Random Mat And Compact Of Fibre Reinforced Composite Material
Abstract:
Provided are a fiber-reinforced composite material shaped product which is isotropic
and has excellent mechanical strength and a random mat for use as an intermediate material
for the shaped composite material.
The random mat includes reinforcing fibers having an average fiber length of 3 to 100
mm and a thermoplastic resin, wherein the reinforcing fibers satisfy the following i) to iii).
i) The reinforcing fibers have a weight-average fiber width (Ww) which satisfies the
following equation (1).
Omm
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DESCRIPTION
Title of the Invention:
RANDOM MAT AND FIBER-REINFORCED COMPOSITE MATERIAL SHAPED
PRODUCT
Technical Field
[OOOl]
The present invention relates to a random mat for use as an intermediate material for
fiber-reinforced composite material shaped products in which a thermoplastic resin is used as
the matrix, and to a fiber-reinforced composite material shaped product obtained from the
random mat.
Background Art
[0002]
Random mats, which are isotropic, are used as fiber-reinforced composite materials in
which carbon fibers, aramid fibers, glass fibers, and the like are used as reinforcing fibers,
from the standpoints of formability and process simplicity. These random mats can be
obtained, for example, by the spray-up method (dry process) in which cut reinforcing fibers
are blown into a shaping die either alone or simultaneously with a thermosetting resin or by a
method (wet process) in which reinforcing fibers which have been cut in advance are added to
a binder-containing slurry and this mixture is formed into a sheet by a papermaking method.
[0003]
Known as a means for improving the mechanical properties of a composite material is
to heighten the volume content ratio of reinforcing fibers (Vf). In the case of random mats
employing cut fibers, however, it has been difficult to heighten the volume content ratio of
reinforcing fibers because of the presence of fibers oriented in three-dimensional directions,
considerable fiber entanglement, etc. Furthermore, in the case of using random mats, it is
difficult to enable the reinforcing fibers to sufficiently exhibit the strength thereof since the
fibers are discontinuous, as compared with the case where continuous fibers are used, and
there has been a problem in that in a shaped product obtained, the development rate of strength
of the reinforcing fibers is as low as up to 50% of the theoretical value. Non-patent
document 1 mentions a composite material produced from a carbon-fiber random mat
employing a thermosetting resin as the matrix. In this composite material, the development
rate of strength is about 44% of the theoretical value.
[0004]
In the case of conventional composite materials employing a thermosetting resin as
the matrix, shaped products have been obtained from intermediate materials called prepregs,
which were obtained by impregnating a reinforcing-fiber base material with a thermosetting
resin in advance, by heating and pressing the intermediate materials for 2 hours or longer
using an autoclave. In recent years, an RTM method has been proposed in which a
reinforcing-fiber base material impregnated with no resin is set in a mold and a thermosetting
resin is then casted thereinto, and a remarkable reduction in shaping time has been attained.
However, even in the case of using the RTM method, 10 minutes or a longer period is required
for each component to be shaped.
Consequently, composite materials obtained using a thermoplastic resin as the matrix,
in place of the conventional thermosetting resin, are attracting attention.
[0005]
Thermoplastic stamping (TP-SMC) in which a thermoplastic resin is used as the
matrix (patent document 1) is a molding method which includes heating chopped fibers
impregnated in advance with a thermoplastic resin to or above the melting point, introducing
the heated fibers into some of the cavity of a mold, immediately closing the mold, and causing
the fibers and the resin to flow within the mold to thereby obtain the shape of a product,
followed by cooling and molding. In this technique, molding can be completed in a period as
short as about 1 minute by using fibers impregnated with a resin in advance. Such techniques
are methods in which molding materials called SMCs or stampable sheets are used. The
thermoplastic stamping has had problems, for example, in that since the fibers and the resin
are caused to flow within the mold, thin-walled products cannot be molded and fiber
orientation is disordered and difficult to control.
[0006]
Patent document 2 proposes, as a means for improving mechanical properties and the
isotropy in a fiber-reinforced thermoplastic resin shaped product, a technique wherein
constituent carbon fibers are evenly dispersed into a single fiber form to thereby avoid the
trouble that resin-rich portions are formed at the spaces between fiber bundles or that the resin
cannot be impregnated into inner parts of fiber bundles, resulting in unimpregnated portions,
and to thereby improve mechanical properties and the isotropy thereof.
Citation List
Patent Documents
[0007]
Patent Document 1 : Japanese Patent No. 4 1 6 1409
Patent Document 2: International Publicatioii WO 20071097436
Non-Patent Document
[OOOS]
Non-Patent Document 1 : Composites, Part A 38 (2007) pp.755-770
Summary of the Invention
Problems that the Invention is to Solve
[0009]
However, in the conventional-art techniques described above, no investigations have
been made on a fiber-reinforced composite material shaped product which is even in
mechanical strength, has excellent tensile strength, and has a high development rate of strength
relative to a theoretical strength.
An objective of the invention is to provide a fiber-reinforced composite material
shaped product which is isotropic and has excellent mechanical strength and a random mat for
use as an intermediate material therefor. In particular, the invention is to provide a
fiber-reinforced composite material shaped product which is a fiber-reinforced composite
material shaped product obtained from the random mat and in which the reinforcing-fiber mat
included therein has small unevenness of thickness, is even in mechanical strength, and has
excellent tensile strength and a high development rate of strength.
Means for Solving the Problems
[OO lo]
The present inventors have found that a fiber-reinforced composite material shaped
product which is excellent in terms of mechanical strength, isotropy thereof, and strength
development can be provided by a random inat which includes both a thermoplastic resin and
discontinuous reinforcing fibers having specific values of weight-average fiber width,
average-fiber-width dispersion ratio, and weight-average fiber thickness. The invention has
been thus completed. More specifically, the inventors have found that by regulating
reinforcing fibers so as to be small and be similar in fiber width, the reinforcing fibers can be
densely incorporated into a random mat and a fiber-reinforced composite material shaped
product which is even and has excellent mechanical strength and a high development rate of
strength can be provided.
Namely, the present invention is: a random mat which includes reinforcing fibers
having an average fiber length of 3-100 mm and a thermoplastic resin, wherein the reinforcing
fibers satisfy the following i) to iii); and a fiber-reinforced composite material shaped product
obtained by shaping the random mat.
i) The reinforcing fibers have a weight-average fiber width (Ww) which satisfies the following
equation (1).
