Title of Invention

PEARLESCENT PIGMENT, PROCESS FOR PORODUCING THE SAME, COATING COMPOSITION AND MULTILAYERED COAT

Abstract This invention relates to a pearlescent pigment, which is composed of flaky alumina substrate particles produced by a hydrothermal process and coat layers formed on the flaky substrate particles and composed of at least one metal oxide including at least a titanium oxide. The metal oxide has an average particle size of from 1 to 500 nm. According to this invention, it is possible to provide a pearlescent pigment, which has wholly uniform photoluminescence and an elegant and silky feel in combination and can fully satisfy artistry as desired.
Full Text PEARLESCENT PIGMENT, PROCESS FOR PRODUCTING
THE SAME, COATING COMPOSITION
AND MULTILAYERED COAT
Technical Field
This invention relates to a pearlescent pigment
obtained by coating surfaces of specific flaky substrate
particles (which may hereinafter be called simply "substrate
particles") with a metal oxide, its production process, and
its use.
Background Art
Known pearlescent pigments include those obtained by
coating surfaces of substrateparticles, suchasmica flakes,
with a metal oxide of large refractive index like titanium
dioxide. In recent years, pearlescent pigments making use
of thin alumina flakes as substrate particles improved in
smoothness, heat resistance and transparency, in which mica
flakes are deficient as substrate particles, have been
proposed (Patent Document 1) . However, when plate alumina
produced by a hydrothermal process is used as substrate
particles in the process described in the above patent
document, adsorbability of particles of a metal oxide on
the alumina is very low, and hence, the particles of the

metal oxide are bound into large aggregates , thereby failing
to provide a pigment equipped with satisfactory
photoluminescence. Even if the metal oxide particles are
adsorbed on the plate alumina, the particles of the metal
oxide which cover the substrate particles are so large that
wholly uniform photoluminescence, from which no graininess
is felt, or smooth and elegant photoluminescence, that is,
silky pearlescence is hardly available. It has, therefore,
been unable to fully satisfy artistry required for various
applications.
Patent Document 1: JP-A-09-255891
Disclosure of the Invention
Problem to Be Solved by the Invention
When the metal oxide coating is conducted using
ordinary substrate particles, the pearlescence of the
conventional pearlescent pigments is not uniform and is
deficient in smoothness as a whole due to the inclusion of
large substrate particles having a large average particle
size and wide reflection areas as mentioned above, although
it has discontinuous strong photoluminescence. In an
attempt to overcome this problem, substrate particles of
small average particle size were used. The above-described
grainy feel was reduced, but it was still unable to derive
any pearlescence having a smooth, elegant, photoluminescent
and silky feel.

With the foregoing circumstances of the conventional
art in view, an object of the present invention is, therefore,
to provide a pearlescent pigment, which has, as a whole,
both uniform photoluminescence and an elegant and silky feel
and can fully satisfy artistry as required.
Another object of the present invention is to provide
a coating composition capable of forming a coat having
characteristic photoluminescence in a single-apply coating
process, a 2-coat 1-bake coating process, a 3-coat 2-bake
coating process or a coating process that forms at least
one pearlescent coat layer between stacked at least one
desired coat layers or on a coat layer.
Means for Solving the Problem
The above-described objects can be achieved by the
present invention to be described hereinafter.
Described specifically, the present invention
provides a pearlescent pigment comprising flaky alumina
substrate particles produced by a hydrothermal process and
coat layers formed on the substrate particles and composed
of at least one metal oxide comprising at least a titanium
oxide, wherein the metal oxide has an average particle size
of from 1 to 500 nm.
In the above-described pearlescent pigment according
to the present invention, it can be preferred that the coat
layers of the metal oxide are mixed layers and/or stacked

layers of two or more metal oxides comprising at least the
titanium oxide; that the flaky alumina substrate particles
have an average particle size of from 0.1 to 50 µm; that
the alumina substrate particles have an aspect ratio
(particle size/thickness) of from 5 to 500; that the alumina
substrate particles have an average particle size a
statistical variation coefficient of which is from 20 to
90; and that the pearlescent pigment has an average particle
size a statistical variation coefficient of which is from
20 to 90.
The present invention also provides a process for the
production of a pearlescent pigment, which comprises
dispersing in water flaky alumina substrate particles
produced by a hydrothermal process and activated at surfaces
thereof by at least one method selected fromplasma treatment,
ultrasonic treatment, acid treatment, alkali treatment,
shock treatment or chemical etching treatment, hydrolyzing
in the resulting dispersion a metal salt comprising at least
a salt of titanium, allowing the resulting metal hydroxide
or metal oxide to deposit on surfaces of the alumina substrate
particles, and then subjecting the resulting deposit to heat
treatment to form, on the surfaces of the substrate particles,
metal oxide coat layers having an average particle size of
from 1 to 500 nm.
Further, the present invention also provides a coating
composition comprising the above-described pearlescent

pigment of the present invention and a film-forming resin.
Preferably, the coating composition can further contain a
liquid medium.
Still further, the present invention also provides
a multilayered coat comprising a base coat layer formed from
the above-described coating composition of the present
invention and a clear coat layer formed on the base coat
layer.
Preferably, the above-described multilayered coat
can have reflected light intensities having a statistical
variation coefficient of not greater than 5 when measured
by a photometer; or a 45°/0° reflection intensity ratio of
not greater than 100 when measured at an elevation angle
of not smaller than 0° by a goniophotometer.
Moreover, the present invention provides a
multilayered coat comprising a colored first base coat layer
formed on a surface of a substrate, a second base coat layer
formed from the above-described coating composition of the
present invention on the colored first base coat layer, and
a clear coat layer formed on the second base coat layer;
a multilayered coat comprising a first coat layer formed
on a surface of a substrate and at least one second coat
layer formed from the above-described coating composition
of the present invention on the first coat layer; and also
a multilayered coat comprising at least two first coat layers
formed one over the other on a surface of a substrate and

at least one second coat layer formed from a coating
composition according to claim 8 between the at least two
first coat layers.
Advantageous Effects of the Present Invention
The present inventors have proceeded with extensive
research to achieve the above-described objects of the
present invention. As a result, it has been found that color
visions of a pearlescent pigment, which was obtained by
activating surfaces of substrate particles obtained by a
hydrothermal process and then by coating the substrate
particles with at least one metal oxide of a particle size
in a range of from 1 to 500 nm, and colored articles making
use of the pigment have such artistry as giving a
graininess-free, smooth, elegant, photoluminescent and
silky color tone. In addition, it has also been found that,
when the above-described various coats are formed on
substrates by using coating compositions containing the
above-described pearlescent pigment, the coats fully show
good artistry.
Best Modes for Carrying out the Invention
The present invention will next be described in further
detail based on certain preferred embodiments.
The term "hydrothermal process" as used herein means
a process that allows crystals of a substrate material such

as alumina to grow in a solvent of high temperature and high
pressure. Conditions for the crystal growth are specific
to the chemical structure of the substrate material, the
solvent, temperature and pressure used, and the like. It
is, therefore, possible to synthesize desired substrate
particles in accordance with an average particle size, an
aspect ratio and the like, which are required for the
substrate particles. The chemical and physical properties
of the substrate particles produced by the hydrothermal
process are unique properties not available from any process
other than the hydrothermal process.
Substrate particles which can be obtained by the
hydrothermal process can include alumina, boehmite, iron
oxide, hydroapatite, zirconia, titanates, titanium oxide,
cobalt hydroxide oxide, calcium silicate and the like. Any
substrate particles may be used insofar as they have
uniformity, smoothness, heat resistance, transparency and
the like and provide artistry as required. However,
preferred is alumina which satisfies the above-described
conditions with a good balance. Flaky alumina substrate
particles which are preferred as mentioned above are known
by themselves, and are available for use in the present
invention, for example, from Kinsei Matec Co., Ltd., for
example, under the trade names of "YFA-02050" (average
particle size: 2.0 µm, aspect ratio: 50), "YFA-07070"
(average particle size: 7.0 µm, aspect ratio: 70),

