Technical Field
[0001] The invention relates to a method for producing a fiber blended yarn, a fiber blended
yarn, and a method for producing a woven fabric or a knit fabric.
Background Art
[0002] Composite material molded bodies made of a resin material with a reinforcing material,
such as a glass fiber or a carbon fiber added thereto, are used for structural parts
of various machines and automobiles, pressure vessels, and tubular structures, etc.
Such composite material molded bodies are demanded to conform to an arbitrary shape
in order to achieve light weight and high strength at the same time.
[0003] As a material forming such composite material molded bodies, a uniformly commingled
continuous fiber blended yarn obtained by mixing a reinforcing fiber and a thermoplastic
resin fiber using a fluid, and a fabric cloth made from such a fiber blended yarn
have been proposed (see, for example, Patent Literature 1). In order to increase impregnation
ability of the fiber blended yarn during molding, fiber blending conditions have been
studied mainly for increasing a fiber blend rate (a degree of commingling of the fibers)
(see, for example, Patent Literature 2). Further, unlike common organic fibers, the
reinforcing fiber tend to be fluffed due to damages, and therefore require precise
control of conditions for opening and mixing the fibers (see, for example, Patent
Literature 3). It is also known that, when the reinforcing fiber is processed in a
highly humid environment, the reinforcing fiber less tends to be bulky, that is, the
reinforcing fiber less tends to be opened (see, for example, Patent Literature 4).
[0004] As described above, during manufacturing of a fiber blended yarn using the reinforcing
fiber, moisture removal has been performed during fiber blending in view of suppressing
damages to the reinforcing fiber and increasing the fiber blend rate. Further, it
has been technical common knowledge that the fibers are handled in a dry atmosphere
in view of suppressing adsorption of moisture, which will be impeditive during a process
of obtaining molded bodies by heating the fiber blended yarn.
Citation List
Patent Literature
[0005]
[Patent Literature 1] Japanese Unexamined Patent Publication No. H2-112916
[Patent Literature 2] Japanese Unexamined Patent Publication No. H3-275729
[Patent Literature 3] Japanese Unexamined Patent Publication No. H4-222246
[Patent Literature 4] Japanese Unexamined Patent Publication No. S59-43141
Summary of Invention
Technical Problem
[0006] However, conventionally known fiber blended yarns and fabric cloths have been developed
mainly for preventing damages to the reinforcing fiber during fiber blending and improving
the fiber blending state to increase impregnation ability during molding. In order
to apply fiber blended yarns and fabric cloths to structural materials, such as automobile
materials, higher strength of the fiber blended yarns and fabric cloths is demanded.
Solution to Problem
[0007] The present inventors have found, through intensive study to solve the above-described
problems in the prior art, that, by performing fiber blending of the thermoplastic
fiber and the reinforcing fiber using a gas in the presence of a liquid, the resulting
molded bodies exhibit high strength and high interface strength, thereby achieving
the present invention.
[0008] Namely, the method for producing a fiber blended yarn of the present invention is
a method for producing a fiber blended yarn comprising at least a thermoplastic resin
fiber and a reinforcing fiber, the method comprising the step of blending the thermoplastic
resin fiber and the reinforcing fiber with an interlace method that uses a gas under
the presence of a liquid.
[0009] It is preferred that the reinforcing fiber contain a liquid in an amount of 300 mass
% or less.
[0010] It is preferred that the interlace method be a fluid disturbance method.
[0011] It is preferred that the reinforcing fiber comprise a water soluble component in
an amount ranging from 0.1 to 5 mass % relative to the reinforcing fiber.
[0012] It is preferred that the reinforcing fiber comprise a hydrophilicity index of 8 degrees
or more.
[0013] Another aspect of the method for producing a fiber blended yarn of the invention
is a method for producing a fiber blended yarn comprising at least a thermoplastic
resin fiber and a reinforcing fiber, the method comprising a step of blending the
fibers with an interlace method that uses a gas after a step of treating the thermoplastic
resin fiber and/or the reinforcing fiber with a liquid.
[0014] It is preferred that the liquid contain an organic material.
[0015] It is preferred that a rate of change of surface tension of the thermoplastic resin
fiber when the organic material in an amount of 10 mass % relative to the thermoplastic
resin fiber is mixed be 30% or less.
[0016] It is preferred that a liquid that is collected during the step of blending the fibers
with the interlace method be mixed with the liquid that is used in the step of treating
with the liquid.
[0017] The fiber blended yarn of the invention is a fiber blended yarn comprising at least
a thermoplastic resin fiber and a reinforcing fiber, the fiber blended yarn comprising
at least two kinds of organic materials, and the at least two kinds of organic materials
adhere to both the reinforcing fiber and the thermoplastic resin fiber.
[0018] It is preferred that a degree of dispersion of the organic materials over surfaces
of the reinforcing fiber and the thermoplastic resin fiber be 5% or more.
[0019] It is preferred that the fiber blended yarn comprise a degree of flexibility of 20
degrees or more.
[0020] It is preferred that the fiber blended yarn comprise a void ratio of 20% or more.
[0021] It is preferred that a total amount of the organic materials be less than 2 mass
% relative to the fiber blended yarn.
[0022] The method for producing a woven fabric or a knit fabric of the invention is a method
for producing a woven fabric or a knit fabric comprising at least a thermoplastic
resin and a reinforcing fiber, the method comprising weaving the reinforcing fiber
that comprises a moisture ratio ranging from 0.1 to 5 mass %.
Advantageous Effects of Invention
[0023] According to the method for producing a fiber blended yarn, the fiber blended yarn,
and the method for producing a woven fabric or a knit fabric of the present invention,
a fiber blended yarn, a woven fabric, and a knit fabric that allow producing fiber-reinforced
resin molded bodies having arbitrary shapes and excellent strength can be obtained.
Brief Description of the Drawings
[0024]
[FIG. 1] FIG. 1 is a schematic view for explaining Taslan processing,
[FIG. 2] FIG. 2 is a schematic view showing a state where fiber blended yarns are
wound around an aluminum die frame used in Examples, and
[FIG. 3] FIG. 3 is a schematic view showing a die used in the Examples.
Description of Embodiments
[0025] Now, the present invention will be described in detail. The following description
is not intended to limit the invention, and various modifications can be made to the
invention within the spirit and scope of the invention.
Fiber blended yarn
[0026] A fiber blended yarn of the present invention refers to a yarn comprising at least
a reinforcing fiber and a thermoplastic resin fiber. The reinforcing fiber and/or
the thermoplastic resin fiber is preferably a multifilament fiber in view of the strength
and ease of handling of the yarn. Each single filament of the multifilament fiber
of the reinforcing fiber may partially be cut; however, a reinforcing fiber bundle
is preferably continuous in view of the strength. The thermoplastic resin fiber may
be in any form; however, it is preferably a continuous fiber in view of the stability
of the fiber blending process.
[0027] How the reinforcing fiber and the thermoplastic resin fiber are mixed is not particularly
limited, and these fibers may be paralleled, filaments of the respective fibers may
be commingled, one of the fibers may cover around the other of the fibers, or these
fibers may be twisted together, for example. In order to increase impregnation ability
during molding and imparting high strength, it is preferred that filaments of the
respective fibers be only partially commingled. Since a lower degree of commingling
results in a more straight reinforcing fiber and thus the reinforcing fiber tends
to exhibit higher strength, having a minimum amount of commingled portions allows
quick impregnation starting from such portions. A commingling ratio of the reinforcing
fiber is preferably in the range from 0.1 to 20%, more preferably in the range from
0.2 to 15%, and even more preferably in the range from 0.3 to 10%. The degree of commingling
is defined by a ratio of filaments of the reinforcing fiber adjacent to filaments
of the thermoplastic resin fiber relative to the total number of filaments in the
reinforcing fiber bundle, and is calculated by observing 20 cross sections at arbitrary
positions of the fiber blended yarn.
[0028] A volume ratio of the reinforcing fiber to the thermoplastic resin fiber in a fiber
blended yarn is preferably in the range from 50 to 900 vol.%, more preferably in the
range from 66 to 400 vol.%, and even more preferably in the range from 81 to 233 vol.%,
in view of achieving high strength and clean appearance.
