U.S. patent application number 10/066906 was filed with the patent office on 2003-04-10 for colored thermoplastic resin compositions for laser welding, colorants therefor of mixtures of amine salts of anthraquinone and monoazo complex dyes, and molded product therefrom.
Invention is credited to Hatase, Yoshiteru, Hayashi, Ryuichi, Koshida, Reiko.
Application Number | 20030068497 10/066906 |
Document ID | / |
Family ID | 29218167 |
Filed Date | 2003-04-10 |
United States Patent
Application |
20030068497 |
Kind Code |
A1 |
Koshida, Reiko ; et
al. |
April 10, 2003 |
Colored thermoplastic resin compositions for laser welding,
colorants therefor of mixtures of amine salts of anthraquinone and
monoazo complex dyes, and molded product therefrom
Abstract
Thermoplastic resin compositions are described in which amine
salts of anthraquinone dyes and monoazo complex dyes are added.
These compositions show superior performance in laser welding
applications.
Inventors: |
Koshida, Reiko; (Utsunomiya,
JP) ; Hatase, Yoshiteru; (Osaka, JP) ;
Hayashi, Ryuichi; (Tokyo, JP) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY
LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1128
4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Family ID: |
29218167 |
Appl. No.: |
10/066906 |
Filed: |
November 13, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60247948 |
Nov 13, 2000 |
|
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|
Current U.S.
Class: |
428/411.1 ;
524/190 |
Current CPC
Class: |
C08K 5/0041 20130101;
Y10S 428/913 20130101; B29K 2995/0022 20130101; B29C 66/1282
20130101; B29C 66/7212 20130101; B29C 66/7212 20130101; B29K
2309/08 20130101; B29K 2077/00 20130101; B29C 66/73365 20130101;
B29C 66/73321 20130101; B29C 66/43 20130101; B29C 66/1122 20130101;
B29C 65/1635 20130101; B29C 66/73921 20130101; B29K 2067/00
20130101; B29C 66/71 20130101; B29K 2995/0027 20130101; B29C
66/7212 20130101; B29C 66/73322 20130101; B29C 66/12841 20130101;
C09B 67/0041 20130101; B29C 65/1616 20130101; Y10T 428/31728
20150401; B29C 66/41 20130101; B29K 2995/0073 20130101; B29C
66/7392 20130101; B29C 65/16 20130101; B29C 66/71 20130101; B29C
66/71 20130101; B29C 66/73361 20130101; Y10T 428/31504 20150401;
Y10T 428/31725 20150401; B29K 2307/04 20130101 |
Class at
Publication: |
428/411.1 ;
524/190 |
International
Class: |
B32B 009/04 |
Claims
In the claims
1. A thermoplastic resin composition for laser welding comprising:
1) thermoplastic resin; and 2) laser-transmitting black colorant
comprising amine salts of anthraquinone dye and monoazo complex
dye.
2. A thermoplastic resin composition for laser welding comprising:
1) thermoplastic resin; and, 2) laser-transmitting black colorant
comprising a mixture of a) amine salt of anthraquinone dyes of
formula [I] or formula [II] wherein Formula [I] is: 13 wherein
R.sup.1 to R.sup.8, which may be the same or different, are
independently selected from the group consisting of H, alkyl, aryl,
alkenyl, alkoxy, amino, hydroxy, halogen atom, acyl, acyloxy,
acylamide, acyl-n-alkylamide, carboxyl, alkoxycarbonyl,
cyclohexylamide, sulfonyl, formula [I-a], or --Y--W, and at least
one of R.sup.1 to R.sup.8 is of formula [I-a]; wherein Y is S, O,
or NH; and wherein W is selected from unsubstituted or substituted
alkyl group, alkenyl group, and unsubstituted or substituted aryl
group; wherein (Z).sup.n+ represents a cation derived from an
organic amine compounds or a basic dye; wherein n is 1 or 2,
m.sup.1 is an integer from 1 to 4 and K.sup.1 is the ratio of
m.sup.1/n; and wherein formula [I-a] is: 14 wherein X is O or NH,
and R.sup.9 to R.sup.13, which may be the same or different, are
independently selected from the group consisting of H, alkyl, aryl,
alkenyl, alkoxy, amino, N-alkylamide, N-arylamide, hydroxy, halogen
atom, acyl, acyloxy, acylamide, acyl-N-alkylamide, carboxyl,
alkoxycarbonyl, or sulfonyl; wherein at least one of R.sup.1 to
R.sup.8 and R.sup.9 to R.sup.13 is sulfonyl group; wherein formula
[II] is: 15 wherein R.sup.47 to R.sup.52, which may be the same or
different, are independently selected from the group consisting of
H, alkyl, aryl, alkenyl, alkoxy, amino, N-alkylamide, N-arylamide,
hydroxy, halogen atom, acyl, acyloxy, acylamide, acyl-N-alkylamide,
carboxyl, alkoxycarbonyl, or sulfonyl; and at least one of R.sup.47
to R.sup.52 is of sulfonyl, and formula J in formula [II] is
selected from formula [II-a] or formula [II-b] and binds two
anthraquinone formula [II-a]: 16 formula [II-b]: 17 wherein
R.sup.53 to R.sup.54, which may be the same or different, are
independently selected from the group consisting of alkyl (having 1
to 8 carbon atoms) or hydrogen, and wherein (F).sup.h+ represents
ammonium ion or a cation derived from an organic amino compounds or
a basic dye wherein h is 1 or 2, m.sup.4 is an integer from 1 to 4
and K.sup.4 is the ratio of m.sup.4/h, and b) monoazo complex dye
represented by the formula [III] formula [III]: 18 wherein
R.sup.39, R.sup.41, which may be the same or different, are C1,
SO.sub.2(--R.sup.44)(--R.sup.45), or SO.sub.2R.sup.43; R.sup.44 and
R.sup.45, which may be the same or different, are independently
hydrogen atom, liner or branched C1-C4 alkyl, R.sup.43 is linear or
branched C1-C4 alkyl; R.sup.40 and R.sup.42, which may be the same
or different, are hydrogen, liner or branched C1-C18 alkyl group,
liner or branched C2-C18 alkenyl group, sulfonamide group, carboxyl
group, mesyl group, hydroxyl group, C1-C18 alkoxy group,
acethylamino group, benzoylamino group, halogen atom or
--CONH--R.sup.46; R.sup.46 is functional group selected from
unsubstituted or substituted liner or branched C1-C18 alkyl or
unsubstituted or substituted C6-C18 aryl group; L.sub.1 and L.sub.2
are independently O or COO; (E).sup.+ are H.sup.+, cation of alkali
metal, ammonium ion, cations of organic amine including aliphatic
primary, secondary and tertiary amines, quaternary ammonium ion;
K.sup.3 is an integer; m.sup.3 is 0, 1 or 2; and M.sup.1 is a metal
having ionic valency from 2 to 4.
3. The composition of claim 1 wherein the laser-transmitting black
colorant comprises amine salts of anthraquinone dye of formula [I]
wherein at least one of R.sup.9, R.sup.10, R.sup.11, R.sup.12 and
R.sup.13 of formula [I-a] is sulfonyl group.
4. The composition of claim 1 wherein the amount of the amine salts
of anthraquinone dyes of formula [I] or formula [II] compared to
the amount of monoazo complex dyes of the formula [III] is in a
ratio of from 5:1 to 1:1.
5. The composition of claim 1 wherein the thermoplastic resin is
polyamide or polyester.
6. The composition of claim 1 further comprising reinforcing
agent.
7. A transparent article for laser beam welding formed from the
composition of claim 1.
8. An article formed by laser welding an opaque article for laser
beam with the transparent article of claim 6 using said laser
beam.