Omm
The process of cutting reinforcing fibers is described. Preferred as the reinforcing
fibers to be cut are the so-called strands, which are in the form of bundles of long single fibers,
because the strands are easily available and handleable. The cutting of reinforcing fibers
preferably is the process of cutting the reinforcing fibers using a knife, e.g., a rotary cutter.
One example of the cutting process using a rotary cutter is shown in Fig. 1. The knife angle
for continuously cutting the reinforcing fibers is not particularly limited. General blades
arranged at an angle of 90 degrees with the fibers may be used, or obliquely arranged blades or
spirally arranged blades may be used. An example of rotary cutters having spiral knives is
shown in Fig. 2.
Since the random mat of the invention is characterized in that the reinforcing fibers
have a controlled small size as described above, it is preferred to control the size such as fiber
width and fiber thickness, of the reinforcing fibers to be subjected to the cutting process, by
any of the widening methods and separating methods described below (see Fig. 3 as well).
[0044]
Methods for widening the fibers are not particularly limited. Examples thereof
include a method in which a widening spreader such as a convex pin is pushed against the
fibers, a method in which an air flow is passed in a direction crossing the running direction of
the fibers, thereby bending the fibers so as to arch leeward, and a method in which the fibers
are vibrated. It is preferable that the widened reinforcing fibers should be regulated so as to
have a desired fiber width by providing, at a later stage, a control roller for regulating the fiber
width.
It is also preferable, in the production of the random mat of the invention, that the
reinforcing fibers which have been thus widened should be separated so as to result in a
smaller reinforcing-fiber width.
[0045]
Methods for separating the fibers are not particularly limited, and examples thereof
include a method in which the strand is divided into thin bundles with a slitter. In the case of
separating the fibers using a slitter, a suitable method for obtaining fibers having a desired
fiber width is to regulate the slit spacing. Furthermore, with respect to slitting blades, a more
preferred method for controlling fiber width is to pass the reinforcing fibers having a certain
fiber width through knife-shaped slitting blades, thereby splitting the fibers, or to pass those
reinforcing fibers through comb-shaped slitter to sort the fibers. It is also possible to select a
sizing agent for the reinforcing fibers and separate the reinforcing fibers, thereby making it
easy to obtain reinforcing fibers having a desired average number of fibers.
[0046]
By conducting fiber separating subsequently to fiber widening in the manner
described above, the reinforcing fibers can be controlled so as to be small and be similar in
fiber width. Consequently, the reinforcing fibers contained in the random mat show excellent
development of the reinforcing function, and the random mat obtained has improved
homogeneity, reduced thickness unevenness, and excellent mechanical strength.
[0047]
Subsequently, a process is conducted in which the cut reinforcing fibers are
introduced into a tapered tube located at a downstream side from the cutter and are sprayed.
Methods for conveying the reinforcing fibers to the tapered tube are not particularly limited.
It is, however, preferred to generate a suction wind velocity within the tapered tube to convey
the reinforcing fibers into the tapered tube by air.
It is also preferable that in the spraying process, compressed air be directly blown
against the reinforcing fibers to thereby suitably widen the distribution of reinforcing-fiber
widths. The width of the distribution may be controlled by regulating the pressure of the
compressed air being blown.
[0048]
It is preferable that the conveyed reinforcing fibers should be sprayed on a breathable
sheet arranged under a spray apparatus. Also from the standpoint of the fixing process
described below, it is preferred to spray the reinforcing fibers on a movable breathable sheet
having a suction mechanism.
In the spraying process, the cut reinforcing fibers may be sprayed on a sheet
simultaneously with a fibrous or powder thermoplastic resin. This method is suitable for
obtaining a random mat including both reinforcing fibers and a thermoplastic resin.
[0049]
Subsequently, the sprayed reinforcing fibers are fixed to obtain a reinforcing-fiber
18
mat. Specifically, a preferred method is to fix the sprayed reinforcing fibers by suctioning air
from under the breathable sheet and thereby obtain a reinforcing-fiber mat. Also even in the
case where a fibrous or powder thermoplastic resin is sprayed simultaneously with the
reinforcing fibers, the thermoplastic resin is fixed together with the reinforcing fibers. This
processing in the fixing process may be conducted in the spraying process successively to the
spraying of the reinforcing fibers, or the like.
[0050]
The thermoplastic-resin addition process may be conducted simultaneously with
processes 1 to 3 described above. For example, a thermoplastic resin in a powder or another
form may be sprayed in the spraying process. In the case where a reinforcing-fiber mat has
been produced without adding a thermoplastic resin during processes 1 to 3 described above, a
thermoplastic resin in the form of a sheet, film, or the like can be placed on or layered to the
reinforcing-fiber mat to obtain a random mat of the invention. In this case, the thermoplastic
resin in the form of a sheet or a film may be in a molten state.
Meanwhile, a thermoplastic resin in the form of a sheet, film, powder, or the like may
be placed on or layered to the random mat obtained through the spraying of a thermoplastic
resin in a powder or another form in the spraying process, as in the case described above.
[005 11
[Manufacture of Fiber-reinforced composite material shaped product]
A fiber-reinforced composite material shaped product can be obtained by molding the
random mat of the invention. Examples of methods for obtaining the fiber-reinforced
composite material shaped product include a method in which the random mat obtained in the
manner described above is heated and pressed with a pressing machine or the like to obtain the
shaped product. Although there are no particular limitations on methods for obtaining the
fiber-reinforced composite material shaped product of the invention, a suitable method for
obtaining the shaped product is to mold the random mat by, for example, vacuum forming,
hydraulic forming, hot pressing, or cold pressing. A suitable method, among these, for
obtaining the fiber-reinforced composite material shaped product of the invention is molding
by cold pressing in which the random mat is heated to or above the melting point or glass
transition point of the thermoplastic resin contained therein and is then sandwiched between
molds kept at a temperature not higher than the melting point or glass transition point of the
resin, thereby obtaining a shape.