[0029] The fiber blended yarn of the invention includes at least two kinds of organic materials,
and the at least two kinds of organic materials adhere to both the reinforcing fiber
and the thermoplastic resin fiber. When both the reinforcing fiber and the thermoplastic
resin fiber have the at least two kinds of organic materials in common, affinity between
these fibers is increased, and thus provides effects of ease of handling as a yarn,
and increased impregnation ability during molding. In view of facilitating enhancement
of these effects, it is preferred that at least one of the organic materials is water
soluble. Further, if the total amount of the organic materials is excessively large,
ease of handling may be lowered, and therefore the total amount of the organic materials
relative to the fiber blended yarn is preferably less than 2 mass %, more preferably
not more than 1.7 mass %, even more preferably not more than 1.4 mass %, and most
preferably not more than 1.1 mass %.
[0030] The number of types of the organic materials adhering to the fiber blended yarn can
be calculated by liquid chromatography mass spectrometry using an appropriate solvent
to extract the organic materials from the fiber blended yarn. In order to find the
amounts of the organic materials adhering to the reinforcing fiber and the thermoplastic
resin fiber in the fiber blended yarn, the reinforcing fiber and the thermoplastic
resin fiber are separated from the fiber blended yarn, and the respective fibers are
water-extracted, and then are solvent-extracted to quantitate the amount of water
soluble components and the amount of non-water soluble components. Further, by performing
NMR measurement on the extracts, sources of the components can be found, that is,
the extracts can be separated into a component (A) contained in the raw material reinforcing
fiber, a component (B) contained in the raw material thermoplastic resin fiber, and
a component (C) contained in a liquid used during the fiber blending. It is preferred
that both the reinforcing fiber and the thermoplastic resin fiber contain the components
(A) and (B) in view of the impregnation property during molding and imparting strength.
[0031] These organic materials adhering to the surfaces of the reinforcing fiber and the
thermoplastic resin fiber are preferably dispersed at a degree of dispersion of 5%
or more in view of the impregnation ability during molding and increasing a final
interface strength in the resulting molded bodies. The degree of dispersion is more
preferably 10% or more, and even more preferably 15% or more. The degree of dispersion
can be calculated as follows. The organic materials are extracted from the fiber blended
yarn and the mass of the organic materials is measured, and then a ratio of the mass
of the organic materials to the mass of the fiber blended yarn is calculated. This
measurement is performed similarly at arbitrary 20 points to calculate an average
value and a standard deviation, and a value obtained by dividing the standard deviation
by the average value is found as the degree of dispersion.
[0032] In view of ease of handling during weaving, knitting, or braiding of the fiber blended
yarn, the fiber blended yarn preferably has a degree of flexibility of 20 degrees
or more, more preferably 40 degrees or more, even more preferably 60 degrees or more,
and most preferably 80 degrees or more. The degree of flexibility of the fiber blended
yarn is determined by: cutting a 20 cm-long piece of the fiber blended yarn; making
a ring of the fiber blended yarn by fixing one end of the yarn to the other end the
yarn using a tape having a width of 1.5 cm; suspending the ring of the fiber blended
yarn vertically with supporting the yarn at the tape-fixed portion (at this time,
if the fiber blended yarn does not become vertical, making it vertical lightly using
the hands); then, vertically inverting the ring of the yarn supported at the tape-fixed
portion such that the fiber blended yarn vertically stands with the tape-fixed portion
positioned below; holding the fiber blended yarn for one minute without touching the
yarn; and measuring an angle of the collapsed fiber blended yarn relative to the vertical
direction. If the fiber blended yarn is bent and there are two angles, a larger angle
is found as the degree of flexibility.
[0033] In view of the balance between ease of handling during a process, such as weaving,
knitting, or braiding, of the fiber blended yarn and ease of handling of the fiber
blended yarn in the form of a woven fabric, a knit fabric, or a braided fabric, it
is preferred that the degree of flexibility of the fiber blended yarn is changeable
depending on moisture absorption by the yarn. An amount of change of the degree of
flexibility of the fiber blended yarn before and after moisture absorption is preferably
30 degrees or more, more preferably 40 degrees or more, and even more preferably 50
degrees or more.
[0034] In view of ease of handling of the fiber blended yarn during weaving, knitting, or
braiding, and suppressing damages to the fiber blended yarn during handling, it is
preferred that the fiber blended yarn include voids in it, and a void ratio is preferably
20% or more, more preferably 25% or more, and even more preferably 30% or more. The
void ratio can be found by wrapping the fiber blended yarn in a shrink tube, pouring
and hardening a colored epoxy resin in the tube, and cutting and polishing the cross-section
to observe the cross-section.
[0035] The area of voids is an area of the colored epoxy resin within the outer perimeter
of the fiber blended yarn, and the outer perimeter of the fiber blended yarn refers
to a figure drawn by connecting the outermost filaments of the yarn.
[0036] The fiber blended yarn may include components other than the reinforcing fiber, the
thermoplastic resin fiber, and the organic materials. Depending on environment in
which the resulting molded bodies are used, it is preferred to add an antioxidant,
an ultraviolet absorber, a colorant, a heat-transfer agent, a heat stabilizing agent,
or the like.
Method for producing fiber blended yarn
[0037] The fiber blended yarn of the invention is produced by blending the reinforcing fiber
and the thermoplastic resin fiber using a gas in the presence of a liquid. The liquid
as used herein refers to a material that is liquid under temperatures and pressures
of processing conditions. The type of the liquid may be selected as appropriate depending
on the processing conditions, and water, an organic solvent, or the like, can be used
as appropriate. Water is particularly preferable in view of the stability. The gas
as used herein refers to a material that is gaseous immediately before contacting
the reinforcing fiber and/or the thermoplastic resin fiber. The type of the gas may
be selected as appropriate depending on the processing conditions, and air, steam,
an organic gas, or the like, may be used as appropriate. Air is preferred in view
of the stability.
[0038] By positively adding the liquid, damages to the reinforcing fiber during the fiber
blending can be suppressed, and, even in a state where the degree of mixing of the
fibers is low, the reinforcing fiber can quickly be impregnated with a resin during
molding, resulting in high tensile strength and interface strength. The amount of
the liquid is not particularly limited, and can appropriately be adjusted depending
on types of the reinforcing fiber and the thermoplastic resin used, a single filament
diameter, fineness, etc. The liquid may be added in the form of steam or liquid. The
liquid is preferably added in the form of liquid in view of the impregnation ability
during molding and strength of the resulting molded bodies. While it is sufficient
that one of the reinforcing fiber and the thermoplastic resin fiber is moisturized,
it is preferred that at least the reinforcing fiber be moisturized, and it is more
preferred that both the reinforcing fiber and the thermoplastic resin fiber be moisturized.
Since it is preferred that the reinforcing fiber and the thermoplastic resin fiber
be moisturized before the fiber blending, a moisturizing step is preferably included
immediately before the fiber blending. It is not necessary that both the reinforcing
fiber and the thermoplastic resin fiber are subjected to the moisturizing step in
order to moisturize them. For example, the reinforcing fiber may be subjected to the
moisturizing step, and then, the reinforcing fiber and the thermoplastic resin fiber
may be paralleled, thereby making the liquid on the reinforcing fiber to migrate onto
the thermoplastic resin fiber.
[0039] It is preferred that the liquid contain an organic material. During the moisturizing
step, the liquid may contain a different type of organic material from an organic
material contained in the liquid. As the former organic material, it is preferred
to add an organic material that imparts the reinforcing fiber and the thermoplastic
resin fiber with a property that is difficult to be originally imparted thereto, such
as one increasing affinity between the reinforcing fiber and the thermoplastic resin
fiber, one imparting hydrophilicity to suppress generation of static electricity,
one imparting a color or a function, such as flame resistance, heat resistance, or
weather resistance, to the resulting molded bodies, or one promoting fiber opening
of the reinforcing fiber during molding to increase impregnation action. Taking the
residual efficiency of the organic material on the fiber blended yarn after the fiber
blending process into account, the organic material is preferably fine-dispersed in
the liquid, and is more preferably in the state of emulsion which is a water dispersion.
[0040] In order to have the impregnation ability and high physical properties in a short-time
molding, the organic material is preferably one that results in a rate of change of
surface tension of the thermoplastic resin fiber of 30% or less, more preferably 20%
or less, even more preferably 15% or less, and most preferably 10% or less, when the
organic material in an amount of 10 mass % relative to the thermoplastic resin fiber
is mixed.
[0041] A difference between the surface tension of the organic material and the surface
tension of the thermoplastic fiber is preferably less than 22, more preferably less
than 17, even more preferably less than 12, and most preferably less than 7. The surface
tension is measured at a temperature higher by 45°C than the higher one of the melting
points of the organic material and the thermoplastic resin fiber.