9. A black colorant suitable for being mixed with a thermoplastic
resin used in laser welding applications applied to a laser welding
comprising a mixture of a) amine salts of anthraquinone dyes of
formula [I] or formula [II] wherein Formula [I] is: 19wherein
R.sup.1 to R.sup.8, which may be the same or different, are
independently selected from the group consisting of H, alkyl, aryl,
alkenyl, alkoxy, amino, hydroxy, halogen atom, acyl, acyloxy,
acylamide, acyl-N-alkylamide, carboxyl, alkoxycarbonyl,
cyclohexylamide, sulfonyl, formula [I-a], or --Y--W, and at least
one of R.sup.1 to R.sup.8 is of formula [I-a]; wherein Y is S, O,
or NH; and wherein W is selected from unsubstituted or substituted
alkyl group, alkenyl group, and unsubstituted or substituted aryl
group; wherein (Z).sup.n+ represents a cation derived from an
organic amine compounds or a basic dye; wherein n is 1 or 2,
m.sup.1 is an integer from 1 to 4 and K.sup.1 is the ratio of
m.sup.1/n; and wherein formula [I-a] is: 20wherein X is O or NH,
and R.sup.9 to R.sup.13, which may be the same or different, are
independently selected from the group consisting of H, alkyl, aryl,
alkenyl, alkoxy, amino, N-alkylamide, N-arylamide, hydroxy, halogen
atom, acyl, acyloxy, acylamide, acyl-N-alkylamide, carboxyl,
alkoxycarbonyl, or sulfonyl; wherein at least one of R.sup.1 to
R.sup.8 and R.sup.9 to R.sup.13 is sulfonyl group; wherein formula
[II] is: 21wherein R.sup.47 to R.sup.52, which may be the same or
different, are independently selected from the group consisting of
H, alkyl, aryl, alkenyl, alkoxy, amino, N-alkylamide, N-arylamide,
hydroxy, halogen atom, acyl, acyloxy, acylamide, acyl-N-alkylamide,
carboxyl, alkoxycarbonyl, or sulfonyl; and at least one of R.sup.47
to R.sup.52 is of sulfonyl, and formula J in formula [II] is
selected from formula [II-a] or formula [II-b] and binds two
anthraquinone; formula [II-a]: 22formula [II-b]: 23wherein R.sup.53
to R.sup.54, which may be the same or different, are independently
selected from the group consisting of alkyl (having 1 to 8 carbon
atoms) or hydrogen, and wherein (F).sup.h+ represents ammonium ion
or a cation derived from an organic amino compounds or a basic dye
wherein h is 1 or 2, m.sup.4 is an integer from 1 to 4 and K.sup.4
is the ratio of m.sup.4/h, and b) monoazo complex dye represented
by the formula [III] formula [III]: 24wherein R.sup.39, R.sup.41,
which may be the same or different, are C1,
SO.sub.2(--R.sup.44)(--R.sup.45), or SO.sub.2R.sup.43; R.sup.44 and
R.sup.45, which may be the same or different, are independently
hydrogen atom, liner or branched C1-C4 alkyl, R.sup.43 is linear or
branched C1-C4 alkyl; R.sup.40 and R.sup.42, which may be the same
or different, are hydrogen, liner or branched C1-C18 alkyl group,
liner or branched C2-C18 alkenyl group, sulfonamide group, carboxyl
group, mesyl group, hydroxyl group, C1-C18 alkoxy group,
acethylamino group, benzoylamino group, halogen atom or
--CONH--R.sup.46; R.sup.46 is functional group selected from
unsubstituted or substituted liner or branched C1-C18 alkyl or
unsubstituted or substituted C6-C18 aryl group; L.sub.1 and L.sub.2
are independently O or COO; (E).sup.+ are H.sup.+, cation of alkali
metal, ammonium ion, cations of organic amine including aliphatic
primary, secondary and tertiary amines, quaternary ammonium ion;
K.sup.3 is an integer; m.sup.3 is 0, 1 or 2; and M.sup.1 is a metal
having ionic valency from 2 to 4.
10. The composition of claim 8 where in the laser-transmitting
black colorant comprises amine salts of anthraquinone dye of
formula [I] where as at least one of R.sup.9, R.sup.10, R.sup.11,
R.sup.12 and R.sup.13 of formula [I-a] is sulfonyl group.
11. The composition of claim 8 where in the ratio of amount of the
amine salts of anthraquinone dyes of formula [I] or formula [II] to
that of monoazo complex dyes of the formula [III] is from 5:1 to
1:1.
Description
[0001] This application claims the benefit of U.S. Provisional
Application No. 60/247,948, filed Nov. 13, 2000.
FIELD OF THE INVENTION
[0002] The instant invention pertains to thermoplastic resin
compositions containing black colorants and suitable for laser
welding. More particularly the invention relates to such
compositions having as colorants mixtures of amine salts of
anthraquinone and monoazo complex dyes.
BACKGROUND OF THE INVENTION
[0003] It is known in the art to join together two articles made of
resins (and respectively opaque and transparent) by positioning
them in contact with each other, transmitting a predetermined
amount of laser beam focused on the junction of them and causing
the junction portion to be melted and joined together ("laser
welding"). Several advantages flow from laser welding versus
conventional methods of joining plastic parts. For example, laser
welding is widely known for its simple operation, labor savings,
improvement of productivity, clear joints, and reduction of
production cost. It is useful in various applications including the
preparation of molded articles, including hollow shapes, in
automobile industries and electric and electronic industries.
Recently, work has intensified in the area of blends of
thermoplastic resin and a colorant containing an organic dye or
pigment. Better control of the conversion of laser energy to heat
is achieved by the addition of such colorants to the resins. Laser
beams penetrate through transparent articles positioned closer to
the laser beam source, and are largely absorbed in the opaque
article, which has a relatively higher absorption coefficient in
comparison with the aforementioned transparent article. Careful
attention to the amount of the colorants therein results in the
junction portion being melted and the articles joined together.
[0004] See for example Japanese Published (Koukoku) Patent
No.62-49850 and Japanese Published (Koukoku) Patent No.5
(93)-42336. Other resin compositions associated with the laser
welding are described in U.S. Pat. No.5,893,959 which discloses
transparent and opaque workpiece parts welded together by a laser
beam along a joining zone. Both parts contain black dye pigments
such as carbon black to cause them to offer a substantially
homogenous visual impression even after welding.
[0005] Other illustrations of the laser welding of compositions are
found in U.S. Pat. No. 5,893,959. For example, the color of the
thermoplastic components may be black (carbon black or nigrosine)
which is commonly and widely used in the automobile industry among
other applications. However, carbon black and nigrosine cannot
transmit a laser beam with a main wavelength in the infra-red
region (1200 nm to 800 nm), such as Nd: YAG laser and a diode
laser, both of which are of wide use in industries.
[0006] Surprisingly, it has now been found that thermoplastic resin
compositions both black in appearance can be used for laser-welded
molded articles for both the transparent and opaque parts subjected
to the laser beam. A significantly improved transmission to
near-infrared light of the laser beam, with excellent and balanced
heat-resistance and mechanical properties as required in automobile
applications, is achieved by including a specific weight percentage
of black dyes comprising a mixture of amine salts of anthraquinone
dyes formed by reacting anthraquinone acid dyes.
[0007] Using these components, thermoplastic resin compositions can
be utilized for laser welding and exhibiting improvements in
moldability, solubility in the thermoplastic resin, bleeding- and
blooming-resistance as well as transparency to the wavelength of a
laser beam and resistance to chemicals.
SUMMARY OF THE INVENTION
[0008] This invention relates to thermoplastic compositions for
laser welding comprising 1) thermoplastic resin and, 2)
laser-transmitting black colorant comprising amine salts of
anthraquinone dye and monoazo complex dye.
[0009] This invention relates to improved thermoplastic resin
compositions for laser welding comprising thermoplastic resin, and
at least one black dye comprising a mixture of (i) amine salts of
anthraquinone dyes of formula [I] or formula [II] and (ii) monoazo
complex dye of formula [III]. Formula [I] is as follows: 1
[0010] wherein R.sup.1 to R.sup.8, which may be the same or
different, are independently selected from the group consisting of
H, alkyl, aryl, alkenyl, alkoxy, amino, hydroxy, halogen atom,
acyl, acyloxy, acylamide, acyl-N-alkylamide, carboxyl,
alkoxycarbonyl, cyclohexylamide, sulfonyl, formula [I-a], or
--Y--W, and at least one of R.sup.1 to R.sup.8 is of formula[I-a];
wherein Y is S, O, or NH; and wherein W is selected from
unsubstituted or substituted alkyl group, alkenyl group; and
unsubstituted or substituted aryl group; wherein (Z).sup.n+
represents ammonium ion or a cation derived from an organic amine
compounds or a basic dye wherein n is 1 or 2, m.sup.1 is an integer
from 1 to 4; and wherein K.sup.1 is the ratio of m.sup.1/n.
