U.S. patent application number 11/566373 was filed with the patent office on 2007-06-28 for granulated colorant and related art.
Invention is credited to Akihiko Hayashi, Satonari Morikawa.
Application Number | 20070149658 11/566373 |
Document ID | / |
Family ID | 38194770 |
Filed Date | 2007-06-28 |
United States Patent
Application |
20070149658 |
Kind Code |
A1 |
Hayashi; Akihiko ; et
al. |
June 28, 2007 |
GRANULATED COLORANT AND RELATED ART
Abstract
A granulated colorant as a granulation product of a powdery
nigrosine dye, that has a bulk density of 0.4 to 0.7 g/ml and a
hardness of 1 to 20 N. A high-concentration master batch obtained
by blending a granulated colorant and a thermoplastic resin, which
comprises 25 to 100 parts by weight of a nigrosine dye in the
granulated colorant per 100 parts by weight of the thermoplastic
resin. A colored composition comprising a granulated colorant or
high-concentration master batch and a thermoplastic resin or
thermoplastic elastomer.
Inventors: |
Hayashi; Akihiko; (Osaka,
JP) ; Morikawa; Satonari; (Osaka, JP) |
Correspondence
Address: |
MCGLEW & TUTTLE, PC
P.O. BOX 9227, SCARBOROUGH STATION
SCARBOROUGH
NY
10510-9227
US
|
Family ID: |
38194770 |
Appl. No.: |
11/566373 |
Filed: |
December 4, 2006 |
Current U.S.
Class: |
524/89 ;
106/493 |
Current CPC
Class: |
C09B 67/0061 20130101;
C09B 67/0095 20130101; C09B 17/02 20130101; C08K 5/0041
20130101 |
Class at
Publication: |
524/89 ;
106/493 |
International
Class: |
C08K 5/34 20060101
C08K005/34; C04B 14/00 20060101 C04B014/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 27, 2005 |
JP |
JP2005-375545 |
Claims
1. Granulated colorant that is a granulation product of a powdery
nigrosine dye, wherein said granulation product has a bulk density
of 0.4 to 0.7 g/ml and a hardness of 1 to 20 N.
2. Granulated colorant of claim 1, wherein said powdery nigrosine
dye has an average particle diameter of 5 to 20 .mu.m.
3. Granulated colorant of claim 1, wherein said powdery nigrosine
dye has a specific surface area of 1.5 to 5.5 m.sup.2/g.
4. Granulated colorant of claim 1, wherein said nigrosine dye has
an Fe content of not more than 1% by weight.
5. Granulated colorant of claim 1, wherein said granulation product
is a cylindrical pellet 2 to 4 mm in diameter.
6. Granulated colorant claim 1, which is a dried product of a
granulated blend of 100 parts by weight of said nigrosine dye and
20 to 55 parts by weight of water.
7. Granulated colorant of claim 5, which is a dried product of a
granulated blend of 100 parts by weight of said nigrosine dye and
20 to 55 parts by weight of water.
8. Method of producing a granulated colorant, which comprises a
blending step for blending a powdery nigrosine dye and water, a
granulation step for obtaining a cylindrical granulation product
from the blend obtained in said blending step using an extrusion
granulating machine, and a drying step for drying the granulation
product obtained in said granulation step, wherein the granulation
product after drying by said drying step has a bulk density of 0.4
to 0.7 g/ml and a hardness of 1 to 20 N.
9. Method of producing a granulated colorant of claim 8, wherein
said blending step is a step for blending 100 parts by weight of
said nigrosine dye and 20 to 55 parts by weight of water using a
rotary mechanical mixer.
10. Method of producing a granulated colorant of claim 8, wherein
said granulation step is a step for obtaining a cylindrical
granulation product having a hardness after drying of 1 to 20 N by
granulating the blend obtained in said blending step, while
adjusting the pressure and/or revolution speed of the extrusion
granulating machine.
11. High-concentration master batch obtained by blending at least
the granulated colorant of claim 1 and a thermoplastic resin,
wherein 25 to 100 parts by weight of the nigrosine dye in said
granulated colorant is contained per 100 parts by weight of said
thermoplastic resin.
12. High-concentration master batch obtained by blending at least
the granulated colorant of claim 5 and a thermoplastic resin,
wherein 25 to 100 parts by weight of the nigrosine dye in said
granulated colorant is contained per 100 parts by weight of said
thermoplastic resin.
13. High-concentration master batch obtained by blending at least
the granulated colorant of claim 6 and a thermoplastic resin,
wherein 25 to 100 parts by weight of the nigrosine dye in said
granulated colorant is contained per 100 parts by weight of said
thermoplastic resin.
14. Method of producing a high-concentration master batch, which
comprises a blending step for blending a powdery nigrosine dye and
water, a granulation step for obtaining a cylindrical granulation
product from the blend obtained in said blending step using an
extrusion granulating machine, a drying step for drying the
granulation product obtained in said granulation step, and a
blend-molding step for blending at least the granulated colorant
obtained via said drying step and a thermoplastic resin, and
molding the blend into a master batch comprising 25 to 100 parts by
weight of the nigrosine dye in said granulated colorant per 100
parts by weight of said thermoplastic resin using an extruding
machine, wherein the granulation product after drying by said
drying step has a bulk density of 0.4 to 0.7 g/ml and a hardness of
1 to 20 N.
15. Colored composition obtained by blending at least the
granulated colorant of claim 1 and a thermoplastic resin or
thermoplastic elastomer, wherein 0.01 to 10 parts by weight of the
nigrosine dye in said granulated colorant is contained per 100
parts by weight of said thermoplastic resin or thermoplastic
elastomer.
16. Colored composition obtained by blending at least the
granulated colorant of claim 5 and a thermoplastic resin or
thermoplastic elastomer, wherein 0.01 to 10 parts by weight of the
nigrosine dye in said granulated colorant is contained per 100
parts by weight of said thermoplastic resin or thermoplastic
elastomer.
17. Colored composition obtained by blending at least the
granulated colorant of claim 6 and a thermoplastic resin or
thermoplastic elastomer, wherein 0.01 to 10 parts by weight of the
nigrosine dye in said granulated colorant is contained per 100
parts by weight of said thermoplastic resin or thermoplastic
elastomer.
18. Colored composition of claim 15, wherein said thermoplastic
resin is one or two or more synthetic resins selected from the
group consisting of polyamide resin, polyethylene terephthalate
resin, polybutylene terephthalate resin, and polyphenylene sulfide
resin.
19. Colored composition of claim 16, wherein said thermoplastic
resin is one or two or more synthetic resins selected from the
group consisting of polyamide resin, polyethylene terephthalate
resin, polybutylene terephthalate resin, and polyphenylene sulfide
resin.
20. Colored composition obtained by blending at least the
high-concentration master batch of claim 11 and a thermoplastic
resin or thermoplastic elastomer, wherein 0.01 to 10 parts by
weight of the nigro sine dye in said high-concentration master
batch is contained per 100 parts by weight of said thermoplastic
resin or thermoplastic elastomer.
21. Colored composition obtained by blending at least the
high-concentration master batch of claim 12 and a thermoplastic
resin or thermoplastic elastomer, wherein 0.01 to 10 parts by
weight of the nigrosine dye in said high-concentration master batch
is contained per 100 parts by weight of said thermoplastic resin or
thermoplastic elastomer.
22. Colored composition obtained by blending at least the
high-concentration master batch of claim 13 and a thermoplastic
resin or thermoplastic elastomer, wherein 0.01 to 10 parts by
weight of the nigro sine dye in said high-concentration master
batch is contained per 100 parts by weight of said thermoplastic
resin or thermoplastic elastomer.
23. Colored composition of claim 20, wherein said thermoplastic
resin is one or two or more synthetic resins selected from the
group consisting of polyamide resin, polyethylene terephthalate
resin, polybutylene terephthalate resin, and polyphenylene sulfide
resin.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a nigrosine granulated
colorant that is used to impart a color to thermoplastic resin and
for other purposes and has good handlability and good
dispersibility in resin, a method of producing the same, a
high-concentration master batch using the granulated colorant, a
method of producing the same, and a colored composition using the
granulated colorant or high-concentration master batch.
[0003] 2. Description of the Prior Art
[0004] Because thermoplastic resins have excellent mechanical and
chemical properties, they are widely used in plastic molding
products in the field of components for automobiles,
electric/electronic products and the like, and the demands are
increasing in the field of engineering plastics. Additionally,
thermoplastic resins are fitted to a broad range of industrial
applications by formulating fibrous reinforcing material in
thermoplastic resins to improve the heat resistance and chemical
resistance, and to confer mechanical properties matching with
various applications. In particular, in the field of automobiles,
bicycles and the like, there has been a remarkable trend toward
replacement of conventional metal parts with fiber-reinforced
thermoplastic resin parts, for the purpose of weight reduction,
manufacturing process rationalization and corrosion prevention.
[0005] Thermoplastic resins are colored for decoration, color
identification, improvement of light fastness of molded products,
content protection and shading and for other purposes, with black
coloring being the most important in the industry. Traditionally,
various inorganic pigments and organic dyes/pigments, such as
carbon black, black metal complex dyes, nigrosine dyes and perinone
black, have been used to impart a black color to thermoplastic
resins. Of these, nigrosine dyes enable imparting vividly black
colors with excellent appearance and surface gloss, and hence have
been widely used to impart a color to thermoplastic resins with
various attempts.
[0006] Specifically, such attempts include a molded blend wherein a
polyamide resin is colored with carbon black and nigrosine
(Japanese Patent Examined Publication No. SHO-60-43379), a glass
fiber-reinforced black polyamide resin composition comprising a
polyamide resin, a surface-treated glass fiber and an azine dye
(Japanese Patent Laid-Open No. HEI-6-128479), a black polyamide
resin composition wherein a polyamide resin is colored with a
nigrosine dye, aniline black and carbon black (Japanese Patent
Laid-Open No. HEI-9-255869), a polyester resin composition wherein
a polyester resin is colored with a dye having a phenazine ring
(nigrosine dye) (Japanese Patent Laid-Open No. HEI-10-292098), a
colored thermoplastic resin composition wherein a crystalline resin
(e.g., polyamide resin, polybutylene terephthalate resin, etc.) is
colored with a modified nigrosine dye and related art (Domestic
Re-publication of PCT International Publication No.
WO00/26302).
[0007] Generally, in coloring a fiber-reinforced thermoplastic
resin, a problem arises that the colorant (particularly black
pigment) is difficult to sufficiently uniformly disperse in the
resin even with a long time of kneading, because a fibrous
reinforcing material is present in the resin. In particular, the
spoilage of the gloss, appearance and the like of the colored
molded product by the fibrous reinforcing material floating on the
surface of the molded product during molding has been problematic.
In this regard, there is room for improving colored resin
compositions comprising a nigrosine dye.
[0008] Additionally, because nigrosine dyes are powders having
small values of bulk density and average particle diameter,
nigrosine dye dusting can occur during dye charge, blending with
the resin, and the like, posing the problem with work environment
deterioration, so that special measures have been required to
prevent the dusting.