[0042] In order to impart good physical properties after the impregnation, a difference
between the SP value (solubility parameter) of the thermoplastic resin fiber and the
SP value of the organic material is preferably less than 3 (cal/cm
3), more preferably less than 2, even more preferably less than 1.5, and most preferably
less than 1.
[0043] Particularly preferred examples of the organic material that meet the above-described
specifications include polymers or oligomers of the same family as the thermoplastic
resin fiber. The "same family" as used herein means that the organic material has
the same functional group as that the repeating unit of the thermoplastic resin fiber
has. For example, in the case where the thermoplastic resin fiber is made of polyamide
66, an organic material having an amide bond is preferably applied.
[0044] In view of controlling the amount of the organic material to be added, the moisturizing
step is preferably effected by a method where a liquid containing the organic material
is spayed and the excessive liquid is collected, or a method where immersion is performed
in a circulating liquid and the concentration of the organic material in the circulating
liquid is controlled. During the fiber blending process using a gas, the excessive
organic material is collected together with the excessive liquid, and it is preferred
that the collected materials be recycled in the moisturizing step.
[0045] The moisture content is not particularly limited, and a moisture content that allows
obtaining the above-described effects may be selected as appropriate. However, in
view of increasing the productivity and minimizing the waste liquid, the moisture
content relative to the reinforcing fiber is preferably not more than 300 mass %,
more preferably not more than 250 mass %, even more preferably not more than 200 mass
%, and most preferably not more than 150 mass %. The moisture content can be found
by stopping the production line in a state where the process is stable, cutting a
portion just before entering the fiber blending process and measuring the weight of
the portion, and then, removing the liquid from the portion and measuring the weight
of the portion.
[0046] The interface shear stress of the reinforcing fiber in the fiber blended yarn preferably
changes relative to the interface shear stress of the raw material reinforcing fiber,
and changes more preferably by 5% or more, even more preferably by 10% or more, and
most preferably by 15% or more relative to the interface shear stress of the raw material
reinforcing fiber. The interface shear stress can be changed by making components,
such as a sizing agent, adhering to the reinforcing fiber migrate due to the liquid.
The interface shear stress can be measure using a microdroplet method.
[0047] A method for reeling the reinforcing fiber can be selected as appropriate, and examples
thereof include reeling from inside, reeling from outside, and roll reeling. In view
of suppressing damages to the yarn in the yarn path, it is preferred that the reinforcing
fiber be moisturized before the reeling. The reinforcing fiber may be kept in the
moisturized state when the reinforcing fiber is produced and coated with a sizing
agent, or may be moisturized before the reinforcing fiber is used. The moisturization
may be achieved by immersing the reinforcing fiber in a predetermined liquid, by spraying
a liquid using an atomizer, or the like, or by holding the reinforcing fiber in high
humidity for a predetermined time. In a case where it is difficult to use the reinforcing
fiber in the moisturized state, roll reeling, which allows reeling the reinforcing
fiber without twisting the reinforcing fiber, is preferred. The moisture content during
reeling is not particularly limited; however, the reinforcing fiber immediately after
the reeling preferably has a degree of flexibility of 5 degrees or more, more preferably
10 degrees or more, and even more preferably 15 degrees or more. The degree of flexibility
can be measured in the same manner as the above-described degree of flexibility of
the fiber blended yarn.
[0048] The fiber blending can be achieved by using a known method depending on the structure
of the fiber blended yarn, and some fiber blending processes may be used in combination.
Now, a method for producing a fiber blended yarn of the reinforcing fiber and the
thermoplastic resin fiber, or a fiber blended yarn comprising mixed filaments of the
reinforcing fiber and the thermoplastic resin fiber, which is a preferred aspect of
the fiber blended yarn, is described.
[0049] For example, a fiber opening and yarn doubling method, wherein fiber opening is performed
using an external force, such as pressure produced by an electrostatic force or fluid
spraying, or pressure produced by pressing with a roller, and then yarn doubling or
paralleling is performed in the state where the reinforcing fiber and the thermoplastic
resin fiber are opened; and an interlace method using a fluid are usable. The interlace
method using a fluid, which allows removing excessive liquid while blending the fibers
using a gas, is preferably used. The interlace method using a fluid is a method where
the fibers are interlaced through the action of the fluid, and examples thereof include
a disturbance method using a fluid and an interlace method (wherein air is blown in
a direction transverse to the yarn). In a case where a carbon fiber, which is easily
damaged by an external force applied from a lateral side, is used as the reinforcing
fiber, the fluid disturbance method is preferably used, and the Taslan (R) method,
wherein air is blown in the same direction as the direction of travel of the yarn,
is particularly preferably used. A thickness of and the number of filaments in a raw
material reinforcing fiber bundle are adjusted as appropriate, and the production
conditions are also adjusted as appropriate.
[0050] Now, the Taslan processing, which is a preferred aspect of the invention, is described.
The Taslan processing is a technique which bind the filaments fed as core filaments
and float filaments into a bulky looped yarn with forces of air. For example, as shown
in FIG. 1, when the core filaments and the float filaments fed by rotation of rollers
pass through a nozzle mounted in a Taslan box, the filaments are disturbed by the
forces of air and bound together. The core filaments are filaments forming the core
of a Taslan yarn, and the float filaments are densely looped around the core filaments.
It is usually preferred that a feeding rate of the float filaments by rollers be set
higher than a feeding rate of the core filaments by rollers. The nozzle is mainly
composed of a housing and a core, and air jets are applied from holes called orifices
provided in the core to bind the filaments together.
[0051] Although it does not matter which of the reinforcing fiber and the thermoplastic
resin fiber forms the core filaments or the float filaments, it is preferred that
the reinforcing fiber be used as the core filaments and the thermoplastic resin fiber
be used as the float filaments in view of the strength. In view of the strength and
the productivity of the fiber blended yarn, a yarn speed is preferably in the range
from 10 to 1000 m/minute, more preferably in the range from 20 to 700 m/minute, even
more preferably in the range from 30 to 500 m/minute, and most preferably in the range
from 50 to 300 m/minute.
[0052] In view of improving the strength of the resulting molded bodies by increasing the
straightness of the yarn, the reinforcing fiber is fed at a rate preferably in the
range from 0 to 10%, more preferably in the range from 0.1 to 5%, even more preferably
in the range from 0.2 to 3%, and most preferably in the range from 0.3 to 1.8% of
the yarn speed. The feeding rate of the thermoplastic resin fiber may be adjusted
arbitrarily in view of adjusting the entwined state with the reinforcing fiber, and
is preferably in the range from 1 to 15%, more preferably in the range from 2 to 10%,
even more preferably in the range from 3 to 7%, and most preferably in the range from
4 to 6%. The ratio of the feeding rate of the float filaments relative to the feeding
rate of the core filaments is preferably in the range from 100 to 600%, more preferably
in the range from 110 to 500%, and even most preferably in the range from 150 to 400%.
In view of suppressing damages to the reinforcing fiber, achieving an adequate interlace
state, and adequately blowing off the liquid, the air pressure is preferably in the
range from 0.5 to 10 kgf/cm
2, more preferably in the range from 1 to 5 kgf/cm
2, and even more preferably in the range from 1.5 to 3 kgf/cm
2. Before entering the Taslan box, the reinforcing fiber and/or the thermoplastic resin
fiber is moisturized, and the liquid is blown off while the fiber blending is performed
using air, thereby controlling the moisture content.
Water soluble component
[0053] It is preferred that the fiber blended yarn of the invention contain a water soluble
component. The "water soluble component" as used herein refers to a compound that
has a solubility of 10 g or more in 100 g of water at 23°C. For example, water soluble
polymers, such as polyvinylpyrrolidone, polyethylene glycol, and derivatives and copolymers
thereof, polyacrylic acid, polysulfonic acid, polyvinyl alcohol, polyvinylacetamide,
cellulose derivatives, starch derivatives, etc., and low molecular weight compounds
having a reactive functional group, such as epoxy resin, and acrylate resin, are preferably
used.
[0054] The water soluble component may be contained in the reinforcing fiber and/or the
thermoplastic resin fiber in the fiber blended yarn. In a case where both the reinforcing
fiber and the thermoplastic resin fiber contain the water soluble component, increased
adhesion between these fibers is achieved, which preferably facilitates impregnation
during molding. Further, it is preferred that the water soluble component be non-uniformly
adhering to surfaces of the reinforcing fiber in view of increasing the interface
strength between the reinforcing fiber and the thermoplastic resin forming a matrix
in the resulting molded body. In view of the balance between the impregnation ability
and the interface strength, the water soluble component is contained in an amount
preferably in the range from 0.1 to 5 mass %, more preferably in the range from 0.3
to 4 mass %, even more preferably in the range from 0.5 to 3 mass %, and most preferably
in the range from 1 to 2 mass % relative to the reinforcing fiber.