[0011] Formula [I-a] is: 2
[0012] wherein X is O or NH, and R.sup.9 to R.sup.13, which may be
the same or different, are independently selected from the group
consisting of H, alkyl, aryl, alkenyl, alkoxy, amino, N-alkylamide,
N-arylamide, hydroxy, halogen atom, acyl, acyloxy, acylamide,
acyl-N-alkylamide, carboxyl, alkoxycarbonyl, or sulfonyl, and at
least one of R.sup.1 to R.sup.8 and R.sup.9 to R.sup.13 is sulfonyl
group. Formula [II] is: 3
[0013] wherein R.sup.47 to R.sup.52, which may be the same or
different, are independently selected from the group consisting of
H, alkyl, aryl, alkenyl, alkoxy, amino, N-alkylamide, N-arylamide,
hydroxy, halogen atom, acyl, acyloxy, acylamide, acyl-N-alkylamide,
carboxyl, alkoxycarbonyl, or sulfonyl, and at least one of R.sup.47
to R.sup.52 is of sulfonyl; and formula J in formula [II] is
selected from formula [II-a] or formula [II-b] and binds two
anthraquinone. formula [II-a]: 4
[0014] formula [II-b]: 5
[0015] wherein R.sup.53 to R.sup.54, which may be the same or
different, are independently selected from the group consisting of
alkyl (having 1 to 8 carbon atoms) or hydrogen,
[0016] and wherein (F).sup.h+ represents ammonium ion or a cation
derived from an organic amino compounds or a basic dye wherein h is
1 or 2, m.sup.4 is an integer from 1 to 4 and K.sup.4 is the ratio
of m.sup.4/h. The monoazo complex dye of formula [III] is as
follows: 6
[0017] wherein R.sup.39 and R.sup.41, which may be the same or
different, are Cl, SO.sub.2(--R.sup.44)(--R.sup.45), or
SO.sub.2R.sup.43; R.sup.44 and R.sup.45, which may be the same or
different, are independently hydrogen atom, linear or branched
C1-C4 alkyl; R.sup.43 is linear or branched C1-C4 alkyl; R.sup.40
and R.sup.42, which may be the same or different, are hydrogen,
linear or branched C1-C18 alkyl group, linear or branched C2-C18
alkenyl group, sulfonamide group, carboxyl group, mesyl group,
hydroxyl group, C1-C18 alkoxy group, acethylamino group,
benzoylamino group, halogen atom or --CONH--R.sup.46; R.sup.46 is a
functional group selected from unsubstituted or substituted linear
or branched C1-C18 alkyl or unsubstituted or substituted C6-C18
aryl group; L.sub.1 and L.sub.2 are independently O or COO;
(E).sup.+ are H.sup.+; cations of alkali metals, ammonium ion,
cations of organic amines selected from the group consisting of
aliphatic primary, secondary and tertiary amines, and quaternary
ammonium ion; K.sup.3 is an integer; m.sup.3 is 0, 1 or 2; and
M.sup.1 is a metal having ionic valency from 2 to 4, preferably
trivalent metal such as Cr, Fe, or bivalent metal such as Cu.
[0018] By using these components, thermoplastic resin compositions
are obtained for laser welding having improved moldability,
solubility in the thermoplastic resin, bleeding- and
blooming-resistance, and resistance to chemicals. Improvements in
transparency to wavelength of a laser beam are also discussed,
particularly at wavelengths exceeding 800 nm by mixing the dye
salts mentioned of the formula [I] or formula [II] with monoazo
complex dyes of the formula [III] at predetermined weight ratios.
Particularly, the mixture serves to significantly improve
transmittance at diode laser beam wavelength than that by monoazo
complex dyes of formula [III] alone. These mixtures improve at the
diode laser beam wavelength much more than that observed with the
monoazo dye alone. See generally, WO01/58997 A1, for a discussion
of thermoplastic resins and monoazo complex dyes. Therefore they
are of interest in industrial diode laser welding.
[0019] The amine salts of anthraquinone dyes used as one of
components comprised in colorant in the invention exhibits colors
of blue, violet or green and the monoazo complex dyes comprised in
the colorants used in the invention are black dyes
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] The invention will be better understood upon having
reference to the drawings herein.
[0021] FIG. 1 is a view of the articles in contact and with a laser
beam applied thereto;
[0022] FIG. 2 is identical to FIG. 1, but with articles of the same
color.
[0023] FIGS. 3-4 depict the laser welding test carried out in this
application.
DETAILED DESCRIPTION OF THE INVENTION
[0024] The aforementioned dye salts of the desired structure
represented by formula [II] or formula [II] used in the invention
are prepared by commonly known methods, conveniently by reacting
anthraquinone dyestuff with organic amine in a solvent. Mixtures of
amine salts of anthraquinone dyes are formed by reacting
anthraquinone acid dyes with organic amine, particularly sulfonyl
group contained the dye reacting with ammonium salts from organic
amine.
[0025] Suitable amines for use in producing the above-mentioned
anthraquinone dyes in dyestuffs include aliphatic amine, alicyclic
amine, alkoxyalkyl amine, amine having alkanol, diamine, amine of
guanidine derivatives, and aromatic amine.
[0026] Basic dyes listed in the color index and useful in the
instant invention include,
[0027] C.I.basic red dye: C.I.basic red1, 2, 3, 4, 5, 6, 8, 9, 10,
11, 12, 13, 15, 16, 17, 19, 20, 26, 27, 35, 36, 37, 48, 49, 52, 53,
54, 66, 68,
[0028] C.I.basic blue dye: C.I.basic blue 1, 2, 3, 4, 5, 6, 7, 8,
9, 10, 11, 12, 13, 14, 15, 18, 20, 21, 22, 23, 24, 25, 26, 35, 36,
37, 45, 46, 47, 49, 50, 55, 56, 60, 62, 67, 75, 77, 79, 80, 81, 83,
87, 88, 89, 90, 94, 95, 96, 97,
[0029] C.I.basic violet dye: C.I.basic violet 1, 2, 3, 4, 5, 6, 7,
8, 10, 11, 12, 13, 14, 15, 16, 17, 20, 21, 23, 24, 25, 27, 40,
[0030] C.I.basic green dye: C.I.basic green 1, 3, 4, 6, 9, 10.
[0031] Examples of anthraquinone acid dyes which are useful in
preparation of the dye salts of formula [I] used as colorant
comprised in the compositions of the invention are given below in
Tables 1-1 and 1-2. Descriptions in the left hand column (such as
"I-2" and "I-13") will assist the reader in understanding
discussions about specific dye salts later in the description.