[0052]
It is preferable, in the molding of the random mat, that the random mat should have
been heated in advance to a temperature which is the melting point or more of the
thermoplastic resin as a matrix in cases when the resin is crystalline, or which is the glass
transition point or more of the thermoplastic resin in cases when the resin is amorphous, and
which is preferably not higher than the decomposition point of the thermoplastic resin. The
pressing medium may have been regulated so as to have a temperature of the melting point or
more or glass transition point or more, of the thermoplastic resin as a matrix, or may have been
regulated so as to have a temperature of the melting point or less or glass transition point or
less thereof. Furthermore, by suitably adding a thermoplastic resin during the molding,
fiber-reinforced composite material shaped products which differ in thickness depending on
purposes can be obtained. The thermoplastic resin to be added is not particularly limited, and
examples thereof include the same thermoplastic resins as those enumerated above in the
section Matrix Resin, With respect to the form of the resin also, use can be made of a molten
resin or a resin in the form of fibers, powder, film, or the like.
These random mats of the invention as such may be used as preforms, or may be
converted to shaped plates and then to shaped products having a final form.
Examples
[0053]
Examples are shown below, but the invention should not be construed as being
limited to the following Examples. With respect to reinforcing fibers and specimens thereof,
the units of fiber length, fiber width, and fiber thickness are mm and the unit of weight is g,
unless otherwise indicated. The densities of the carbon fibers and thermoplastic resins used
in the following Examples and Comparative Examples are as follows.
PAN-based carbon fibers "Tenax" (registered trademark) STS40-24K: 1.75 g/cm3
PAN-based carbon fibers "Tenax" (registered trademark) IMS6O-24K: 1.80 g/cm3
PAN-based carbon fibers "Tenax" (registered trademark) HTS40-12K: 1.76 g/cm3
PAN-based carbon fibers "Tenax" (registered trademark) UTS50-24K: 1-79 g/cm3
PAN-based carbon fibers "Tenax" (registered trademark) HTS40-6K: 1.76 g/cm3
Polypropylene: 0.9 1 g/cm3
Polycarbonate: 1.20 g/cm3
Polyamide-6: 1.14 g/cm3
[0054]
[Method for Determining Number-average Fiber Width and Weight-average Fiber Width of
Reinforcing Fibers in Random Mat]
The random mat is cut into 100 mm x 100 mm, and 300 reinforcing fibers are
randomly taken out with a tweezers. With respect to the reinforcing fibers taken out, the
fiber width (W,), fiber weight (w,), and fiber thickness (t,) of each fiber are measured and
recorded. For the measurements of fiber width and fiber thickness, a vernier caliper capable
of measuring down to 11100 mm is used. For weight measurement, a balance capable of
measuring down to 11100 mg is used. With respect to reinforcing fibers which were too
small to measure the weight thereof, reinforcing fibers having the same fiber width were put
together and weighed. In the case where two or more kinds of reinforcing fibers are used, the
fibers are sorted by kinds, and the measurement and evaluation are made for each kind.
After the measurements of fiber width (W,) and fiber weight (wi) with respect to all
the fibers taken out, the number-average fiber width (Wn) is determined using the following
equation (4).
Wn = CW,/I (4)
I is the number of reinforcing fibers, and the value thereof is 300 except for the case
where the number of the fibers is less than 300.
Furthermore, the weight-average fiber width (Ww) of the reinforcing fibers is
determined from the total weight (w) of the reinforcing fibers using the following equation (5).
Ww = C(W,xw,/w) (5)
In cases when the reinforcing fibers are unable to be separated from the thermoplastic
resin to raise difficulties in the measurements, the thermoplastic resin is removed, for example,
by heating the random mat, for example, at 500°C for about 1 hour and the measurements are
thereafter performed.
[0055]
[Method for Determining Dispersion ratio (WwIWn) of Reinforcing Fibers]
The average-fiber-width dispersion ratio (WwIWn) is determined from the
number-average fiber width (Wn) and weight-average fiber width (Ww) of the reinforcing
fibers obtained, using the following equation (6).
Average-fiber-width dispersion ratio (WwIWn) = (weight-average fiber width
(Ww))/(number-average fiber width (Wn)) (6)
[0056]
[Method for Determining Weight-average Fiber Thickness of Reinforcing Fibers in Random
Mat]
All the reinforcing fibers taken out are subjected to measurements of fiber thickness
(1,) and fiber weight (w,) in the manner described above, and the weight-average fiber
thickness (t) is thereafter determined using the following equation (7).
t = C(t,xw,/w) (7)
[0057]
[Method for Determining Number-average Fiber Width and Weight-average Fiber Width of
Reinforcing Fibers in Fiber-reinforced composite material shaped product]
The average fiber widths of the reinforcing fibers in the fiber-reinforced composite
material shaped product are determined by cutting the shaped composite material into 100 mm
x 100 mm, heating the cut piece in an oven at 500°C for about 1 hour to remove the resin,
subsequently taking out fibers in the same manner as for the random mat, and measuring the
fiber width (W,), fiber weight (w,), and the like.
[005S]
[Method for Determining Average Fiber Length L in Reinforcing-Fiber Mat or
Random Mat]
A hundred reinforcing fibers are randomly taken out from the reinforcing-fiber mat or
random mat using a tweezers, and the fiber length L, of each reinforcing fiber is measured
using a vernier caliper down to 1 mm and recorded. It is preferable that the area over which
reinforcing fibers are taken out should be sufficiently large as compared with the fiber lengths.
From the individual fiber lengths L, obtained, the average fiber length L is determined
using the following expression.
L = CL,/lOO
In cases when the reinforcing fibers are unable to be separated from the thermoplastic
resin to raise difficulties in the measurements, the thermoplastic resin is removed, for example,
by heating the random mat, for example, at 500°C for about 1 hour and the measurements are
thereafter performed.
[0059]
[Method for Determining Thickness Unevenness of Reinforcing-Fiber Mat in Random Mat]
The coefficient of variation CV of the thickness of the reinforcing-fiber mat in the
random mat was calculated in the following manner, and the thickness unevenness was
evaluated on the basis of the results. The higher the coefficient of variation CV (%) is, the
larger the thickness unevenness of the fibers is.
Meanwhile, in cases when the thermoplastic resin is unable to be separated from the
random mat, making it impossible to determine the thickness unevenness of the
reinforcing-fiber mat, the thermoplastic resin is removed by heating in the same manner as for
the fiber-reinforced composite material shaped product described below and the measurement
is thereafter performed.