[0055] The water soluble component may be added to the raw materials, may be added when
the fiber blending is performed, or may be added after the fiber blended yarn is produced.
In view of facilitating the non-uniform adhesion to the surfaces of the reinforcing
fiber, it is preferred that the water soluble component be added to the raw material
reinforcing fiber. In the case were the reinforcing fiber contains the water soluble
component, the water soluble component contacting the liquid during the fiber blending
process migrates due to the liquid. With this, the water soluble component is distributed
over the surfaces of the reinforcing fiber, and also migrates onto the thermoplastic
resin fiber.
Reinforcing fiber
[0056] As the reinforcing fiber, those commonly used in molded bodies of reinforcing fiber
composite materials can be used, and preferred examples thereof include, but are not
limited to, at least one selected from the group consisting of glass fiber, carbon
fiber, aramid fiber, ultra-high strength polyethylene fiber, polybenzazole-based fiber,
liquid crystal polyester fiber, polyketone fiber, metal fiber, and ceramic fiber.
Glass fiber, carbon fiber, and aramid fiber are preferred in view of the mechanical
physical properties, thermal properties, and versatility, and carbon fiber is preferred
in view of the elasticity.
[0057] A single filament diameter of the reinforcing fiber is not particularly limited;
however, the single filament diameter is preferably in the range from 1 to 22 µm,
more preferably in the range from 3 to 17 µm, and even more preferably in the range
from 5 to 12 µm in view of the strength and ease of handling of the resulting molded
bodies. The number of filaments in a reinforcing fiber bundle may be set as appropriate
depending on ease of handling, and a reinforcing fiber bundle of 3,000 filaments,
6,000 filaments, 12,000 filaments, or 24,000 filaments may preferably be used.
[0058] A sizing agent is preferably used with the reinforcing fiber, and also a coupling
agent for forming interfaces between the reinforcing fiber and the thermoplastic resin,
a binder for improving ease of handling of the reinforcing fiber and assisting formation
of interfaces between the thermoplastic resin and the coupling agent, a lubricant
for improving ease of handling of the reinforcing fiber, etc., are preferably used.
[0059] The sizing agent changes the condition of the surfaces of the reinforcing fiber.
It is preferred that the reinforcing fiber have high affinity to the liquid used in
the fiber blending process in view of the strength of the fiber blended yarn and strength
of the resulting molded bodies. The state where "the reinforcing fiber has high affinity
to the liquid" refers to such a state that, when the reinforcing fiber bundle is cut
into a piece having a length of about 5 cm and put in a bath of the liquid, the reinforcing
fiber bundle is spread into fibers.
[0060] It is preferred that the sizing agent be applied in the form of a liquid or gas in
view of achieving uniform application to the reinforcing fiber. In a case where a
compound having high melting and boiling points is used, the sizing agent may be applied
while being heated, or may be dissolved in a solvent to be applied. As other components,
an antioxidant, an ultraviolet absorber, a colorant, a heat-transfer agent, a heat
stabilizing agent, etc., may be included.
[0061] The type of the sizing agent may be selected using an interface strength with the
matrix resin that is found according to a microdroplet test as described, for example,
in Japanese Unexamined Patent Publication No.
2015-67926. However, since the sizing agent may be volatilized or altered due to heat, it is
preferred that the test is conducted after the sizing agent is subjected to a heat
history during molding. It is preferred to use the previously described water soluble
component as the sizing agent.
[0062] The lubricant contributes to improving adjustability of and prevention of damages
to the reinforcing fiber, and improving fiber openability. As the lubricant, any of
common liquid or solid lubricative materials suitable for the purpose can be used,
and examples thereof include, but are not limited to, one or more selected from: animal,
vegetable, or mineral waxes, such as carnauba wax and lanolin wax; and surfactants,
such as fatty acid amide, fatty acid ester, fatty acid ether, aromatic ester, and
aromatic ether.
[0063] The binder contributes to improving binding and the interface adhesion strength of
the reinforcing fiber. As the binder, a polymer or a thermoplastic resin suitable
for the purpose can be used. Examples of the polymer include, but are not limited
to, thermosetting resins, such as: epoxy resins, such as bisphenol A epoxy resin;
phenol resins obtained by reacting various phenols with formalin; urea resins obtained
by reacting urea with formalin; and melamine resins obtained by reacting melamine
with formalin. Further, polyurethane resins, such as one synthesized from an isocyanate
(such as m-xylylene diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), and isophorone
diisocyanate) and a polyester or polyether diol can also be used favorably.
[0064] The thermoplastic resin used as the binder is not particularly limited, and examples
thereof include polyolefin resin, polyamide resin, polyacetal resin, polycarbonate
resin, polyester resin, polyether ketone, polyether ether ketone, polyether sulfone,
polyphenylene sulfide, thermoplastic polyether imide, thermoplastic fluorine resin,
and modified thermoplastic resins obtained by modifying the above-listed resins. Using
the same type of thermoplastic resin and/or modified thermoplastic resin as the thermoplastic
resin fiber forming the fiber blended yarn is preferred in view of improving the adhesion
between the reinforcing fiber and the thermoplastic resin fiber of the resulting composite
material molded bodies.
[0065] In view of increasing the efficiency of the fiber blending process, the reinforcing
fiber used in the invention has a hydrophilicity index of preferably 8 degrees or
more, more preferably 30 degrees or more, and even more preferably 60 degrees or more.
The hydrophilicity index as used herein is a unique index for compatibility to the
fiber blending process of the invention. The hydrophilicity index is found by performing
a measurement which is similar to that for finding the degree of flexibility of the
fiber blended yarn in a dry state and a wet state, as shown in Examples, and calculating
a difference between measurement values obtained in these states.
Thermoplastic resin fiber
[0066] As the thermoplastic resin fiber, fibers made of matrix resins commonly used in composite
materials can be used. Preferred examples thereof include continuous fibers obtained
by melting and spinning at least one thermoplastic resin selected from: polyolefin
resins, such as polyethylene, polypropylene; polyamide resins, such as polyamide 6,
polyamide 66, polyamide 46; polyester resins, such as polyethylene terephthalate,
polybutylene terephthalate, polytrimethylene terephthalate; polyacetal resins, such
as polyoxymethylene; polycarbonate resins; polyether ketone; polyether ether ketone;
polyether sulfone; polyphenylene sulfide; thermoplastic polyether imide; thermoplastic
fluorine resins, such as tetrafluoroethylene-ethylene copolymer; and modified thermoplastic
resins obtained by modifying these resins.
[0067] Among these thermoplastic resins, polyolefin resins, polyamide resins, polyester
resins, polyether ketone, polyether ether ketone, polyether sulfone, polyphenylene
sulfide, thermoplastic polyether imide, and thermoplastic fluorine resins are preferred.
In view of the mechanical physical properties and versatility, polyolefin resins,
modified polyolefin resins, polyamide resins, and polyester resins are more preferred.
Further, in view of the thermal physical properties, polyamide resins and polyester
resins are even more preferred. Still further, in view of the durability against repeated
load, polyamide resins are still more preferred, and aliphatic polyamide resins, in
particular, polyamide 6 and polyamide 66 can favorably be used.
[0068] The thermoplastic resin fiber may contain a lubricant, an antioxidant, an ultraviolet
absorber, a colorant, a heat-transfer agent, a heat stabilizing agent, etc., and it
is preferred to add a compound having high affinity to the liquid used during the
fiber blending in view of increasing the fiber blending efficiency, and increasing
the impregnation ability by sharing this compound with the reinforcing fiber.
Woven fabric, knit fabric
[0069] It is preferred that the fiber blended yarn of the invention be processed into a
fabric to use the fabric as an intermediate material for obtaining fiber-reinforced
resin molded bodies. The form of the fabric is not particularly limited, and examples
thereof may include a unidirectional reinforced material wherein the fiber blended
yarns are paralleled in a certain direction, a fabric cloth using a composite yarn,
for example, a woven fabric or a knit fabric, lace, felt, a non-woven fabric, a film
or a plate-like body, etc. As the intermediate material, a flexible unidirectional
reinforced material, a woven fabric, a knit fabric, lace, felt, and a non-woven fabric
are preferred in view of the shape conformity to the die in manufacturing of the fiber-reinforced
resin molded bodies, a knit fabric, a unidirectional reinforced material, and a woven
fabric are more preferred in view of less bends and higher strength of the reinforcing
fiber, and a knit fabric and a woven fabric are even more preferred in view of the
shape stability.
