, lignocellulose-based materials may be included as the
cellulose-based materials, and wood fibers, chips, and the like can also be used. That is, the lignin
derivative may be further complexed to the lignocellulose-based material.
[0015]
Cellulose-based materials can also be used in acoustic materials as cellulosic-based substrates
that themselves constitute a two-dimensional or three-dimensional construct. In particular,
fibrous materials such as fibrous materials can be used as dense bodies such as entangled bodies
or laminates or aggregates, and particulate cellulose materials can be used as dense bodies to
form a two-dimensional or three-dimensional structure. Here, the compact body includes one
having a natural lignocellulose structure as well as one densified by heat pressure and the like.
The cellulose-based substrate may be artificial or naturally occurring. Specific examples of the
cellulose-based substrate include, for example, so-called pulp paper sheets (entangled bodies), as
well as boards made of various chips and fibers, and artificial bodies such as herbs and the like
Constructs can also be used. In addition, natural constructions such as wood sheets, plates, and
other three-dimensional shaped cuttings may be used.
[0016]
Such a cellulose-based substrate is a porous body having voids on the surface or in the interior,
such as an entangled body or an aggregate of cellulosic fibers, it is easy to hold the lignin
derivative in the voids. The form of the cellulose-based substrate is selected according to the
application, and a entangled body or a dense body can be used as a cone of the speaker unit, etc.
A dense body or a dense body is used as a sound board of an instrument. And complexes of
entangled bodies and the like can be used.
[0017]
In addition, regardless of the form, such various cellulose-type materials can use what performed
the pressure processing, heat processing, etc.
[0018]
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The acoustic material may be naturally derived or artificially obtained, such as cellulose-based
materials, cellulose-based polymer materials such as rayon, lactic acid-based polymer materials,
alcohol-based polymer materials, and acrylic-based polymer materials, as well as cellulose-based
materials. Molecular materials can also be included.
These polymeric materials also include waste-derived materials. As glass-based materials, various
glasses, tempered glass and the like can be used.
[0019]
(Lignin Derivative) The lignin derivative which is another component of the present acoustic
material is a lignophenol derivative and its secondary derivative. First, lignophenol derivatives
are described. The lignophenol derivative is a derivative derived from a lignin-containing material
such as a lignocellulosic material by a phenol compound, and is a compound having the following
(a) and / or (b): (A) A first 1,1-bisarylpropane unit (first unit) in which a carbon atom ortho to a
phenolic hydroxyl group of a phenol compound is bonded to a carbon atom at the C1 position of
an arylpropane unit of lignin (first unit) b) a second 1,1-bisarylpropane unit (second unit) in
which a carbon atom at a position para to a phenolic hydroxyl group of a phenol compound is
bonded to a carbon atom at the C1 position of an arylpropane unit of lignin
[0020]
The lignophenol derivative can also comprise an arylpropane unit in which no phenolic
compound has been introduced. In the following, preferred production processes for obtaining
lignophenol derivatives are described and then the chemical and physical properties are
described.
[0021]
Lignophenol derivatives can generally be obtained by contacting a lignin-containing material,
preferably a lignocellulosic material, which is affinity (solvated) with a predetermined phenolic
compound with an acid. In addition, about the more general description regarding a lignophenol
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derivative and its manufacturing process, already Unexamined-Japanese-Patent No. 2-23701,
Unexamined-Japanese-Patent No. 9-278904, international publication WO99 / 14223, 200164494, No. 2001-261839, 2001-131201 and 2001-34233 (All the contents described in these
patent documents are incorporated herein by reference).
[0022]
In the process of producing lignophenol derivatives, a lignocellulosic material is previously
solvated with a phenolic compound, or the phenolic compound is sorbed onto a lignocellulosic
material, and then the phenolic compound solvated lignocellulosic material is treated with an
acid The contact relaxes the complex state of lignocellulose, and at the same time, selectively
grafts the phenolic compound at the C1 position (benzyl position) of the arylpropane unit of
natural lignin to form a lignophenol derivative and simultaneously It is also a method by which
lignocellulosic material can be separated into cellulose and lignophenol derivatives. A
lignophenol derivative is itself a mixture of polymers derived from lignin obtained by reaction
and separation from lignin-containing materials such as lignocellulosic materials, and natural or
naturally-derived (natural lignin processed When obtained from a lignin-containing material, the
molecular weight of the introduced phenolic compound and the introduced amount of the
phenolic compound in the obtained polymer vary depending on the type of lignin as the raw
material as well as the reaction conditions.
[0023]
(Lignin-Containing Material) The “lignin-containing material” used in the present invention
may maintain a structure derived from lignin having an arylpropane unit. Specifically, various
materials which are mainly wood, for example, various materials which are wood, for example,
lignocellulosic materials such as wood powder, chips, etc., and agricultural waste and industry
associated with wood resources such as waste wood, scrap wood and waste paper. Waste can be
mentioned. Moreover, as a kind of wood to be used, arbitrary kinds, such as a softwood and a
hardwood, can be used. Furthermore, as the lignin-containing material, various herbaceous
plants, related agricultural wastes and industrial wastes can also be used. In addition, modified
products of lignin by-produced in the process of pulp production can also be used.
[0024]
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(Phenolic Compound) As a phenolic compound, a monohydric phenol compound, a bivalent
phenol compound, or a trivalent phenol compound can be used. Specific examples of the
monovalent phenol compound include phenol which may have one or more substituents,
naphthol which may have one or more substituents, and one or more substituents. Good anthrols,
anthroquinoneols which may have one or more substituents, and the like. Specific examples of
the divalent phenol compound include catechol which may have one or more substituents,
resorcinol which may have one or more substituents, and even if it has one or more substituents.