1TABLE 1-1 Pro. Ex. No. R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8 K.sup.1(Z).sup.n+ I-1 R.sup.2 =
R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.4 = OH, R.sup.1 =
R.sup.3 = I-a, Rosin anmmonium Formula[I-a]: X = NH, R.sup.11 =
NO.sub.2, R.sup.9 = SO.sub.3H or SO.sub.3.sup.-, R.sup.10 =
R.sup.12 = R.sup.13 = H I-2 R.sup.2 = R.sup.3 = R.sup.5 = R.sup.6 =
R.sup.7 = R.sup.8 = H, R.sup.4 = OH, R.sup.1 = I-a,
H.sub.3N.sup.+(CH.sub.2).sub.6NH.sub.2 Formula[I-a]: X = NH,
R.sup.11 = CH.sub.3, R.sup.9 = SO.sub.3.sup.-, R.sup.10 = R.sup.12
= R.sup.13 = H I-3 R.sup.2 = R.sup.3 = R.sup.5 = R.sup.6 = R.sup.7
= R.sup.8 = H, R.sup.1 = I-a, 'R.sup.4 = Y-W,
C.sub.12H.sub.25N.sup.+H.sub.3 Formula[I-a]: X = NH, R.sup.11 =
CH.sub.3, R.sup.9 = SO.sub.3.sup.-, R.sup.10 = R.sup.12 = R.sup.13
= H Y--W: Y = NH, W = CH.sub.3 I-4 R.sup.2 = R.sup.3 = R.sup.5 =
R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.1 = R.sup.4 = I-a,
(C.sub.4H.sub.9).sub.4N.sup.+ Formula[I-a]: X = NH, R.sup.11 =
CH.sub.3, R.sup.9 = SO.sub.3H or SO.sub.3.sup.-, R.sup.10 =
R.sup.12 = R.sup.13 = H I-5 R.sup.2 = R.sup.3 = R.sup.5 = R.sup.6 =
R.sup.7 = R.sup.8 = H, R.sup.1 = R.sup.4 = I-a,
H.sub.3N.sup.+(CH.sub.2).sub.6NH.- sub.2 Formula[I-a]: X = NH,
R.sup.9 = R.sup.11 = R.sup.13 = CH.sub.3, R.sup.12 = SO.sub.3H or
SO.sub.3.sup.-, R.sup.10 = H I-6 R.sup.2 = R.sup.3 = R.sup.5 =
R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.1 = R.sup.4 = I-a,
(N.sup.+H.sub.3).sub.2CNH Formula[I-a]: X = NH, R.sup.11 =
CH.sub.3, R.sup.9 = SO.sub.3.sup.-, R.sup.10 = R.sup.12 = R.sup.13
= H I-7 R.sup.2 = R.sup.3 = R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 =
H, R.sup.1 = R.sup.4 = I-a, H.sub.3N.sup.+(CH.sub.2-
).sub.6NH.sub.2 Formula[I-a]: X = NH, R.sup.11 = C.sub.4H.sub.9,
R.sup.9 = SO.sub.3H or SO.sub.3.sup.-, R.sup.10 = R.sup.12 =
R.sup.13 = H I-8 R.sup.2 = R.sup.3 = R.sup.5 = R.sup.7 = R.sup.8 =
H, R.sup.1 = R.sup.4 = I-a, R.sup.6 = Y-W,
H.sub.3N.sup.+(CH.sub.2).sub- .4NH.sub.2 Formula[I-a]: X = NH,
R.sup.11 = CH.sub.3, R.sup.9 = SO.sub.3H or SO.sub.3.sup.-,
R.sup.10 = R.sup.12 = R.sup.13 = H Y-W: Y = S, W = methylphenyl I-9
R.sup.2 = R.sup.3 = R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H,
R.sup.1 = R.sup.4 = I-a, 2(H.sub.3N.sup.+(CH.sub.2).sub.6NH.sub.2)
Formula[I-a]: X = NH, R.sup.11 = C.sub.4H.sub.9, R.sup.9 =
SO.sub.3.sup.-, R.sup.10 = R.sup.12 = R.sup.13 = H I-10 R.sup.2 =
R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.3 =
SO.sub.3.sup.-, R.sup.4 = NH.sub.2, R.sup.1 = I-a,
N-trimethyl-N-benzyl Formula[I-a]: X = NH, R.sup.11 =
N(C.sub.3H.sub.7)COCH.sub.3, R.sup.9 = R.sup.10 = R.sup.12 =
R.sup.13 = H Anmmonium I-11 R.sup.2 = R.sup.5 = R.sup.7 = R.sup.8 =
H, R.sup.3 = R.sup.6 = SO.sub.3.sup.-, R.sup.4 = NH.sub.2, R.sup.1
= I-a, 2(CH.sub.3).sub.4N.sup.+ Formula[I-a]: X = NH, R.sup.11 =
NHCOCH.sub.3, R.sup.9 = R.sup.10 = R.sup.12 = R.sup.13 = H I-12
R.sup.2 = R.sup.3 = R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H,
R.sup.1 = R.sup.4 = I-a, Diphenylguanidine Formula[I-a]: X = NH,
R.sup.9 = R.sup.11 = R.sup.13 = CH.sub.3, R.sup.12 = SO.sub.3H or
SO.sub.3.sup.-, anmmonium R.sup.10 = H I-13 R.sup.2 = R.sup.3 =
R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.1 = R.sup.4 = I-a,
Bis(p-methylphenyl) Formula[I-a]: X = NH, R.sup.11 = CH.sub.3,
R.sup.9 = SO.sub.3H or SO.sub.3.sup.-, R.sup.10 = R.sup.12 =
R.sup.13 = H guanidine anmmonium I-14 R.sup.2 = R.sup.3 = R.sup.4 =
R.sup.5 = R.sup.6 = R.sup.7 = H, R.sup.1 = R.sup.8 = I-a,
C.sub.12H.sub.25N.sup.+H.- sub.3 Formula[I-a]: X = NH, R.sup.11 =
CH.sub.3, R.sup.9 = SO.sub.3H or SO.sub.3.sup.-, R.sup.10 =
R.sup.12 = R.sup.13 = H I-15 R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8
= H, R.sup.1 = R.sup.4 = NH.sub.2, R.sup.2 = R.sup.3 = I-a,
(CH.sub.3).sub.4N.sup.+ Formula[I-a]: X = O, R.sup.11 = CH.sub.3,
R.sup.9 = SO.sub.3H or SO.sub.3.sup.-, R.sup.10 = R.sup.12 =
R.sup.13 = H Pro. Ex. No. = Product Example Number
[0032]
2TABLE 1-2 Pro. Ex. No. R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8 K.sup.1(Z).sup.n+ I-16 R.sup.5 =
R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.1 = R.sup.4 = NH.sub.2,
R.sup.2 = R.sup.3 = I-a, H.sub.3N.sup.+(CH.sub.2).sub.6NH.sub.2
Formula[I-a]: X = O, R.sup.11 = SO.sub.3H or SO.sub.3.sup.-,
R.sup.9 = R.sup.10 = R.sup.12 = R.sup.13 = H I-17 R.sup.3 = R.sup.6
= R.sup.7 = R.sup.8 = H, R.sup.2 = CH.sub.3, R.sup.4 = NH.sub.2,
R.sup.5 = SO.sub.3H or SO.sub.3.sup.-, R.sup.1 = I-a,
C.sub.4H.sub.9N.sup.+H.sub.3 Formula[I-a]: X = NH, R.sup.11 =
CH.sub.3, R.sup.9 = SO.sub.3H or SO.sub.3.sup.-, R.sup.10 =
R.sup.12 = R.sup.13 = H I-18 R.sup.3 = R.sup.6 = R.sup.7 = R.sup.8
= H, R.sup.2 = Br, R.sup.4 = NH.sub.2, R.sup.5 = SO.sub.3H or
SO.sub.3.sup.-, R.sup.1 = I-a,
H.sub.3N.sup.+(CH.sub.2).sub.4NH.sub.2 Formula[I-a]: X = NH,
R.sup.11 = CH.sub.3, R.sup.9 = SO.sub.3H or SO.sub.3.sup.-,
R.sup.10 = R.sup.12 = R.sup.13 = H I-19 R.sup.2 = R.sup.6 = R.sup.7
= R.sup.8 = H, R.sup.3 = OC.sub.12H.sub.25, R.sup.4 = NH.sub.2,
R.sup.5 = SO.sub.3H or SO.sub.3.sup.-, R.sup.1 = I-a,
C.sub.2H.sub.5OC.sub.3H.sub.6NH.sub.3.sup.+ Formula[I-a]: X = NH,
R.sup.11 = SO.sub.3H or SO.sub.3.sup.-, R.sup.9 = R.sup.10 =
R.sup.12 = R.sup.13 = H I-20 R.sup.2 = R.sup.3 = R.sup.6 = R.sup.7
= H.sup.,R.sup.4 = R.sup.8 = OH.sup.,R.sup.1 = R.sup.5 = I-a,
(C.sub.8H.sub.17).sub.4N.sup.+ Formula[I-a]: X = NH, R.sup.11 =