[0070] The woven fabric may be a biaxial woven fabric or a triaxial woven fabric. The type
of weave of the woven fabric is not particularly limited, and examples thereof may
include plain weave, twill weave, sateen weave, leno weave, and gauze weave.
[0071] In view of the strength of the resulting fiber-reinforced resin molded bodies, twill
weave, which results in lower crimp ratio of the reinforcing fiber, is more preferred.
[0072] As the knit fabric, for example, a so-called non-crimp fabric, i.e, a multi-axial
warp-knitted fabric is preferred in view of the strength, and examples of the stitch
of the knit fabric may include tricot, combination, etc.
Weaving or knitting process
[0073] The method used to obtain the intermediate material in the form of fabric is not
particularly limited, and can be selected depending on the use and the purpose.
[0074] For example, the woven fabric is obtained using a loom, such as a shuttle loom, a
rapier loom, an air jet loom, or a water jet loom, and at least partially contains
the fiber blended yarn. As a preferred example, the woven fabric may be obtained by
inserting weft yarns through warp yarns of fibers including the fiber blended yarn.
In view of stably obtaining the woven fabric with suppressed damages to the reinforcing
fiber, a rapier loom is preferably used. In order to stabilize the tension of the
woven fabric to facilitate obtaining the woven fabric having uniform quality, the
width of the rapier loom is preferably 60 cm or more, more preferably 80 cm or more,
and even more preferably 100 cm or more. While the quality is stabilized when the
width is above a certain value, it is preferred to determine the width as appropriate
in view of ease of use depending on the yarn used. In a case where a glass fiber or
a carbon fiber is used in the reinforcing fiber bundle, the width is preferably not
more than 6 m, more preferably not more than 5 m, even more preferably not more than
4 m, and most preferably not more than 3 m.
[0075] The knit fabric can be produced using a knitting machine, such as a latch needle
circular knitting machine, a flatbed knitting machine, a tricot knitting machine,
or a raschel knitting machine, to knit fibers that at least partially include the
composite yarn.
[0076] The non-woven fabric can be obtained by forming a sheet-like collection of fibers
called "web" of fibers at least partially including the composite yarn, and then bonding
the fibers by using a physical action, such as using a needlepunching machine, a stitchbonding
machine, or a columnar jet flow machine, by using a thermal action, such as using
an emboss roll, or by using an adhesive.
[0077] With respect to other forms of the intermediate material, etc., the method described
in Japanese Unexamined Patent Publication No.
2015-101794 can be used as appropriate.
[0078] In the invention, it is preferred that the process of obtaining the woven fabric
or the knit fabric be performed in a state where the reinforcing fiber is moisturized.
By handling the reinforcing fiber in the moisturized state, fluff can be prevented,
and the straightness of the reinforcing fiber in the woven fabric or knit fabric can
be increased, thereby increasing the strength of the molded body. In view of the relationship
between the strength and the ease of handling, the moisture ratio is preferably in
the range from 0.1 to 5 mass %, more preferably in the range from 0.2 to 4 mass %,
and even more preferably in the range from 0.3 to 3 mass % relative to the reinforcing
fiber.
[0079] The timing of the moisturization of the reinforcing fiber is not limited, and may
be during the process of producing the fiber blended yarn, or during spooling the
produced fiber blended yarn, or a moisturization step may be performed separately
after the produced fiber blended yarn has been spooled. Further, the moisturization
may be performed during warping as a preparation step for weaving or knitting, during
reaching-in or drawing-in, or immediately before insertion of weft yarns. In view
of the strength and the impregnation ability, it is preferred that the reinforcing
fiber be moisturized before the fiber blended yarn is produced, and the moisture amount
be adjusted during the fiber blending before weaving or knitting.
[0080] In the invention, after the woven fabric or knit fabric is produced, the fabric can
be immersed in a liquid to increase the impregnation ability, and also to increase
the interface strength and the strength of the resulting molded bodies. The fabric
in this stage may include only the reinforcing fiber, or the reinforcing fiber and
a thermoplastic resin. The thermoplastic resin may be in the form of powder, film,
woven fabric, or fiber. The thermoplastic resin in the form of powder or fiber is
preferred in view of reducing a distance to the reinforcing fiber, and the thermoplastic
resin in the form of fiber is preferred in view of the stability of the fabric. The
thermoplastic resin in the form of fiber may be blended in advance with the reinforcing
fiber, or may be in the form of a mixed woven fabric or a mixed knit fabric with the
reinforcing fiber. The state of the reinforcing fiber can be adjusted as appropriate
by lightly squeezing the reinforcing fiber after the fiber is immersed in the liquid.
Molding method
[0081] A fiber-reinforced resin molded body can be produced using the above-described fiber
blended yarn or the intermediate material as a forming material. It should be noted
that the method for producing a fiber-reinforced resin molded body is not limited
to one described below, and various methods can be applied.
[0082] For example, a base material (preferably in the form of a woven fabric or a knit
fabric) to form a fiber-reinforced resin molded body is cut according to a desired
molded body, and a necessary number of sheets of the base material suitable for the
thickness of the final product are stacked, and the stack is set to conform to the
shape of a die. At this time, using the above-described intermediate material allows
increasing the degree of freedom with respect to the die comparing to conventional
common composite plates made of a reinforcing fiber impregnated with a resin, and
molding with high degree of freedom in shape can be achieved even when the design
of molded body includes differences in level. A step of drying the base material may
be included before the base material is set in the die. The drying step may be performed
before and/or after the cutting.
[0083] The sheets of the base material may be cut one by one, or a stack of a desired number
of sheets of the base material may be cut. In view of the productivity, it is preferred
to cut a stack of sheets of the base material. The cutting may be achieved using any
method, and examples thereof may include a water jet, a blade press machine, a hot
blade press machine, a laser, and a plotter.
[0084] After the base material is set in the die, the die is closed and compressed. Then,
the temperature of the die is controlled to a temperature equal to or higher than
the melting point of the thermoplastic resin forming the fiber-reinforced resin molded
body to melt and shape the thermoplastic resin. The die compression pressure is not
particularly limited; however, it is preferably 1 MPa or more, and more preferably
3 MPa or more.
[0085] A hybrid molded body may be produced with the process for producing a fiber-reinforced
resin molded body, wherein the intermediate material is set in the die and the die
is closed and compressed, and a predetermined thermoplastic resin composition is injected
into the die after a predetermined time and molded in the die, such that the thermoplastic
resin fiber and the predetermined thermoplastic resin composition are joined.
Use application
[0086] The fiber-reinforced resin molded body is favorably applicable to structural materials
for aircrafts, automobiles, construction materials, sports goods, etc.
[0087] Examples of application to automobiles may include, but are not limited to, a chassis/frame,
underside parts, driving system parts, interior parts, exterior parts, functional
parts, and other parts.
Examples
[0088] Specific examples of the present invention and comparative examples are shown below,
which are not intended to limit the invention.
Carbon fiber (CF)
Carbon fiber A (CF-A)
[0089] 2.9 mass % of polyvinylpyrrolidone (water soluble component) was adhered as a sizing
agent to a PAN (polyacrylonitrile) carbon fiber having a standard elasticity with
a single filament diameter of 7 µm, a filament number of 12000, and a density of 1.81
g/cm
3. The fiber was immersed in water to remove the sizing agent to separate it into filaments
and a tensile test was conducted on a 5 cm-long piece, and a fracture load was found
to be 6.2 g. That is, the strength of the fiber bundle was calculated to be about
2,000 MPa. The hydrophilicity index was 80.
Carbon fiber B(CF-B)
[0090] 0.11 mass % of bisphenol A polyethylene glycol ether (an average repeating unit number
of the polyethylene glycol was 9.3), which is a water soluble component, and 0.1 mass
% of a long-chain hydrocarbon compound, which is a non-water soluble component, were
adhered as a sizing agent to a PAN (polyacrylonitrile) carbon fiber having a standard
elasticity with a single filament diameter of 7 µm, a filament number of 12000, and
a density of 1.81 g/cm
3. The strength of the fiber bundle was 4,500MPa, and the hydrophilicity index was
12.
Carbon fiber C (CF-C)
[0091] A carbon fiber was prepared in the same manner as the carbon fiber A except that
the amount of polyvinylpyrrolidone in the sizing agent was 0.08 mass %. The hydrophilicity
index was 50.
Thermoplastic resin fiber
[0092] LEONA® 470/144BAU (available from Asahi Kasei Fibers Co., Ltd.) having a fineness
of 470 dtex and a filament number of 144 was used, which contained 0.9% of water soluble
components.