1) The random mat is cut into 100 mm x 100 mm, and the thermoplastic resin is separated.
The reinforcing-fiber mat is put into a sealable bag, which is depressurized to -0.09 MPa or
less.
2) Marks are put on the bag at intervals of 10 mm in a lattice pattern, and the thickness is
measured with a micrometer down to 111,000 mm. The measurement is made on five lines x
five rows, i.e., on 25 points.
3) The thickness of the bag is subtracted from each measured thickness, and an average value
and a standard deviation are calculated. The coefficient of variation CV of the fiber thickness
is calculated using the following expression.
Coefficient of variation CV (%) = [(standard deviation) I (average value)] x 100 (3)
[0060]
[Method for Determining Thickness Unevenness of Reinforcing-Fiber Mat in Fiber-reinforced
composite material shaped product]
In the case where the reinforcing-fiber mat of the fiber-reinforced composite material
shaped product is evaluated for thickness unevenness, the fiber-reinforced composite material
shaped product of a flat plate shape is cut into 100 mm x 100 mm, and this cut piece is heated
in an oven at 500°C for about 1 hour to remove the thermoplastic resin. Thereafter,
dimensions of the resultant mat are measured in the same manner and placed on a smooth flat
plate. Subsequently, the each flat plate is put into a sealable bag and thickness measurement
is conducted on 25 points in the same manner as for the random mat, except that the
thicknesses of both the bag and the flat plate are subtracted from each measurement thickness.
Thus, the coefficient of variation CV of the thickness was determined.
[006 11
[Evaluation of the Degree of Impregnation with Thermoplastic Resin in Fiber-reinforced
composite material shaped product (Shaped Plate)]
The degree of impregnation in the fiber-reinforced composite material shaped product
(shaped plate) is evaluated through an ultrasonic flaw detection test. The degree of
impregnation was evaluated by conducting a flaw detection test with an ultrasonic flaw
detection imaging device (SDS-WIN; Krautkramer Japan Co., Ltd.) under the conditions of a
flaw-detector frequency of 5 MHz and a scanning pitch of 2.0 mm x 2.0 mm. In the
evaluation, a cross-section of a portion where the reflected-wave intensity was 90% or higher
was subjected to a microscopic examination to ascertain that there were no defects or voids
therein. The larger the area proportion of portions having a high reflected-wave intensity
(70% or higher in the Examples) in the flaw detection test is, the denser the inner part of the
shaped plate is and the higher the degree of impregnation with the thermoplastic resin in the
shaped plate is. Meanwhile, the larger the area proportion of portions having a low
reflected-wave intensity (50% or less in the Examples) is, the larger the amount of fine voids
present in the inner part of the shaped plate is and the larger the amount of unimpregnated
portions in the shaped plate is.
[0062]
[Tensile Test]
Test pieces were cut out of the fiber-reinforced composite material shaped product
(shaped plate) using a water jet and examined for tensile strength and tensile modulus in
reference to JIS K 7164 using a universal testing machine manufactured by Instron Corp.
The shape of the test pieces was type IB-B. The chuck-to-chuck distance was 11 5 mm, and
the test speed was 10 mmlmin. The test pieces were cut out along an arbitrary direction
(0-degree direction) and along the direction perpendicular thereto (90-degree direction), and
the tensile strength and tensile modulus were measured for each in the two directions. With
respect to the tensile modulus, the ratio (E6) obtained by dividing the larger value by the
smaller value was calculated.
[0063]
[Calculation of Development Rate of Property relative to Theoretical Strength]
The development rate of property (%) relative to a theoretical value was determined
from the tensile strength of the shaped plate obtained in the manner described above and from
the tensile strength of the reinforcing fibers (carbon fibers) included in the shaped plate,
through the following calculation.
Development rate of property (%) = [(tensile strength of shaped product)l(theoretica1
strength of shaped product)] x 100
Here, the theoretical strength of the shaped product was determined from the tensile
strength (Ff) of the reinforcing fibers contained in the shaped product, the breaking stress (om)
of the matrix resin, the volume content ratio (Vf) of the reinforcing fibers, and the coefficient
of orientation (qe) of the fibers on the basis of a law of mixture regarding the strength of
composite materials, using the following expression.
Theoretical strength of shaped product (MPa) = (qoxFfxVf)+ om(l-Vf)
(Here, the coefficient of orientation q~ was used q0=318, which is the value for
in-plane random orientation.)
[0064]
[EXAMPLE 11
As reinforcing fibers, PAN-based carbon fiber strand "Tenax" (registered trademark)
STS40-24K (fiber diameter, 7.0 pm; fiber width 10 mm; tensile strength, 4,000 MPa),
manufactured by Toho Tenax Co., Ltd., was subjected to fiber widening to increase the width
thereof to 22 mm. Before being subjected to treatment with a separation apparatus, the
widened reinforcing-fiber strand was passed through rollers having an inner width of 20 mm
to thereby regulate the fiber width precisely to 20 mm. Disk-shaped separation blades made
of a cemented carbide were used as the separation apparatus to slit the 20 mm-wide
reinforcing-fiber strand at intervals of 0.8 mm. Furthermore, a rotary cutter made of a
cemented carbide and equipped with blades at intervals of 20 mm was used as a cutting device
to cut the slit strand so as to result in a fiber length of 20 mm. A tapered tube was arranged
just under the rotary cutter. Compressed air was supplied into this tapered tube to thereby
introduce the reinforcing fibers into the tapered tube and convey the fibers therethrough at a
suction wind velocity of 5 mlsec. Polypropylene (J-106G, manufactured by Prime Polymer
Co., Ltd.) which had been pulverized and classified so as to have an average particle diameter
of 500 pm was supplied as a matrix resin through the sidewall of the tapered tube.
Subsequently, a movable conveyor net was arranged under the outlet of the tapered tube, and
the reinforcing fibers were supplied thereto from the tapered tube while conducting suction
with a blower arranged under the net, thereby obtaining a random mat having a fiber areal
weight of 1,500 g/m2. The form of the reinforcing fibers in the random mat was examined
and, as a result, it was found that the fiber axes of the reinforcing fibers were substantially
parallel to a plane of the random mat and the reinforcing fibers were randomly dispersed in the
plane.