CH.sub.3, R.sup.9 = SO.sub.3H or SO.sub.3.sup.-, R.sup.10 =
R.sup.12 = R.sup.13 = H I-21 R.sup.2 = R.sup.3 = R.sup.5 = R.sup.6
= R.sup.7 = R.sup.8 = H, R.sup.1 = R.sup.4 = I-a,
2(H.sub.3N.sup.+(CH.sub- .2).sub.6NH.sub.2) Formula[I-a]: X = NH,
R.sup.9 = R.sup.11 = R.sup.13 = CH.sub.3, R.sup.12 =
SO.sub.3.sup.-, R.sup.10 = H I-22 R.sup.2 = R.sup.5 = R.sup.6 =
R.sup.7 = R.sup.8 = H, R.sup.3 = SO.sub.3.sup.-, R.sup.4 =
NH.sub.2, R.sup.1 = I-a, C.sub.4H.sub.9N.sup.+H.sub.3 Formula[I-a]:
X = NH, R.sup.11 = NHCOCH.sub.3, R.sup.9 = R.sup.10 = R.sup.12 =
R.sup.13 = H I-23 R.sup.2 = R.sup.3 = R.sup.5 = R.sup.6 = R.sup.7 =
R.sup.8 = H, R.sup.1 = R.sup.4 = I-a,
H.sub.3N.sup.+(CH.sub.2).sub.6NH.sub.2 Formula[I-a]: X = NH,
R.sup.11 = CH.sub.3, R.sup.9 = SO.sub.3H or SO.sub.3.sup.-,
R.sup.10 = R.sup.12 = R.sup.13 = H I-24 R.sup.2 = R.sup.3 = R.sup.4
= R.sup.5 = R.sup.6 = R.sup.7 = H, R.sup.1 = R.sup.8 = I-a,
C.sub.2H.sub.5OC.sub.3H.sub.6NH.sub.3.sup.+ Formula[I-a]: X = NH,
R.sup.11 = CH.sub.3, R.sup.9 = SO.sub.3H or SO.sub.3.sup.-,
R.sup.10 = R.sup.12 = R.sup.13 = H I-25 R.sup.2 = R.sup.5 = R.sup.6
= R.sup.7 = R.sup.8 = H, R.sup.3 = SO.sub.3.sup.-, R.sup.4 =
NH.sub.2, R.sup.1 = I-a, H.sub.3N.sup.+(CH.sub.2).sub.6NH.sub.2
Formula[I-a]: X = NH, R.sup.11 = NHCOCH.sub.3, R.sup.9 = R.sup.10 =
R.sup.12 = R.sup.13 = H I-26 R.sup.2 = R.sup.5 = R.sup.6 = R.sup.7
= R.sup.8 = H, R.sup.3 = SO.sub.3.sup.-, R.sup.4 = NH.sub.2,
R.sup.1 = I-a, Cyclohexyl Formula[I-a]: X = NH, R.sup.11 =
N(CH.sub.3)COCH.sub.3, R.sup.9 = R.sup.10 = R.sup.12 = R.sup.13 = H
anmmonium I-27 R.sup.2 = R.sup.3 = R.sup.5 = R.sup.6 = R.sup.7 =
R.sup.8 = H, R.sup.1 = R.sup.4 = I-a,
C.sub.2H.sub.5OC.sub.3H.sub.6N.sup.+H.sub.3 Formula[I-a]: X = NH,
R.sup.9 = R.sup.11 = R.sup.13 = CH.sub.3, R.sup.12 = SO.sub.3H or
SO.sub.3.sup.-, R.sup.10 = H I-28 R.sup.2 = R.sup.3 = R.sup.5 =
R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.4 = OH, R.sup.1 = I-a,
H.sub.3N.sup.+(CH.sub.2).sub.6NH.sub.2 Formula[I-a]: X = NH,
R.sup.11 = CH.sub.3, R.sup.9 = SO.sub.3.sup.-, R.sup.10 = R.sup.12
= R.sup.13 = H I-29 R.sup.2 = R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8
= H, R.sup.3 = SO.sub.3.sup.-, R.sup.4 = NH.sub.2, R.sup.1 = I-a,
N-trimethyl-N-benzyl Formula[I-a]: X = NH, R.sup.11 =
N(CH.sub.3)COCH.sub.3, R.sup.9 = R.sup.10 = R.sup.12 = R.sup.13 = H
Anmmonium I-30 R.sup.3 = R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H,
R.sup.1 = R.sup.4 = OH, R.sup.2 = I-a, N-tributhyl-N-benzyl
Formula[I-a]: X = NH, R.sup.9 = CH.sub.3, R.sup.11 =
SO.sub.3.sup.-, R.sup.10 = R.sup.12 = R.sup.13 = H anmmonium I-31
R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.1 = R.sup.4 =
NH.sub.2, R.sup.3 = SO.sub.3.sup.-, R.sup.2 = I-a,
C.sub.4H.sub.9N.sup.+H.sub.3 Formula[I-a]: X = O, R.sup.9 =
R.sup.10 = R.sup.11 = R.sup.12 = R.sup.13 = H I-32 R.sup.3 =
R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.4 = NH.sub.2, R.sup.2 =
R.sup.5 = SO.sub.3H or SO.sub.3.sup.-, R.sup.1 = I-a, Benzylurea
anmmonium Formula[I-a]: X = NH, R.sup.11 = C.sub.12H.sub.25,
R.sup.9 = R.sup.10 = R.sup.12 = R.sup.13 = H I-33 R.sup.2 = R.sup.5
= R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.3 = SO.sub.3.sup.-,
R.sup.4 = NH.sub.2, R.sup.1 = I-a,
H.sub.3N.sup.+(CH.sub.2).sub.6NH.sub.2 Formula[I-a]: X = NH,
R.sup.10 = COOC.sub.2H.sub.5, R.sup.9 = R.sup.11 = R.sup.12 =
R.sup.13 = H Pro. Ex. No. = Product Example Number
[0033] Examples of anthraquinone acid dyes which are useful in
preparation of the dye salts of formula [II] used as colorants in
the compositions of the invention are given below in Table 2.
3TABLE 2 Pro. Ex. No. J R.sup.47 R.sup.48 R.sup.49 R.sup.50
R.sup.51 R.sup.52 K.sup.4(F).sup.h+ II-1 Formula [II-a]
SO.sub.3.sup.- NH.sub.2 H SO.sub.3.sup.- NH.sub.2 H
2(H.sub.3N.sup.+(CH.sub.2).sub.6NH.sub.2).sup.+ II-2 formula [II-a]
SO.sub.3.sup.- NH.sub.2 H SO.sub.3H NH.sub.2 H
H.sub.3N.sup.+(CH.sub.2).sub.6NH.sub.2 II-3 formula [II-a]
SO.sub.3.sup.- OH H SO.sub.3H OH H C.sub.12H.sub.25N.sup.+H.sub.3
II-4 Formula [II-b], SO.sub.3.sup.- NH.sub.2 H NH.sub.2 Cl H
C.sub.2H.sub.5OC.sub.3H.sub.6N.sup.+H.sub.3 R.sup.53 = R.sup.54 = H
II-5 formula [II-b], SO.sub.3.sup.- NH.sub.2 H SO.sub.3H NH.sub.2 H
Bis(p-methylphenyl) R.sup.53 = R.sup.54 = CH.sub.3 guanidine
anmmonium II-6 formula [II-b], SO.sub.3.sup.- NH.sub.2 H
SO.sub.3.sup.- NH.sub.2 H
H.sub.3N.sup.+(CH.sub.2).sub.4N.sup.+H.sub.3 R.sup.53 = R.sup.54 =
CH.sub.3 II-7 formula [II-b], SO.sub.3.sup.- NH.sub.2 H SO.sub.3H
NH.sub.2 H Rosin anmmonium R.sup.53 = R.sup.54 = H II-8 formula
[II-b], SO.sub.3.sup.- NH.sub.2 H SO.sub.3H NH.sub.2 H
H.sub.3N.sup.+(CH.sub.2).sub.6NH.sub.2 R.sup.53 = R.sup.54 = H II-9
formula [II-b], SO.sub.3.sup.- OH OCH.sub.3 SO.sub.3H OH OCH.sub.3
(C.sub.4H.sub.9).sub.4N.sup.+ R.sup.53 = H, R.sup.54 = phenyl II-10
formula [II-b], SO.sub.3.sup.- C.sub.3H.sub.9 C.sub.3H.sub.9
SO.sub.3H H H N-tributhyl-N-benzyl R.sup.53 = R.sup.54 = H
Anmmonium Pro. Ex. No. = Product Example Number
[0034] Representative momoazo complex dyes represented by the
formula [III] have a number of characteristics associated with
them. For example, suitable cations for use in the monoazo complex
dyes are H.sup.+; cations of alkali metal, ammonium ion, cations of
organic amine including aliphatic primary, secondary and tertiary
amines, and quaternary ammonium ion.