Method for molding unidirectional material
[0093] Test pieces were obtained according to the procedure shown below with a target width
of 20mm, a target length of 200mm, and a target thickness of 1mm. Two test pieces
(molded bodies) were obtained by one molding process. The molding machine used was
a hydraulic molding machine (available from Shoji Co., Ltd.) having a maximum die
compression force of 50 tons.
[0094] As shown in FIG. 2, the fiber blended yarns were wound around an aluminum die frame.
The aluminum die frame had a thickness of 5mm, and the number of winding turns was
a minimum number with which a total sectional area of the fiber blended yarns of not
less than 20 mm
2 was achieved. The die frame with the fiber blended yarns was set in a die as shown
in FIG. 3 including a COR (core) and a CAV (cavity) with a clearance of 0.5 mm.
[0095] The interior of the molding machine was heated to a temperature of 300°C, and the
die was installed therein. Then, the die was compressed with a die compression force
of 5 MPa to effect compression molding. The molding time was 10 minutes from when
the melting point of the main component of the matrix resin (e.g., 265°C if the main
component was polyamide 66) was reached, and then the die was quenched and opened
to remove the molded bodies.
Method for molding woven fabric
[0096] As the molding machine, a hydraulic molding machine (available Shoji Co., Ltd.) with
a maximum die compression force 50 tons was used.
[0097] A stack of a predetermined number of sheets of the woven fabric cut to a length of
9.5 cm and a width of 19.5 cm was charged in a die having a length of 10 cm, a width
of 20 cm, and a thickness of 2 mm. It should be noted that the number of sheets was
a minimum number with which a volume of 40 cm
3 or more of the woven fabric was achieved.
[0098] The interior of the molding machine was heated to a temperature of 300°C, and the
die was installed therein. Then, the die was compressed with a die compression force
of 5 MPa to effect compression molding. The molding time was 10 minutes from when
the melting point of the main component of the matrix resin (e.g., 265°C if the main
component was polyamide 66) was reached, and then the die was quenched and opened
to remove the molded bodies.
Tensile strength, tensile elasticity, and strength development ratio of unidirectional
material
[0099] The test pieces were vacuum dried at 80°C for two days before tests. Tabs made of
a glass fiber reinforced resin (GFRP) having a thickness of 2 mm, a width of 20 mm,
and a length of 50 mm were attached with an instant glue to both ends of each test
piece such that a distance between the tabs was 100 mm. A strain gauge (KFGS-5-120-C1-23
available from Kyowa Electronic Instruments Co., Ltd.) was attached at the center
of the test piece to be measured.
[0100] Tensile tests were performed at a tensile speed of 1 mm/minute using a 100 kN tensile
tester available from Instron and a dynamic strain gauge available from Kyowa Electronic
Instruments Co., Ltd. The maximum load was found as a tensile strength (MPa), and
the maximum slope of a strain-load curve was found as a tensile elasticity.
[0101] A measured value of tensile strength relative to a theoretical strength calculated
according to the equation below was found as a strength development ratio of the unidirectional
material.
Tensile strength, tensile elasticity, and strength development ratio of woven fabric
[0102] The test pieces were vacuum dried at 80°C for two days before tests. Each test pieces
was cut into a dumbbell shape (having a length of 100 mm, a length of parallel portion
of 6 mm, and a thickness of 2 mm). Tabs made of a glass fiber reinforced resin (GFRP)
having a thickness of 2 mm, a width of 13 mm, and a length of 22.5 mm were attached
with an instant glue to both ends of each test piece such that a distance between
the tabs was 50 mm. A strain gauge (KFGS-5-120-C1-23 available from Kyowa Electronic
Instruments Co., Ltd.) was attached at the center of the test piece to be measured.
[0103] Tensile tests were performed at a tensile speed of 1 mm/minute using a 10 kN tensile
tester available from Instron and a dynamic strain gauge available from Kyowa Electronic
Instruments Co., Ltd., in 0-90 degrees directions. The maximum load was found as a
tensile strength (MPa), and the maximum slope of a strain-load curve was found as
a tensile elasticity.
[0104] A measured value of tensile strength relative to a theoretical strength calculated
according to the equation below was found as a strength development ratio. A composite
material has higher strength in the direction of fibers and lower strength in the
direction perpendicular to the fibers. In the examples of the invention and the comparative
examples, the density of the warp yarns and the density of the weft yarns were the
same, and therefore a half value of the unidirectional material was found as the theoretical
strength of the tensile strength of the woven fabric.
Volume fraction of reinforcing fiber
[0105] Measurements were performed according to the burning method defined in JIS K7075.
Un-impregnation ratio
[0106] Five cross-sections at arbitrary positions were cut from the molded body and embedded
in epoxy resin, and were polished with care so as not to break the reinforcing fiber.
Observation was performed using a microscope, and areas occupied by the fiber bundle,
the thermoplastic resin, and voids, respectively, were found from the obtained images
to calculate a ratio of the area of voids relative to the entire area. The measurement
was performed for four points per cross-section, and a median value of data for the
total of 20 points was found as the un-impregnation ratio.
Amount of water soluble components in reinforcing fiber, thermoplastic fiber, and
fiber blended yarn
[0107] The fibers in an amount of 3.5 g were collected and immersed in 60 ml of pure water,
and heated at 80°C for 8 hours. Then, filtration was performed, and washing with 40ml
of pure water was performed twice. All the liquids were collected and mixed to be
used as an analyte solution, and the analyte solution was freeze-dried to collect
the components dissolved therein. The mass of the collected components was measured
to quantitate the amount of water soluble components.
Amount of components adhering to reinforcing fiber and thermoplastic resin fiber in
fiber blended yarn
[0108] The fiber blended yarn was cut into a suitable length and the reinforcing fiber and
the polyamide fiber were completely separated therefrom. Water extraction was performed
on each of the fibers to quantitate the amount of water soluble components adhering
thereto. Thereafter, ratios of a component (A) originated from the reinforcing fiber
and a component (B) originated from the polyamide fiber were calculated and quantitated
using NMR. It should be noted that the amount of components adhering to the reinforcing
fiber was shown in mass percent relative to the reinforcing fiber, and the amount
of components adhering to the thermoplastic fiber was shown in mass percent relative
to the thermoplastic fiber.
[0109] However, with respect to Example 2, of which the raw material reinforcing fiber contained
a non-water soluble component, extraction using chloroform was conducted after the
water extraction to perform quantitation in the similar manner, and the amount of
the non-water soluble component was added to the amount of the water soluble components.
[0110] Further, an organic component (C) was added to the liquid only in Example 8. With
respect to the reinforcing fiber, the organic component (C) was extracted using hexafluoro-2-propanol
and quantitated. With respect to the polyamide fiber, a weight per length was measured,
and an increase relative to the raw materials was found as the amount of the organic
component (C).
Commingling ratio of reinforcing fiber in fiber blended yarn
[0111] The degree of commingling is defined by a ratio of the number of filaments of the
reinforcing fiber adjacent to filaments of the thermoplastic resin fiber relative
to the total number of the filaments in the reinforcing fiber bundle. The fiber blended
yarn wrapped in a shrink tube was cut, and the cross sections were observed using
an optical microscope to calculate the ratio by image processing. The total of 20
cross sections at arbitrary positions were observed and an average value was calculated.
Void ratio of fiber blended yarn
[0112] The fiber blended yarn was wrapped in a shrink tube, a colored epoxy resin was injected
and hardened in the tube, and then cut and polished to observe the cross section.
[0113] The area of voids is an area of the colored epoxy resin within the outer perimeter
of the fiber blended yarn, and the outer perimeter of the fiber blended yarn refers
to a figure drawn by connecting the outermost filaments of the yarn.
Degree of dispersion of organic material
[0114] The organic materials were extracted from the fiber blended yarn using a solvent
and the mass of the organic materials was measured, and then a ratio of the mass of
the organic materials to the mass of the fiber blended yarn was calculated. This measurement
was performed similarly at arbitrary 20 points to calculate an average value and a
standard deviation, and a value calculated by dividing the standard deviation by the
average value was found as the degree of dispersion.