[0009] Furthermore, a master batch of nigrosine dye is produced by,
for example, blending a resin and a dye in a mechanical mixer such
as a Henschel mixer or blender, and extrusion-molding the blend
using a single-screw extruder or twin-screw extruder into a resin
pellet. In this manufacturing process, however, drawbacks,
including phenomena such as bridging in the hopper and unsmooth
feed of raw materials (resin, nigrosine dye, etc.) into the screw
during extrusion kneading due to fluidity differences between
nigrosine dye and resin, and a lack of fluidity due to dye wetting
and adhesion as a result of dye exposure to the gas from the resin,
additives and the like in the extrusion process, have been likely.
As such, nigrosine dyes are extremely poorly handlable; it has been
difficult to fill a nigrosine dye in a master batch at high
concentrations.
[0010] The present invention has been developed in view of the
aforementioned problems in the prior art, and is intended to
provide a colorant that modifies the dusting of nigrosine dye,
ensures good handlability in transportation, packaging, charge and
the like, is unlikely to lose shape during the handling, and
enables good and uniform dispersion of a nigrosine dye in a resin
by blending or kneading with the resin in various forms of color
imparting, including coloring a resin containing a fibrous
reinforcing material and high-concentration resin coloring, a
method of producing the same, a master batch that does not exhibit
bridging or separation of a colorant from resin during blending or
kneading said colorant with the resin during production and
uniformly contains a high concentration of nigrosine dye, a method
of producing the same, and a colored composition that uniformly
contains a nigrosine dye, has a well controlled crystallization
temperature with nigrosine dye, enables easier commercialization of
products that must meet the rigorous demands for precision molding
and dimensional accuracy, confers good appearance and surface gloss
to molded products, has excellent light fastness, undergoes little
color changes over time, and has good mechanical properties.
SUMMARY OF THE INVENTION
[0011] Accomplishing the above-described object, the granulated
colorant of the present invention is a granulated colorant that is
a granulation product of a powdery nigrosine dye, wherein the
granulation product has a bulk density of 0.4 to 0.7 g/ml and a
hardness of 1 to 20 N.
[0012] The aforementioned hardness (hardness determined using a
KIYA type hardness meter) is preferably 2 to 15 N, more preferably
3 to 12 N. By rendering the granulated colorant to have such a
hardness, both good handlability during transportation and the like
and good dispersibility of nigrosine dye in resin can be achieved
at the same time.
[0013] The above-described powdery nigrosine dye in the granulated
colorant of the present invention preferably has an average
particle diameter of 5 to 20 .mu.m. The specific surface area of
the powdery nigrosine dye is preferably 1.5 to 5.5 m.sup.2/g. The
Fe content of the above-described nigrosine dye in the granulated
colorant of the present invention is preferably not more than 1% by
weight.
[0014] The above-described granulation product of the present
invention can be cylindrical. Preferably, the above-described
granulation product of the present invention is a cylindrical
pellet having a diameter of 2 to 4 mm. More preferably, the
diameter is 2.5 to 3.5 mm. The length of the cylindrical pellet is
preferably 7 to 12 mm. More preferably, the length is 8 to 10
mm.
[0015] The problems of the present invention are well solved by a
granulated colorant in the form of such pellets wherein the
granulation product has a bulk density of 0.4 to 0.7 g/ml and a
hardness of 1 to 20 N.
[0016] The above-described granulated colorant is preferably a
dried product of a granulated blend of 100 parts by weight of a
nigrosine dye and 20 to 55 parts by weight of water.
[0017] The method of producing a granulated colorant of the present
invention comprises a blending step for blending a powdery
nigrosine dye and water, a granulation step for obtaining a
cylindrical granulation product from the blend obtained in said
blending step using an extrusion granulating machine, and a drying
step for drying the granulation product obtained in said
granulation step, wherein the granulation product after drying by
said drying step has a bulk density of 0.4 to 0.7 g/ml and a
hardness of 1 to 20 N. The aforementioned hardness is preferably 2
to 15 N, more preferably 3 to 12 N.
[0018] The blending step in the above-described method of producing
a granulated colorant is preferably a step for blending 100 parts
by weight of a nigrosine dye and 20 to 55 parts by weight of water
using a rotary mechanical mixer. The granulation step in the
above-described method of producing a granulated colorant is
preferably a step for obtaining a cylindrical granulation product
having a hardness after drying of 1.0 to 20 N, preferably 2 to 15
N, more preferably 3 to 12 N by granulating the blend obtained in
said blending step, while adjusting the pressure and/or revolution
speed of the extrusion granulating machine.
[0019] The high-concentration master batch of the present invention
is a master batch obtained by blending at least the above-described
granulated colorant and a thermoplastic resin, wherein 25 to 100
parts by weight of a nigrosine dye in the aforementioned granulated
colorant is contained per 100 parts by weight of the aforementioned
thermoplastic resin.
[0020] The method of producing a high-concentration master batch of
the present invention comprises a blending step for blending a
powdery nigrosine dye and water, a granulation step for obtaining a
cylindrical granulation product from the blend obtained in said
blending step using an extrusion granulating machine, a drying step
for drying the granulation product obtained in said granulation
step, and a blend-molding step for blending at least the granulated
colorant obtained via said drying step and a thermoplastic resin,
and molding the blend into a master batch comprising 25 to 100
parts by weight of the nigrosine dye in said granulated colorant
per 100 parts by weight of said thermoplastic resin using an
extruding machine, wherein the granulation product after drying by
said drying step has a bulk density of 0.4 to 0.7 g/ml and a
hardness of 1 to 20 N. The aforementioned hardness is preferably 2
to 15 N, more preferably 3 to 12 N.
[0021] The colored composition of the present invention is a
colored composition obtained by blending at least the granulated
colorant of the present invention or the high-concentration master
batch of the present inventionl, and a thermoplastic resin or
thermoplastic elastomer, wherein 0.01 to 10 parts by weight of the
nigrosine dye in said granulated colorant or high-concentration
master batch is contained per 100 parts by weight of said
thermoplastic resin or thermoplastic elastomer.
[0022] The present inventors found that it is possible to prevent
nigrosine dye dusting, to ensure shape stability for the
granulation product during handling in transportation, packaging,
charge and the like, and to prevent drawbacks, including phenomena
such as bridging in the hopper and unsmooth feed of raw materials
(resin, nigrosine dye, etc.) into the screw, due to fluidity
differences of a colorant from the resin, and a lack of fluidity
due to dye wetting by the gas from the extruding machine, during
blending or kneading with the resin during production of a master
batch or colored composition, by granulating a powdery nigrosine
dye into a granulation product (preferably into a cylindrical form)
while adjusting the hardness and bulk density, and developed the
present invention.
[0023] The granulated colorant of the present invention modifies
nigrosine dye dusting, ensures good handlability in transportation,
packaging, charge and the like, is unlikely to lose shape during
the handling, and prevents bridging and separation from the resin
in the screw feeder and the like or ununiform dispersion in the
resin to ensure good fluidity and stable dispersibility and enable
good dispersion of the nigrosine dye in the resin during blending
or kneading with the resin in various forms of color imparting to a
resin, including coloring a resin containing a fibrous reinforcing
material and high-concentration resin coloring.
[0024] The high-concentration master batch of the present
invention, which uniformly comprises at a high concentration a
nigrosine dye, can be produced without bridging or separation of
colorant from the resin during blending or kneading the granulated
colorant of the present invention with the resin in the
production.
[0025] The colored composition of the present invention uniformly
comprises a nigrosine dye, has a well controlled crystallization
temperature with nigrosine dye, enables easier commercialization of
products that must meet the rigorous demands for precision molding
and dimensional accuracy, confers good appearance and surface gloss
to molded products, has excellent light fastness, undergoes little
color changes over time, has good mechanical properties, and is
best suited as a material for sophisticated molding pro ducts.
[0026] The granulated colorant of the present invention modifies
nigrosine dye dusting, ensures increased safety for the work
environment, and permits easier transportation, packaging and
charge, thus ensuring much better handlability compared with
powdery nigrosine. The granulated colorant of the present invention
also exhibits good fluidity and stable dispersibility in resin, and
is suitably used to produce a high-concentration master batch and
an ordinary-concentration resin composition.
[0027] Also, because the nigrosine dye in the granulated colorant
of the present invention functions as a positively charged charge
control agent, it enables suitable use of the granulated colorant
of the present invention in manufacturing a toner for developing
electrostatic images utilizing the good dispersibility thereof in
resin.
[0028] Furthermore, because the granulated colorant of the present
invention functions as a black oil-soluble nigrosine dye, it can be
suitably used in solution in a solvent and the like in recording
liquids, writing instrument ink and the like, and can also be used
as a colorant for leather and the like.
[0029] Because the colored composition of the present invention has
low anisotropy and is excellent in heat resistance, sliding quality
and dimensional accuracy, is excellent in mechanical properties,
particularly in impact strength, and confers excellent surface
appearance to molded products, it is useful as an engineering
plastic in, for example, electric/electronic components such as
connectors, sockets, relay case switches, variable condenser cases,
optical pickups, plugs, printed substrates, tuners, speakers,
microphones, headphones, FDD chassis, motor brush holders, parabola
antennas, computer-related components, VTR components, television
components, irons, hair dryers, electric rice cooker components,
microwave oven components, acoustic components, audio/laser discs,
compact discs, lighting components, refrigerator components, air
conditioner components, and word processor components; office
machine components such as typewriter parts; telephone-related
components, facsimile-related components, copying machine-related
components, washing devices, motor components, lighters,
machine-related components; optical equipment/precision
equipment-related components such as microscopes, binoculars,
cameras, and watches and clocks; automobile/vehicle-related
components such as alternator connectors, IC regulators, various
valves such as exhaust gas valves, various fuel supply/exhaust/air
intake system pipes, air intake nozzles, intake manifolds, fuel
pumps, engine coolant joints, carburetor main bodies, carburetor
spencers, air flowmeters, starter switches, transmission wire
harnesses, window washer nozzles, air conditioner panel switch
substrates, fuse connectors, horn terminals, electric appliances
insulation panels, and igniter cases; and various other
applications.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] FIG. 1 is a graph showing the results of a fluidity test
using a powder fluidity analyzer.
[0031] FIG. 2 is a graph showing the results of a fluidity test
using a simple fluidity tester.
DETAILED DESCRIPTION OF THE INVENTION
Nigrosine Dyes Used in the Present Invention
[0032] As the nigrosine dye which is a raw material for the
granulated colorant (granulation product of powdery nigrosine dye)
of the present invention, the black azine-series condensed mixture
described as C.I. SOLVENT BLACK 5, C.I. SOLVENT BLACK 5:1, C.I.
SOLVENT BLACK 5:2 and C.I. SOLVENT BLACK 7 in the COLOR INDEX can
be suitably used (in this specification, C.I. Generic Names are
described according to the third edition of the COLOUR INDEX).
Synthesis of the nigrosine dye can be achieved by, for example,
oxidizing and dehydrate-condensing aniline, aniline hydrochloride
and nitrobenzene in the presence of iron chloride at a reaction
temperature of 160 to 180.degree. C. Nigrosine is produced as a
mixture of various different compounds depending on reaction
conditions, raw materials charged, charge ratio and the like; for
example, it is postulated that nigrosine may be a mixture of
various triphenazineoxazines represented by the following Formula
(I) or (II) and phenazineazine compounds represented by Formulas
(III) to (VI).