Good hydroquinone etc. are mentioned. As a specific example of a trivalent phenol compound,
pyrogallol etc. which may have one or more substituents are mentioned.
[0025]
In the present invention, among monohydric phenol compounds, dihydric phenol compounds
and trihydric phenol compounds, one kind or two or more kinds can be used, preferably
monohydric phenol is used. The type of substituent which may be possessed by the monovalent
to trivalent phenol compound is not particularly limited, and may have any substituent, but
preferably it is an electron-withdrawing group (such as a halogen atom And lower alkyl groupcontaining substituents having, for example, 1 to 4 carbon atoms, preferably 1 to 3 carbon
atoms. The lower alkyl group-containing substituent is, for example, a lower alkyl group (such as
a methyl group, an ethyl group or a propyl group) or a lower alkoxy group (such as a methoxy
group, an ethoxy group or a propoxy group). Further, it may have an aromatic substituent such
as an aryl group (such as a phenyl group). Moreover, it may be a hydroxyl group-containing
substituent.
[0026]
The 1,1-bis (aryl) propane unit is formed by bonding of these phenolic compounds to the carbon
at the C1 position of the arylpropane unit of lignin at a carbon atom ortho or para to the phenolic
hydroxyl group. It will be done. Therefore, in order to secure at least one introduction site, it is
preferable that at least one of the ortho and para positions has no substituent. The unit formed
by bonding the ortho position carbon atom of the phenolic hydroxyl group of the phenolic
compound to the C1 position is the first unit, and the para position carbon atom of the phenolic
hydroxyl group of the phenolic compound is bonded to the C1 position The unit thus formed is
the second unit.
[0027]
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From the above, in the present invention, one or two or more kinds of phenol compounds of
various substituted forms having at least one unsubstituted ortho position or para position other
than unsubstituted phenol derivatives may be appropriately selected and used. it can. The first
unit and the second unit exhibit different functions, for example, in an alkali treatment step
described later. The ortho-linkage unit abolishes the phenolic hydroxyl group in the phenol
compound introduced by mild alkali treatment and forms an aryl coumaran structure in the unit,
and the strong alkali treatment changes the molecular form along with the aryl group transfer. .
In any case, the ortho-binding unit contributes to the efficient depolymerization of lignophenol
derivatives by alkali treatment.
[0028]
On the other hand, the second unit does not cause the aryl coumaran structure in the lignin
derivative or the subsequent change in molecular form by alkali treatment, and does not
contribute to the reduction in molecular weight in the unit site. Therefore, it can be said that it
has a function to impart alkali treatment resistance. In addition, in the lignophenol derivative, the
frequency of introduction of the crosslinkable functional group in the subsequent secondary
derivatization step to the obtained lignophenol derivative is controlled by selecting the kind of
the phenol compound to be used, and as a result, the crosslinkability is achieved The crosslinking
reactivity of the body (prepolymer) can be controlled.
[0029]
As will be described later, the introduction site of the crosslinkable group is in the ortho and para
positions with respect to the phenolic hydroxyl group. Further, the introduction site of the
introduced phenolic compound into lignin's phenylpropane unit is also ortho or para to the
phenolic hydroxyl group. Therefore, the introduction site and amount of the crosslinkable
functional group to the introduced phenol compound are controlled by the introduction mode of
the substituent to the ortho position and para position (maximum 3 sites) with respect to the
phenolic hydroxyl group in the introduced phenol compound The amount introduced to the
lignin mother side can also be controlled.
[0030]
Thus, crosslinkability can be achieved later by introducing into the lignin one or two or more
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types of phenol compounds having crosslinkable group introduction sites having different
reactivity, or phenol compounds that have no or a number of introduction sites, and are
combined. At the time of introduction of a group, the introduction site and the number of
crosslinkable groups can be controlled, and as a result, the crosslink density of a crosslinked
body obtained by crosslinking the crosslinkable body can also be controlled.
[0031]
Also, in order to obtain a lignophenol derivative having a first unit, a phenol compound having no
substituent at at least one ortho position (preferably all ortho positions) is used.
Also, a phenol compound having a substituent at at least one ortho position (2- or 6-position) and
no substituent at the para-position (4-position) (typically, a 2,4-substituted monohydric phenol
derivative Is preferred. Most preferably, it is a phenol compound (typically, a 4-position
substituted monohydric phenol compound) having no substituent at all ortho positions and
having a substituent at the para position. Therefore, it is possible to use one or two or more kinds
of 4-substituted phenol compounds and 2,4-substituted phenol compounds in combination.
[0032]
In order to obtain a lignophenol derivative having a second unit, a phenol compound having no
substituent at the para position (typically, a 2-position (or 6-position) substituted monohydric
phenol compound) is preferable, and more preferable Simultaneously use a phenol compound
(typically a 2,6-substituted monohydric phenol compound) having a substituent at the ortho
position (preferably, all the ortho positions). That is, it is preferable to use one kind or two or
more kinds in combination of a 2-position (or 6-position) substituted phenol compound and a 2,
6-substituted phenol.
[0033]
Preferred specific examples of the phenol derivative include o-cresol, p-cresol, 2,6dimethylphenol, 2,4-dimethylphenol, 2-methoxyphenol (Guaiacol), 2,6-dimethoxyphenol,
catechol, resorcinol, Homocatechol, pyrogallol and phloroglucinol and the like. By using p-cresol,
high introduction efficiency can be obtained.