"YFA-05070" (average particle size: 5.0 µm, aspect ratio:
70), "YFA-10030" (average particle size: 10.0 µm, aspect
ratio: 27), etc.
The average particle size of the substrate particles
may be from 0.1 to 50 µm, preferably from 0.3 to 30 µm, more
preferably from 0.5 to 20 µm. An average particle size
greater than 50 µm is not preferred in that the resulting
pearlescent pigment strongly reflects light to impair a silky
color tone. On the other hand, an average particle size
smaller than 0.1 µm is not preferred in that the resulting
pearlescent pigment strongly scatters light to impair a silky
color tone. The aspect ratio of the substrate particles
may be from 5 to 500, preferably from 7 to 300, more preferably
from 10 to 200. An aspect ratio smaller than 5 is not
preferred in that the substrate particles is poor in
orientation and interference light (pearlescence) is hardly
available from the resulting pearlescent pigment. On the
other hand, an aspect ratio greater than 500 is not preferred
in that the substrate particles are prone to breakage during
handling such as circulation, mixing and dispersion.
Further, the particle size distribution of the
substrate particles may be from 20 to 90, preferably from
25 to 80, more preferably from 30 to 70 in terms of statistical
variation coefficient (CV value) . This CV value means the
percentage of a standard deviation based on an average
particle size in a particle size distribution, and indicates

the degree of scattering of the particle size distribution.
It is to be noted that each particle size distribution was
measured by "MULTISIZER3 COULER COUNTER" (trade name;
manufacture by Beckman Coulter, Inc.) and its statistical
variation coefficient was also calculated.
When the CV value of the substrate particles is 20
or greater, small particle-size particles, which produce
scattered light, and particles, which produce rather strong
reflected light, are well-balanced so that the resulting
pearlescent pigment can be provided with a silky color tone.
When the CV value of the substrate particles is smaller than
20, on the other hand, the particle size distribution of
the substrate particles is extremely narrow, but small
particle-size particles, which produce scattered light, and
large particle-size particles, which produce rather strong
reflected light, both decrease, resulting in the lack of
a balance between scattered light and reflected light so
that the resulting pearlescent pigment is deprived of a silky
color tone. On the other hand, a CV value of the substrate
particles, which is greater than 90, is not preferred in
that scattered light and reflected light are poorly balanced
and the resulting pearlescent pigment is also provided with
an impaired silky color tone.
The pearlescent pigment according to the present
invention can be obtained by activating the surfaces of the
substrate particles and then coating the surfaces with at

least one metal oxide. In the pearlescent pigment according
to the present invention, the metal oxide is required to
have a particle size of from 1 to 500 nm, preferably from
3 to 300 nm, more preferably from 5 to 200 nm. When the
particles size of the metal oxide with which the substrate
particles are coated fall within the range of from 1 to 500
nm, the metal oxide has high crystallinity so that the
refractive index inherent to the metal oxide is fully
exhibited. Moreover, the top surfaces of the coats of the
pearlescent pigment are smooth and produce sufficient
reflected light. As a result, a satisfactory interference
color is produced, so that graininess-free, smooth and
elegant photoluminescence, that is, a silky feel is higher,
thereby making it possible to fully satisfy artistry as
desired.
It is to be noted that the above-described particle
size indicates the particle size of metal oxide particles
or aggregates of metal oxide particles after hydrolysis or
sintering. The average particle size of each metal oxide
was calculated from 50 particles chosen at random from a
micrograph obtained by a scanning electron microscope,
"FE-SEMS-4800" (tradename; manufactured by Hitachi, Ltd.) .
When the particle size of the metal oxide exceed 500
nm, the metal oxide layers have substantial surface roughness
so that reflected light from the pearlescent pigment is
considerably weakened and no sufficient interference color

is produced. When the particle size of the metal oxide is
smaller than 1 nm, on the other hand, the metal oxide is
provided with substantially reduced crystallinity so that
the refractive index inherent to the metal oxide is not
available. As a result, the pearlescent pigment does not
produce any sufficient interference color. Even if the
coats of the metal oxide are specified in thickness, a
sufficient interference color cannot be obtained unless the
metal oxide forming the coat layers is controlled in particle
size.
By the coats of the metal oxide, the resulting
pearlescent pigment is provided with a silver tone color
or, when the coats is increased in thickness, with an
interference color. Further, the surf aces of the substrate
particles may be coated with a colored metal oxide, for
example, with an iron oxide to obtain a reddish or blackish,
pearlescent pigment. Furthermore, the pearlescent pigment
may be provided with still higher saturation by adsorbing
fine particles of a coloring pigment, which will be described
subsequently herein, on the surfaces of the pearlescent
pigment.
The pearlescent pigment according to the present
invention can also be obtained by coating the surfaces of
the above-described substrate particles with a mixture of
two or more metal oxides or by stacking and coating two or
more metal oxide layers stepwise on the surfaces of the

above-described substrate particles. By coating with such
a mixture or by conducting such stacking and coating,
physical properties not available from a single metal oxide
alone can be obtained, for example, light resistance, water
resistance and the like can be improved. Especially by
successively stacking two or more metal oxides into an
increased number of layers, a pearlescent pigment of still
higher photoluminescence can be obtained.
Furthermore, the pearlescent pigment according to the
present invention may preferably have a particle size
distribution the statistical variation coefficient (CV
value) ranges from 20 to 90. Its reasons are similar to
those mentioned above in connection with the substrate
particles.
A description will next be made of the process of the
present invention for the production of the pearlescent
pigment. The pearlescent pigment can be obtained by coating
the surfaces of the substrate particles with the metal oxide
having the particle size of from 1 to 500 nm.
For a general pearlescent pigment, it is necessary
to control the particle size of a metal oxide to be deposited
on substrate particles after hydrolysis or sintering and
the aggregation property of the particles such that the
particles of the metal oxide are arrayed on the surfaces
of the substrate surfaces. The process described in Patent
Document 1 referred to in the above, however, is practically

impossible to control the partible size, aggregation and
arraying of the metal oxide, and therefore, cannot obtain
a pearlescent pigment capable of producing sufficient
interference light, because substrate particles produced
by a hydrothermal process are extremely high in surface
smoothness and have low adsorbing ability for the metal oxide
on their surfaces, and the aggregation of the metal oxide
itself tends to proceed easily. As a result, the metal oxide
exists as large aggregates and has low adsorbability on the
surfaces of the substrate particles. Even when adsorbed,
the resulting coats of the metal oxide are not uniform in
thickness and the top surfaces of the coats become rough.
Accordingly, reflected light is considerably weakened so
that no sufficient interference color is produced.
Even if the substrate particles produced by the
hydrothermal process are coated with the metal oxide by a
known technique and moreover, the resulting coats are
specified in thickness, it is still impossible to control
the particle size and aggregation property of the metal oxide
forming the coat layers and to obtain a pearlescent pigment
having a sufficient interference color unless the adsorbing
ability of the surfaces of the substrate particles is
improved.
In the present invention, it was found that by
activating beforehand the surfaces of the substrate
particles produced by the hydrothermal process, the