##STR00001##
[In Formulas (I) to (VI), X.sup.- represents an anion, for example,
Cl.sup.- or OH.sup.-.]
[0033] Examples of commercially available nigrosine dyes include
Spirit Black SB, Spirit Black SSBB, Spirit Black AB (all are
categorized under C.I. SOLVENT BLACK 5); Nigrosine Base SA,
Nigrosine Base SAP, Nigrosine Base SAP-L, Nigrosine Base EE,
Nigrosine Base EE-L, Nigrosine Base EX, Nigrosine Base EX-BP (all
are categorized under C.I. SOLVENT BLACK 7) and the like [all are
product names of nigrosines manufactured by Orient Chemical
Industries, Ltd.]. From among these nigrosine dyes, desired one
meeting the requirements can be selected.
[0034] The aforementioned nigrosine dye can, for example, be one
having an average particle diameter of 5 to 30 .mu.m. Preferably,
the average particle diameter is 5 to 20 .mu.m, more preferably 5
to 15 .mu.m. By using such a nigrosine dye, it is possible to
obtain a granulation product having a hardness that meets the
requirement of the present invention at high yield.
[0035] As an example of the method of determining the average
particle diameter in this case, a method can be mentioned that
comprises adding water to the dye, previously mixed with an
activator, and performing a determination under particular
conditions. Examples of useful analyzers include a precision
distribution analyzer [Multilyzer III (product name): manufactured
by Beckman Coulter, K.K.], a laser diffraction/scattering particle
size distribution tester [product number: LA-910, manufactured by
Horiba Ltd.] and the like.
[0036] To obtain a granulated colorant of good quality, it is
preferable that the aforementioned nigrosine dye have a specific
surface area of 1.5 to 5.5 m.sup.2/g, as determined by the BET
method. More preferably, the specific surface area is 2.5 to 4.0
m.sup.2/g. When a nigrosine dye is blended with a binder and
granulated by compression extrusion and the like using a
granulating machine, it is possible to obtain a granulation product
at good yield by appropriately blending a nigrosine dye having a
specific surface area of 1.5 to 5.5 m.sup.2/g, as determined by the
BET method, with a binder (e.g., water); the granulation product
obtained is capable of well exhibiting the effect of the present
invention.
[0037] Furthermore, it is important that the nigrosine dye in the
granulated colorant of the present invention should be a nigrosine
dye having an Fe content of not more than 1.0% by weight. More
preferably, the Fe content is not more than 8000 ppm. The
dispersibility and compatibility of the nigrosine dye for the resin
are thereby improved, so that a particularly good
high-concentration master batch is obtained. The Fe content in such
a nigrosine can be determined by atomic absorptiometry.
[0038] A treatment to reduce the Fe content of such a nigrosine
can, for example, be performed as described below. Specifically,
the Fe content in the nigrosine dye after drying can be reduced or
adjusted by removing the iron hydroxide separating during the base
treatment of nigrosine with the addition of sodium hydroxide to the
nigrosine condensation product obtained by condensing aniline and
aniline hydrochloride with nitrobenzene in the presence of ferric
chloride, using a centrifuge such as a screw decanter or a
Sharpless centrifuge.
[0039] A particularly preferable nigrosine dye is a nigrosine dye
having low contents of the reaction starting material aniline and
the reaction solvent nitrobenzene. Specifically, a nigrosine dye
having an aniline content of not more than 2000 ppm, preferably not
more than 1000 ppm (more preferably not more than 700 ppm), and a
nitrobenzene content of not more than 500 ppm (more preferably not
more than 300 ppm) can be mentioned. As examples of the method of
purifying such a nigrosine dye, the following methods (1) to (6)
can be mentioned. [0040] (1) A method of adding a solvent having a
boiling point of 100 to 230.degree. C., and removing the aniline
and/or nitrobenzene along with the solvent under heating and
reduced pressure. Examples of such solvents include xylene,
toluene, ethylbenzene, mesitylene, decahydronaphthalene, dibutyl
ether, ethylene glycol and the like. [0041] (2) A method of washing
the nigrosine dye with a solution in which aniline and/or
nitrobenzene is soluble, and removing the solvent. As examples of
such a solution, organic solvents (e.g., alcohols, glycols),
aqueous solutions, mixed solutions of organic solvents and water,
or acidic solutions of these solvents or solutions can be
mentioned. [0042] (3) A method of removing the aniline and/or
nitrobenzene simply by heating at reduced pressure. [0043] (4) A
method of thermal distillation. [0044] (5) A method of distillation
such as steam distillation. [0045] (6) A method of oxidation using
oxygen, ozone, bleaching powder or another oxidant.
Nigrosine Dye Granulation Process for Obtaining a Granulated
Colorant
[0046] The granulated colorant of the present invention is a
granulation product of a powdery nigrosine dye, which granulation
product has a bulk density of 0.4 to 0.7 g/ml and a hardness of 1
to 20 N, preferably 2 to 15 N, and more preferably 3 to 12 N.
[0047] When using the granulated colorant of the present invention,
it can be effective even if a mixture of the granulated colorant of
the present invention and an ungranulated nigrosine dye (e.g.,
powdery nigrosine dye) is used as the colorant. For example, when
the granulated colorant of the present invention accounts for at
least 70% by weight (preferably not less than 75% by weight, more
preferably not less than 80% by weight) of the nigrosine dye used
as the colorant, it can be fully effective.
[0048] As a suitable shape of the granulation product, a
cylindrical pellet having a diameter (o) of 2 to 4 mm can be
mentioned. A preferable length thereof is 7 to 12 mm.
[0049] In the present invention, a granulation product having a
cross-section not completely circular but with an irregularity of
not more than 20% of the diameter, a granulation product having a
nearly circular cross-section, such as an ellipsoidal or deformed
circle, and/or a granulation product having a cross-section the
shape and dimensions of which are not constant in the axial
direction, can also be deemed a cylindrical granulation
product.
[0050] Regarding the shape of the granulation product, a
non-cylindrical column is acceptable. For example, the granulation
product may be a non-cylindrical columnar pellet of 2 to 4 mm (more
preferably 2.5 to 3.5 mm) in height and width and 3 to 10 mm (more
preferably 8 to 10 mm) in length.
[0051] Although the method of granulation to obtain the granulated
colorant of the present invention is not subject to limitation,
extrusion granulation can be mentioned as a suitably used method.
As the extrusion granulating machine for performing extrusion
granulation, the forward pressing screw type, lateral pressing
screw type, forward pressing ram type, lateral pressing roll type,
downward pressing roll type, lateral pressing basket type, and
downward pressing screen type and the like can be mentioned, with
preference given to, for example, a downward pressing roll type
extrusion granulating machine.
[0052] The method of producing the granulated colorant of the
present invention comprises a blending step for blending a powdery
nigrosine dye and water, a granulation step for obtaining a
cylindrical granulation product from the blend obtained in the
aforementioned blending step using an extrusion granulating
machine, and a drying step for drying the granulation product
obtained in the aforementioned granulation step, wherein the
granulation product after drying by the aforementioned drying step
has a bulk density of 0.4 to 0.7 g/ml, and a hardness of 1 to 20 N,
preferably 2 to 15 N, and more preferably 3 to 12 N. The blending
step is preferably a step for blending 100 parts by weight of a
nigrosine dye and 20 to 55 parts by weight of water (preferably 30
to 45 parts by weight of water) using a rotary mechanical mixer.
The granulation step is preferably operated using a granulating
machine such as an extrusion granulating machine.
[0053] Hardness is important to the granulated colorant of the
present invention. By appropriately adjusting the hardness thereof,
the granulated colorant of the present invention is obtained with
two characteristics: a loss of shape is unlikely and stability and
ease of handling are maintained during transportation, charge and
the like, and the nigrosine is well dispersible in the resin during
blending or kneading with the resin in coloring the resin at the
time of resin molding and the like. The hardness of the granulated
colorant (i.e., the granulation product after the granulation
drying step) is 1 to 20 N. Preferably, the hardness is 2 to 15 N,
more preferably 3 to 12 N.
[0054] Adjustment of the hardness of the granulated colorant of the
present invention can be achieved by, for example, adjusting the
granulation pressure and/or revolution speed of the extrusion
granulating machine in the granulation step for granulating the
blend obtained in the blending step using the extrusion granulating
machine. In addition to this adjustment of the hardness in the
granulation step, a granulation product with an appropriately
adjusted hardness can be obtained efficiently by adjusting the
hardness of the blend after the blending step for blending a nigro
sine dye and a binder preferably to 1 to 20 N, more preferably to 2
to 15 N.
[0055] In addition to water, non-water binders can be used as the
binder for obtaining the granulated colorant of the present
invention. Examples of the binder other than water alone include a
surfactant, wax, metal soap, polyethylene glycol, or a mixture of
any of these and water.
[0056] Examples of the aforementioned surfactant include a
non-ionic surfactant, anionic surfactant, and cationic surfactant
can be used.
[0057] Examples of the aforementioned non-ionic surfactant include
polyoxyalkylene alkyl ether, polyoxyalkylene lauryl ether,
polyoxyethylene oleyl ether, polyoxyethylene alkylphenyl ether,
polyoxyethylene glycol fatty acid ester, alkylalkanolamide,
polyoxyethylene polyoxypropylene glycol and the like.
[0058] Examples of the aforementioned anionic surfactant include a
benzenesulfonic acid optionally having 0 to 2 alkyl groups or
hydroxyl groups or a salt thereof, an alkyldiphenyl ether sulfonic
acid or a salt thereof, .alpha.-olefinsulfonic acid or a salt
thereof, polystyrenesulfonic acid or a salt thereof, an alkyl
sulfuric acid ester or a salt thereof, a polyoxyethylene alkyl
ether sulfuric acid ester or a salt thereof, a polyoxyethylene
alkylphenyl ether sulfuric acid ester or a salt thereof, an alkyl
ether phosphoric acid ester salt, an alkylphosphoric acid ester and
the like.
[0059] Examples of the aforementioned cationic surfactant include
lauryl trimethyl ammonium chloride, didecyl dimethyl ammonium
chloride and the like.
[0060] Examples of the aforementioned wax include what are
generally known as polyethylene wax, polypropylene wax, synthetic
wax, paraffin wax, micro wax, montan wax, ester wax, ceresin wax,
and chloride wax. Preferably, the aforementioned wax is a
polyethylene wax having a molecular weight of 500 to 10000.
[0061] Examples of the aforementioned metal soap include salts of
stearic acid, palmitic acid, lauric acid, octylic acid, ricinoleic
acid, oleic acid, naphthenic acid and the like with metals such as
magnesium, zinc, calcium, aluminum, potassium, barium, lithium,
cadmium, strontium, and tin.
[0062] In addition to a nigrosine dye, the granulated colorant,
high-concentration master batch or colored composition in the
present invention may comprise a known dye or pigment within the
bounds of the purpose of the present invention. Black dyes/pigments
include carbon black and aniline black. Auxiliary colorants and the
like for color adjustment include various organic dyes/pigments
such as of the azo series, azo series metal complex, azomethine
series, anthraquinone series, quinacridone series, dioxazine
series, diketopyrrolopyrrole series, anthrapyridone series,
isoindolinone series, indanethrone series, perinone series,
perylene series, indigo series, thioindigo series, quinophthalone
series, quinoline series, and triphenylmethane series.