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[0034]
By selecting the type of phenolic compound used in this process, the properties of the resulting
lignophenol derivative can be controlled, and in turn, the properties of the secondary derivative
obtained by further processing it secondarily can be controlled. . For example, by selecting the
type of the phenolic compound, the amount of the phenolic compound introduced, the hydroxyl
equivalent, and the like can be adjusted. By adjusting these, for example, the crosslinkable site in
the crosslinkable body, the crosslink density in the crosslinker, and the like can be adjusted. In
addition, since the cross-linked structure when cross-linked with the crosslinkable lignophenol
derivative is different depending on the amount and position of the phenolic hydroxyl group, the
cross-linked structure and the like can be adjusted depending on the type and the introduction
amount of the phenolic compound. Therefore, various properties such as mechanical strength,
water resistance, and acoustic characteristics of the acoustic material can be controlled by using
the lignin derivative including the lignophenol derivative and the secondary derivative thereof.
[0035]
The introduction frequency of the phenol compound varies depending on the presence, position,
size and the like of the substituent of the phenol compound to be introduced. Therefore, the
introduction frequency can be adjusted. In particular, the introduction frequency can be easily
adjusted by steric hindrance due to the size of the substituent. When it is intended to control the
introduction position and the like by using a substituent, if a lower alkyl group is used as a
substituent, the introduction frequency can be easily controlled depending on the carbon number
and the branched form. When the substituent is a methyl group, the introduction frequency can
be maintained high to control the introduction position.
[0036]
(Acid) In the present process, the acid to be added to the lignin-containing material is not
particularly limited, but it is preferable to have an effect of swelling cellulose. For example, at
least 65 wt% sulfuric acid (preferably 72 wt% sulfuric acid), at least 85 wt% phosphoric acid, at
least 38 wt% hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid,
formic acid, etc. It can be mentioned. Preferred acids are 65 wt% or more (more preferably 72
wt% or more) sulfuric acid, 85 wt% or more (more preferably 95 wt% or more) phosphoric acid,
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trifluoroacetic acid, or formic acid.
[0037]
(Production Process of Lignophenol Derivative) The following three methods can be mentioned
as methods for converting lignin in a lignin-containing material into lignophenol derivatives and
separating them. In addition, it is not limited to these methods, Moreover, these methods can be
changed suitably and can also be used. Moreover, in the manufacturing process of the
lignophenol derivative shown below, although it demonstrates using lignocellulosic material as a
raw material, it can apply to the lignin containing material in general which does not contain very
much, such as a cellulose. In addition, the carbohydrate in the various crude purified fractions
shown below is contained in the case where it is mainly based on a lignocellulosic material as a
raw material.
[0038]
The first method is the method described in JP-A-2-233701. For example, a liquid phenol
compound (cresol or the like) is infiltrated into lignocellulosic material such as wood flour, lignin
is solvated with a phenol derivative, and then concentrated acid (eg 72% sulfuric acid as
lignocellulose material) Concentrated phosphoric acid etc.) is added to dissolve the cellulose
component. According to this method, the lignin-solvated phenol compound and the
concentrated acid in which the cellulose component is dissolved form a two-phase separation
system. The lignin solvated by the phenolic compound is contacted with the acid only at the
interface where the phenolic compound phase contacts with the concentrated acid phase, and the
cation of the high reaction site (α position) of the lignin produced in this process is attacked by
the phenolic derivative Be done. As a result, a lignophenol derivative in which a phenol derivative
is introduced to the alpha carbon of the aromatic ring of lignin is formed in the phenol
compound phase.
[0039]
Lignophenol derivatives can be extracted from this phenolic phase. For extraction of lignophenol
derivatives, for example, precipitates obtained by adding a phenol compound phase to a large
excess of ethyl ether are collected, dissolved in acetone, acetone insoluble fractions are removed
by centrifugation, and acetone soluble fractions are removed. The fraction is concentrated, and
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the acetone soluble fraction is further added dropwise to a large excess of diethyl ether, and the
precipitate is collected, and the solvent is evaporated from the precipitate and then dried in a
phosphorus pentoxide-containing desiccator.
[0040]
In addition to the purified lignophenol derivative thus obtained, various fractions containing the
lignophenol derivative obtained in the first method can be used instead of the lignophenol
derivative. For example, it may be the phenol compound phase (liquid phase) in the above step,
or both of the phenol compound phase (phenol compound phase and water phase (total reaction
liquid). The insoluble fraction obtained by adding excess water to the aqueous solution), the
insoluble fraction after water washing (deacidification), and the dried fraction thereof (these
insoluble fractions are referred to as a first crudely purified fraction. )などである。
Furthermore, a lignophenol affinity solvent such as acetone or alcohol may be added to the first
crude purified fraction to extract a lignophenol derivative into these solvents, and the insoluble
fraction at this time may be a lignophenol derivative. May be included with carbohydrates etc.
(Such insoluble fraction is referred to as the second crudely purified fraction). Therefore, such an
insoluble fraction can also be used in place of the lignophenol derivative. These various insoluble
fractions may contain carbohydrates as well as lignophenol derivatives and acids unless they are
thoroughly washed.
[0041]
In the second method, a lignocellulose-based material is impregnated with a solvent (for example,
ethanol or acetone) in which a solid or liquid phenolic compound is dissolved, and then the
solvent is distilled off to make the lignocellulose-based material The phenol compound is sorbed
(phenol compound sorption step). Next, concentrated acid is added to the lignocellulosic material
to dissolve the cellulose component. As a result, as in the first method, lignin solvated with a
phenolic compound contacts with an acid at the interface where the phenolic compound and
concentrated acid are in contact, and is attacked by the phenolic compound to form a
lignophenol derivative. Ru. The lignophenol derivative is contained in the insoluble fraction
obtained by pouring the entire reaction solution after this concentrated acid treatment into
excess water, and this insoluble fraction is, for example, acetone or alcohol as described above
for the lignophenol derivative. The product of a lignophenol derivative can be obtained by
fractionation and purification using a lignophenol derivative compatible solvent or ether of
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[0042]
In the same manner as in the first method, in addition to the purified lignophenol derivative thus
obtained, the above-mentioned water-insoluble fraction or the insoluble fraction after water
washing (deacidification) and / or the dry fraction These various fractions are referred to as a
third crudely purified fraction. Can be used in place of lignophenol derivatives. Furthermore,
since the lignophenol derivative can be contained also in the insoluble fraction when the above
water insoluble fraction is extracted into the lignophenol derivative affinity solvent, this insoluble
fraction (hereinafter referred to as the fourth crudely purified fraction). Can be used in place of
lignophenol derivatives.