particles of the metal oxide can be eVenly adsorbed as fine
particles on the surfaces of the substrate particles. For
the above-described surface activation, usable examples
include plasma treatments such as thermal plasma treatment
and low-temperature plasma treatment, ultrasonic treatment,
acid treatment, alkali treatment, tumbling-medium-assisted
dispersion treatment, shock treatments such as
high-pressure shock treatment and sand blasting treatment,
ozone treatment, and chemical etching treatments such as
electrochemical treatment. These treatments can be applied
either singly or in combination.
Treatment gas usable in plasma treatment can be one
of or a combination of two or more of nitrogen, ammonia,
a mixed nitrogen-hydrogen gas, oxygen-containing gases such
as oxygen, ozone, water vapor, carbon monoxide, carbon
dioxide, nitrogen monoxide and nitrogen dioxide, rare gases
such as helium, argon, neon and xenon, halogen gases such
as fluorine, chlorine and iodine, and mixed gases obtained
by mixing fluorocarbon gases, such as tetrafluorocarbon,
hexafluorocarbon and hexafluoropropylene, in
oxygen-containing gases at volume ratios not greater than
1/2.
Examples of a method for generating the
above-described plasma include the method that a direct
current is applied to a gas to effect plasma decomposition,
the method that a radiofrequency voltage is applied to a

gas to effect plasma decomposition, the method that a gas
is subjected to plasma decomposition by electron cyclotron
resonance, and the method that a gas is thermally decomposed
by a hot filament.
As the pressure of the treatment gas upon the
above-described plasma treatment, 1 x 10"4 to 100 Torr is
preferred because a low pressure requires a costly vacuum
chamber and vacuum pumping system. The actual treatment
gas pressure is appropriately determined depending on the
excitation means within the above-described pressure range.
However, 1 x 10-2 to 100 Torr is more preferred because it
is possible to apply a direct current or radiofrequency
current capable of generating a plasma even when the system
is simple and the treatment gas pressure is relatively high.
The inputted electric power required for the
above-described plasma treatment differs depending on the
area and shape of electrodes. Lower electric power results
in a low plasma density so that more time is required for
the treatment. On the other hand, higher electric power
induces uneven treatment. The electric power may,
therefore, be from 20 to 200 W preferably.
When the construction of the electrodes employed in
the above-described plasma treatment is the parallel plate
type, the coaxial cylinder type, the curved counter plate
type or the hyperbolic counter plate type, a voltage is
applied by the capacity coupling method. When a

radiofrequency voltage is applied, it can be applied in an
induction manner by using external electrodes. The
distance between the electrodes is appropriately determined
depending on the treatment pressure and the substrate
particles, and can be set desirably at a possible shortest
distance for plasma treatment because a longer distance leads
to a lower plasma density and requires higher electric power.
The time of the plasma treatment is determined
depending on the inputted electric power. In general,
however, 1 to 60 minutes are preferred because a shorter
plasma treatment time cannot achieve a sufficient degree
of activation of the substrate particles while no significant
improvement can be expected in the degree of activation of
the substrate particles even when the plasma treatment time
is made excessively long. Concerning the temperature
during the plasma treatment, neither heating nor cooling
is absolutely needed.
The above-described plasma treatment is required to
be evenly applied over the entire surfaces of the flaky
substrate particles. It is, therefore, preferred to
conduct the plasma treatment while rolling the flaky
substrate particles. Such mixing methods can include the
method that the flaky substrate particles are sealed in a
vessel and are tumbled together with the vessel and the method
that the flaky substrate particles are mixed by vibrations.
An appropriate mixing method can be determined depending

on the particle size and amount of the flaky substrate
particles to be treated.
Any ultrasonic oscillator can be used in the ultrasonic
treatment insofar as its oscillating frequency is in a range
of from 50 Hz to 100 KHz and its output power is in a range
of from 20 to 1, 000 W. An oscillating frequency lower than
50 Hz leads to a substantial reduction in the surface
uniformity of the energy distribution of ultrasonic waves
striking the flaky substrate particles, and hence to
insufficient activation. An oscillating frequency higher
than 100 KHz, on the other hand, leads to a substantial
reduction in the overall energy density, and also to
insufficient activation of the substrate particles. Even
within the above-described range, cavitations may still
occur depending on the structure and material of a tank to
be used and on the kind of a dispersing medium to be used.
In such a case, it is desired to increase the oscillation
frequency or to lower the output power such that the treatment
system can be kept under conditions which do not cause
cavitations.
In the present invention, ultrasonic vibrations can
be applied either continuously or intermittently. It is,
however, preferred to apply ultrasonic vibrations by
controlling them to appropriate conditions within the
above-described frequency range of from 50 Hz to 100 KHz
and the above-described power output range of from 20 to

1,000 W.
An acid usable in the acid treatment can be one of
or a combination of two or more of inorganic acids such as
hydrochloric acid, nitric acid, sulfuric acid, phosphoric
acid and carbonic acid, organic acids such as acetic acid,
citric acid and benzoic acid, and resin acids such as acrylic
resins and rosin. An alkali usable in the alkali treatment
can be one of or a combination of two or more of alkali metal
salts such as caustic soda and caustic potash, alkaline earth
metal salts such as calcium hydroxide, and weak bases such
as ammonia, sodium carbonate, aniline and phenol.
The concentration and temperature of an acid or alkali
solution in the acid treatment or alkali treatment may be
in a range of from 0.1 to 99 wt% and a range of from 5 to
95°C, respectively, although an efficient treatment
temperature may be more preferably from 15 to 70°C. The
treatment time is suitably determined depending on the
concentration and temperature, with a range of from 5 minutes
to 6 hours being preferred. The acid or alkali treatment
may be repeated twice or more, or the acid and alkali
treatments may be alternately conducted at least once. The
acid treatment or alkali treatment also effects a pH
adjustment, so that a pH buffer may be used. Further, a
surfactant, organic solvent and/or the like may also be used
as aid(s) in combination.
The shock treatment is a method for physically

activating the substrate particles. Specific methods
include partial grinding of the surfaces of the substrate
particles by shaking or collision, and also, polishing by
tumbling. Treatment methods which can achieve such partial
grinding or polishing include dispersing shock treatment
by a homogenizer, dissolver, sand mill, high-speed mixer
or paint conditioner, high-pressure shock treatment by a
high-pressure homogenizer, sand blasting treatment, jet
mill treatment, and the like.
The concentration of the substrate particles in the
liquid medium in the shock treatment may be from 1 to 200
wt%, with from 5 to 150 wt% being preferred. A concentration
lower than 1 wt% results in a poor shock efficiency, while
a concentration higher than 200 wt% results in thickening
so that the shock treatment is rendered difficult. For the
shock treatment that needs a medium upon effecting the same,
glass beads, steel balls, zirconia beads and the like can
be used, and the weight ratio of the medium to the substrate
particles may be from 0 to 1,000 wt%, preferably from 0 to
500 wt%. It is not particularly needed to use a medium when
the activation of the surfaces of the substrate particles
can be sufficiently achieved by the collision of the
substrate particles themselves.
In the shock treatment, a pH buffer may be used.
Further, a surfactant, organic solvent and/or the like may
also be used as aid(s) in combination. The time of the