[0063] In addition to the above-described ingredients, the
granulated colorant may be supplemented as appropriate with
commonly used heat stabilizers, antioxidants, ultraviolet
absorbents, fillers and the like
High-concentration Master Batch Production Process Using the
Granulated Colorant
[0064] The high-concentration master batch of the present invention
is a master batch obtained by blending at least the above-described
granulated colorant of the present invention and a thermoplastic
resin, which comprises 25 to 100 parts by weight (more preferably
60 to 100 parts by weight) of a nigrosine dye in the granulated
colorant per 100 parts by weight of the thermoplastic resin. The
high-concentration master batch of the present invention can also
be obtained using a mixture of the granulated colorant of the
present invention and an ungranulated nigrosine dye (e.g., powdery
nigrosine dye) as the colorant. For example, when the granulated
colorant of the present invention accounts for at least 70% by
weight (preferably not less than 75% by weight, more preferably not
less than 80% by weight) of the nigrosine dye used as the colorant,
the high-concentration master batch of the present invention
uniformly comprising a nigrosine dye at a high concentration can be
obtained.
[0065] The effect of the high-concentration master batch of the
present invention is remarkable particularly when the nigrosine dye
concentration is high. Hence, the high-concentration master batch
of the present invention permits easy and sure obtainment of a
master batch uniformly comprising a nigrosine dye at a high
concentration (e.g., not less than 40% by weight). In the case of a
conventional master batch wherein a powdery nigrosine dye is
dry-blended, the nigrosine dye concentration is about 20 to 40% by
weight, the upper limit being about 40% by weight. However, a
high-concentration master batch using the granulated colorant of
the present invention can be made to have a nigrosine dye
concentration of 40 to 50% by weight or more, and prevents bridging
and the like by the nigrosine dye in the hopper in the master batch
production step.
[0066] The high-concentration master batch of the present invention
is obtained by a production method comprising a blending step for
blending a powdery nigrosine dye and water, a granulation step for
obtaining a cylindrical granulation product from the blend obtained
in the aforementioned blending step using an extrusion granulating
machine, a drying step for drying the granulation product obtained
in the aforementioned granulation step (wherein the granulation
product after drying by the drying step has a bulk density of 0.4
to 0.7 g/ml and a hardness of 1 to 20 N, preferably 2 to 15 N, more
preferably 3 to 12 N), and a blend-molding step for blending at
least the granulated colorant obtained via the aforementioned
drying step and a thermoplastic resin, and molding the blend into a
master batch comprising 25 to 100 parts by weight of a nigrosine
dye in the aforementioned granulated colorant per 100 parts by
weight of the aforementioned thermoplastic resin using an extruding
machine (e.g., master batch in the form of resin pellet).
Specifically, a master batch in the form of pellet can be obtained
by, for example, blending the granulated colorant of the present
invention and a resin, and if necessary other materials, as
uniformly as possible, by an optionally chosen method of blending,
homogenizing this blend by kneading in a molten state using a
heated extruding machine, then extruding it into wire shape and
cutting the wire to a desired length.
[0067] As the aforementioned thermoplastic resin, polyamide (nylon)
resin, polyethylene resin, polypropylene resin, polyethylene
terephthalate resin, polybutylene terephthalate resin,
polyphenylene sulfide resin, polycarbonate resin, polysulfone resin
and polyether ether ketone resin and the like can be mentioned. The
high-concentration master batch of the present invention can also
be formulated with various additives (e.g., auxiliary colorant, wax
etc.) as necessary.
Colored Composition Using the Granulated Colorant or Master
Batch
[0068] The colored composition of the present invention is a
colored composition obtained by blending at least the granulated
colorant of the present invention or the high-concentration master
batch of the present invention and a thermoplastic resin or
thermoplastic elastomer, wherein 0.01 to 10 parts by weight
(preferably 0.01 to 5 parts by weight) of a nigrosine dye in the
aforementioned granulated colorant or high-concentration master
batch is contained per 100 parts by weight of the aforementioned
thermoplastic resin or thermoplastic elastomer. An ungranulated
nigrosine dye (e.g., powdery nigrosine dye) can be used as a
colorant along with a granulated colorant, as described above.
[0069] Examples of the thermoplastic resin in the colored
composition of the present invention include polyamide (nylon)
resin, polyethylene resin, polypropylene resin, polyethylene
terephthalate resin, polybutylene terephthalate resin,
polyphenylene sulfide resin, polycarbonate resin, polysulfone
resin, polyether ether ketone resin and the like. These
thermoplastic resins can be used alone or in combination of two or
more kinds. A copolymer or mixture based mainly on these polymers;
or a polymer alloy comprising these thermoplastic resins at not
less than 10% by weight, and the like can also be used.
[0070] A preferable thermoplastic resin is 1 or 2 or more synthetic
resins selected from the group consisting of polyamide resin,
polyethylene terephthalate resin, polybutylene terephthalate resin,
and polyphenylene sulfide resin.
[0071] Examples of the thermoplastic elastomer in the colored
composition of the present invention include thermoplastic
elastomers such as polystyrene-series thermoplastic elastomers,
polyolefin-series thermoplastic elastomers, polyurethane-series
thermoplastic elastomers, and polyester-series thermoplastic
elastomers.
[0072] The colored composition of the present invention produces
molded products having excellent impact resistance and appearance,
and is highly practical. The colored composition of the present
invention has an at least 10% better elongation characteristic
compared with the same composition, but not containing a
colorant.
[0073] The colored composition of the present invention can contain
a reinforcing material and a filling material, as long as the
object of the present invention is not interfered with. Examples of
these reinforcing materials and filling materials include fibrous,
powdery, granular or tabular inorganic fillers such as glass fiber,
carbon fiber, aromatic polyamide fiber, gypsum fiber, brass fiber,
stainless steel fiber, steel fiber, ceramic fiber, boron whisker
fiber, graphite, mica, talc, silica, calcium carbonate, glass
beads, glass flakes, glass microbaloons, clay, wallastenite,
titanium oxide, and molybdenum disulfide. These reinforcing
materials and filling materials may be those treated with a
coupling agent such as of the silane-series or titanate-series, and
other surface treatment agents.
[0074] In the case of glass fiber, for example, the content thereof
is preferably 5 to 120 parts by weight per 100 parts by weight of
thermoplastic resin. If the glass fiber content is less than 5
parts by weight, a satisfactory reinforcing effect is difficult to
achieve with the glass fiber; if the glass fiber content exceeds
120 parts by weight, the moldability tends to decrease. Preferably,
the glass fiber content is 10 to 60 parts by weight, particularly
preferably 20 to 50 parts by weight, per 100 parts by weight of
thermoplastic resin.
[0075] Furthermore, the colored composition of the present
invention can be formulated with various additives as required.
Examples of such additives include auxiliary colorants, dispersing
agents, stabilizers, plasticizers, modifiers, ultraviolet
absorbents or light stabilizers, antioxidants,
antibacterial/antifungal agents, antistatic agents, flame
retardants, and elastomers for improved impact resistance.
[0076] Examples of modifiers include silicon compounds such as
amino-modified silicone oil and alkyl-modified silicone oil.
[0077] Examples of ultraviolet absorbents or light stabilizers
include benzotriazole compounds, benzophenone compounds, salicylate
compounds, cyanoacrylate compounds, benzoate compounds, oxalide
compounds, hindered amine compounds and niccolates.
[0078] Examples of antioxidants include phenol compounds,
phosphorus compounds, sulfur compounds and thioether compounds.
[0079] Examples of antibacterial/antifungal agents include
2-(4'-thiazolyl)-benzimidazole, 10,10'-oxybisphenoxarsine,
N-(fluorodichloromethylthio)phthalimide and
bis(2-pyridylthio-1-oxide)zinc.
[0080] Examples of flame retardants include halogen-containing
compounds such as tetrabromobisphenol A derivatives,
hexabromodiphenyl ether and tetrabromophthalic anhydride;
phosphorus-containing compounds such as triphenyl phosphate,
triphenyl phosphite, red phosphorus and ammonium polyphosphate;
nitrogen-containing compounds such as urea and guanidine;
silicon-containing compounds such as silicone oil, organic silane
and aluminum silicate; and antimony compounds such as antimony
trioxide and antimony phosphate.
[0081] Molding of the colored composition of the present invention
can be achieved by various ordinary means of molding. For example,
a colored pellet of the colored composition of the present
invention can be molded using a processing machine such as an
extruder, injection molding machine or roll mill. It is also
possible to blend pellets or powder of a thermoplastic resin, the
granulated colorant or high-concentration master batch of the
present invention, and, if necessary, various additives, in an
appropriate mixer, and molding this colored composition. Any
commonly used method of molding can be employed, e.g., injection
molding, extrusion molding, compression molding, blow molding,
vacuum molding, injection blow molding, rotation molding, calender
molding, and solution casting.
EXAMPLES
[0082] The present invention is hereinafter described in more
detail by means of the following Examples, which, however, are not
to be construed as limiting the scope of the invention. In the
description below, "part(s) by weight" is abbreviated as
"part(s)".
[0083] Examples 1 to 10 and Comparative Examples 1 to 6 pertain to
granulated colorants and master batches.
Example 1
(1) Production of Granulated Colorant (Nigrosine Dye:
Water=100:35)
[0084] After 2000 g of Nigrosine Base SAP (name of a product
manufactured by Orient Chemical Industries, Ltd.; a nigrosine dye
as C.I. Solvent Black 7, having a specific surface area of 3.50
m.sup.2/g, an average particle diameter of 7 .mu.m, an Fe content
of 6000 ppm, an aniline content of 1.50% by weight, a nitrobenzene
content of 0.1% by weight, and a product pH of 5.1) and 700 g of
water were blended in a kneader for 3 minutes, the blend was
removed.
[0085] This blend was subjected to extrusion granulation treatment
using an extrusion granulating machine (Disc Pelletter F-5 model, a
commercial product manufactured by DALTON Corporation) with a
selected disc die opening diameter of 3 mm, while adjusting the
roller revolution speed (120 rpm) and keeping a constant roller
pressure (100 kg/cm.sup.2), to yield a wet colorant comprising a
cylindrical pellet (granulation product) and partially ungranulated
material. This pellet was removed and its hardness was determined
to be 4.9 N using a hardness meter (KIYA type hardness meter:
WPF1600). The bulk density of the granulation product was 0.64
g/ml.
[0086] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant comprising 86% by weight of a cylindrical
pellet. The colorant obtained was sieved to yield a cylindrical
pellet of o2.92 mm.times.9.23 mm (granulated colorant A-1). The
hardness of the cylindrical pellet was determined to be 9.8 N using
a hardness meter (KIYA type hardness meter: WPF1600). The bulk
density o f the granulation pro duct was 0.50 g/ml.
(2) Production of Master Batch (Nigrosine Dye:Resin=30:70)
[0087] 30 parts of granulated colorant A-1 and 70 parts of
polyamide 6 resin (ZYTEL [registered trademark] 7331 JNC: name of a
product manufactured by DuPont) were blended in a small tumbler.