[0035] Suitable amines for use in producing the above-mentioned
monoazo complex dyes and common in dyestuffs include aliphatic
amine, alicyclic amine, alkoxyalkyl amine, amine having alkanol,
diamine, amine of guanidine derivatives, and aromatic amine.
[0036] Suitable metals for producing the above-mentioned monoazo
complex dyes include metals having ionic valency from 2 to 4, more
preferably trivalent metal such as Cr, Fe, or bivalent metal such
as Cu.
[0037] Examples of the metal azo complex dyes of formula [III] are
identified below in Tables 3 and 4. These are classified as
formulas [III-a] and [III-b] respectively.
[0038] Formula [III-a]: 7
4TABLE 3 Pro. Ex. No. R.sup.39 R.sup.40 R.sup.41 R.sup.42 M.sup.1
L.sub.1 L.sub.2 m.sup.3 K.sup.3(E).sup.+ III-1 Cl H Cl H Cr O O 1
H.sup.+ III-2 SO.sub.2NH.sub.2 H SO.sub.2NH.sub.2 H Cr O O 1
H.sup.+ III-3 Cl H Cl H Cu O O 1 H.sup.+ III-4 SO.sub.2CH.sub.3 H
SO.sub.2CH.sub.3 H Cr O O 1 H.sup.+ III-5 Cl H Cl H Fe O O 1
K.sup.+ III-6 Cl benzoylamido Cl Benzoylamido Fe O O 1 H.sup.+
III-7 SO.sub.2NH.sub.2 H SO.sub.2NH.sub.2 H Cu O O 1 H.sup.+ III-9
Cl NHCOCH.sub.3 Cl NHCOCH.sub.3 Cr O O 1 NH.sub.4.sup.+ III-10 Cl H
Cl H Cr O O 1 C.sub.4H.sub.9CH(C.sub.2H.sub.5)OC.sub.3H.sub.6-
NH.sub.3.sup.+ III-11 Cl H Cl H Fe O O 1
C.sub.4H.sub.9CH(C.sub.2H.- sub.5)CH.sub.2NH.sub.3.sup.+ III-12 Cl
C.sub.8H.sub.17 Cl C.sub.8H.sub.17 Cr O O 1 NH.sub.4.sup.+ III-13
Cl H Cl H Cu COO COO 1 H.sup.+ III-14 SO.sub.2NH.sub.2 H
SO.sub.2NH.sub.2 H Cr O O 1 (C.sub.4H.sub.9).sub.4N.sup.+ III-15
SO.sub.2NH.sub.2 NHC.sub.4H.sub.9 SO.sub.2NH.sub.2 NHC.sub.4H.sub.9
Cr O O 1 H.sup.+ Pro. Ex. No. = Product Example Number
[0039] Formula [III-b]: 8
5TABLE 4 Pro. Ex. No. R.sup.39 R.sup.40 R.sup.41 R.sup.42 M.sup.1
L.sub.1 L.sub.2 m.sup.3 K.sup.3(E).sup.+ III-16 Cl H Cl H Fe O O 1
H.sup.+ III-17 SO.sub.2NH.sub.2 H SO.sub.2NH.sub.2 H Cu O O 1
H.sup.+ III-18 Cl H Cl H Cr O O 1 C.sub.12H.sub.25NH.sub.3.sup.+
III-19 Cl H Cl H Cu O O 1
C.sub.2H.sub.5OC.sub.3H.sub.6NH.sub.3.sup.+ III-20 Cl
C.sub.4H.sub.9 Cl C.sub.4H.sub.9 Cr COO COO 1 H.sup.+ Pro. Ex. No.
= Product Example Number
[0040] Examples of the black dyes containing a mixture of the dye
salts of formula [I] or formula [II] and the metal azo complex dyes
of formula [III] are below:
EXAMPLE 1
Black Dye
[0041] The anthraquinone dye salt of formula [1-21]: the monoazo
complex dye of the following formula [III-1] in a weight ratio of
1:1.
EXAMPLE 2
Black Dye
[0042] The anthraquinone dye salt of formula [I-21]: the monoazo
complex dye of the following formula [III-1] in a weight ratio of
3:1.
EXAMPLE 3
Black Dye
[0043] The anthraquinone dye salt of formula [I-6]: the monoazo
complex dye of the following formula [III-1] in a weight ratio of
2:1.
EXAMPLE 4
Black Dye
[0044] The anthraquinone dye salt of formula [I-23]: the monoazo
complex dye of the following formula [III-5] in a weight ratio of
2:1.
EXAMPLE 5
Black Dye
[0045] The anthraquinone dye salt of formula [II-8]: the monoazo
complex dye of the following formula [III-1] in a weight ratio of
3:1.
EXAMPLE 6
Black Dye
[0046] The anthraquinone dye salt of formula [I-5]: the monoazo
complex dye of the following formula [III-1]: anthraquinone yellow
dye of the following formula [a] in a weight ratio of 4:3:1.
[0047] Formula [a]: 9
EXAMPLE 7
Black Dye
[0048] The anthraquinone dye salt of formula [I-21]: the monoazo
complex dye of the following formula [III-1]: perinone red dye of
the following formula [b] in a weight ratio of6:3:1.
[0049] Formula [b]: 10
[0050] The anthraquinone dye salt of formula [I-21]: the
anthraquinone dye salt of formula [II-5]: the monoazo complex dye
of the following formula [III-14] in a weight ratio of 2:2:1.
[0051] The thermoplastic resins for use in the inventive
compositions include polyamides, polyesters, and the like as are
commonly used in making a molded product. As the examples of the
polyamide resins utilized in the present invention, condensation
products of dicarboxylic acids and diamines, condensation products
of aminocarboxylic acids and ring-opening polymerization products
of cyclic lactams can be cited. As examples of dicarboxylic acids,
adipic acid, azelaic acid, sebacic acid, dodecanedioic acid,
isophthalic acid and terephthalic acid can be cited. As examples of
diamines, tetramethylene diamine, hexamethylene diamine,
octamethylene diamine, nonamethylene diamine, dodecamethylene
diamine, 2-methylpentamethylene diamine, 2-methyloctamethylene
diamine, trimethylhexamethylene diamine,
bis(p-aminocyclohexyl)methane, m-xylene diamine and p-xylene
diamine may be cited. As the example of aminocarboxylic acid,
11-aminododecanoic acid can be cited. As the examples of cyclic
lactam, caprolactam and laurolactam can be cited. As the specific
examples of condensation products and ring-opening polymerization
products, aliphatic polyamides such as nylon 6, nylon 66, nylon 46,
nylon 610, nylon 612, nylon 11, nylon 12, semi-aromatic polyamides
such as polymetaxylene adipamide (nylon MXD6), polyhexamethylene
terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon
6I) and polynonamethylene terephthalamide (nylon 9T), and
copolymers and mixtures of these polymers can be cited. As the
examples of the copolymers, nylon 6/66, nylon 66/6I, nylon 6I/6T
and nylon 66/6T can be cited.
[0052] A wide range of common polyester molding compositions useful
for blending with colorants in the practice of the present
invention are know in the art. These include polymers which are, in
general, condensation products of dicarboxylic acids and diols.
Dicarboxylic acids can be selected from the group consisting of
adipic acid, azelaic acid, sebacic acid, dodecanedioic acid,
terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid
and diphenyl dicarboxylic acid, and diols can be selected from the
group consisting of ethylene glycol, propylene glycol, butanediol,
hexanediol, neopentyl glycol, cyclohexanediol, and bisphenol.A.
Preferred polyesters include polyethylene terephthalate (PET),
polypropylene terephthalate (3GT), polybutylene terephthalate
(PBT), polyethylene 2,6-naphthalate (PEN), polycyclohexane
dimethylene terephthalate (PCT) and copolymers and mixtures
thereof. As the examples of the copolymers, some of dicarboxylic
acids or some of diols can be added to the condensation products.
Polyester polymers may be copolymerized a little amount of
components like trimesic acid, trimellitic acid, pyromellitic acid,
glycerol, and pentaerythritol which have more than 3 functional
groups.
[0053] Additional other polymers such as polycarbonate can also be
presented, provided that the essential characteristics of the
composition of the present invention are not substantially
altered.