[0043]
As an alternative to the second method, a lignophenol derivative produced by concentrated acid
treatment can be extracted with a liquid phenol compound. Such liquid phenol compound of
lignophenol derivative can be handled in the same manner as the liquid phenol compound phase
obtained in the first method.
[0044]
In addition, as a third method, there is a method for producing a lignophenol derivative described
in JP-A-2001-131201. This method mixes a mixture containing a phenol derivative and a
lignocellulosic substance and an acid with an inert low boiling hydrophobic organic solvent,
separates the obtained mixture into three layers by centrifugation, and the middle of the three
layers. It is characterized by including a step of recovering the layer. Alternatively, the phenol
derivative and the lignocellulosic substance dissolved in the hydrophobic organic solvent may be
mixed in advance to remove an excess amount of the organic solvent and the phenol derivative,
and the remaining mixture may be mixed with the acid. And a step of recovering the intermediate
layer obtained by reacting the lignocellulosic substance with an acid and centrifuging. Such an
intermediate layer has a high concentration of lignophenol. This intermediate layer can be
washed with water and deacidified by repeating recovery of the water insoluble fraction several
times. The obtained water-insoluble fraction can be dried and then extracted with acetone for the
lignophenol derivative. The acetone phase can be concentrated to dryness, added dropwise to a
large excess of diethyl ether, the insoluble fraction washed further with diethyl ether and purified
by evaporating the solvent.
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[0045]
The lignophenol derivative thus obtained from the lignin-containing material comprises the first
and / or second unit as described above and may have the following properties. However, the
present invention is not intended to limit the lignophenol derivative to those having the following
properties. (1) The weight average molecular weight is about 2000 to about 20000. The weight
average molecular weight can be measured in terms of polystyrene by column chromatography.
(2) There is almost no conjugated system in the molecule and the color tone is extremely light. It
is typically a pale pink white powder. (3) It has a solid-liquid phase transition point at about 150
° C. to 180 ° C. from softwood and at about 130 ° C. to 160 ° C. from hardwood. (4)
Methanol, ethanol, acetone, dioxane, pyridine, tetrahydrofuran, dimethylformamide, N-methyl-2pyrrolidone, dimethylformamide, dimethyl sulfoxide, ethylene glycol monomethyl ether, ethylene
glycol monoethyl ether (hereinafter referred to as lignophenol) It is also easily dissolved in an
alkaline solution, etc.).
[0046]
In addition, the lignophenol derivative collect | recovered from the lignophenol-type molded
object which contained the lignophenol derivative can also be used as a lignophenol derivative.
From such lignophenol-based moldings, one or more solvents selected from the above-mentioned
lignophenol derivative-affinitive solvents such as acetone, ethanol, methanol, dioxane, etc.,
mixtures of these with water, and alkaline solutions (including alkaline aqueous solutions) In the
solvent, the lignophenol derivative is recovered. This lignophenol derivative is reusable.
According to this method, lignophenol derivatives can be repeatedly reused, leading to effective
use of resources.
[0047]
(Secondary Derivative) The lignin derivative used in the present invention includes a secondary
derivative obtained by further performing a chemical modification on this lignophenol derivative.
Secondary derivatives include crosslinkable derivatives of lignophenol derivatives and coumaran
derivatives.
[0048]
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The crosslinkable derivative is a derivative having a crosslinkable reactive group at the ortho
position and / or para position of the phenolic hydroxyl group of the lignin derivative. In the
reaction for introducing a crosslinkable group, for example, a lignophenol derivative is reacted
with a crosslinkable group-forming compound under alkaline conditions to crosslink the
crosslinkable group in the ortho position and / or para position of the phenolic hydroxyl group in
the lignophenol derivative. Can be implemented by introducing That is, the present derivative can
be obtained by mixing and reacting a lignophenol derivative with a crosslinkable group-forming
compound in a state in which the phenolic hydroxyl group of the lignophenol derivative used can
be dissociated. The state in which the phenolic hydroxyl group of the lignophenol derivative can
be dissociated is usually formed in an appropriate alkaline solution. The type, concentration and
solvent of the alkali used are not particularly limited as long as the phenolic hydroxyl group of
the lignophenol derivative is dissociated. For example, a 0.1 N aqueous solution of sodium
hydroxide can be used.
[0049]
Under such conditions, the crosslinkable group is introduced at the ortho position or para
position of the phenolic hydroxyl group, so the introduction position of the crosslinkable group is
roughly determined by the type and combination of the phenol compound used. That is, when disubstituted in the ortho and para positions, no crosslinkable group is introduced into the
introduced phenol nucleus, and is introduced into the phenolic aromatic nucleus on the lignin
parent side. Since the phenolic aromatic nucleus on the lignin parent side is mainly present at the
polymer end of the lignophenol derivative, a prepolymer having a crosslinkable group introduced
mainly at the polymer end is obtained. In addition, in the case of 1 or less substitution in the
ortho and para positions, a crosslinkable group is introduced into the introduced phenolic
nucleus and the phenolic aromatic nucleus of the lignin matrix. Therefore, in addition to the end
of the polymer chain, a crosslinkable group is introduced over the length to obtain a
multifunctional prepolymer.