When a master batch was prepared from this blend using a twin-screw
extruder (manufactured by PLABOR Co., Ltd., model BT-30-S2-42L),
the entire volume was successfully processed with no problems
concerning feed measuring and stranding. After the stranding, the
master batch was cooled in a water chamber, then cut into specified
length using a pelletizer. The black master batch A-1 obtained was
identified as pellets uniformly containing the nigrosine dye.
Example 2
(1) Production of Granulated Colorant (Nigrosine
Dye:Water=100:35)
[0088] After 2000 g of Nigrosine Base SAP and 700 g of water were
blended in a kneader for 3 minutes, the blend was removed. This
blend was subjected to extrusion granulation treatment using an
extrusion granulating machine (Disc Pelletter F-5 model) with a
selected disc die opening diameter of 2 mm, while adjusting the
roller revolution speed and keeping a constant roller pressure, to
yield a wet colorant comprising a cylindrical pellet (granulation
product) and partially ungranulated material. This pellet was
removed and its hardness was determined to be 1.96 N using a
hardness meter (KIYA type hardness meter: WPF1600). The bulk
density of the granulation product was 0.59 g/ml.
[0089] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant containing 80% by weight of a cylindrical
pellet. The colorant obtained was sieved to yield a cylindrical
pellet of o1.92 mm.times.9.37 mm (granulated colorant A-2). The
hardness of the cylindrical pellet was determined to be 3.92 N
using a hardness meter (KIYA type hardness meter: WPF1600).
(2) Production of Master Batch (Nigrosine Dye:Resin=50:50)
[0090] 50 parts of granulated colorant A-2 and 50 parts of
polyamide 66 resin (ZYTEL 101 NC010: name of a product manufactured
by DuPont) were blended in a small tumbler. When a master batch was
prepared from this blend using a twin-screw extruder (manufactured
by PLABOR Co., Ltd., model BT-30-S2-42L), the entire volume was
successfully processed with no problems concerning feed measuring
and stranding. After the stranding, the master batch was cooled in
a water chamber, then cut into specified length using a pelletizer.
The black master batch A-2 obtained was identified as pellets
uniformly containing the nigro sine dye.
Example 3
(1) Production of Granulated Colorant (Nigrosine
Dye:Water=100:47.8)
[0091] After 2000 g of Nigrosine Base SAP and 950 g of water were
blended in a kneader for 3 minutes, the blend was removed. This
blend was subjected to extrusion granulation treatment using an
extrusion granulating machine (Disc Pelletter F-5 model) with a
selected disc die opening diameter of 5 mm, while adjusting the
roller revolution speed and keeping a constant roller pressure, to
yield a wet colorant comprising a cylindrical pellet (granulation
product) and partially ungranulated material. This pellet was
removed and its hardness was determined to be 6.86 N using a
hardness meter (KIYA type hardness meter: WPF1600). The bulk
density of the granulation product was 0.60 g/ml.
[0092] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant comprising 78% by weight of a cylindrical
pellet. The colorant obtained was sieved to yield a cylindrical
pellet of o4.93 mm.times.15.48 mm (granulated colorant A-3). The
hardness of the cylindrical pellet was determined to be 8.82 N
using a hardness meter (KIYA type hardness meter: WPF1600). The
bulk density of the granulation product was 0.48 g/ml.
[0093] 50 parts of granulated colorant A-3 and 50 parts of
polyamide 66 resin (ZYTEL 101 NC010: name of a product manufactured
by DuPont) were blended in a small tumbler. When a master batch was
prepared from this blend using a twin-screw extruder (manufactured
by PLABOR Co., Ltd., model BT-30-S2-42L), the entire volume was
successfully processed with no problems concerning feed measuring
and stranding. After the stranding, the master batch was cooled in
a water chamber, then cut into specified length using a pelletizer.
The black master batch A-3 obtained was identified as pellets
uniformly containing the nigro sine dye.
Example 4
(1) Production of Granulated Colorant (Nigrosine
Dye:Water=100:25)
[0094] After 2000 g of Nigrosine Base SA (name of a product
manufactured by Orient Chemical Industries, Ltd.; a nigrosine dye
as C.I. Solvent Black 7, having a specific surface area of 3.35
m.sup.2/g, an average particle diameter of 12 .mu.m, an Fe content
of 6100 ppm, an aniline content of 1.53% by weight, a nitrobenzene
content of 0.1% by weight, and a product pH of 4.9) and 500 g of
water were blended in a kneader for 3 minutes, the blend was
removed. This blend was subjected to extrusion granulation
treatment using an extrusion granulating machine (Disc Pelletter
F-5 model) with a selected disc die opening diameter of 3 mm, while
adjusting the roller revolution speed and keeping a constant roller
pressure, to yield a wet colorant comprising a cylindrical pellet
(granulation product) and partially ungranulated material. This
pellet was removed and its hardness was determined to be 6.66 N
using a hardness meter (KIYA type hardness meter: WPF1600). The
bulk density of the granulation product was 0.57 g/ml. The wet
colorant obtained was dried at 70.degree. C. for 5 hours to yield a
colorant comprising 88% by weight of a cylindrical pellet. The
colorant obtained was sieved to yield a cylindrical pellet of o2.96
mm.times.9.58 mm (granulated colorant A-4). The hardness of the
cylindrical pellet was determined to be 12.35 N using a hardness
meter (KIYA type hardness meter: WPF1600). The bulk density of the
granulation pro duct was 0.51 g/ml.
(2) Production of Master Batch (Nigrosine Dye:Resin=50:50)
[0095] 50 parts of granulated colorant A-4 and 50 parts of
polyamide 66 resin (ZYTEL [registered trademark] 101 NC010: name of
a product manufactured by DuPont) were blended in a small tumbler.
When a master batch was prepared from this blend using a twin-screw
extruder (manufactured by PLABOR Co., Ltd., model BT-30-S2-42L),
the entire volume was successfully processed with no problems
concerning feed measuring and stranding. After the stranding, the
master batch was cooled in a water chamber, then cut into specified
length using a pelletizer. The black master batch A-4 obtained was
identified as pellets uniformly containing the nigrosine dye.
Example 5
(1) Production of Granulated Colorant (Nigrosine
Dye:Water=100:42.5)
[0096] After 2000 g of Nigrosine Base SA and 850 g of water were
blended in a kneader for 3 minutes, the blend was removed. This
blend was subjected to extrusion granulation treatment using an
extrusion granulating machine (Disc Pelletter F-5 model) with a
selected disc die opening diameter of 3 mm, while adjusting the
roller revolution speed and keeping a constant roller pressure, to
yield a wet colorant comprising a cylindrical pellet (granulation
product) and partially ungranulated material. This pellet was
removed and its hardness was determined to be 2.25 N using a
hardness meter (KIYA type hardness meter: WPF1600). The bulk
density of the granulation product was 0.55 g/ml.
[0097] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant comprising 90% by weight of a cylindrical
pellet. The colorant obtained was sieved to yield a cylindrical
pellet of o2.92 mm.times.9.47 mm (granulated colorant A-5). The
hardness of the cylindrical pellet was determined to be 3.33 N
using a hardness meter (KIYA type hardness meter: WPF1600). The
bulk density of the granulation product was 0.44 g/ml.
(2) Production of Master Batch (Nigrosine Dye:Resin=50:50)
[0098] 50 parts of granulated colorant A-5 and 50 parts of
polyamide 66 resin (ZYTEL 101 NC010) were blended in a small
tumbler. When a master batch was prepared from this blend using a
twin-screw extruder (manufactured by PLABOR Co., Ltd., model
BT-30-S2-42L), the entire volume was successfully processed with no
problems concerning feed measuring and stranding. After the
stranding, the master batch was cooled in a water chamber, then cut
into specified length using a pelletizer. The black master batch
A-5 obtained was identified as pellets uniformly containing the
nigrosine dye.
Example 6
(1) Production of Granulated Colorant (Nigrosine
Dye:Water=100:53.5)
[0099] After 2000 g of Nigrosine Base SA and 1070 g of water were
blended in a kneader for 3 minutes, the blend was removed. This
blend was subjected to extrusion granulation treatment using an
extrusion granulating machine (Disc Pelletter F-5 model) with a
selected disc die opening diameter of 3 mm, while adjusting the
roller revolution speed and keeping a constant roller pressure, to
yield a wet colorant comprising a cylindrical pellet (granulation
product) and partially ungranulated material. This pellet was
removed and its hardness was determined to be 0.98 N using a
hardness meter (KIYA type hardness meter: WPF1600). The bulk
density of the granulation product was 0.52 g/ml.
[0100] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant comprising 92% by weight of a cylindrical
pellet. The colorant obtained was sieved to yield a cylindrical
pellet of o2.61 mm.times.8.79 mm (granulated colorant A-6). The
hardness of the cylindrical pellet was determined to be 1.08 N
using a hardness meter (KIYA type hardness meter: WPF1600). The
bulk density of the granulation product was 0.40 g/ml.
(2) Production of Master Batch (Nigrosine Dye:Resin=50:50)
[0101] 50 parts of granulated colorant A-6 and 50 parts of
polyamide 66 resin (ZYTEL 101 NC010) were blended in a small
tumbler. When a master batch was prepared from this blend using a
twin-screw extruder (manufactured by PLABOR Co., Ltd., model
BT-30-S2-42L), the entire volume was successfully processed with no
problems concerning feed measuring and stranding. After the
stranding, the master batch was cooled in a water chamber, then cut
into specified length using a pelletizer. The black master batch
A-6 obtained was identified as pellets uniformly containing the
nigrosine dye.
Example 7
(1) Production of Granulated Colorant (Nigrosine
Dye:Water=100:35)
[0102] After 2000 g of Spirit Black AB (name of a product
manufactured by Orient Chemical Industries, Ltd.; a nigrosine dye
as C.I. Solvent Black 5, having a specific surface area of 3.59
m.sup.2/g, an average particle diameter of 7 .mu.m, an Fe content
of 7000 ppm, an aniline content of 1.8% by weight, a nitrobenzene
content of trace, and a product pH of 4.0) and 700 g of water were
blended in a kneader for 3 minutes, the blend was removed. This
blend was subjected to extrusion granulation treatment using an
extrusion granulating machine (Disc Pelletter F-5 model) with a
selected disc die opening diameter of 3 mm, while adjusting the
roller revolution speed and keeping a constant roller pressure, to
yield a wet colorant comprising a cylindrical pellet (granulation
product) and partially ungranulated material. This pellet was
removed and its hardness was determined to be 6.47 N using a
hardness meter (KIYA type hardness meter: WPF1600). The bulk
density of the granulation pro duct was 0.56 g/ml.
[0103] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant comprising 89% by weight of a cylindrical
pellet. The colorant obtained was sieved to yield a cylindrical
pellet of o2.95 mm.times.9.12 mm (granulated colorant A-7). The
hardness of the cylindrical pellet was determined to be 8.13 N
using a hardness meter (KIYA type hardness meter: WPF1600). The
bulk density of the granulation product was 0.49 g/ml.