shock treatment is determined depending on the concentration
of the substrate particles and the type and amount of the
medium. However, the substrate particles cannot be
provided with a sufficient degree of activation when the
time of the shock treatment becomes short, and no substantial
improvement can be expected in the activation degree of the
substrate particles even when the time of the shock treatment
is made excessively long. Therefore, 1 to 60 minutes are
preferred in general. It is to be noted that the
above-described physical activation treatment requires the
payment of an attention to substantial changes in particle
size distribution and CV value because, when the intensity
of shock on the substrate particles is increased, the
treatment is not limited to the surface activation of the
substrate particles and may also break the substrate
particles.
In addition, other conventional treatments,
including chemical etching treatments such as ozone
treatment, UV treatment and electrochemical treatment, can
also be used widely.
The pearlescent pigment according to the present
invention can also be obtained by adsorbing a hydrated oxide
of a metal such as titanium, zirconium, tin or iron with
a particle size of from 1 to 500 nm on the surface-treated
substrate particles by a known method, for example, by a
method that thermally hydrolyzes a salt of the metal in water

in which the substrate particles have been dispersed or by
a method that subjects the salt of the metal to neutralization
hydrolysis with an alkali in the water; and then by calcining
the hydrated oxide. By conducting this calcination step
in a reducing atmosphere, the metal oxide is converted into
a low-valence titanium oxide or a low-valence iron oxide,
so that a pearlescent pigment tinged in a black color can
be obtained. Additional artistry can be also imparted by
a known method in addition to the use of the metal oxide.
The atomic weight of the metal in the water-soluble
metal salt required to obtain pearlescence (interference
color) may be from 2.0 x 10-5 mol to 2.0 x 10-1 mol, more
preferably from 4.0 x 10-5 mol to 1.0 x 10-1 mol. If the
atomic weight of the metal is lower than 2.0 x 10-5 mol,
the flaky substrate particles cannot be coated so that no
interference light is produced. If the atomic weight of
the metal exceeds 1.0 x 10-1 mol, inconveniences arise in
that, even if the flaky substrate particles can be coated,
cracks tend to occur in the coat layers after calcinations,
and as a result, the intensity of interference light is
lowered.
A description will next be made about the coating
composition according to the present invention. The
coating composition according to the present invention
contains the above-described pearlescent pigment of the
present invention and a film-forming resin, and preferably,

may contain the pearlescent pigment and film-forming resin
in a liquid medium. Usable examples of the film-forming
resin include, but are not limited to, film-forming resins
employed in the field of conventionally-known coating
compositions, such as acrylic resins, acrylic melamine
resins, vinyl chloride-vinyl acetate copolymer resins,
alkyd resins, polyester resins, polyurethane resins and
amino resins.
As a solvent for dissolving or dispersing the
pearlescent pigment and film-forming resin, one
conventionally and commonly known to be useful in coating
compositions can be used. Specific examples include water,
toluene, xylene, butyl acetate, methyl acetate, acetone,
methyl ethyl ketone, methyl isobutyl ketone, methanol,
ethanol, butanol, cyclohexane, and the like. These
solvents may also be used as mixed solvents.
In the coating composition according to the present
invention, the pearlescent pigment of the present invention
may be used in a proportion of from 0.005 to 50 parts by
weight, preferably from 0.1 to 30 parts by weight per 100
parts by weight of the film-forming resin. Use of the
pearlescent pigment in a proportion of smaller than 0.005
parts by weight cannot obtain a coating composition the
provision of which is one of the objects of the present
invention. On the other hand, use of the pearlescent pigment
in a proportion of greater than 50 parts by weight can obtain

a coating composition the provision of which is one of the
objects of the present invention, but is not preferred
because the resulting coats are provided with reduced
physical properties.
In the present invention, the above-described
pearlescent pigment can be used singly or in combination
with one or more other pigments. As coloring pigments usable
in combination, pigments employed in ordinary coating
compositions and the like can be used. Specific examples
include phthalocyanine pigments, quinacridone pigments,
perylene pigments, anthraquinone pigments, DPP pigments,
metal complex pigments, transparent iron oxide pigments,
carbon black, titanium oxide, and zinc oxide. Further, as
metal powder pigments, aluminum powder, copper powder,
stainless steel powder, and the like can be mentioned. Among
these, aluminum powder is used most commonly. As special
metal pigments, metal colloids and the like can be used.
As mica pigments usable in combination in the present
invention, conventionally-known mica pigments can be widely
used in combination, and illustrative are transparent pearl
mica and colored mica. As light interference pigments,
interference mica, interference alumina, interference mica
(interference glass) and the like can be mentioned. In
addition, one or more of fillers, antistatic agents,
stabilizers, antioxidants, UV absorbers and the like can
also be added as needed in the coating composition according

to the present invention.
When the coating composition according to the present
invention contains the pearlescent pigment of the present
invention and another pigment, a base coating composition
containing the pearlescent pigment of the present invention
and another base coating composition containing the another
pigment can be prepared beforehand and these two types of
base coating compositions can then be blended together into
the coating composition as desired, or as an alternative,
the pearlescent pigment and the another pigment can be mixed
together at the beginning and can then be formulated into
the coating composition.
The coating composition obtained as described above
is applied onto a substrate such as a metal plate, glass
plate, ceramic plate or plastic plate, to which surface
preparation may have been applied as needed, by spray coating,
electrostatic coating, flow coating, roll coating or the
like, dried and then crosslinked and cured to form a colored
coat layer.
The coat formed by applying the coating composition
of the present invention onto a substrate has a color tone
of a graininess-free, smooth, elegant and silky feel,
compared with conventional TiO2-based pearlescent pigments
for coatings. Owing to the possession of the
above-described properties, coats having excellent
characteristic photoluminescence, which are not seen on

coats available from conventional coating
compositions, can be formed in a single-apply coating
process, a 2-coat 1-bake coating process, a 3-coat 2-
bake coating process or a coating process that forms,
with a coating composition containing the pearlescent
pigment of the present invention, at least one coat
layer between stacked two desired coat layers of at
least one kind or on a desired coat layer.
A coat can also be formed by using the above-
described colored coat layer as a base coat layer;
applying a clear coating composition, which has been
prepared by dissolving or dispersing a resin having
low compatibility with the above-described film
forming resin in an organic solvent, on the base coat
layer; drying the clear coating composition; an then
subjecting it to heat treatment. The coat formed by
applying the coating composition of the present
invention onto the substrate has graininess-free
smooth, elegant, silky photoluminescence. Namely, the
pearlescent pigment according to the present invention
is formed of uniform particles, and therefore, is free
of a localized strong photoluminescent feel associated
with large particles and has continuous uniform
photoluminescence. Moreover, reflected light and
scattered light are well-balanced, thereby presenting
a smooth, elegant and silky feel.
A localized strong photoluminescent feel occurs
as a result of discontinuous specular reflection of
light, which has entered into the coat, by the
pearlescent pigment. A

difference between a localized strong photoluminescent feel
and a uniform photoluminescent feel can be quantitated by
measuring specular light intensities of a continuous surface
of a coat, statistically calculating the degrees of
scattering, that is, the dissemination of the specular light
intensities, and comparing their variances with each other.
No particular limitation is imposed on a photometer insofar
as it can measure the specular light intensities of the
continuous surface of the coat, but preferred is a photometer
which can measure specular light intensities while moving
a surface of a specimen in the direction of an X-axis on
the system. As a specific example, a three-dimensional
goniophotometer, "GP-200" (trade name; manufactured by
Murakami Color Research Laboratory Co., Ltd.) , or the like
can satisfy the above-mentioned measurement conditions.
A coat obtained from the coating composition according
to the present invention is provided with uniform,
graininess-free, smooth photoluminescence in visual
perception when its quantitated variance is 5 or smaller.
When its quantitated variance is greater than 5, on the other
hand, the coat is provided with glaring, grainy
photoluminescence in visual perception and cannot be
provided with uniform, graininess-free, smooth
photoluminescence in visual perception.
Light, which has entered into a coat, is separated
into specular light and scattered light, and is reflected