[0050]
The type of crosslinkable group to be introduced into the lignophenol derivative is not
particularly limited. Any aromatic nucleus on the lignin mother side or an aromatic nucleus of the
introduced phenolic compound may be used. As a crosslinkable group, a hydroxymethyl group, a
hydroxyethyl group, a hydroxypropyl group, 1-hydroxy valeraldehyde group etc. can be
10-05-2019
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mentioned. The crosslinkable group-forming compound is an electrophilic compound which
forms or retains a crosslinkable group after bonding. For example, formaldehyde, acetaldehyde,
propionaldehyde, glutaraldehydes and the like can be mentioned. Formaldehyde is preferably
used in consideration of the introduction efficiency and the like.
[0051]
From the viewpoint of efficiently introducing the crosslinkable group when reacting the
lignophenol derivative with the crosslinkable group-forming compound, the crosslinkable groupforming compound is an aromatic nucleus of the arylpropane unit of lignin in the lignophenol
derivative and / or It is preferable to add 1 mole or more of the introduced phenol nucleus. More
preferably, it is 10 molar times or more, and further preferably 20 molar times or more.
[0052]
Next, a crosslinkable group is introduce | transduced into a phenol nucleus by heating this liquid
as needed in the state in which a lignophenol derivative and a crosslinkable group formation
compound exist in an alkaline liquid. Although heating conditions are not specifically limited as
long as a crosslinkable group is introduce | transduced, 40-100 degreeC is preferable. If it is less
than 40 ° C., the reaction rate of the crosslinkable group forming compound is so low that it is
not preferable, and if it is higher than 100 ° C., side reactions other than introducing
crosslinkable groups to lignin such as reaction of the crosslinkable group forming compound
itself are activated. Not so desirable. More preferably, it is 50 to 80 ° C., for example, about 60
° C. is particularly preferable. The reaction is stopped by cooling the reaction solution, acidified
(by about pH 2) with an appropriate concentration of hydrochloric acid or the like, and the acid
and unreacted crosslinkable group-forming compound are removed by washing, dialysis or the
like. After dialysis, the sample is recovered by lyophilization. If necessary, dry under reduced
pressure over phosphorus pentoxide.
[0053]
The crosslinkable secondary derivative thus obtained has a crosslinkable group in the position
ortho and / or para to the phenolic hydroxyl group in the lignophenol derivative. In addition, the
introduction amount of the crosslinkable group is usually about 0.01 to 1.5 mol / C 9 unit in
many cases. Since the crosslinkable derivative has a crosslinkable group together with the
10-05-2019
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phenolic hydroxyl group, it can be cross-linked in the production of the present composite
material, and the processability can be improved.
[0054]
(Cumaran Derivative) As shown in FIG. 1, the coumaran derivative is a derivative having a
coumaran unit obtained by introducing a bisarylpropane unit of a lignophenol derivative into a
coumaranized phenol compound. Such a derivative can be obtained by contacting a lignophenol
derivative having a first unit with an alkali. Preferably it heats simultaneously. For example, in a
lignophenol derivative having a first unit in which the ortho position of the phenolic hydroxyl
group of the introduced phenolic compound is introduced into the C1 position, alkali treatment
causes an attack of the C2 carbon by the phenoxide ion of the introduced phenolic compound. .
That is, in the mild alkali treatment, the phenolic hydroxyl group of the introduced phenolic
compound is dissociated, and the resulting phenoxide ion attacks the C2 position constituting the
C2 aryl ether bond in the form of an intramolecular nucleophilic reaction to cause the C2 aryl
ether The bond is cleaved and the introduced phenol nucleus forms a coumaran skeleton with
part of the phenylpropane unit into which it is introduced. At the same time, the lignophenol
derivative is depolymerized by this intramolecular nucleophilic reaction, and cleavage of the C2
aryl ether bond generates a phenolic hydroxyl group in the mother nucleus of the next lignin that
has been linked by the ether bond. .
[0055]
Specifically, the alkali treatment is performed by dissolving a lignophenol derivative in an alkali
solution, reacting it for a certain period of time, and heating if necessary. The alkaline solution
that can be used for this treatment is only required to be capable of dissociating the phenolic
hydroxyl group of the introduced phenolic compound in the lignophenol derivative, and the type
and concentration of alkali, type of solvent, etc. are not particularly limited. . If dissociation of the
phenolic hydroxyl group occurs under alkali, the coumaran structure is formed by the adjacent
group participation effect. For example, sodium hydroxide solution can be used for lignophenol
derivatives into which p-cresol has been introduced. For example, the alkali concentration range
of the alkali solution can be 0.5 to 2 N, and the treatment time can be about 1 to 5 hours. In
addition, lignophenol derivatives in an alkaline solution easily express a coumaran structure by
being heated. Conditions such as temperature and pressure at the time of heating can be set
without particular limitation. For example, the molecular weight reduction of the lignophenol
derivative can be achieved by heating the alkaline solution to 100 ° C. or higher (for example,
about 140 ° C.). Furthermore, the alkaline solution may be heated to a temperature above its
10-05-2019
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boiling point under pressure to lower the molecular weight of the crosslinked lignophenol
derivative.
[0056]
It is known that, at the same alkaline solution and at the same concentration, when the heating
temperature is in the range of 120 ° C. to 140 ° C., the higher the heating temperature, the
lower the molecular weight by C2-aryl ether bond cleavage is promoted. Although the heating
temperature in the alkali treatment is not particularly limited, it can be performed at 80 ° C. or
more and 200 ° C. or less as needed. If the temperature is significantly lower than 80 ° C., the
reaction does not proceed sufficiently, and if the temperature exceeds 200 ° C., undesirable side
reactions are likely to be derived. As a preferable example of the process for formation of the
Klaman structure and the molecular weight reduction accompanying it, the condition of using a
0.5 N aqueous solution of sodium hydroxide as an alkaline solution and heating for 60 minutes at
140 ° C. in an autoclave may be mentioned it can. In particular, this treatment condition is
preferably used for p-cresol or 2,4-dimethylphenol derivatized lignophenol derivatives.