Degree of flexibility of fiber blended yarn, and hydrophilicity index of reinforcing
fiber
[0115] The degree of flexibility of the fiber blended yarn was determined by: cutting a
20 cm-long piece of the fiber blended yarn immediately after produced; making a ring
of the fiber blended yarn by fixing one end of the yarn to the other end the yarn
using a tape having a width of 1.5 cm; suspending the ring of the fiber blended yarn
vertically with supporting the yarn at the tape-fixed portion (at this time, if the
fiber blended yarn did not become vertical, making it vertical lightly using the hands);
then, vertically inverting the ring of the yarn supported at the tape-fixed portion
such that the fiber blended yarn vertically stood with the tape-fixed portion positioned
below; holding the fiber blended yarn for one minute without touching the yarn; and
measuring an angle of the collapsed fiber blended yarn relative to the vertical direction.
When the fiber blended yarn was bent and there were two angles, a larger angle was
found as the degree of flexibility. This measurement was performed at arbitrary 20
points, and an average value was calculated.
[0116] The hydrophilicity index of the reinforcing fiber was found by performing a measurement
which is similar to that for finding the degree of flexibility of the fiber blended
yarn in a dry state and a wet state, and calculating a difference between measurement
values obtained in these states. The hydrophilicity index in the dry state was measured
after vacuum drying at 25°C for 2 hours. The hydrophilicity index in the wet state
was found by preparing a sheet of KIMTOWEL (available from Nippon Paper Industries
Co., Ltd.) folded in four on which 50 ml of distilled water was uniformly sprayed,
placing a sample that had been measured in the dry state in the KIMTOWEL and keeping
it still for 10 seconds without applying a load, and thereafter performing the measurement.
Surface tension, rate of change of surface tension
[0117] Measurements were performed using a contact angle measurement instrument, DM500,
available from Kyowa Interface Science Co., Ltd., according to a suspension method
(Laplace method). Since the melting point of the polyamide 66 is 265°C, the measurement
was performed one minute after the formation of a droplet at 310°C in nitrogen atmosphere.
The melt density was calculated as 1 g/cc. Since this measurement had to be performed
in a sufficiently dry state, the polyamide 66 was vacuum dried at 90°C for two days
as a pretreatment for the measurement.
[0118] In the polyamide 66 (thermoplastic resin fiber), an organic material in an amount
of 10 mass % relative to the polyamide 66 was mixed using a twin-screw extruder under
low shear conditions. The surface tension was measured in the same manner to calculate
a rate of change of the surface tension.
Measurement of interface shear stress
[0119] Measurements were performed according to a microdroplet test using a composite material
interface property evaluation equipment HM410 (available from Tohei Sangyo Co., Ltd.)
[0120] A single filament was removed from the raw material reinforcing fiber or the reinforcing
fiber in the fiber blended yarn, and set on the composite material interface property
evaluation equipment. On the equipment, the thermoplastic resin used as a raw material
of the thermoplastic resin fiber was melted to form a droplet on the single filament
of the reinforcing fiber, and sufficiently cooled to room temperature to obtain a
measurement sample. The measurement sample was again set on the equipment and the
droplet was nipped using a blade of the equipment and the single filament of the reinforcing
fiber was made to travel at a speed of 0.06 mm/minute on the equipment to measure
a maximum pulling load f(N) at which the droplet was pulled out, and an interface
adhesion strength τ was calculated according to the equation below:
(wherein f is a maximum pulling load (N), R is a diameter (m) of the single filament
of the reinforcing fiber, and 1 is a particle diameter (m) of the droplet in the pulling
direction).
[0121] The rate of change of the interface shear stress was found by calculating an absolute
percentage value of a difference between an interface shear stress of the reinforcing
fiber removed from the fiber blended yarn and an interface shear stress of the raw
material reinforcing fiber relative to the interface shear stress of the raw material
reinforcing fiber.
Example 1
[0122] One carbon fiber A and ten polyamide fibers were paralleled and passed through flowing
water at a flow rate of 45ml/minute, and then passed through rollers and introduced
into a Taslan box, where Taslan processing was performed with an air pressure of 2.0
kgf/cm
2 to obtain a fiber blended yarn. The yarn was spooled at a yarn speed of 65 m/minute,
the raw material carbon fiber was fed at 66 m/minute, and the raw material polyamide
fibers were fed at 68 m/minute.
Example 2
[0123] A fiber blended yarn was obtained in the same manner as in Example 1 except that
the carbon fiber B was used. The non-water soluble component remained on the carbon
fiber after the fiber blending.
Example 3
[0124] A fiber blended yarn was obtained in the same manner as in Example 1 except that
the amount of water was 85 ml/minute.
Example 4
[0125] A fiber blended yarn was obtained in the same manner as in Example 1 except that
the number of the polyamide fibers was six.
Example 5
[0126] One carbon fiber A and ten polyamide fibers were paralleled and passed through flowing
water at a flow rate of 45ml/minute, and then introduced into an interlace nozzle
(KC-AJI-L, having a diameter of 1.5 mm, propulsion-type, available from KYOCERA Corporation),
and a fiber blended yarn was obtained at an air pressure of 0.5 kg/cm
2 and a processing speed of 50 m/minute.
Example 6
[0127] The fiber blended yarn obtained in Example 1 was introduced in a water bath and spooled
to reduce the amount of polyvinylpyrrolidone to 0.08 mass %.
Example 7
[0128] The carbon fiber A was used after left for three days at a humidity of not more than
95%. Further, during production of the fiber blended yarn, 30ml of water was sprayed
using an atomizer at intervals of 1.5 minutes to moisturize a carbon fiber bobbin.
One carbon fiber A was passed through flowing water at a flow rate of 30 ml/minute.
Thereafter, the carbon fiber and ten polyamide fibers were paralleled and introduced
into a Taslan box, where Taslan processing was performed with an air pressure of 2.0
kgf/cm
2 to obtain a fiber blended yarn. The yarn was spooled at a yarn speed of 65 m/minute,
the raw material carbon fiber was fed at 66 m/minute, and the raw material polyamide
fibers were fed at 68 m/minute.
Example 8
[0129] A fiber blended yarn was obtained in the same manner as in Example 7 except that
a polyamide emulsion (SEPOLSION PA200, available from Sumitomo Seika Chemicals Co.,
Ltd.) diluted five times was used in place of the flowing water.
[0130] The surface tension of the polyamide 66 was 29.9 mN/m, the surface tension of solids
in the polyamide emulsion was 35 mN/m, the surface tension of a mixture obtained by
mixing the solids of the polyamide emulsion and the polyamide 66 was 31.0 mN/md, and
a rate of change of the surface tension was 3.7%.
[0131] The molding time was one minute from when the melting point was reached.
Example 9
[0132] A fiber blended yarn was obtained in the same manner as in Example 1 except that
the flow rate of the flowing water was 300ml/minute and the filaments were introduced
into the Taslan box immediately after contacting with the flowing water.
Example 10
[0133] A fiber blended yarn was obtained in the same manner as in Example 7 except that
the number of the polyamide fibers was 14.
Example 11
[0134] A fiber blended yarn was obtained in the same manner as in Example 1 except that
the carbon fiber was dried before used, the yarn was spooled at a speed of 45 m/minute,
the carbon fiber was fed at a speed of 46 m/minute, and the polyamide fibers were
fed at a speed of 48 m/minute. The operation speed was decreased since the reeling
was not smooth.
Comparative Example 1
[0135] A fiber blended yarn was obtained in the same manner as in Example 1 except that
the water was not used. Fluff of the CF was generated in the environment.
Comparative Example 2
[0136] One carbon fiber A and ten polyamide fibers were paralleled and spooled without any
treatment. Fluff of the CF was generated in the environment.
Comparative Example 3
[0137] The carbon fiber C and ten polyamide fibers were introduced into a Taslan box, where
Taslan processing was performed with an air pressure of 2.0 kgf/cm
2 to obtain a fiber blended yarn. The yarn was spooled at a yarn speed of 65 m/minute,
the raw material carbon fiber was fed at 66 m/minute, and the raw material polyamide
fibers were fed at 68 m/minute. Fluff of the CF was generated in the environment.
Comparative Example 4
[0138] One carbon fiber A and ten polyamide fibers were paralleled and introduced into a
water bath filled with water. The water was circulated with a pump at a flow rate
of 20 m/minute to open the fibers with the water flow. The opened fibers were laid
together and introduced into a water jet nozzle, where the fibers were blended by
turbulent flow of water fed at a rate of 10 kg/cm
2. The yarn speed was 20 m/minute, and the carbon fiber A and the polyamide fibers
were fed at 22 m/minute. The resulting yarn was spooled and dried at 150°C for 10
hours.
Example 12
[0139] The fiber blended yarn obtained in Example 1 was woven using a rapier loom to obtain
a woven fabric of 4/4 twill weave with a density of six yarns/inch. The moisture content
of the carbon fiber during the weaving process was 5 mass %.