(2) Production of Master Batch (Nigrosine Dye:Resin=30:70)
[0104] 30 parts of granulated colorant A-7 and 70 parts of
polyamide 66 resin (ZYTEL 101 NC010) were blended in a small
tumbler. When a master batch was prepared from this blend using a
twin-screw extruder (manufactured by PLABOR Co., Ltd., model
BT-30-S2-42L), the entire volume was successfully processed with no
problems concerning feed measuring and stranding. After the
stranding, the master batch was cooled in a water chamber, then cut
into specified length using a pelletizer. The black master batch
A-7 obtained was identified as pellets uniformly containing the
nigrosine dye.
Example 8
(1) Production of Granulated Colorant (Nigrosine
Dye:Water=100:35)
[0105] After 2000 g of Nigrosine Base EEL (name of a product
manufactured by Orient Chemical Industries, Ltd.; a nigrosine dye
as C.I. Solvent Black 7, having a specific surface area of 3.83
m.sup.2/g, an average particle diameter of 12 .mu.m, an Fe content
of 5000 ppm, an aniline content of 0.15% by weight, a nitrobenzene
content of trace, and a product pH of 7.3) and 700 g of water were
blended in a kneader for 3 minutes, the blend was removed. This
blend was subjected to extrusion granulation treatment using an
extrusion granulating machine (Disc Pelletter F-5 model) with a
selected disc die opening diameter of 3 mm, while adjusting the
roller revolution speed and keeping a constant roller pressure, to
yield a wet colorant comprising a cylindrical pellet (granulation
product) and partially ungranulated material. This pellet was
removed and its hardness was determined to be 1.86 N using a
hardness meter (KIYA type hardness meter: WPF1600). The bulk
density of the granulation pro duct was 0.54 g/ml.
[0106] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant comprising 74% by weight of a cylindrical
pellet. The colorant obtained was sieved to yield a cylindrical
pellet of o2.96 mm.times.8.11 mm (granulated colorant A-8). The
hardness of the cylindrical pellet was determined to be 4.02 N
using a hardness meter (KIYA type hardness meter: WPF1600). The
bulk density of the granulation product was 0.44 g/ml.
(2) Production of Master Batch (Nigrosine Dye:Resin=50:50)
[0107] 50 parts of granulated colorant A-8 and 50 parts of
polyamide 6 resin (ZYTEL 7331 JNC) were blended in a small tumbler.
When a master batch was prepared from this blend using a twin-screw
extruder (manufactured by PLABOR Co., Ltd., model BT-30-S2-42L),
the entire volume was successfully processed with no problems
concerning feed measuring and stranding. After the stranding, the
master batch was cooled in a water chamber, then cut into specified
length using a pelletizer. The black master batch A-8 obtained was
identified as pellets uniformly containing the nigrosine dye.
Example 9
(1) Production of Granulated Colorant (Nigrosine
Dye:Water=100:35)
[0108] After 2000 g of Nigrosine Base EX (name of a product
manufactured by Orient Chemical Industries, Ltd.; a nigrosine dye
as C.I. Solvent Black 7, having a specific surface area of 3.39
m.sup.2/g, an average particle diameter of 12 .mu.m, an Fe content
of 2000 ppm, an aniline content of 0.06% by weight, a nitrobenzene
content of trace, and a product pH of 6.9) and 700 g of water were
blended in a kneader for 3 minutes, the blend was removed. This
blend was subjected to extrusion granulation treatment using an
extrusion granulating machine (Disc Pelletter F-5 model) with a
selected disc die opening diameter of 3 mm, while adjusting the
roller revolution speed and keeping a constant roller pressure, to
yield a wet colorant comprising a cylindrical pellet (granulation
product) and partially ungranulated material. This pellet was
removed and its hardness was determined to be 5.59 N using a
hardness meter (KIYA type hardness meter: WPF1600). The bulk
density of the granulation product was 0.61 g/ml.
[0109] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant comprising 92% by weight of a cylindrical
pellet. The colorant obtained was sieved to yield a cylindrical
pellet of o3.02 mm.times.8.66 mm (granulated colorant A-9). The
hardness of the cylindrical pellet was determined to be 7.74 N
using a hardness meter (KIYA type hardness meter: WPF1600). The
bulk density o f the granulation pro duct was 0.53 g/ml.
(2) Production of Master Batch (Nigrosine Dye::Resin=50:50)
[0110] 50 parts of granulated colorant A-9 and 50 parts of
polyamide 66 resin (ZYTEL 101 NC010) were blended in a small
tumbler. When a master batch was prepared from this blend using a
twin-screw extruder (manufactured by PLABOR Co., Ltd., model
BT-30-S2-42L), the entire volume was successfully processed with no
problems concerning feed measuring and stranding. After the
stranding, the master batch was cooled in a water chamber, then cut
into specified length using a pelletizer. The black master batch
A-9 obtained was identified as pellets uniformly containing the
nigrosine dye.
Example 10
(1) Production of Granulated Colorant
[0111] As a result of treatment of 2000 g of Nigrosine Base SAP
using a dry granulating machine (Roller Compacter model WP160x60;
manufactured by MATSUBO Corporation), a colorant containing 87% by
weight of a good flaky product of 0.25 to 4 mm was obtained. The
colorant obtained was sieved to yield a flaky product (granulated
colorant A-10).
(2) Production of Master Batch (Nigrosine Dye:Resin=30:70)
[0112] 30 parts of granulated colorant A-10 and 70 parts of
polyamide 6 resin (ZYTEL 7331 JNC) were blended in a small tumbler.
When a master batch was prepared from this blend using a twin-screw
extruder (manufactured by PLABOR Co., Ltd., model BT-30-S2-42L),
the entire volume was successfully processed with no problems
concerning feed measuring and stranding. After the stranding, the
master batch was cooled in a water chamber, then cut into specified
length using a pelletizer. The black master batch A-10 obtained was
identified as pellets uniformly containing the nigrosine dye.
(3) Production of Master Batch (Nigrosine Dye:Resin=30:70)
[0113] 30 parts of granulated colorant A-10 and 70 parts of
polyamide 66 resin (ZYTEL 101 NC010) were blended in a small
tumbler. When a master batch was prepared from this blend using a
twin-screw extruder (manufactured by PLABOR Co., Ltd., model
BT-30-S2-42L), the entire volume was successfully processed with no
problems concerning feed measuring and stranding. After the
stranding, the master batch was cooled in a water chamber, then cut
into specified length using a pelletizer. The black master batch
A-10B obtained was identified as pellets uniformly containing the
nigrosine dye.
Example 11
(1) Production of Granulated Colorant (Nigrosine
Dye:Water=100:35)
[0114] After 2000 g of Nigrosine Base SAP and 700 g of water were
blended in a kneader for 3 minutes, the blend was removed. This
blend was subjected to extrusion granulation treatment using an
extrusion granulating machine (Disc Pelletter F-5 model) with a
selected disc die opening diameter of 3 mm, while adjusting the
roller revolution speed and keeping a constant roller pressure, to
yield a wet colorant comprising a cylindrical pellet (granulation
product) and partially ungranulated material. This pellet was
removed and its hardness was determined to be 5.11 N using a
hardness meter (KIYA type hardness meter: WPF1600). The bulk
density of the granulation product was 0.62 g/ml.
[0115] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant A-11 comprising 87% by weight of a
cylindrical pellet (granulated colorant). This pellet was removed
and determined to be a cylindrical pellet of o2.93 mm.times.9.28 mm
having a hardness of 9.71 N. The bulk density of the granulation
product was 0.51 g/ml.
(2) Production of Master Batch (Nigrosine Dye:Resin=30:70)
[0116] 30 parts of colorant A-11 and 70 parts of polyamide 6 resin
(ZYTEL [registered trademark] 7331 JNC: name o f a pro duct
manufactured by DuPont) were blended in a small tumbler. When a
master batch was prepared from this blend using a twin-screw
extruder (manufactured by PLABOR Co., Ltd., model BT-30-S2-42L),
the entire volume was successfully processed with no problems
concerning feed measuring and stranding. After the stranding, the
master batch was cooled in a water chamber, then cut into specified
length using a pelletizer. The black master batch A-11 obtained was
identified as pellets uniformly containing the nigrosine dye.
Example 12
(1) Production of Granulated Colorant
[0117] As a result of treatment of 2000 g of Nigrosine Base SAP
using a dry granulating machine (Roller Compacter model WP160x60;
manufactured by MATSUBO Corporation), a colorant A-12 comprising
85% by weight of a good flaky product of 0.25 to 4 mm (granulated
colorant) was obtained.
(2) Production of Master Batch (Nigrosine Dye:Resin=30:70)
[0118] 30 parts of colorant A-12 and 70 parts of polyamide 6 resin
(ZYTEL 7331 JNC) were blended in a small tumbler. When a master
batch was prepared from this blend using a twin-screw extruder
(manufactured by PLABOR Co., Ltd., model BT-30-S2-42L), the entire
volume was successfully processed with no problems concerning feed
measuring and stranding. After the stranding, the master batch was
cooled in a water chamber, then cut into specified length using a
pelletizer. The black master batch A-12 obtained was identified as
pellets uniformly containing the nigrosine dye.
Example 13
(1) Production of Granulated Colorant (Colorant:Water=100:35)
[0119] After 1500 g of Nigrosine Base SAP, 500 g of carbon black
(#960B, manufactured by Mitsubishi Chemical Corporation) and 700 g
of water were blended in a kneader for 3 minutes, the blend was
removed. This blend was subjected to extrusion granulation
treatment using an extrusion granulating machine (Disc Pelletter
F-5 model) with a selected disc die opening diameter of 3 mm, while
adjusting the roller revolution speed and keeping a constant roller
pressure, to yield a wet colorant comprising a cylindrical pellet
(granulation product) and partially ungranulated material. This
pellet was removed and its hardness was determined to be 5.78 N
using a hardness meter (KIYA type hardness meter: WPF1600). The
bulk density of the granulation product was 0.65 g/ml.
[0120] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant comprising 97.3% by weight of a
cylindrical pellet. The colorant obtained was sieved to yield a
cylindrical pellet of o2.99 mm.times.9.35 mm (granulated colorant
A-13). The hardness of the cylindrical pellet was determined to be
4.31 N using a hardness meter (KIYA type hardness meter: WPF1600).
The bulk density of the granulation pro duct was 0.57 g/ml.
(2) Production of Master Batch (Colorant:Resin=50:50)
[0121] 50 parts of granulated colorant A-13 and 50 parts of
polyamide 6 resin (ZYTEL 7331 JNC) were blended in a small tumbler.
When a master batch was prepared from this blend using a twin-screw
extruder (manufactured by PLABOR Co., Ltd., model BT-30-S2-42L),
the entire volume was successfully processed with no problems
concerning feed measuring and stranding. After the stranding, the
master batch was cooled in a water chamber, then cut into specified
length using a pelletizer. The black master batch A-13 obtained was
identified as pellets uniformly containing the nigrosine dye and
carbon black.
Example 14
(1) Production of Granulated Colorant (Colorant:Water=100:42.5)
[0122] After 1500 g of Nigrosine Base SAP, 500 g of carbon black
(#960B, manufactured by Mitsubishi Chemical Corporation) and 850 g
of water were blended in a kneader for 3 minutes, the blend was
removed. This blend was subjected to extrusion granulation
treatment using an extrusion granulating machine (Disc Pelletter
F-5 model) with a selected disc die opening diameter of 3 mm, while
adjusting the roller revolution speed and keeping a constant roller
pressure, to yield a wet colorant comprising a cylindrical pellet
(granulation product) and partially ungranulated material. This
pellet was removed and its hardness was determined to be 3.63 N
using a hardness meter (KIYA type hardness meter: WPF1600). The
bulk density of the granulation product was 0.63 g/ml.