[0057]
In addition, introduction of the crosslinkable group mentioned above and coumaranization can be
given to a lignophenol derivative, a derivative which has a crosslinkable group and a coumaran
unit can also be manufactured, and this derivative is also contained in a secondary derivative.
Further, various functional groups such as an acyl group and a carboxyl group can be introduced
as a substituent or the like to various secondary derivatives such as crosslinkable derivatives and
coumaran derivatives besides lignophenol derivatives. The derivatives introduced are also
included in the secondary derivatives. In an acoustic material, these secondary derivatives can be
used alone or in combination thereof.
[0058]
(Acoustic Material) The present acoustic material is formed by combining a cellulose-based
material and a lignin derivative. The form of complexation is not particularly limited, but the
form in which the cellulose-based material is dispersed in the lignin derivative matrix, the form in
which the lignin derivative is dispersed in the cellulose-based material matrix, or both of them. It
may be in the form of forming a continuous phase, but typically, it has a composite form in which
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a lignin derivative is supported on a cellulose-based substrate having a two-dimensional or threedimensional structure.
[0059]
Various methods can be employed to combine the cellulose-based material and the lignin
derivative, but (1) non-dispersed cellulose having a predetermined shape such as a sheet or a
three-dimensional shape other than a sheet There are a method in which a lignin derivative is
supplied to a system material for complexation, and a method (2) in which a dispersed cellulosebased material and a lignin derivative are complexed to give a predetermined shape thereof.
[0060]
(1) In the case where a lignin derivative is complexed to a cellulose-based material having a
predetermined shape: The cellulose-based material forms an entangled state or an aggregation
state to impart a lignin derivative to a cellulose-based substrate having a predetermined shape
After immersing and impregnating a cellulose-based substrate with a lignin derivative solution in
which a lignin derivative is dissolved, or applying or impregnating the solution onto a cellulosebased substrate by spraying or brushing, the solvent of the lignin derivative solution is distilled
off. Can be adopted.
By evaporating the solvent, the lignin derivative is supported on the cellulose-based substrate.
Moreover, it can heat and / or pressurize as needed with solvent distillation or after solvent
distillation. In addition, the cellulose-based substrate having the lignin derivative once loaded can
be heated and / or pressurized to give a final shape. The lignin derivative tends to migrate to the
surface of the cellulose-based substrate as the solvent evaporates. Thus, for example,
dichloromethane (boiling point 39.8 ° C., 20 ° C. vapor pressure 356 mmHg), acetone (boiling
point 56.5 ° C., 20 ° C. vapor pressure 180 mmHg), tetrahydrofuran (boiling point 66.0 ° C.,
20 ° C. vapor pressure 176 mmHg) etc. When a low-boiling lignin derivative dissolving solvent
having a boiling point of 100 ° C. or less is used, an acoustic material can be obtained which
carries a high concentration of lignin derivative on the surface side of the cellulose-based
substrate. Also, ethylene glycol monomethyl ether (boiling point 124.3 ° C., 20 ° C. vapor
pressure 6.2 mmHg), ethylene glycol monoethyl ether (boiling point 134.8 ° C., 20 ° C. vapor
pressure 3.8 mmHg), ethylene glycol monobutyl ether (boiling point 171.2 ° C.) When using a
high-boiling solvent such as ethylene glycol (boiling point 197.6 ° C) with a boiling point of
more than 100 ° C, lignin derivatives are almost uniformly supported on the entire cellulosebased substrate Sound material can be obtained. As such a high boiling point solvent, the boiling
point is preferably 120 ° C. or more. From the viewpoint of solubility, it is preferable to use
10-05-2019
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glycol or recalled monoalkyl ether. In addition, the support effect of the lignin derivative to the
base material at the time of using a high boiling point solvent is not particularly limited as long
as it is a base material which is not dissolved in the dissolution solvent of not only cellulose base
materials but also these lignin derivatives. Be done.
[0061]
Also, for example, a sheet-like or plate-like cellulose-based substrate can be laminated via a lignin
derivative. Specifically, the whole of a cellulose-based substrate or the surface layer side of which
a lignin derivative is supported may be laminated and heat-pressed, and further, a coating layer
of a lignin derivative may be formed between them and then laminated. You may
[0062]
According to such a method, it is possible to easily construct a form in which a lignin derivative is
supported on a cellulose-based substrate which is a two-dimensional or three-dimensional
structure mainly composed of a cellulose-based material.
[0063]
(2) When the dispersed cellulose-based material and the lignin derivative are complexed There
are two types, dry method and wet method, to apply the lignin derivative to the dispersed
cellulose-based material such as powdery one. .
As a dry method, a dispersed cellulose-based material containing cellulose-based fibers and the
like and a powdery lignin derivative are dry-mixed, and the mixture is directly heated and / or
pressurized to be molded, or temporarily It is possible to adopt a method of molding and then
heating and / or pressing for molding. The preforming may be performed by heating and / or
pressing, and needle punching or air felting may be adopted depending on the shape (fibrous or
the like) of the cellulose-based material.
[0064]
In addition, as a wet method, a dispersed cellulose-based material is mixed with a lignin
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derivative in a suitable solvent, the solvent is distilled away from the mixture, and the lignin
derivative is adhered to the dispersed cellulose-based material, With or after removal, the lignin
derivative and the dispersed cellulose-based material can be shaped by heating and / or pressing.