[0054] The mixture of the amine salts of anthraquinone dyes of
formula [I] or formula [II] with the monoazo complex dyes of the
formula [III] is present in amount of from 0.01 to 1% by weight
when the composition comprises polyamide 6 as at least the major
component of the polyamide resin composition.
[0055] The ratio of amount of the amine salts of anthraquinone dyes
of formula [I] or formula [II] to that of monoazo complex dyes of
the formula [III] may be specialized for applications requiring
different properties associated with the laser welding.
Particularly, the preferable ratio of amount of them is from 5:1 to
1:1. If the ratio of amount of them is more than 5:1 (in other
words if the amount of the amine salts of anthraquinone dyes is too
much), there cannot obtain black colorant as colored resin
compositions. On the other hand, if the ratio of amount of them is
less than 1:1 (in other words if the amount of the monoazo complex
dyes is too much), transmittance in diode laser beam wavelength
(808 nm) is deteriorate.
[0056] The composition of the present invention may contain an
inorganic filler or reinforcing agent that includes, for example,
fibrous reinforcement such as glass fiber and carbon fiber, glass
flakes, glass beads, talc, kaolin, wollastonite, silica, calcium
carbonate, potassium titanate and mica. Glass fiber and glass
flakes are a preferred selection. Glass fibers suitable for use in
the present invention are those generally used as reinforcing
agents for thermoplastic resins and thermosetting resins. The
preferred amount of glass fiber in the resin composition of the
present invention is from about 5 to about 120 parts by weight,
with respect to 100 parts by weight of the thermoplastic resin. If
it is under 5 weight percent, it would be difficult to give
sufficient reinforcement from the glass fiber, and if it is over
120 weight percent, it would have poor processibility and poor
transparency to laser. It is preferable to use about 5 to about 100
weight percent, and particularly preferable at about 15 to about 85
weight percent.
[0057] One or more optional compounds selected from a wide variety
of compounds tailored for different applications of the resin
compositions can be contained in the composition according to the
present invention, as is understood among those having skill in the
art.
[0058] Typically, additive compounds can include flame retardants,
impact modifiers, viscosity modifiers, heat resistance improvers,
lubricants, antioxidants and UV-and other stabilizers. The
thermoplastic resin compositions of the present invention may have
such additive compounds in suitable amounts so as not to harm
characteristic properties of the composition.
[0059] In the present invention, thermoplastic resin compositions
are provided that are suitable for laser welding, including
transparent articles for laser beam transmission to achieve welding
together with the opaque article for laser beam absorption.
Suitable opaque articles and its compositions are described for
example in DE-A-4432081.
[0060] FIG. 1 is an illustration of a conventional laser welding
arrangement. A laser beam 1 is transmitted through the first
article 2 to the second article 3 containing laser beam absorbing
combination, and the surface 4 of the second article 3 that have
absorbed the laser energy 1 is melted and pressed with the surface
of the first article 2 to weld them together. As shown in FIG. 2,
two thermoplastic components must have different transmission and
absorption coefficients and it is difficult to weld two articles
having the same color. However, a problem with conventional
compositions associated with the laser welding is that when a laser
beam 1 is transmitted through the first article 2 to the second
article 3 containing laser beam absorbing combination, and the
surface 4 of the second article 3 that have absorbed the laser
energy 1 is melted and pressed with the surface of the first
article 2 to weld them together, as shown in FIG. 1, two
thermoplastic components have to have different transmission and
absorption coefficients and it is difficult to weld two articles
having the same color. Therefore, a significant attribute of the
instant invention is the use of both laser transmitting and laser
absorbing parts molded by using two different compositions of which
one is to transmit laser beam and another is to absorb it. Both are
black in appearance and have other necessary properties for
molding.
EXAMPLES
[0061] The present invention is illustrated by the following
examples and comparative examples.
Example A
[0062] 400 grams of (unreinforced) Nylon 6 ZYTEL pellets (available
from E. I. DuPont de Nemours and Co., under the product name
ZYTEL.RTM. 7301) were dried under vacuum at 120.degree. C., for
more than 8 hours, then mixed with a mixture of amine salt of
anthraquinone dye of formula [I-21] (0.40 g) with monoazo complex
black dye represented by the following formula [III-1] (0.40 g) in
a stainless tumble mixer with stirring for one hour. The mixture
was then injection molded to form the injection molded test
specimens (whose sizes are 48 mm.times.86 mm.times.3 mm) using
K50-C produced by Kawaguchi Steel K. K. and the cylinder
temperature was set to 250.degree. C. Mold temperature was
60.degree. C. Good and uniformly black appearance and surface gloss
without color shading of the specimens were observed.
Example B
[0063] 400 grams of (unreinforced) Nylon 6 ZYTEL pellets (available
from E. I. DuPont de Nemours and Co., under the product name
ZYTEL.RTM. 7301) were dried under vacuum at 120.degree. C., for
more than 8 hours, then mixed with a mixture of amine salt of
anthraquinone dye of formula [I-21] (0.40 g) with monoazo complex
black dye of the following formula [III-2] (0.40 g) in a stainless
tumble mixer with stirring for one hour. The mixture was then
injection molded to form the injection molded test specimens (whose
sizes are 48 mm.times.86 mm.times.3 mm) using K50-C produced by
Kawaguchi Steel K. K. and the cylinder temperature was set to
250.degree. C. Mold temperature was 60.degree. C. Good and
uniformly black appearance and surface gloss without color shading
of the specimens were observed.
Example C
[0064] 400 grams of (unreinforced) Nylon 66 ZYTEL101 pellets
(available from E. I. DuPont de Nemours and Co.) were dried under
vacuum at 120.degree. C., for more than 8 hours, then mixed with a
mixture of amine salt of anthraquinone dye of formula [II-8] (0.40
g) with monoazo complex black dye represented by the following
formula [III-1] (0.40 g) in a stainless tumble mixer with stirring
for one hour. The mixture was then injection molded to form the
injection molded test specimens (whose sizes are 48 mm.times.86
mm.times.3 mm) using K50-C produced by Kawaguchi Steel K. K. and
the cylinder temperature was set to 290.degree. C. Mold temperature
was 60.degree. C. Good and uniformly black appearance and surface
gloss without color shading of the specimens were observed.
Comparative Example D
[0065] 400 grams of (unreinforced) Nylon 6 ZYTEL pellets (available
from E. I. DuPont de Nemours and Co., under the product name
ZYTEL.RTM. 7301) were dried under vacuum at 120.degree. C., for
more than 8 hours, then mixed with a mixture of anthraquinone green
dye of the following formula [c] (0.40 g) with monoazo complex
black dye of the formula [III-1] (0.40 g) in a stainless tumble
mixer with stirring for one hour. The mixture was then injection
molded to form the injection molded test specimens (whose sizes are
48 mm.times.86 mm.times.3 mm) using K50-C produced by Kawaguchi
Steel K. K. and the cylinder temperature was set to 250.degree. C.
Mold temperature was 60.degree. C. Black appearance of the
specimens were observed.
[0066] Formula [c]: 11
[0067] 400 grams of (unreinforced) Nylon 6 ZYTEL pellets (available
from E. I. DuPont de Nemours and Co., under the product name
ZYTEL.RTM. 7301) were dried under vacuum at 120.degree. C., for
more than 8 hours, then mixed with a mixture of anthraquinone
violet dye of the following formula [d] (0.40 g) with monoazo
complex black dye (C.I.Acid Black 52 diphenylguanidine salts) (0.40
g) in a stainless tumble mixer with stirring for one hour. The
mixture was then injection molded to form the injection molded test
specimens (whose sizes are 48 mm.times.86 mm.times.3 mm) using
K50-C produced by Kawaguchi Steel K. K. and the cylinder
temperature was set to 250.degree. C. Mold temperature was
60.degree. C. Good and uniformly black appearance and surface gloss
without color shading of the specimens were observed.