[0123] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant A-14 comprising 99.2% by weight of a
cylindrical pellet (granulated colorant). This pellet was removed
and determined to be a cylindrical pellet of o2.98 mm.times.9.32
mm. The hardness of the cylindrical pellet was determined to be
3.04 N using a hardness meter (KIYA type hardness meter: WPF1600).
The bulk density of the granulation product was 0.54 g/ml.
(2) Production of Master Batch (Colorant:Resin=50:50)
[0124] 50 parts of colorant A-14 and 50 parts of polyamide 66 resin
(ZYTEL 101 NC010) were blended in a small tumbler. When a master
batch was prepared from this blend using a twin-screw extruder
(manufactured by PLABOR Co., Ltd., model BT-30-S2-42L), the entire
volume was successfully processed with no problems concerning feed
measuring and stranding. After the stranding, the master batch was
cooled in a water chamber, then cut into specified length using a
pelletizer. The black master batch A-14 obtained was identified as
pellets uniformly containing the nigrosine dye and carbon
black.
Example 15
(1) Production of Granulated Colorant (Colorant:Water=100:35)
[0125] After 2000 g of Nigrosine Base SAP, 60 g of PEG200
(polyethylene glycol, average molecular weight 200) and 700 g of
water were blended in a kneader for 3 minutes, the blend was
removed. This blend was subjected to extrusion granulation
treatment using an extrusion granulating machine (Disc Pelletter
F-5 model) with a selected disc die opening diameter of 3 mm, while
adjusting the roller revolution speed and keeping a constant roller
pressure, to yield a wet colorant comprising a cylindrical pellet
(granulation product) and partially ungranulated material. This
pellet was removed and its hardness was determined to be 2.02 N
using a hardness meter (KIYA type hardness meter: WPF1600). The
bulk density of the granulation product was 0.52 g/ml.
[0126] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant comprising 99.5% by weight of a
cylindrical pellet. The colorant obtained was sieved to yield a
cylindrical pellet of o2.98 mm.times.9.25 mm (granulated colorant
A-15). The hardness of the cylindrical pellet was determined to be
2.55 N using a hardness meter (KIYA type hardness meter: WPF1600).
The bulk density of the granulation product was 0.45 g/ml.
(2) Production of Master Batch (Colorant:Resin=50:50)
[0127] 50 parts of granulated colorant A-15 and 50 parts of
polyamide 66 resin (ZYTEL 101 NC010) were blended in a small
tumbler. When a master batch was prepared from this blend using a
twin-screw extruder (manufactured by PLABOR Co., Ltd., model
BT-30-S2-42L), the entire volume was successfully processed with no
problems concerning feed measuring and stranding. After the
stranding, the master batch was cooled in a water chamber, then cut
into specified length using a pelletizer. The black master batch
A-15 obtained was identified as pellets uniformly containing the
nigrosine dye and carbon black.
Example 16
(1) Production of Granulated Colorant (Nigrosine
Dye:Water=100:35)
[0128] After 2000 g of Nigrosine Base SAP, 20 g of NOIGEN XL-40
(polyoxyalkylene alkyl ether nonionic surfactant) and 700 g of
water were blended in a kneader for 3 minutes, the blend was
removed. This blend was subjected to extrusion granulation
treatment using an extrusion granulating machine (Disc Pelletter
F-5 model) with a selected disc die opening diameter of 3 mm, while
adjusting the roller revolution speed and keeping a constant roller
pressure, to yield a wet colorant comprising a cylindrical pellet
(granulation product) and partially ungranulated material. This
pellet was removed and its hardness was determined to be 8.73 N
using a hardness meter (KIYA type hardness meter: WPF1600). The
bulk density of the granulation product was 0.54 g/ml.
[0129] The wet colorant obtained was dried at 70.degree. C. for 5
hours to yield a colorant comprising 92.7% by weight of a
cylindrical pellet. The colorant obtained was sieved to yield a
cylindrical pellet of o2.97 mm.times.9.32 mm (granulated colorant
A-16). The hardness of the cylindrical pellet was determined to be
10.98 N using a hardness meter (KIYA type hardness meter: WPF1600).
The bulk density of the granulation product was 0.48 g/ml.
(2) Production of Master Batch (Nigrosine Dye:Resin=50:50)
[0130] 50 parts of granulated colorant A-16 and 50 parts of
polyamide 66 resin (ZYTEL 101 NC010) were blended in a small
tumbler. When a master batch was prepared from this blend using a
twin-screw extruder (manufactured by PLABOR Co., Ltd., model
BT-30-S2-42L), the entire volume was successfully processed with no
problems concerning feed measuring and stranding. After the
stranding, the master batch was cooled in a water chamber, then cut
into specified length using a pelletizer. The black master batch
A-16 obtained was identified as pellets uniformly containing the
nigrosine dye.
Comparative Example 1
(1) Production of Master Batch (Nigrosine Dye:Resin=30:70)
[0131] 30 parts of Nigrosine Base SAP and 70 parts of polyamide 6
resin (ZYTEL 7331 JNC) were blended in a small tumbler. When a
master batch was prepared from this blend using a twin-screw
extruder (manufactured by PLABOR Co., Ltd., model BT-30-S2-42L),
the blend formed bridges in the feed hopper to make its feed
unstable, and the molded product strand was in a very bad
condition, including ununiform thickness and strand breaks. The
master batch obtained by cutting the molded product obtained using
the twin-screw extruder into specified length was unstable in
shape; various shapes of pellets (black master batch B-1) were
obtained.
Comparative Example 2
(1) Production of Master Batch (Nigrosine Dye:Resin=50:50)
[0132] 50 parts of Nigrosine Base SAP and 50 parts of polyamide 6
resin (ZYTEL 7331 JNC) were blended in a small tumbler. When a
master batch was prepared from this blend using a twin-screw
extruder (manufactured by PLABOR Co., Ltd., model BT-30-S2-42L),
the blend formed bridges in the feed hopper to make its feed
unstable, and the molded product strand was in a very bad
condition, including ununiform thickness and strand breaks. The
production was discontinued since the feed became impossible during
the operation.
Comparative Example 3
(1) Production of Master Batch (Nigrosine Dye:Resin=30:70)
[0133] 30 parts of Nigrosine Base SAP and 70 parts of polyamide 66
resin (ZYTEL 101 NC010) were blended in a small tumbler. When a
master batch was prepared from this blend using a twin-screw
extruder (manufactured by PLABOR Co., Ltd., model BT-30-S2-42L),
the blend formed bridges in the feed hopper to make its feed
unstable, and the molded product strand was in a very bad
condition, including ununiform thickness and strand breaks. The
master batch obtained by cutting the molded product obtained using
the twin-screw extruder into specified length was unstable in
shape; various shapes of pellets (black master batch B-2) were
obtained.
Comparative Example 4
(1) Production of Master Batch (Nigrosine Dye:Resin=50:50)
[0134] 50 parts of Nigrosine Base SAP and 50 parts of polyamide 66
resin (ZYTEL 101 NC010) were blended in a small tumbler. When a
master batch was prepared from this blend using a twin-screw
extruder (manufactured by PLABOR Co., Ltd., model BT-30-S2-42L),
the blend formed bridges in the feed hopper to make its feed
unstable, and the molded product strand was in a very bad
condition, including ununiform thickness and strand breaks. The
production was discontinued since the feed became impossible during
the operation.
Comparative Example 5
[0135] (1) Production of Master Batch (Nigrosine
dye:Resin=40:60)
[0136] 40 parts of Nigrosine Base SAP and 60 parts of polyamide 6
resin (ZYTEL 7331 JNC) were blended in a small tumbler. When a
master batch was prepared from this blend using a twin-screw
extruder (manufactured by PLABOR Co., Ltd., model BT-30-S2-42L),
the blend formed bridges in the feed hopper to make its feed
unstable, and the molded product strand was in a very bad
condition, including ununiform thickness and strand breaks. The
master batch obtained by cutting the molded product obtained using
the twin-screw extruder into specified length was unstable in
shape; various shapes of pellets (black master batch C-1) were
obtained.
Comparative Example 6
(1) Production of Master Batch (Nigrosine Dye:Resin=40:60)
[0137] 40 parts of Nigrosine Base SAP and 60 parts of polyamide 66
resin (ZYTEL 101 NC010) were blended in a small tumbler. When a
master batch was prepared from this blend using a twin-screw
extruder (manufactured by PLABOR Co., Ltd., model BT-30-S2-42L),
the blend formed bridges in the feed hopper to make its feed
unstable, and the molded product strand was in a very bad
condition, including ununiform thickness and strand breaks. The
master batch obtained by cutting the molded product obtained using
the twin-screw extruder into specified length was unstable in
shape; various shapes of pellets (black master batch C-2) were
obtained.
Example 17
[0138] (a) Fluidity Test Using Powder Fluidity Analyzer
[0139] A fluidity comparison test was performed using the
granulated colorant A-1 obtained in Example 1, the granulated
colorant A-10 obtained in Example 10, and the raw material
Nigrosine Base SAP. [0140] Instrument used: powder fluidity
analyzer FT-4 (manufactured by Sysmex Corporation) [0141] Measuring
conditions: flow rate test [0142] Flow rate test: Changes in
fluidity at four different blade speeds (100 mm/sec, 70 mm/sec, 40
mm/sec, 10 mm/sec) were evaluated. The results are shown in Table 1
and FIG. 1. As the rate of the figure changes shown in Table 1 and
FIG. 1 decreases, the fluidity is evaluated to be better.
TABLE-US-00001 [0142] TABLE 1 Granulated Granulated Nigrosine Blade
speed colorant A-1 colorant A-10 Base SAP 100 mm/sec 5374 4354 712
70 mm/sec 5390 4382 858 40 mm/sec 5550 4570 1122 10 mm/sec 5604
4608 1654
[0143] As a result of the above-described flow rate test,
granulated colorant A-1 and granulated colorant A-10 exhibited
constant fluidity independent of the changes in flow rate (blade
speed). Because Nigrosine Base SAP is powdery and hence has small
particle-to-particle gaps, it is speculated that the lower portion
of the sample is compacted in the container due to the weight of
the upper portion of the sample; if the blade speed is slow, this
compaction proceeds to increase the resistance of the lower portion
of the sample, which is considered to be among the causes of the
fluidity reduction.
(b) Fluidity Test Using Simple Fluidity Tester
[0144] Test method: A simple fluidity tester having an opening with
a shutter capable of forming a circular opening permitting
adjustment of the diameter thereof at the center of the base of a
300-ml cylindrical container was used. After the sample was filled
in the simple fluidity tester with the shutter closed, the shutter
was gradually opened, and the portion of the sample fallen for each
opening diameter was weighed. The measured results are shown in
Table 2 and FIG. 2. Both PA resin in Table 2 and 6-nylon in FIG. 2
refer to polyamide 6 resin.