In addition, when mixing the dispersed cellulose material and lignin derivative in a solvent, the
mixture is made into a sheet by the sheet formation, and then the solvent is distilled off, and the
sheet is made acoustically attached to the lignin derivative. Materials can also be obtained.
Furthermore, the sheet-like body thus obtained can be heated and / or pressurized to form a
strong molded body, or the sheet-like body may be heated and / or pressurized in a laminated
state.
[0065]
In the above production method (2), when a dispersed cellulose-based material is used, a molding
method for imparting a shape is conventionally used for molding of dispersed cellulose-based
materials, such as molding, compression molding, and paper making. Various molding methods
can be used. Further, in the wet method, the lignin derivative may be in the form of being soluble
in a solvent or in the form of particulate matter insoluble in the solvent.
[0066]
In the methods (1) and (2) for producing these acoustic materials, when distilling off the solvent
in which the lignin derivative is suspended or dissolved, by applying pressure, water is used as a
plasticizer in the process of solvent evaporation. At the same time, hydrogen bond between lignin
derivative and cellulosic material and hydrogen bond between cellulosic material can be
generated at the same time.
[0067]
Moreover, in the manufacturing methods (1) and (2) of these acoustic materials, it is preferable
to heat the heating performed for shape provision more than the softening temperature of a
lignin derivative.
As a result, a molded article with improved water resistance can be obtained. Moreover, the
molded object excellent in the intensity | strength and integrity which can easily implement postprocessing, such as cutting, can be obtained.
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[0068]
Heating and / or pressing can also be carried out with water vapor on the cellulosic material and
the lignin derivative. If steam is generated in the heating step, the steam can contribute to the
further expression of hydrogen bonds in the molded body, and a strong molded body can be
obtained. Since water is inherently present in the cellulose-based material and the lignin
derivative prior to heating and / or pressurization, water is generated by heat pressure in a
sealed space to generate water vapor, or water vapor is externally generated. I will supply.
Preferably, hot pressure is applied in an enclosed space that has been exposed to steam from the
outside.
[0069]
When a lignophenol derivative having a first unit is used as the lignin derivative, the acoustic
material is a composite of a lignin derivative and a cellulose-based material in the acoustic
material by supplying a solvent having an affinity to the lignophenol derivative. The structures
can be disassembled and the respective material recovered. In addition, by alkali treatment, a
lignophenol derivative in the acoustic material can be coumaran derivatized and depolymerized
to recover a lignin component.
[0070]
When a crosslinkable derivative is used as the lignin derivative, a three-dimensional crosslink
structure of the lignin derivative is formed in the acoustic material by providing a heating step to
cause a crosslinking reaction, and the water resistance and strength are thereby obtained. And
the acoustic material which is excellent in dimensional stability can be obtained. The heating step
for such crosslinking may be performed concomitantly with the shaping step or may be
performed independently.
[0071]
When a crudely purified fraction containing any one or more of a phenol compound, an acid and
a carbohydrate in addition to a lignin derivative is used as the lignin derivative, the strength of
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the obtained acoustic material is further improved. . When a crudely purified fraction containing
a lignin derivative and a phenolic compound is used, a condensation reaction occurs between the
lignin and the phenolic compound upon heating to form a three-dimensional higher-order
structure in the molded body It is guessed that. Furthermore, when using a crudely purified
fraction containing a lignin derivative, a phenol compound and an acid, lignin is converted to a
lignophenol derivative-like compound by the coexistence of the lignin derivative, the phenol
compound and the acid, The strength of the molded body is improved. Furthermore, when a
crudely purified fraction containing a lignin derivative and a carbohydrate is used, the strength is
particularly improved in that the affinity with a cellulose-based material containing a hydrophilic
polymer such as cellulose or lignocellulose is improved. Will be
[0072]
In addition, the lignin derivative used for manufacture of such an acoustic material is useful as a
material for acoustic material manufacture or for improving an acoustic effect. Therefore, a
composition containing a lignin derivative or a crudely purified fraction containing the lignin
derivative, or a liquid agent composition in which the lignin derivative or the crudely purified
fraction is suspended or dissolved in a solvent is used as an acoustic material for the cellulose
material. It can be used as a manufacturing agent and an acoustic property improver. In addition,
these compositions can be used as a coating for forming a coating layer containing a lignin
derivative, if necessary, for immersion, application, impregnation by a spray, or the like.
[0073]
Further, a mixture (composition) containing a lignin derivative or a roughly purified fraction and
a dispersed cellulose-based material used in the various manufacturing methods described above
is a composition for molding an acoustic material, a composition for repairing an acoustic
material, or an acoustic It can also be used as a composition for forming a coating layer for
forming a surface layer or an inner layer having good properties.
[0074]
In the acoustic material, the weight ratio of the lignin derivative to the cellulose-based material is
preferably 0.1 parts by weight or more and 50 parts by weight or less of the lignin derivative
with respect to 100 parts by weight of the cellulose-based material.
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Within this range, both the bonding strength of the lignin derivative and the effect of improving
the acoustic characteristics can be obtained.
[0075]
In the acoustic material thus obtained, the acoustic characteristics of the cellulose-based material
are improved by combining the cellulose-based material and the lignin derivative, and the
acoustic characteristics of the internal material such as the internal loss and the propagation
speed are approximated. . Further, the present acoustic material has excellent moldability and
processability, and is a new material capable of adjusting acoustic characteristics by adjusting the
composition and the like of the cellulose-based material and the lignin derivative.
[0076]
Therefore, the present acoustic material can be used as an acoustic member for a speaker such
as a cone, a center cap, a sub cone, etc., and an acoustic plate of a flat plate type speaker, a
muffling plate for attenuating other sound sources, transmission or cutoff of sound of a specific
wavelength Can be used as an acoustic filter.