[0065]
In the random mat obtained, the reinforcing fibers had an average fiber length of 20
mm and a weight-average fiber thickness of 0.06 mm. The reinforcing fibers constituting the
random mat had a weight-average fiber width (Ww) of 0.66 mm, a number-average fiber
width (Wn) of 0.43 mm, and a dispersion ratio (WwIWn) of 1.52.
The random mat obtained was heated at 4.0 MPa for 10 minutes with a pressing
device heated at 220°C, thereby obtaining a shaped plate having a thickness of 1.9 mm. The
shaped plate obtained was evaluated for the thickness unevenness of the reinforcing-fiber mat.
As a result, the coefficient of variation CV of the thickness was found to be 6.4%.
Furthermore, the ultrasonic flaw detection test was conducted and, as a result, portions in
which the reflected-wave intensity was 70% or higher were observed in a ratio of 80% or
more.
In the shaped plate obtained, the volume content ratio of the reinforcing fibers was 45
~01%. The shaped plate was evaluated for tensile property in accordance with JIS 7164 and,
as a result, the shaped plate was found to have a tensile strength of 490 MPa, a development
rate of properties relative to theoretical strength of 73%, and a tensile modulus ratio between
0-degree direction and 90-degree direction of 1.06.
[0066]
[EXAMPLE 21
As reinforcing fibers, PAN-based carbon fiber strand "Tenax" (registered trademark)
IMS60-24K (fiber diameter, 5.0 pm; fiber width 10 mm; tensile strength, 5,800 MPa),
manufactured by Toho Tenax Co., Ltd., was subjected to fiber widening to increase the width
thereof to 26 mm. Before being subjected to treatment with a separation apparatus, the
widened reinforcing-fiber strand was passed through rollers having an inner width of 25 mm
to thereby regulate the fiber width precisely to 25 mm. Disk-shaped separation blades made
of a cemented carbide were used as the separation apparatus to slit the 25 mm-wide
reinforcing-fiber strand at intervals of 1.4 mm. Furthermore, a rotary cutter made of a
cemented carbide and equipped with blades at intervals of 45 mm was used as a cutting device
to cut the slit strand so as to result in a fiber length of 45 mm. A tapered tube was arranged
just under the rotary cutter. Compressed air was supplied into this tapered tube to thereby
introduce the reinforcing fibers into the tapered tube and convey the fibers therethrough at a
suction wind velocity of 5 mlsec. A polycarbonate ("Panlite" (registered trademark) L-1225Y,
manufactured by Teijin Chemicals Ltd.) which had been pulverized and classified so as to
have an average particle diameter of 500 pm was supplied as a matrix resin through the
sidewall of the tapered tube. Subsequently, a movable conveyor net was arranged under the
outlet of the tapered tube, and the reinforcing fibers were supplied thereto from the tapered
tube while conducting suction with a blower arranged under the net, thereby obtaining a
random mat having a fiber areal weight of 2,500 g/m2. The form of the reinforcing fibers in
the random mat was examined and, as a result, it was found that the fiber axes of the
reinforcing fibers were substantially parallel with a plane of the random mat and the
reinforcing fibers were randomly dispersed in the plane.
[0067]
In the random mat obtained, the reinforcing fibers had an average fiber length of 45
mm and a weight-average fiber thickness of 0.05 mm. The reinforcing fibers constituting the
random mat had a weight-average fiber width (Ww) of 1.25 mm, a number-average fiber
width (Wn) of 0.69 mm, and a dispersion ratio (WwIWn) of 1.80.
The random mat obtained was heated at 4.0 MPa for 10 minutes with a pressing
device heated at 300°C, thereby obtaining a shaped plate having a thickness of 4.0 mm. The
shaped plate obtained was evaluated for the thickness unevenness of the reinforcing-fiber mat.
As a result, the coefficient of variation CV of the thickness was found to be 9.0%.
Furthermore, the ultrasonic flaw detection test was conducted and, as a result, portions in
which the reflected-wave intensity was 70% or higher were observed in a ratio of 80% or
more.
In the shaped plate obtained, the volume content ratio of the reinforcing fibers was 35
~01%. The shaped plate was evaluated for tensile property in accordance with JIS 7164 and,
as a result, the shaped plate was found to have a tensile strength of 540 MPa, a development
rate of properties relative to theoretical strength of 71%, and a tensile modulus ratio between
0-degree direction and 90-degree direction of 1.07.
[0068]
[EXAMPLE 31
As reinforcing fibers, PAN-based carbon fiber strand "Tenax" (registered trademark)
STS40-24K (fiber diameter, 7.0 pm; fiber width 10 mm; tensile strength, 4,000 MPa),
manufactured by Toho Tenax Co., Ltd., was subjected to fiber widening to increase the width
thereof to 16 mm. Before being subjected to treatment with a separation apparatus, the
widened reinforcing-fiber strand was passed through rollers having an inner width of 15 mm
to thereby regulate the fiber width precisely to 15 mm. Disk-shaped separation blades made
of a cemented carbide were used as the separation apparatus to slit the 15 mm-wide
reinforcing-fiber strand at intervals of 0.5 mm. Furthermore, a rotary cutter made of a
cemented carbide and equipped with blades at intervals of 12 mm was used as a cutting device
to cut the slit strand so as to result in a fiber length of 12 mm. A tube having a small hole
was prepared as a spray apparatus, and compressed air was supplied thereto using a
compressor. In this stage, the velocity of the wind discharged through the small hole was 50
m/sec. Furthermore, a tapered tube was arranged under the spray apparatus. Subsequently,
a movable conveyor net was arranged under the outlet of the tapered tube, and the reinforcing
fibers were supplied thereto from the tapered tube while conducting suction with a blower
arranged under the net, thereby obtaining a reinforcing-fiber mat having a fiber areal weight of
700 cg/m2. The form of the reinforcing fibers in the reinforcing-fiber mat was examined and,
as a result, it was found that the fiber axes of the reinforcing fibers were substantially parallel
to a plane of the random mat and the reinforcing fibers were randomly dispersed in the plane.
[0069]
Subsequently, a molten matrix resin was supplied to the surface of the mat.