TABLE-US-00002 TABLE 2 Opening diameter (mm) 5 8 10 12 15 20 25 30
35 40 45 PA resin (g) 0.42 0.56 77.06 80.49 82.48 84.53 87.23 90.36
-- -- -- Granulated 0.48 0.69 0.69 1.12 75.35 80.73 84.57 89.59 --
-- -- colorant A-1 (g) Granulated 1.00 1.00 1.42 1.42 53.83 57.57
70.17 78.71 -- -- -- colorant A-10 (g) Nigrosine Base 1.01 1.01
1.01 1.01 1.51 2.22 2.22 3.06 6.79 9.83 71.38 SAP (g)
[0145] Based on these results of the fluidity determination, an
approximation curve were generated to obtain equations showing the
relationship between opening diameter (abscissa: x) and the ratio
by weight of the portion of sample fallen to the entire sample
(ordinate: y), and the opening diameter corresponding to a fall of
50% by weight of the sample quantity filling in the simple fluidity
tester, x.sub.50, was calculated. As the opening diameter x.sub.50
decreases, the fluidity is evaluated to be better.
[0146] The equations showing the relationship between opening
diameter (abscissa: x) and the ratio by weight of the portion of
sample fallen to the entire sample (ordinate: y) and the opening
diameter corresponding to a fall of 50% by weight of the sample
quantity, x.sub.50, for each sample are shown below. [0147]
Polyamide 6 resin: y=38.251x-305.45 [0148] (If y=50, x.sub.50=9.29
mm) [0149] Granulated colorant A-1: y=24.744x-295.82 [0150] (If
y=50, x.sub.50=13.9 mm) [0151] Granulated colorant A-10:
y=17.469x-208.20 [0152] (If y=50, x.sub.50=14.7 mm) [0153]
Nigrosine Base SAP: y=12.309x-482.53 [0154] (If y=50, x.sub.50=43.3
mm)
[0155] As shown above, the fluidities of granulated colorant A-1
and granulated colorant A-10 were relatively close to the fluidity
of polyamide 6 resin, whereas the fluidity of Nigrosine Base SAP,
which is a powdery nigrosine, was much inferior to the fluidities
of granulated colorant A-1 and granulated colorant A-10. Comparing
the fluidities of granulated colorant A-1, which is in the form of
a cylindrical pellet, and granulated colorant A-10, which is in the
form of a flake, granulated colorant A-1 exhibited better
fluidity.
[0156] Examples A and B and Comparative Examples A and B pertain to
non-reinforced black polyamide resin compositions.
Example A
[0157] 1000 g of polyamide 66 resin (ZYTEL 101L-NC10: name of a
product manufactured by DuPont) and 2.0 g of granulated colorant
A-1 (Example 1) were placed in a stainless steel tumbler and
vigorously stirred for 20 minutes.
[0158] The mixture obtained was kneaded in a molten state at
300.degree. C. using a vent type extruding machine (manufactured by
Enpura Sangyo, product name: E30SV) and treated by a conventional
method to yield colored pellets, which were vacuum-dried at
120.degree. C. for 6 hours. After drying, the pellets were molded
into a test plate at 280 to 300.degree. C. by an ordinary method
using an injection molding machine (produced by Kawaguchi Tekko,
product name: KM50-C). A bluish black molded test plate with good
compatibility between the resin and the dye [48.times.86.times.3
(mm)] was obtained.
Example B
[0159] 1000 g of polyamide 66 resin (ZYTEL 101L-NC10) and 6.7 g of
black master batch A-1 (Example 1) were placed in a stainless steel
tumbler and vigorously stirred for 20 minutes.
[0160] The mixture obtained was kneaded in a molten state at
300.degree. C. using a vent type extruding machine (manufactured by
Enpura Sangyo, product name: E30SV) and treated by a conventional
method to yield colored pellets, which were vacuum-dried at
120.degree. C. for 6 hours. After drying, the pellets were molded
into a test plate at 280 to 300.degree. C. by an ordinary method
using an injection molding machine (produced by Kawaguchi Tekko,
product name: KM50-C). A bluish black molded test plate with good
compatibility between the resin and the dye [48.times.86.times.3
(mm)] was obtained.
Comparative Example A
[0161] 1000 g of polyamide 66 resin (ZYTEL 101L-NC10) and 2.0 g of
Nigrosine Base SAP were placed in a stainless steel tumbler and
vigorously stirred for 20 minutes.
[0162] The mixture obtained was kneaded in a molten state at
300.degree. C. using a vent type extruding machine (manufactured by
Enpura Sangyo, product name: E30SV) and treated by a conventional
method to yield colored pellets, which were vacuum-dried at
120.degree. C. for 6 hours. After drying, the pellets were molded
into a test plate at 280 to 300.degree. C. by an ordinary method
using an injection molding machine (produced by Kawaguchi Tekko,
product name: KM50-C). A bluish black molded test plate with good
compatibility between the resin and the dye [48.times.86.times.3
(mm)] was obtained.
Comparative Example B
[0163] 1000 g of polyamide 66 resin (ZYTEL 101L-NC10) and 6.7 g of
black master batch B-2 (Comparative Example 3) were placed in a
stainless steel tumbler and vigorously stirred for 20 minutes.
[0164] The mixture obtained was kneaded in a molten state at
300.degree. C. using a vent type extruding machine (manufactured by
Enpura Sangyo, product name: E30SV) and treated by a conventional
method to yield colored pellets, which were vacuum-dried at
120.degree. C. for 6 hours. After drying, the pellets were molded
into a test plate at 280 to 300.degree. C. by an ordinary method
using an injection molding machine (produced by Kawaguchi Tekko,
product name: KM50-C). A bluish black molded test plate with good
compatibility between the resin and the dye [48.times.86.times.3
(mm)] was obtained.
[0165] Examples C and D and Comparative Examples C and D pertain to
glass fiber-reinforced black polyamide resin compositions.
Example C
[0166] 500 g of glass fiber-reinforced polyamide 66 resin (ZYTEL
[registered trademark] 70G-33L: name of a product manufactured by
DuPont) and 1.0 g of granulated colorant A-1 (Example 1) were
placed in a stainless steel tumbler and vigorously stirred for 1
hour.
[0167] The mixture obtained was kneaded in a molten state at
300.degree. C. using a vent type extruding machine (manufactured by
Enpura Sangyo, product name: E30SV) and treated by a conventional
method to yield colored pellets, which were vacuum-dried at
120.degree. C. for 6 hours. After drying, the pellets were molded
into a test plate at 280 to 300.degree. C. by an ordinary method
using an injection molding machine (produced by Kawaguchi Tekko,
product name: KM50-C). A bluish black molded test plate with good
compatibility between the resin and the dye [48.times.86.times.3
(mm)] was obtained. The same treatment was performed but the mold
was replaced with a mold for Izod impact test pieces, to obtain an
Izod impact test piece.
Example D
[0168] 500 g of glass fiber-reinforced polyamide 66 resin
(manufactured by DuPont, product name: ZYTEL 70G-33L) and 3.34 g of
black master batch A-1 (Example 1) were placed in a stainless steel
tumbler and vigorously stirred for 1 hour.
[0169] The mixture obtained was kneaded in a molten state at
300.degree. C. using a vent type extruding machine (manufactured by
Enpura Sangyo, product name: E30SV) and treated by a conventional
method to yield colored pellets, which were vacuum-dried at
120.degree. C. for 6 hours. After drying, the pellets were molded
into a test plate at 280 to 300.degree. C. by an ordinary method
using an injection molding machine (produced by Kawaguchi Tekko,
product name: KM50-C). A bluish black molded test plate with good
compatibility between the resin and the dye [48.times.86.times.3
(mm)] was obtained. The same treatment was performed but the mold
was replaced with a mold for Izod impact test pieces, to obtain an
Izod impact test piece.
Comparative Example C
[0170] 500 g of glass fiber-reinforced polyamide 66 resin (ZYTEL
70G-33L) and 1.0 g of Nigrosine Base SAP were placed in a stainless
steel tumbler and vigorously stirred for 1 hour.
[0171] The mixture obtained was kneaded in a molten state at
300.degree. C. using a vent type extruding machine (manufactured by
Enpura Sangyo, product name: E30SV) and treated by a conventional
method to yield colored pellets, which were vacuum-dried at
120.degree. C. for 6 hours. After drying, the pellets were molded
into a test plate at 280 to 300.degree. C. by an ordinary method
using an injection molding machine (produced by Kawaguchi Tekko,
product name: KM50-C). A bluish black molded test plate with good
compatibility between the resin and the dye [48.times.86.times.3
(mm)] was obtained. The same treatment was performed but the mold
was replaced with a mold for Izod impact test pieces, to obtain an
Izod impact test piece.
Comparative Example D
[0172] 500 g of glass fiber-reinforced polyamide 66 resin (ZYTEL
70G-33L) and 3.34 g of black master batch B-1 (Comparative Example
1) were placed in a stainless steel tumbler and vigorously stirred
for 1 hour.
[0173] The mixture obtained was kneaded in a molten state at
300.degree. C. using a vent type extruding machine (manufactured by
Enpura Sangyo, product name: E30SV) and treated by a conventional
method to yield colored pellets, which were vacuum-dried at
120.degree. C. for 6 hours. After drying, the pellets were molded
into a test plate at 280 to 300.degree. C. by an ordinary method
using an injection molding machine (produced by Kawaguchi Tekko,
product name: KM50-C). A bluish black molded test plate with good
compatibility between the resin and the dye [48.times.86.times.3
(mm)] was obtained. The same treatment was performed but the mold
was replaced with a mold for Izod impact test pieces, to obtain an
Izod impact test piece.
[0174] For the black molded plates obtained in Examples C and D and
Comparative Examples C and D, surface gloss was measured using a
gloss meter. The results are shown in Table 3. Greater values
indicate higher glossiness.
TABLE-US-00003 TABLE 3 20.degree. 60.degree. 85.degree. Example C
57.9 85.7 99.2 Example D 56.3 86.5 99.7 Comparative Example C 54.2
85.0 97.5 Comparative Example D 53.8 84.2 97.3
[0175] The black molded plates obtained in Examples C and D showed
better surface glossiness at all angles of incidence than the black
molded plates obtained in Comparative Examples C and D.
[0176] For the Izod impact test pieces obtained in Examples C and D
and Comparative Examples C and D, Izod impact values were measured.
The results are shown in Table 4. NATURAL in Table 4 indicates an
Izod impact test piece obtained by molding non-colored glass
fiber-reinforced polyamide 66 resin (ZYTEL 70G-33L) in the same
manner as Example C.
TABLE-US-00004 TABLE 4 Ave Max Min CV NATURAL 8.52 8.84 8.29 0.22
Example C 5.78 6.57 4.67 0.75 Example D 6.69 7.33 6.15 0.43
Comparative Example C 5.27 6.20 4.23 0.77 Comparative Example D
5.00 6.01 2.89 1.34 Ave: average value; Max: maximum value; Min:
minimum value; CV: standard deviation
[0177] The results obtained showed that the Izod impact test pieces
obtained in Examples C and D had Izod impact values about 20%
better than those of the Izod impact test pieces obtained in
Comparative Examples C and D.
* * * * *