[0077]
Furthermore, soundboards and components of rubbed string instruments such as violins, violas,
cellos and double basses, soundboards and components of stringed instruments such as acoustic
guitars, electric guitars, harps, chopsticks, Taisho strings, harpsichords and strings of stringed
instruments such as pianos Plates and members, sound boards such as marimba and silophone,
body parts such as drums and drums, members, bodies such as wood blocks and clapping trees,
bodies and members such as woodwinds, and wood products that constitute all musical
instruments The present acoustic material can be used.
[0078]
Furthermore, the present acoustic material can be used as a wall material or panel constituting
an outer inner wall or the like, a sound insulation material constituting a part or the whole of a
ceiling material, a sound insulation material, or a sound absorption material.
[0079]
In addition, a composition containing lignin derivative or crudely purified fraction can be
complexed with a cellulose-based material to form a surface layer or an inner layer excellent in
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acoustic characteristics, and thus a part of the cellulose-based material is used. Acoustic
materials having an acoustic material phase can also be used for the various applications
described above.
[0080]
Furthermore, according to the composition containing the lignin derivative and the coarsely
purified fraction together with the cellulose-based material, acoustics in which the cellulosebased material and the lignin derivative are complexed on the surface or inside of the base made
of different materials other than the cellulose-based material A material phase can be formed,
and such an acoustic material can also be used for the various applications described above.
[0081]
EXAMPLES Hereinafter, the present invention will be specifically described by way of examples,
but the present invention is not limited to these examples.
[0082]
(Preparation of Lignophenol Derivative) A solution prepared by dissolving 1 kg of acetone
defatted cedar wood powder in 500 g of p-cresol dissolved in 7 L of acetone is permeated, and
then the solvent is distilled off to sorb p-cresol (3 mol / l). C9 unit) was prepared.
5 L of 72% sulfuric acid is added to the total amount of sorption wood flour 1.5 kg (1 kg of wood
flour + 0.5 kg of cresol), and after stirring for 1 hour at 30 ° C., disperse in 10 times the amount
of sulfuric acid Thereafter, washing with water was repeated until the supernatant became
neutral.
The obtained precipitate was dried at 40 ° C. to obtain a crude lignophenol derivative (here,
crude lignocresol).
Crude lignocresol was further dried by vacuum drying (50 mmHg, 72 hours).
[0083]
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The dried crude lignocresol (500 g) was extracted by stirring with 3 L of acetone for 2 hours,
250 g of Radiolite # 900 was further added, and the mixture was stirred for 1 hour.
300 g of Radiolite # 900 was spread on a polypropylene filter cloth (with a particle retention
diameter of 5 μm), and the acetone extract containing this filter aid was filtered.
Acetone was added to the residue on the filter cloth containing the filter aid, stirred and filtered
twice, the filtrates were combined and finally made up to 5 liters.
The concentrated acetone extract was added dropwise to 50 L of diisopropyl ether (IPE), and the
resulting precipitate was filtered through the polypropylene filter cloth to remove the precipitate.
A series of washing operations of filtering the precipitate on the filter cloth with 1.8 L of IPE:
water mixture (1: 1 = vol: vol) and then washing the precipitate further with water was repeated
three times. The washed solid was dried under reduced pressure at 40 ° C. for 210 hours to
obtain a purified product.
[0084]
(Production of a Speaker Using a Lignophenol Derivative-Loaded Cellulose-Based Substrate for
Corn) Lignophenol derivative 20 wt% ethylene prepared with respect to corn paper
(manufactured by banana corn pulp) of FOSTEX 10 cm full-range speaker (FE103E) The glycol
monomethyl ether solution was completely supplied by spray and impregnated, and partially
applied and impregnated using a brush. In addition, in supplying a lignophenol derivative
solution to corn paper, masking was performed to parts other than corn paper. The total supply
of lignophenol derivative solution to corn paper was about 2 ml. Then, it air-dried in a draft
overnight, and also the acoustic material was produced by distilling off a solvent using a
ventilation dryer at 40 degreeC for 24 hours. In this acoustic material, about 25 parts by weight
of the lignophenol derivative was carried with respect to 100 parts by weight of the cellulosebased material. As a control, the same amount of solvent was supplied to the same corn paper
and air dried in the same manner. The speaker unit which performed these processing to corn
paper was put into the bass reflex type speaker box (E102) of FOSTEX company, and the speaker
was completed.
[0085]
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(Acoustic Sensory Test) In the acoustic sensory test, an amplifier (ARCAM A65 Plus) and a CD
switchably connected to the speaker unit (two speakers) of the example prepared above and the
speaker unit (two speakers) of the control example respectively A player (CD62T made by
ARCAM) was prepared. The speaker set and the control of the example can not be determined for
each of about 30 seconds from the beginning of each of the five classical music songs using
these systems for 19 subjects, in a state in which the speaker of the example or the control is the
speaker. The viewers were watched under the same conditions for each of the example speaker
sets, and it was tested which sound was preferred for the speaker unit. The results are shown in
Table 1.
[0086]
[0087]
As shown in Table 1, the subject who felt that the sound by the speaker unit of the example was
preferable was 87.4% on an average of five songs.
In addition, many subjects felt that the speaker unit of the example had effects such as presence
(sense of spread), three-dimensional sound, and long reverberation, and that the sound was
smaller. From the above, it can be seen that the speaker unit of the embodiment having a
cellulose-based substrate carrying a lignophenol derivative as a cone reflects the acoustic
characteristic of wood that the sound propagation speed is fast and the internal loss is large. The
[0088]
It is a figure which shows the coumaran unit with which a coumaran derivative is equipped.
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