out of the coat. By balancing the specular light and the
scattered light with each other, a smooth, elegant, silky
color tone is obtained as visual perception. Light other
than specular light scatters in all directions, and exists
as three-dimensional scattered light. By
three-dimensionally capturing the specular light and the
three-dimensional scattered light, a perception close to
a state that they are viewed by the human can be reproduced.
The above-mentioned specular light can be measured by a
photometer shown in the system. No particular limitation
is imposed on the photometer insofar as it can measure the
reflection intensity at a desired elevation angle while
changing the receiving angle. Preferred is, however, a
three-dimensional goniophotometer which can continuously
measure reflected light. As a specific example, a
three-dimensional goniophotometer, "GP-200", or the like
can satisfy the above-mentioned measurement conditions.
A silky feel of a coat can be quantitated by measuring
the intensities of reflected light and scattered light at
a desired elevation angle with a three-dimensional
goniophotometer; measuring the reflection intensity at 45°
receiving angle, which is in the neighborhood of specular
light, and the reflection intensity at 0° receiving angle,
which corresponds to representative scattered angle; and
then determining the intensity ratio (45°/0°) of the
intensity at 45° to that at 0°. A coat obtained from the

coating composition according to the present invention is
provided with a smooth, elegant, silky photoluminescent feel
in visual perception when the (45°/0°) reflection intensity
ratio of the intensity at 45° receiving angle to that at
0° receiving angle is 100 or smaller. When the (45°/0°)
reflection intensity ratio of the intensity at 45° receiving
angle to that at 0° receiving angle is greater than 100,
on the other hand, no silky photoluminescent feel can be
obtained in visual perception.
The pearlescent pigment according to the present
invention has a small particle size and a large aspect ratio
so that, even when its content is high in a coat, it is oriented
and the surface smoothness is not lost. Because the
pearlescent pigment according to the present invention is
a pearlescent pigment making use of chemically-unif ormplate
particles produced by a hydrothermal process, it is also
unique in optical characteristics, is excellent in the
balance between reflected light and scattered light,
presents photoluminescence of a graininess-free, smooth,
elegant and silky feel, and can provide a coat of excellent
finish. In a coated color making use of a general pearlescent
pigment, on the other hand, the adoption of a small average
particle size results in non-uniform plate particles having
a small aspect ratio and the fine pigment is not oriented
in the resulting coat, leading to a drawback that the coat
is provided with significantly-reduced photoluminescence

or the smoothness of a clear finish is impaired. As an
optical characteristic, reflected light and scattered light
are poorly balanced so that an elegant and silky feel cannot
be obtained.
The pearlescent pigment according to the present
invention is extremely good, as it is, as a pigment for
ceramics, plastics, inks, toners, inkjet inks and cosmetics.
Further, depending on these applications, treatments are
applied the pearlescent pigment to impart water resistance,
weatherability, chemical resistance, color fastness and
high dispersibility as needed, and the thus-treated
pearlescent pigment is used for the respective applications.
Examples
The present invention will next be described in further
detail based on Examples and Comparative Examples, although
the present invention shall not be limited by the following
Examples. It is to be noted that in the following Examples
and Comparative Examples, the designations of "parts" and
"%" are on a weight basis.
[Production Examples of Pearlescent Pigments]
Example 1
"YFA-02050" (average particle size: 2.0 µm, aspect
ratio: 50, CV value: 45), plate alumina produced by a
hydrothermal process (hydrothermally produced alumina),
(20 g) was placed in a flask having an internal capacity

of 1 L. After the interior of the flask was depressurized
to 0.05 Torr, a radiofrequency voltage of 13.56 MHz was
applied under an oxygen atmosphere at 0.11 Torr by a powder
plasma treatment system ("PT-500", trade name; manufactured
by Samco International, Inc.) to conduct plasma treatment
at room temperature for 5 minutes (inputted electric power:
40 W) .
In another flask having an internal capacity of 1 L,
sodium sulfate (anhydride, 20 g) was added to desalted water
(300 mL) and was dissolved with stirring. To the resultant
solution, the plate alumina (20 g) which had been subjected
to plasma treatment as described above was added, followed
by dispersion with stirring. A solution (28 g) of titanium
chloride, the titanium concentration of which was 16.5%,
was charged into the dispersion. The thus-obtained mixture
was stirred, heated and then refluxed for 4 hours.
Subsequently, insoluble solid matter was collected by
filtration, washed with water, dried, and then subjected
to heat treatment at 700°C for 1 hour. Water was added to
the thus-obtained treated matter, and with stirring, the
free salts were caused to dissolve. Insoluble solid matter
was then collected by filtration, washed with water and dried
to obtain TiC>2-coated plate alumina (Example 1) .
Example 2
"YFA-07070" (average particle size: 7.0 µm, aspect
ratio: 70, CV value: 44), hydrothermally produced alumina,

(20 g) was placed in a flask having an internal capacity
of 1 L, and desalted water (300 mL) was added to disperse
the alumina with stirring. The dispersion was subjected
to ultrasonic treatment (inputted electric power: 180 W,
frequency: 20 KHz) at room temperature for 15 minutes by
an ultrasonic processor ("UD-200", trade name; manufactured
by Tomy Seiko Co., Ltd.). Subsequently, sodium sulfate
(anhydride, 20 g) was added and was dissolved with stirring.
A solution (20 g) of titanium chloride, the titanium
concentration of which was 16.5%, was charged into the
dispersion. The thus-obtained mixture was stirred, heated
and then refluxed for 4 hours. Insoluble solid matter was
then collected by filtration, washed with water, dried, and
then subjected to heat treatment at 700°C for 1 hour. Water
was added to the thus-obtained treated matter, and with
stirring, the free salts were caused to dissolve. Insoluble
solid matter was then collected by filtration, washed with
water and dried to obtain TiO2-coated plate alumina (Example
2).
Example 3
"YFA-05070" (average particle size: 5.0 µm, aspect
ratio: 70, CV value: 37), hydrothermally produced alumina,
(20 g) was placed in a flask having an internal capacity
of 1 L, and desalted water (300 mL) was added to disperse
the alumina with stirring. 35% hydrochloric acid (20 g)
was charged into the dispersion, followed by acid treatment

at room temperature for 15 minutes.
Sodium sulfate (anhydride, 40 g) was then added and
dissolved with stirring. A16.5%solution (30g) of titanium
chloride and a 50% solution (1.9 g) of stannic chloride were
charged into the dispersion. The thus-obtained mixture was
stirred, heated and then refluxed for 4 hours. Further,
insoluble solid matter was collected by filtration, washed
with water, dried, and then subjected to heat treatment at
800°C for 30 minutes. Water was added to the thus-obtained
treatedmatter, and with stirring, the free salts were caused
to dissolve. Insoluble solid matter was then collected by
filtration, washed with water and dried to obtain mixed
TiO2/SnO2-coated plate alumina (Example 3).
Example 4
"YFA-02050", hydrothermally produced alumina, (20 g)
was placed in a flask having an internal capacity of 1 L,
and desalted water (300 mL) was added to disperse the alumina
with stirring. Caustic soda (10 g) was added to the
dispersion, followedby alkali treatment at room temperature
for 15 minutes. Using 35% hydrochloric acid, the pH of the
mixture was then adjusted to pH 2, and sodium sulfate
(anhydride, 40 g) was added and then dissolved with stirring.
A solution (28 g) of titanium chloride, the titanium
concentration of which was 16.5%, and a 50% solution (1.0
g) of stannic chloride were charged into the dispersion.
The thus-obtained mixture was stirred, heated and then