Specifically, a polyamide-6 resin (A1030, manufactured by Unichika, Ltd.) was used as a
matrix resin and melted, and the molten resin of a film shape having a thickness of 0.6 mm
was extruded, at the same speed as the conveyor line speed, from a T-die having a width of 1
m and arranged over the conveyor net at a distance of 5 cm therefrom and was supplied to the
whole surface of the mat. In this operation, that portion of the surface of the reinforcing-fiber
mat to which the resin was being supplied was heated with an infrared ray heater to prevent
the resin from cooling and solidifying.
The apparatus was operated under such conditions that the reinforcing-fiber supply
amount was set at 1,400 glmin and the matrix-resin supply amount was set at 1,360 glmin.
As a result, a random mat constituted by the reinforcing fibers and the thermoplastic resin was
formed on the fixing net. Subsequently, this mat was heated and pressed with a pair of
heating rollers having a set temperature of 280°C, thereby obtaining a random mat in which
the resin was evenly impregnated.
[0070]
In the random mat obtained, the reinforcing fibers had an average fiber length of 12
mm and a weight-average fiber thickness of 0.06 mm. The reinforcing fibers constituting the
random mat had a weight-average fiber width (Ww) of 0.32 mm, a number-average fiber
width (Wn) of 0.16 mm, and a dispersion ratio (WwIWn) of 1.96.
The random mat obtained was heated at 4.0 MPa for 10 minutes with a pressing
device heated at 260°C, thereby obtaining a shaped plate having a thickness of 1.0 mm.
The shaped plate obtained was evaluated for the thickness unevenness of the
reinforcing-fiber mat. As a result, the coefficient of variation CV of the thickness was found
to be 6.8%. Furthermore, the ultrasonic flaw detection test was conducted and, as a result,
portions in which the reflected-wave intensity was 70% or higher were observed in a ratio of
80% or more.
In the shaped plate obtained, the volume content ratio of the reinforcing fibers was 40
~01%. The shaped plate was evaluated for tensile property in accordance with JIS 7164 and,
as a result, the shaped plate was found to have a tensile strength of 440 MPa, a development
rate of properties relative to theoretical strength of 73%, and a tensile modulus ratio between
0-degree direction and 90-degree direction of 1.04.
[0071]
[EXAMPLE 41
As reinforcing fibers, PAN-based carbon fiber strand "Tenax" (registered trademark)
HTS40-12K (fiber diameter 7.0 pm; fiber width 8 mm; tensile strength, 4,200 MPa),
manufactured by Toho Tenax Co., Ltd., was subjected to fiber widening to increase the width
thereof to 16 mm. Before being subjected to treatment with a separation apparatus, the
widened reinforcing-fiber strand was passed through rollers having an inner width of 15 mm
to thereby regulate the fiber width precisely to 15 mm. Disk-shaped separation blades made
of a cemented carbide were used as the separation apparatus to slit the 15 mm-wide
reinforcing-fiber strand at intervals of 0.5 mm. Furthermore, a rotary cutter made of a
cemented carbide and equipped with blades at intervals of 15 mm was used as a cutting device
to cut the slit strand so as to result in a fiber length of 15 mm. A tapered tube was arranged
just under the rotary cutter. Compressed air was supplied into this tapered tube to introduce
the fibers into the tapered tube and convey the fibers therethrough at a suction wind velocity of
5 mlsec. A polycarbonate ("Panlite" (registered trademark) L-1225Y, manufactured by Teijin
Chemicals Ltd.) which were pulverized and classified so as to have an average particle
diameter of 500 pm was supplied as a matrix resin through the sidewall of the tapered tube.
Subsequently, a movable conveyor net was arranged under the outlet of the tapered tube, and
the reinforcing fibers were supplied thereto from the tapered tube while conducting suction
with a blower arranged under the net, thereby obtaining a random mat having a fiber areal
weight of 2,640 g/m2. The form of the reinforcing fibers in the random mat was examined
and, as a result, it was found that the fiber axes of the reinforcing fibers were substantially
parallel to a plane of the random mat and the reinforcing fibers were randomly dispersed in the
plane.
100721
In the random mat obtained, the reinforcing fibers had an average fiber length of 15
mm and a weight-average fiber thickness of 0.04 mm. The reinforcing fibers constituting the
random mat had a weight-average fiber width (Ww) of 0.47 mm, a number-average fiber
width (Wn) of 0.36 mm, and a dispersion ratio (WwIWn) of 1.3 1.
The random mat obtained was heated at 4.0 MPa for 10 minutes with a pressing
device heated at 300°C, thereby obtaining a shaped plate having a thickness of 3.0 mm. The
shaped plate obtained was evaluated for the thickness unevenness of the reinforcing-fiber mat.
As a result, the coefficient of variation CV of the thickness was found to be 5.6%.
Furthermore, the ultrasonic flaw detection test was conducted and, as a result, portions in
which the reflected-wave intensity was 70% or higher were observed in a ratio of 80% or
more.
In the shaped plate obtained, the volume content ratio of the reinforcing fibers was 50
~01%. The shaped plate was evaluated for tensile property in accordance with JIS 7164 and,
as a result, the shaped plate was found to have a tensile strength of 585 MPa, a development
rate of properties relative to theoretical strength of 74%, and a tensile modulus ratio between
0-degree direction and 90-degree direction of 1.04.