Comparative Example 5
[0140] A woven fabric was obtained in the same manner as in Example 12 except that the fiber
blended yarn obtained in Comparative Example 3 was used.
Table 1
|
|
Example 1 |
Example 2 |
Example 3 |
Example 4 |
Example 5 |
Example 6 |
Example 7 |
Example 8 |
Example 9 |
Raw materials |
Reinforcing fiber |
CF-A |
CF-B |
CF-A |
CF-A |
CF-A |
Fiber blended yarn obtained in Example 1 was introduced in water bath water bath and
spooled and spooled |
CF-A |
CF-A |
CF-A |
Thermoplastic resin fiber |
10 polyamide fibers |
10 polyamide fibers |
10 polyamide fibers |
6 polyamide fibers |
10 polyamide fibers |
10 polyamide fibers |
10 polyamide fibers |
10 polyamide fibers |
Fiber blending process |
Taslan processing |
Taslan processing |
Taslan processing |
Taslan processing |
Interlace |
Taslan processing |
Taslan processing |
Taslan processing |
Amount of water soluble components in reinforcing fiber |
2.9% |
0.11% |
2.9% |
2.9% |
2.9% |
2.9% |
2.9% |
2.9% |
Amount of water soluble components in thermoplastic resin fiber |
0.9% |
0.9% |
0.9% |
0,9% |
0.9% |
0.9% |
0.9% |
0.9% |
Fiber blending process |
Fiber blending speed |
65 |
65 |
65 |
65 |
50 |
65 |
65 |
65 |
Degree of flexibility of reinforcing fiber before reeling |
30 |
15 |
30 |
30 |
30 |
60 |
60 |
30 |
Water |
45 ml/min. |
45ml/min. |
85 ml/min. |
45ml/min. |
45ml/min, |
30ml/min. |
30 ml/min. |
300 ml/min. |
Moisture ratio during fiber blending |
80% |
40% |
150% |
60% |
80% |
120% |
100% |
300% |
Fiber blended yarn |
Commingling ratio |
8% |
6% |
7% |
4% |
5% |
8% |
9% |
9% |
5% |
|
Degree of dispersion of organic material |
16% |
6% |
13% |
14% |
17% |
5% |
21% |
15% |
10% |
|
Component A in reinforcing fiber |
1.6 |
0.15 |
0.97 |
1.3 |
1.2 |
0.08 |
1.3 |
0.8 |
0.5 |
|
Component B in reinforcing fiber |
0.15 |
0.14 |
0.1 |
0.17 |
0.14 |
0.01 |
0.13 |
0.07 |
0.02 |
|
Component C in reinforcing fiber |
- |
- |
- |
- |
- |
- |
- |
1.2 |
- |
|
Component A in polyamide fibers |
0.23 |
0.02 |
0.17 |
0.27 |
0.24 |
0.03 |
0.25 |
0.05 |
0.12 |
|
Component B in polyamide fibers |
0.08 |
0.08 |
0.05 |
0.06 |
0.07 |
0.01 |
0.09 |
0.01 |
0.02 |
|
Component C in polyamide fibers |
- |
- |
- |
- |
- |
- |
- |
0.4 |
- |
|
Degree of flexibility of fiber blended yarn |
100 |
24 |
86 |
115 |
104 |
68 |
90 |
85 |
70 |
|
Void ratio of fiber blended yarn |
31 |
27 |
25 |
30 |
26 |
25 |
33 |
27 |
24 |
|
Rate of change of interface shear stress |
30 |
10 |
33 |
29 |
28 |
10 |
35 |
40 |
14 |
Molded body |
Volume fraction of reinforcing fiber |
63.2 |
63.3 |
60.9 |
65.1 |
63.6 |
58 |
59 |
56 |
62 |
Un-impregnation ratio (%) |
0.35 |
0.03 |
0.4 |
0.4 |
0.8 |
0.1 |
0.05 |
0.01 |
0.3 |
Tensile strength |
1107 |
2222 |
1007 |
983 |
910 |
950 |
1235 |
1210 |
1020 |
Strength development ratio |
86 |
77 |
81 |
74 |
70 |
80 |
102 |
105 |
80 |
Tensile elasticity |
126.3 |
131.9 |
130.1 |
131.9 |
121 |
126 |
140 |
137 |
125 |
Table 2
|
|
Example 10 |
Example 11 |
Comp. Ex. 1 |
Comp. Ex. 2 |
Comp Ex. 3 |
Comp, Ex. 4 |
Example 12 |
Comp. Ex. 5 |
Raw materials |
Reinforcing fiber |
CF-A |
CF-A |
CF-A |
CF-A |
CF-C |
CF-A |
|
|
Thermoplastic resin fiber |
14 polyamide fibers |
10 polyamide fibers |
10 polyamide fibers |
10 polyamide fibers |
10 polyamide fibers |
10 polyamide fibers |
|
|
Fiber blending process |
Taslan processing |
Taslan processing |
Taslan processing |
Paralleled a nd spooled |
Taslan processing |
In water, turbulent flow |
|
|
Amount of water soluble components in reinforcing fiber |
2.9% |
2.9% |
2.9% |
2.9% |
0.08% |
29% |
|
|
Amount of water soluble components in thermoplastic resin fiber |
0.9% |
0.9% |
0.9% |
0.9% |
0.9% |
0.9% |
|
|
Fiber blending process |
Fiber blending speed |
65 |
45 |
65 |
65 |
65 |
20 |
|
|
Degree of flexibility of reinforcing fiber before reeling |
60 |
3 |
30 |
30 |
10 |
30 |
|
|
Water |
30 ml/min. |
45 ml/min. |
None |
None |
None |
In water |
|
|
Moisture ratio during fiber blending |
120% |
70% |
0% |
0% |
0% |
>>500% |
Woven fabric made of fiber blended yarn obtained in Example 1 |
Woven fabric made of fiber blended yarn obtained in Comp. Ex. 3 |
Fiber blended yarn |
Commingling ratio |
10% |
7% |
3% |
3% |
3% |
30% |
|
|
|
Degree of dispersion of organic material |
24% |
18% |
4% |
4% |
3% |
1 % |
|
|
|
Component A in reinforcing fiber |
1.2 |
1.7 |
2.9 |
2.9 |
0.08 |
0 |
|
|
|
Component B in reinforcing fiber |
0.15 |
0.15 |
0 |
0 |
0 |
0 |
|
|
|
Component C in reinforcing fiber |
- |
- |
- |
- |
- |
- |
|
|
|
Component A in polyamide fibers |
0.26 |
0.22 |
0 |
0 |
0 |
0 |
|
|
|
Component B in polyamide fibers |
0.08 |
009 |
09 |
09 |
0.9 |
0 |
|
|
|
Component C in polyamide fibers |
- |
- |
- |
- |
- |
- |
|
|
|
Degree of flexibility of fiber blended yarn |
110 |
95 |
8 |
6 |
10 |
12 |
|
|
|
Void ratio of fiber blended yarn |
32 |
31 |
19 |
12 |
17 |
15 |
|
|
|
Rate of change of interface shear stress |
32 |
28 |
0 |
0 |
0 |
-25 |
|
|
Molded body |
Volume fraction of reinforcing fiber |
46 |
61 |
64.1 |
65.3 |
62 |
62 |
60 |
60 |
Un-impregnation ratio (%) |
0.04 |
0.39 |
8.7 |
>10 |
6 |
1.5 |
0.34 |
5.8 |
Tensile strength |
979 |
1056 |
620 |
420 |
660 |
800 |
567 |
360 |
Strength development ratio |
102 |
84 |
47 |
31 |
52 |
63 |
92 |
58 |
Tensile elasticity |
135 |
122 |
95 |
80 |
105 |
110 |
55.3 |
45 |
[0141] The test pieces of the fiber blended yarns of Examples 1 to 11 exhibited excellent
tensile strength, tensile elasticity, and strength development ratio. The woven fabric
obtained in Comparative Example 5 generated much fluff, and litter of the carbon fiber
in the environment was observed. The woven fabric of Comparative Example 5 exhibited
lower tensile strength, tensile elasticity, and strength development ratio than the
test piece of the woven fabric of Example 12.
Industrial Applicability
[0142] According to the method for producing a fiber blended yarn, the fiber blended yarn,
and the method for producing a woven fabric or a knit fabric of the present invention,
an intermediate material that is favorably applicable to reinforced materials for
materials required to have high level mechanical physical properties, such as structural
parts of various machines, automobiles, etc., can be obtained, and thus the present
invention has industrial applicability.