refluxed for 4 hours.
1 Insoluble solid matter was then collected by
filtration, washed with water, dried, and then subjected
to heat treatment at 800°C for 30 minutes. Water was added
to the thus-obtained treated matter, and with stirring, the
free salts were caused to dissolve. Insoluble solid matter
was then collected by filtration, washed with water and dried
to obtain mixed TiO2/SnO2-coated plate alumina (Example 4) .
Example 5
"YFA-07070", hydrothermally produced alumina, (20 g)
was placed in a flask having an internal capacity of 1 L,
and desalted water (300 mL) was added to disperse the alumina
with stirring. The dispersion was subjected to ultrasonic
treatment (inputted electric power: 180 W, frequency: 20
KHz) at room temperature for 15 minutes by the ultrasonic
processor ("UD-200") . Nitric acid (20 g) was then charged,
followed by acid treatment at room temperature for 15
minutes.
A 50% solution (1. 0 g) of stannic chloride was charged
into the dispersion, and the resulting mixture was adjusted
to pH 6. 0 with a solution of sodium hydroxide. Subsequently,
insoluble solid matter was collected by filtration, washed
with water, and then dried to obtain SnO2-coated plate alumina.
Sodium sulfate (anhydride, 20 g) was dissolved in desalted
water (300 mL). In the thus-obtained solution, the
above-described SnO2-coated plate alumina which had been

crushed was added and dispersed. A solution (20 g) of
titanium chloride, the titanium concentration of which was
16.5%, was charged into the dispersion. The thus-obtained
mixture was stirred, heated and then refluxed for 4 hours.
Subsequently, insoluble solid matter was collected by
filtration, washed with water, dried, and then subjected
to heat treatment at 800°C for 1 hour. Water was added to
the thus-obtained treated matter, and with stirring, the
free salts were caused to dissolve. Insoluble solid matter
was then collected by filtration, washed with water and dried
to obtain stacked SnO2/TiO2-coated plate alumina (Example
5).
Example 6
"YFA-07070", hydrothermally produced alumina, (20 g)
was placed in a plastic bottle having an internal capacity
of 250 mL, and desalted water (100 mL) and 2-mm glass beads
(100g) were added, followed by shock treatment for 30 minutes
on a paint conditioner. Desalted water (200 mL) was then
added to the dispersion, and the resultant mixture was
stirred. A 50% solution (1.0 g) of stannic chloride was
charged into the dispersion, and the resulting mixture was
adjusted to pH 6.0 with a solution of sodium hydroxide.
Subsequently, insoluble solid matter was collected by
filtration, washed with water, and then dried to obtain
SnO2-coated plate alumina.
Sodium sulfate (anhydride, 20 g) was dissolved in

desalted water (300 mL) . In the thus-obtained solution,
the above-described SnO2-coated plate alumina which had been
crushed was added and dispersed. A solution (20 g) of
titanium chloride, the titanium concentration of which was
16.5%, was charged into the dispersion. The thus-obtained
mixture was stirred, heated and then refluxed for 4 hours.
Subsequently, insoluble solid matter was collected by
filtration, washed with water, dried, and then subjected
to heat treatment at 800°C for 1 hour. Water was added to
the thus-obtained treated matter, and with stirring, the
free salts were caused to dissolve. Insoluble solid matter
was then collected by filtration, washed with water and dried
to obtain stacked SnO2/TiO2-coated plate alumina (Example
6).
Example 7 & Example 8
"YFA-10030" (average particle size: 10.0 µm, aspect
ratio: 27, CV value: 50), hydrothermally produced alumina,
(20 g) was placed in a flask having an internal capacity
of 1 L. After the interior of the flask was depressurized
to 0.05 Torr, a radiofrequency voltage of 13.56 MHz was
applied under a water vapor atmosphere at 0.11 Torr by the
powder plasma treatment system ("PT-500") to conduct plasma
treatment at room temperature for 5 minutes (inputted
electric power: 40 W) . In another flask having an internal
capacity of 1 L, sodium sulfate (anhydride, 20 g) was added
to desalted water (300 mL) and was dissolved with stirring.

To the resultant solution, the plate alumina (20 g) which
had been subjected to plasma treatment as described above
was added, followed by dispersion with stirring.
On the side, a solution (50 g) of titanium chloride,
the titanium concentration of which was 16.5%, was dissolved
in desalted water (300 mL) to provide a solution A. After
the plate alumina dispersion was adjusted to pH 2.0 with
hydrochloric acid and was heated to 80°C, the solution A
was charged at a constant rate over 4 hours by a metering
pump until the substrate particles were provided with an
interference silver color. During the charging, a 10%
solution of sodium hydroxide was added to maintain the pH
of the dispersion at 2.0 and the temperature of the dispersion
was also maintained at 80°C.
After the solution A was charged until the substrate
particles were provided with the interference silver color,
the dispersion was heated for 1 hour under reflux.
Subsequently, insoluble solid matter was collected by
filtration, washed with water, dried, and then subjected
to heat treatment at 700°C for 1 hour. Water was added to
the thus-obtained treated matter, and with stirring, the
free salts were caused to dissolve. Insoluble solid matter
was then collected by filtration, washed with water and dried
to obtain TiO2-coated plate alumina (Example 7) . Further,
TiO2-coated plate alumina (Example 8) was obtained by
conducting similar processing as in Example 7 except that

the hydrothermally-produced alumina was changed to
"YFA-07070".
Comparative Example 1
Sodium sulfate (anhydride, 20 g) was added to desalted
water (300 mL) and was dissolved with stirring. To the
resultant solution, plate alumina A (average particle size:
55 µm, aspect ratio: 30, CV value: 95) (20 g) which was not
a hydrothermal product was added, followed by dispersion
with stirring. A solution (30 g) of titanium chloride, the
titanium concentration of which was 16.5%, was charged into
the dispersion. The thus-obtained mixture was stirred,
heated and then refluxed for 4 hours. Subsequently,
insoluble solid matter was collected by filtration, washed
with water, dried, and then subjected to heat treatment at
700°C for 1 hour. Water was added to the thus-obtained
treated matter, and with stirring, the free salts were caused
to dissolve. Insoluble solid matter was then collected by
filtration, washed with water and dried to obtain TiO2-coated
plate alumina (Comparative Example 1).
Comparative Example 2
Sodium sulfate (anhydride, 20 g) was added to desalted
water (300 mL) and was dissolved with stirring. To the
resultant solution, plate alumina B (average particle size:
10 µm, aspect ratio: 4.0, CV value: 60) (20 g) which was not
a hydrothermal product was added, followed by dispersion
with stirring. A solution (30 g) of titanium chloride, the