[0073]
[COMPARATIVE EXAMPLE 11
As reinforcing fibers, PAN-based carbon fiber strand "Tenax" (registered trademark)
HTS40-12K (fiber diameter, 7.0 pm; fiber width 8 mm; tensile strength, 4,200 MPa),
manufactured by Toho Tenax Co., Ltd., was subjected to fiber widening to increase the width
thereof to 16 mm. Before being subjected to treatment with a separation apparatus, the
widened reinforcing-fiber strand was passed through rollers having an inner width of 15 mm
to thereby regulate the fiber width precisely to 15 mm. Disk-shaped separation blades made
of a cemented carbide were used as the separation apparatus to slit the reinforcing-fiber strand
at intervals of 3.2 mm. Furthermore, a rotary cutter made of a cemented carbide and
equipped with blades at intervals of 15 mm was used as a cutting device to cut the slit strand
so as to result in a fiber length of 15 mm. A tapered tube was arranged just under the rotary
cutter. Compressed air was supplied into this tapered tube to introduce the fibers into the
tapered tube and convey the fibers therethrough at a suction wind velocity of 5 mlsec. A
polycarbonate ("Panlite" (registered trademark) L- 1225 Y, manufactured by Teijin Chemicals
Ltd.) which were pulverized and classified so as to have an average particle diameter of 500
pm was supplied as a matrix resin through the sidewall of the tapered tube. Subsequently, a
movable conveyor net was arranged under the outlet of the tapered tube, and the reinforcing
fibers were supplied thereto from the tapered tube while conducting suction with a blower
arranged under the net, thereby obtaining a random mat having a fiber areal weight of 2,640
g/m2. The form of the reinforcing fibers in the random mat was examined and, as a result, it
was found that the fiber axes of the reinforcing fibers were substantially parallel to a plane of
the random mat and the reinforcing fibers were randomly dispersed in the plane.
[0074]
In the random mat obtained, the reinforcing fibers had an average fiber length of 15
mm and a weight-average fiber thickness of 0.05 mm. The reinforcing fibers constituting the
random mat had a weight-average fiber width (Ww) of 3.02 mm, a number-average fiber
width (Wn) of 2.27 mm, and a dispersion ratio (Ww/Wn) of 1.33.
The random mat obtained was heated at 4.0 MPa for 10 minutes with a pressing
device heated at 300°C, thereby obtaining a shaped plate having a thickness of 3.0 mm. The
shaped plate obtained was evaluated for the thickness unevenness of the reinforcing-fiber mat.
As a result, the coefficient of variation CV of the thickness was found to be 18.4%.
Furthermore, the ultrasonic flaw detection test was conducted and, as a result, portions in
which the reflected-wave intensity was 70% or higher were observed in a ratio of 80% or
more.
In the shaped plate obtained, the volume content ratio of the reinforcing fibers was 50
~01%. The shaped plate was evaluated for tensile property in accordance with JIS 7164 and,
as a result, the shaped plate was found to have a tensile strength of 420 MPa, a development
rate of properties relative to theoretical strength of 53%, and a tensile modulus ratio between
0-degree direction and 90-degree direction of 1.16.
[0075]
[EXAMPLE 51
As reinforcing fibers, PAN-based carbon fiber strand "Tenax" (registered trademark)
UTS50-24K (fiber diameter, 6.9 pm; fiber width 10 mm; tensile strength, 5,000 MPa),
manufactured by Toho Tenax Co., Ltd., was subjected to fiber widening to increase the width
thereof to 22 mm. Before being subjected to treatment with a separation apparatus, the
widened reinforcing-fiber strand was passed through rollers having an inner width of 20 mm
to thereby regulate the fiber width precisely to 20 mm. Disk-shaped separation blades
arranged at intervals of 2.6 mm and 2.2 mm alternately were used as the separation apparatus
to slit the reinforcing-fiber strand. Furthermore, a rotary cutter made of a cemented carbide
and equipped with blades at intervals of 30 mm was used as a cutting device to cut the slit
strand so as to result in a fiber length of 30 mm. A tapered tube was arranged just under the
rotary cutter. Compressed air was supplied into this tapered tube to introduce the fibers into
the tapered tube and convey the fibers therethrough at a suction wind velocity of 5 mlsec.
Polyamide-6 ("A103OU, manufactured by Unichika, Ltd.) which was pulverized and classified
so as to have an average particle diameter of 500 pm was supplied as a matrix resin through
the sidewall of the tapered tube. Subsequently, a movable conveyor net was arranged under
the outlet of the tapered tube, and the reinforcing fibers were supplied thereto from the tapered
tube while conducting suction with a blower arranged under the net, thereby obtaining a
random mat having a fiber areal weight of 4,000 g/m2. The form of the reinforcing fibers in
the random mat was examined and, as a result, it was found that the fiber axes of the
reinforcing fibers were substantially parallel to a plane of the random mat and the reinforcing
fibers were randomly dispersed in the plane.
In the random mat obtained, the reinforcing fibers had an average fiber length of 30
mm and a weight-average fiber thickness of 0.07 mrn. The reinforcing fibers constituting the
random mat had a weight-average fiber width (Ww) of 2.20 mm, a number-average fiber
width (Wn) of 1.39 mm, and a dispersion ratio (WwIWn) of 1.58.
The random mat obtained was heated at 4.0 MPa for 10 minutes with a pressing
device heated at 280°C, thereby obtaining a shaped plate having a thickness of 5.0 mm. The
shaped plate obtained was evaluated for the thickness unevenness of the reinforcing-fiber mat.
As a result, the coefficient of variation CV of the thickness was found to be 13.3%.
Furthermore, the ultrasonic flaw detection test was conducted and, as a result, portions in
which the reflected-wave intensity was 70% or higher were observed in a ratio of 80% or
more.
In the shaped plate obtained, the volume content ratio of the reinforcing fibers was 45
~01%. The shaped plate was evaluated for tensile property in accordance with JIS 7164 and,
as a result, the shaped plate was found to have a tensile strength of 550 MPa, a development
rate of properties relative to theoretical strength of 65%, and a tensile modulus ratio between
0-degree direction and 90-degree direction of 1.09.
[0076]
[COMPARATIVE EXAMPLE 21
As reinforcing fibers, PAN-based carbon fiber strand "Tenax" (registered trademark)
UTS50-24K (fiber diameter, 6.9 pm; fiber width 10 mm; tensile strength, 5,000 MPa),
manufactured by Toho Tenax Co., Ltd., was subjected to fiber widening to increase the width
thereof to 22 mm. Before being subjected to treatment with a separation apparatus, the
widened reinforcing-fiber strand was passed through rollers having an inner width of 20 mm
to thereby regulate the fiber width precisely to 20 mm. A part of the reinforcing-fiber strand
widened to a width of 20 mm was slit at intervals of 4.2 mm, and the other part thereof was slit
at intervals of 0.3 mm. The two kinds of slit strands were supplied in the same amount to a
cutting device. A rotary cutter made of a cemented carbide and equipped with blades at
intervals of 20 mm was used as the cutting device to cut the slit strands so as to result in a fiber
length of 20 mm.
A tapered tube was arranged just under the rotary cutter. Compressed air was
supplied into this tapered tube to introduce the fibers into the tapered tube and convey the
fibers therethrough at a suction wind velocity of 5 mlsec. Polyamide-6 ("A1030",
manufactured by Unichika, Ltd.) which were pulverized and classified so as to have an
average particle diameter of 500 pm was supplied as a matrix resin through the sidewall of the
tapered tube. Subsequently, a movable conveyor net was arranged under the outlet of the
tapered tube, and the carbon fibers were supplied thereto from the tapered tube while
conducting suction with a blower arranged under the net, thereby obtaining a random mat
having a fiber areal weight of 2,380 g/m2. The form of the reinforcing fibers in the random
mat was examined and, as a result, it was found that the fiber axes of the reinforcing fibers
were substantially parallel to a plane of the random mat and the reinforcing fibers were
randomly dispersed in the plane.
In the random mat obtained, the reinforcing fibers had an average fiber length of 20
mm and a weight-average fiber thickness of 0.06 mm. The reinforcing fibers constituting the
random mat had a weight-average fiber width (Ww) of 2.21 mm, a number-average fiber
width (Wn) of 0.54 mm, and a dispersion ratio (WwIWn) of 4.08.
The random mat obtained was heated at 4.0 MPa for 10 minutes with a pressing
device heated at 280°C, thereby obtaining a shaped plate having a thickness of 3.0 mm. The
shaped plate obtained was evaluated for the thickness unevenness of the reinforcing-fiber mat.
As a result, the coefficient of variation CV of the thickness was found to be 16.2%.
Furthermore, the ultrasonic flaw detection test was conducted and, as a result, portions in
which the reflected-wave intensity was 70% or higher were observed in a ratio of 80% or
more.
In the shaped plate obtained, the volume content ratio of the reinforcing fibers was 45
~01%. The shaped plate was evaluated for tensile property in accordance with JIS 7164 and,
as a result, the shaped plate was found to have a tensile strength of 490 MPa, a development
rate of properties relative to theoretical strength of 58%, and a tensile modulus ratio between
0-degree direction and 90-degree direction of 1.08.
[0077]
[COMPARATIVE EXAMPLE 31
As reinforcing fibers, PAN-based carbon fiber strand "Tenax" (registered trademark)
HTS40-6K (fiber diameter, 7.0 pm; fiber width 6 mm; tensile strength, 4,200 MPa),
manufactured by Toho Tenax Co., Ltd., was used. A roving cutter equipped with blades at
intervals of 6 mm was used to cut the reinforcing-fiber strand so as to result in a fiber length of
6 mm. These reinforcing fibers cut with the roving cutter were supplied to a conveyor net
arranged just under the cutter, thereby obtaining a reinforcing-fiber mat having a fiber areal
weight of 2,640 g/m2. The form of the reinforcing fibers in the reinforcing-fiber mat was
examined and, as a result, it was found that the fiber axes of the reinforcing fibers were
substantially parallel to a plane of the random mat and the reinforcing fibers were randomly
dispersed in the plane.
In the reinforcing-fiber mat obtained, the reinforcing fibers had an average fiber
length of 6.1 mm and a weight-average fiber thickness of 0.05 mm. The reinforcing fibers
constituting the reinforcing-fiber mat had a weight-average fiber width (Ww) of 5.81 mm, a
number-average fiber width (Wn) of 5.25 mm, and a dispersion ratio (WwlWn) of 1.11.
A polycarbonate film ("Panlite" (registered trademark) L-1225Y, manufactured by
Teijin Chemicals Ltd.) of 1,8 15 glm2 was layered on each surface of the reinforcing-fiber mat
having reinforcing-fiber areal weight of 2,640 g/m2, and the layered body was heated and
pressed with a pair of heating roller having a set temperature of 300°C, thereby obtaining a
random mat in which the resin was evenly impregnated.
The random mat obtained was heated at 4.0 MPa for 10 minutes with a pressing
device heated at 300°C, thereby obtaining a shaped plate having a thickness of 3.1 mm. The
shaped plate obtained was evaluated for the thickness unevenness of the reinforcing-fiber mat.
As a result, the coefficient of variation CV of the thickness was found to be 32.4%.
Furthermore, the ultrasonic flaw detection test was conducted and, as a result, portions in
which the reflected-wave intensity was 70% or higher were observed in a ratio of 47%. It
was ascertained that this shaped plate had unimpregnated portions inside.
In the shaped plate obtained, the volume content ratio of the reinforcing fibers was 49
~01%. The shaped plate was evaluated for tensile property in accordance with JIS 71 64 and,
as a result, the shaped plate was found to have a tensile strength of 380 MPa, a development
rate of properties relative to theoretical strength of 4896, and a tensile modulus ratio between
0-degree direction and 90-degree direction of 1.32.
Industrial Applicability
[0078]
The random mat and fiber-reinforced composite material shaped product obtained
according to the invention have excellent mechanical strength and are excellent in terms of the
isotropy thereof. Consequently, the random mat and the shaped composite material are
usable for or as various constituent members, e.g., inside plates, outside plates, and constituent
members for motor vehicles, the frames or housings of various electrical products or machines,
or the like.
[0079]
While the invention has been described in detail and with reference to specific
embodiments thereof, it will be apparent to one skilled in the art that various changes and
modifications can be made therein without departing from the spirit and scope thereof.
This application is based on a Japanese patent application filed on July 31, 2012
(Application No. 2012-1 69936), the contents thereof being incorporated herein by reference.
Description of the Reference Numerals
[OOSO]
1. Reinforcing fibers
2. Pinch roller
3. Rubber roller
4. Rotary cutter main body
5. Blade
6. Cut reinforcing fibers
7. Blade pitch
8. Widened reinforcing fibers
9. Widening device
10. Fiber-width control roller
11. Slitter for separating
12. Separated reinforcing fibers
3 5
CLAIMS
1. A random mat, comprising:
reinforcing fibers having an average fiber length of 3 to 100 mm; and
a thermoplastic resin,
wherein the reinforcing fibers satisfy the following i) to iii):
i) the reinforcing fibers have a weight-average fiber width (Ww) which
satisfies the following equation (1):
Omm