titanium concentration of which was 16.5%, was charged into
the dispersion. The thus-obtained mixture was stirred,
heated and then refluxed for 4 hours. Subsequently,
insoluble solid matter was collected by filtration, washed
with water, dried, and then subjected to heat treatment at
700°C for 1 hour. Water was added to the thus-obtained
treated matter, and with stirring, the free salts were caused
to dissolve. Insoluble solid matter was then collected by
filtration, washed with water and dried to obtain TiO2-coated
plate alumina (Comparative Example 2).
Comparative Example 3
TiO2-coated plate alumina (Comparative Example 3) was
obtained as in Example 1 except that the plate alumina
("YFA-02050") was used without the plasma treatment.
Comparative Example 4
TiO2-coated plate alumina (Comparative Example 4) was
obtained as in Example 2 except that the plate alumina
("YFA-07070") was used without the ultrasonic treatment.
Comparative Example 5
Mixed TiO2/SnO2-coated plate alumina (Comparative
Example 5) was obtained as in Example 3 except that the plate
alumina ("YFA-05070") was used without the acid treatment.
Comparative Example 6
Mixed TiO2/SnO2-coated plate alumina (Comparative
Example 6) was obtained as in Example 4 except that the plate
alumina ("YFA-02050") was used without the alkali

treatment.
Comparative Example 7
A commercial product composed of mica coated with
titanium oxide, "IRIODIN 225 WII" (trade name, product of
Merck Ltd., Japan) , was provided as Comparative Example 7.
The average particle sizes (µm), aspect ratios and
CV values of the substrate particles used in Examples 1-8
and Comparative Examples 1-6 and the particle sizes (nm)
and CV values of the metal oxides of the pearlescent pigments
obtained in Examples 1-8 and Comparative Examples 1-7 were
determined and presented together in Table 1. Each average
particle size and its corresponding aspect ratio were
calculated from 50 particles chosen at random from a
micrograph obtained by a scanning electron microscope
"ERA-8000" (manufactured by Elionix Inc.). Each CV value
is a value calculated as a statistical variation coefficient
based on a measurement performed by using "MULTISIZER3
COULTER COUNTER". The average particle size of each metal
oxide was calculated from 50 particles chosen at random from
a micrograph obtained by "FE-SEM S-4800".



Production Example of Automotive Paints
This example illustrates production and evaluation
examples upon using the pearlescent pigments of the present
invention as coating compositions. Evaluated formulation
examples are presented together in Table 2.



Mixtures of the formulations A-H were separately
subjected to simple dispersion processing in a sand mill.
Further, the resulting dispersion (50 parts, each) of the
formulations A-H and a mixture (50 parts) of the formulation
P were combined into intimate mixtures, respectively, to
obtain coating compositions A-H (Table 3) . Those coating
compositions each contained 8.55 parts of the pearlescent
pigment per 100 parts of the coating composition, and will
be referred to as "example paint A-H".
Mixtures of the formulations I-O were separately
subjected to simple dispersion processing in a sand mill.
Further, the resulting dispersion (50 parts, each) of the
formulations I-O and a mixture (50 parts) of the formulation
P were combined into intimate mixtures, respectively, to
obtain coating compositions I-O (Table 3). Those coating
compositions each contained 8.55 parts of the pearlescent
pigment per 100 parts of the coating composition, and will
be referred to as "comparative example paint I-O".
The example paints A-H, which contained the
pearlescent pigments obtained above in Examples 1-8,
respectively, and the comparative example paints I-O, which
contained the pearlescent pigments obtained above in
Comparative Examples 1-7, respectively, were applied on
black coat paper sheets by a bar coater (No. 6), respectively.
After dried at room temperature for 30 minutes, the paints
were baked and cured at 120°C for 30 minutes to prepare coated

specimens.
With respect to each of those coated specimens, the
uniformity of photoluminescence was evaluated visually and
was also measured by a three-dimensional goniophotometer
("GP-200") under the following conditions: reflectance
measurement, light source: A light, incident angle: 45°,
receiving angle: 45°, receiver slit: 0.4 mm square, moving
measurement over 40 mm along X-axis on specimen surface,
data sampling intervals: 0.1 mm; and the statistic variance
of the reflection intensity was calculated. The measuring
instrument is depicted in FIG. 1, one example of graphs
obtained by the measurements is shown in FIG. 2, and the
measurement results are presented in Table 3.
] Further, graininess-free, smooth conditions of each
coated specimen were evaluated visually and were also
measured by the three-dimensional goniophotometer
("GP-200") under the following conditions: reflectance
measurement, light source: A light, incident angle: 45°,
receiving angles: 45° and 0°, elevation angle: 2.5°; and the
reflection intensity ratio (45°/0°) was calculated. One
example of graphs obtained by the measurements is shown in
FIG. 3, and the measurement results are presented in Table
3.



Compared with the comparative example paints, the
example paints were lower in variance that indicates the
degree of scattering of photoluminescence and had uniform
photoluminescence as a whole. In addition, the example
paints were lower in reflection intensity ratio at receiving
angles 45° and 0° than the comparative example paints, and
also had a smooth and silky feel well-balanced in specular
light and scattered light.
Moreover, cosmetics, plastics, ceramics, inks,
toners and inkjet ink compositions which contain pearlescent
pigments of the present invention also have, as a whole,
both uniform photoluminescence and graininess-free, smooth
and elegant photoluminescence, that is, a silky feel, and
can fully satisfy artistry as required.
Industrial Applicability
The pearlescent pigment according to the present
invention has, as a whole, uniform photoluminescence and
a color tone having a graininess-free, smooth and elegant
photoluminescence, that is, a silky feel, and therefore,
is optimal for fields where such a color tone is required,
for example, for fields such as ceramics, resins, paints,
construction materials, inks, toners, inkjet ink
compositions and cosmetics and also for fields where
artistry is required.

Brief Description of the Drawings
[FIG. 1] A schematic depicting a measuring instrument.
[FIG. 2] A measurement graph of variations in reflection
intensity against the moving distance along an X-axis.
[FIG. 3] A measurement graph of variations in
three-dimensional gonioreflectance (elevation angle:
2.5°).
1: Light source
2: Specimen
3: Photoreceptor
4: X-axis
5: Y-axis
6: Z-axis
7: Incident angle
8: Receiving angle
9: Elevation angle
10: Comparative example paint 0
11: Comparative example paint C
12: Comparative example paint A

WE CLAIM;
[1] A pearlescent pigment comprising flaky alumina substrate particles
produced by a hydrothermal process and coat layers formed on said flaky
substrate particles and composed of at least one metal oxide comprising
at least a titanium oxide, wherein said metal oxide has an average
particle size of from 40 to 80 nm, a statistical variation coefficient of an
average particle size of said flaky alumina substrate particles is from 37
to 50, and a statistical variation coefficient of an average particle size of
said pearlescent pigment is from 40 to 53.
[2] The pearlescent pigment as claimed in claim 1, wherein said coat
layers of said metal oxide are mixed layers and/or stacked layers of two
or more metal oxides comprising at least said titanium oxide.
[3] The pearlescent pigment as claimed in claim 1, wherein said flaky
substrate particles have an average particle size of from 2.0 to 50 µm.
[4] The pearlescent pigment as claimed in claim 1, wherein said flaky
alumina substrate particles have an aspect ratio (particle size/thickness)
of from 5 to 500.
[5] The pearlescent pigment as claimed in claim 1, wherein a difference
between said statistical variation coefficient of an average particle size of
said pearlescent pigment and said statistical variation coefficient of an
average particle size of said flaky alumina substrate particles is from 1 to
3.

[6]A process for the production of a pearlescent pigment, which
comprises dispersing in water flaky alumina substrate particles produced
by a hydrothermal process and activated at surfaces thereof by at least
one method selected from plasma treatment, ultrasonic treatment, acid
treatment, alkali treatment, shock treatment or chemical etching
treatment, hydrolyzing in the resulting dispersion a metal salt
comprising at least a salt of titanium, allowing the resulting metal
hydroxide or metal oxide to deposit on surfaces of said alumina substrate
particles, and then subjecting the resulting deposit to heat treatment to
form, on said surfaces of said alumina substrate particles, metal oxide
coat layers having an average particle size of from 40 to 80 nm and said
pearlescent pigment having an average particle size a statistical variation
coefficient of which is from 40 to 53.
[7]A coating composition comprising a pearlescent pigment as claimed in
claim 1 and a film-forming resin.
[8]The coating composition as claimed in claim 7, further comprising a
liquid medium.
[9]A multilayered coat comprising a base coat layer formed from a coating
composition as claimed in claim 7 and a clear coat layer formed on said
base coat layer.
[10] The multilayered coat as claimed in claim 9, which has reflected
light intensities having a statistical variation coefficient of not greater
than 5 when measured by a photometer.

[11]The multilayered coat as claimed in claim 9, which has a 45°/0°
reflection intensity ratio of not greater than 100 when measured at an
elevation angle of not smaller than 0° by a goniophotometer.
[12]A multilayered coat comprising a colored first base coat layer formed
on a surface of a substrate, a second base coat layer formed from a
coating composition as claimed in claim 7 on said first base coat layer,
and a clear coat layer formed on said second base coat layer.
[13]A multilayered coat comprising a first coat layer formed on a surface
of a substrate and at least one second coat layer formed from a coating
composition as claimed in claim 7 on said first coat layer.
[14]A multilayered coat comprising at least two first coat layers formed
one over the other on a surface of a substrate and at least one second
coat layer formed from a coating composition as claimed in claim 7
between said at least two first coat layers.


This invention relates to a pearlescent pigment, which is
composed of flaky alumina substrate particles produced by a
hydrothermal process and coat layers formed on the flaky substrate
particles and composed of at least one metal oxide including at
least a titanium oxide. The metal oxide has an average particle
size of from 1 to 500 nm. According to this invention, it is possible
to provide a pearlescent pigment, which has wholly uniform
photoluminescence and an elegant and silky feel in combination
and can fully satisfy artistry as desired.

Documents:

01291-kolnp-2008-abstract.pdf

01291-kolnp-2008-claims.pdf

01291-kolnp-2008-correspondence others.pdf

01291-kolnp-2008-description complete.pdf

01291-kolnp-2008-drawings.pdf

01291-kolnp-2008-form 1.pdf

01291-kolnp-2008-form 2.pdf

01291-kolnp-2008-form 3.pdf

01291-kolnp-2008-form 5.pdf

01291-kolnp-2008-international publication.pdf

01291-kolnp-2008-others.pdf

01291-kolnp-2008-pct request form.pdf

1291-KOLNP-2008-(01-03-2012)-CORRESPONDENCE.pdf

1291-KOLNP-2008-ABSTRACT 1.1.pdf

1291-KOLNP-2008-AMANDED CLAIMS.pdf

1291-KOLNP-2008-ASSIGNMENT.pdf

1291-KOLNP-2008-CLAIMS 1.1.pdf

1291-KOLNP-2008-CORRESPONDENCE OTHERS 1.2.pdf

1291-KOLNP-2008-CORRESPONDENCE OTHERS 1.3.pdf

1291-KOLNP-2008-CORRESPONDENCE OTHERS 1.4.pdf

1291-KOLNP-2008-CORRESPONDENCE OTHERS 1.5.pdf

1291-KOLNP-2008-CORRESPONDENCE OTHERS-1.1.pdf

1291-KOLNP-2008-CORRESPONDENCE-1.6.pdf

1291-KOLNP-2008-CORRESPONDENCE.pdf

1291-KOLNP-2008-DESCRIPTION (COMPLETE) 1.1.pdf

1291-KOLNP-2008-DESCRIPTION COMPLETE 1.1.pdf

1291-KOLNP-2008-DESCRIPTION COMPLETE 1.2.pdf

1291-KOLNP-2008-DESCRIPTION COMPLETE.pdf

1291-KOLNP-2008-DRAWINGS 1.1.pdf

1291-KOLNP-2008-EXAMINATION REPORT REPLY RECIEVED.pdf

1291-KOLNP-2008-EXAMINATION REPORT.pdf

1291-KOLNP-2008-FORM 1-1.1.pdf

1291-KOLNP-2008-FORM 13.1.pdf

1291-kolnp-2008-form 13.pdf

1291-KOLNP-2008-FORM 18.1.pdf

1291-kolnp-2008-form 18.pdf

1291-KOLNP-2008-FORM 2-1.1.pdf

1291-KOLNP-2008-FORM 26.1.pdf

1291-KOLNP-2008-FORM 26.pdf

1291-KOLNP-2008-FORM 3-1.1.pdf

1291-KOLNP-2008-FORM 3.pdf

1291-KOLNP-2008-FORM 5.pdf

1291-KOLNP-2008-GRANTED-ABSTRACT.pdf

1291-KOLNP-2008-GRANTED-CLAIMS.pdf

1291-KOLNP-2008-GRANTED-DESCRIPTION (COMPLETE).pdf

1291-KOLNP-2008-GRANTED-DRAWINGS.pdf

1291-KOLNP-2008-GRANTED-FORM 1.pdf

1291-KOLNP-2008-GRANTED-FORM 2.pdf

1291-KOLNP-2008-GRANTED-SPECIFICATION.pdf

1291-KOLNP-2008-INTERNATIONAL PRELIMINARY REPORT.pdf

1291-KOLNP-2008-INTERNATIONAL SEARCH AUTHORITY REPORT-1.1.pdf

1291-KOLNP-2008-INTERNATIONAL SEARCH AUTHORITY REPORT.pdf

1291-KOLNP-2008-OTHERS 1.1.pdf

1291-KOLNP-2008-OTHERS 1.2.pdf

1291-KOLNP-2008-OTHERS.pdf

1291-KOLNP-2008-PETITION UNDER SECTION 8(1).pdf

1291-KOLNP-2008-REPLY TO EXAMINATION REPORT.pdf

1291-KOLNP-2008-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf

1291-KOLNP-2008-TRANSLATED COPY OF PRIORITY DOCUMENT1.1.pdf


Patent Number 252048
Indian Patent Application Number 1291/KOLNP/2008
PG Journal Number 17/2012
Publication Date 27-Apr-2012
Grant Date 23-Apr-2012
Date of Filing 31-Mar-2008
Name of Patentee DAINICHISEIKA COLOR & CHEMICALS MFG. CO. LTD.
Applicant Address 7-6, NIHONBASHI BAKURO-CHO 1-CHOME, CHUO-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 ABE TAKASHI C/O DAINICHISEIKA COLOR & CHEMICALS MFG. CO. LTD. 7-6, NIHONBASHI BAKURO-CHO 1-CHOME, CHUO-KU, TOKYO 103-8383
2 TAKAMI SHOTOKU C/O DAINICHISEIKA COLOR & CHEMICALS MFG. CO. LTD. 7-6, NIHONBASHI BAKURO-CHO 1-CHOME, CHUO-KU, TOKYO 103-8383
3 MATSUZAKI SATORU C/O DAINICHISEIKA COLOR & CHEMICALS MFG. CO. LTD. 7-6, NIHONBASHI BAKURO-CHO 1-CHOME, CHUO-KU, TOKYO 103-8383
PCT International Classification Number C09C 3/06, B05D 1/36
PCT International Application Number PCT/JP2006/319713
PCT International Filing date 2006-10-02
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2005-290148 2005-10-03 Japan