[0068] Formula [d]: 12
Test Procedures
[0069] (1) Transmission Properties
[0070] Transmittance (T) in the range of 400 nm to 1200 nm of the
test plates with laser beams having respective wavelengths of 940
nm (Semiconductor laser) and 1064 nm (YAG laser) was measured using
a U-3410 spectrometer producted by Hitachi with 60 .phi. sphere
photometer for wavelength from ultraviolet to near-infrared. The
ratio (TA) of transmission with 940 nm : transmission with 1064 nm,
the ratio (TB) of transmission with 940 nm: transmission of natural
resin are determined and compared between the examples and the
ratio (TC) of transmission with 1064 nm: transmission of natural
resin are determined and compared between the examples.
[0071] (2) Appearance and surface gloss
[0072] Appearance of the test plates were evaluated by measuring
Reflection Density (OD) of the test plates by Refelection Density
meter TR-927 produced by Macbeth. Test is plates having higher OD
values are judged to have better surface smoothness and rich in
gloss.
[0073] (3) Light Resistance
[0074] Each test plate was exposed to Xenon Weather Meter (
produced by Toyo Seiki K. K., trade name: AtlasCI-4000) for 150
hours according to the following condictions, the amount of color
fading and discoloration E between "before" and "after" light
irradiation was determined and measured using a colorimeter
(produced by Juki, trade name: JP 7000).
6 Conditions of Light Resistance Test Procedure Radial illumination
(W/m.sup.2)(E) 60 Black standard temperature (.degree. C.) 83 Rain
test N Chamber temeparture (.degree. C.) 55 Moisture (%) 50
[0075] The test plate having greater E are judged to have greater
discoloring and fading.
[0076] (4) Thermal Resistance
[0077] The amount of color fading and discoloration E between
before and after each test plate being placed and kept in an oven
at 160.degree. C. for 15 days was determined and measured using a
colorimeter (produced by Juki, trade name: JP 7000).
[0078] (5) Moisture Resistance
[0079] The amount of color fading and discoloration E between
before and after each test plate being placed and kept in a
thermoregulator at 80.degree. C. (a humidity was 95%) for one week
was determined and measured using a calorimeter (produced by Juki,
trade name: JP 7000).
[0080] (6) Solubility Resistance in organic solvents
[0081] The amount of color fading and discoloration E between
before and after each test plate being immersed in ethyleneglycol
and made airtight, then kept in thermoregulator at 40.degree. C.
for 48 hours was determined and measured using a colorimeter
(produced by Juki, trade name: JP 7000).
[0082] The test plate having greater E are judged to have greater
discoloring and fading.
[0083] The results are set forth in the following Table 5.
7 TABLE 5 Comparative Comarative Example A Example B Example C
Example D Example E Transmission TA 0.83 0.82 0.77 0.63 0.48 TB
0.81 0.90 0.74 0.62 0.45 TC 0.90 1.03 0.89 0.96 0.93 OD 2.55 2.51
2.49 2.52 2.43 Light Resistance .DELTA.E 1.16 1.29 -- 1.33 1.39
Thermal Resistance .DELTA.E 0.51 0.60 0.72 0.80 0.75 Solubility
Resistance Test Plate 0.18 0.15 -- 0.84 0.68 .DELTA.E Solvent 0.09
0.04 -- 1.05 0.83 Moisture Resistance .DELTA.E 0.14 0.16 0.26 1.22
0.94
[0084] This testing demonstrates that Examples A, B and C showed as
high transmittance as a natural resin at a main wavelength in
infra-red region (800 nm to 1200 nm). In Examples A, B and C,
thermal, solubility and moisture resistances were good, compared
with Comparative Examples D and E. Because Comparative Examples D
and E including a neutral anthraquinone have property to dissolve
from the test piece in ethyleneglycol and have high possibility to
discolor in rich humid atmosphere.
[0085] In Example F; G and Comparative Example H, we inspected the
influence of the transmittance is inspected against the ratio of
amine salt of anthraquinone dye to monoazo complex black dye.
Example F
[0086] 400 grams of (unreinforced) Nylon 6 ZYTEL pellets (available
from E. I. DuPont de Nemours and Co., under the product name
ZYTEL.RTM. 7301) were dried under vacuum at 120.degree. C., for
more than 8 hours, then mixed with a mixture of amine salt of
anthraquinone dye of formula [I-21] (0.53 g) with monoazo complex
black dye represented by the following formula [III-I] (0.27 g) in
a stainless tumble mixer with stirring for one hour. The mixture
was then injection molded to form the injection molded test
specimens (whose sizes are 48 mm.times.86 mm.times.3 mm) using
K50-C produced by Kawaguchi Steel K. K. and the cylinder
temperature was set to 250.degree. C. Mold temperature was
60.degree. C. Good and uniformly black appearance and surface gloss
without color shading of the specimens were observed.
Example G
[0087] 400 grams of (unreinforced) Nylon 6 ZYTEL pellets (available
from E. I. DuPont de Nemours and Co., under the product name
ZYTEL.RTM. 7301) were dried under vacuum at 120.degree. C., for
more than 8 hours, then mixed with a mixture of amine salt of
anthraquinone dye of formula [I-21] (0.60 g) with monoazo complex
black dye represented by the following formula [III-1] (0.20 g) in
a stainless tumble mixer with stirring for one hour. The mixture
was then injection molded to form the injection molded test
specimens (whose sizes are 48 mm.times.86 mm.times.3 mm) using
K50-C produced by Kawaguchi Steel K. K. and the cylinder
temperature was set to 250.degree. C. Mold temperature was
60.degree. C. Good and uniformly black appearance and surface gloss
without color shading of the specimens were observed.
Comparative Example H
[0088] 400 grams of (unreinforced) Nylon 6 ZYTEL pellets (available
from E. I. DuPont de Nemours and Co., under the product name
ZYTEL.RTM. 7301) were dried under vacuum at 120.degree. C., for
more than 8 hours, then mixed with monoazo complex black dye
represented by the following formula [III-1] (0.80 g) in a
stainless tumble mixer with stirring for one hour. The mixture was
then injection molded to form the injection molded test specimens
(whose sizes are 48 mm.times.86 mm.times.3 mm) using K50-C produced
by Kawaguchi Steel K. K. and the cylinder temperature was set to
250.degree. C. Mold temperature was 60.degree. C. Good and
uniformly black appearance and surface gloss without color shading
of the specimens were observed.
[0089] Table 6 provides a comparison of Examples F, G and
Comparative Example H.
8 TABLE 6 Comparative Example F Example G Example H Transmission TA
0.85 0.88 0.43 TB 0.82 0.85 0.42 TC 0.90 0.90 0.88 OD 2.45 2.45
2.45 Thermal Resistance .DELTA.E 0.36 0.56 0.25 Moisture Resistance
.DELTA.E 0.26 0.36 0.20 Comparative Example H showed low
transmittance at diode laser wavelength (800 nm to 950 nm).
Therefor, it is not a good candidate.
Example I
Example M, Comparative Example N, O Laser welding test
[0090] Pellets of unreinforced nylon 6 (available from E. I. DuPont
de Nemours and Co., under the product name ZYTEL.RTM. 7301) and
dyes were dry-blended with the amount described on the table 7. The
blended material was molded into test pieces for laser welding,
with dimension illustrated as FIG. 3, on the K50-C injection
molding machine (manufactured by Kawaguchi Steel K. K.) with
cylinder temperature set at 250.degree. C. and mold temperature set
at 60.degree. C. Transmittance of the 2-mm thick part of the above
molded test piece was measured with U-3410 spectrometer
(manufactured by Hitachi) and transmittance at 940 nm was
recorded.
[0091] Laser welding was conducted using two pieces of the test
pieces described above, combined as illustrated in FIG. 4. Each
Example from I to M and Comparative Example N was used as Upper
test piece and Comparative Example O was used as Lower test piece.
Diode laser (wavelength 940 nm, manufactured by Rofin-Sinar Laser
GmbH) was irradiated at 50 W power and with speed at 1 m/minute,
with 3 mm diameter. Strength of the welded test pieces was measured
on Autograph (manufactured by Shimazu Seisakusho) by pulling apart
at 50 mm/minute and its maximum load was recorded.
[0092] In FIG. 3 herein, there is shown a lower test piece 10 used
in the laser welding test of these examples. The noted dimensions
create a notch in the test piece 10. The upper test piece 9 is of
the same construction and dimensions. In FIG. 4, there is show the
joinder of upper test piece 9 to lower test piece 10, and the
movement of the laser 11 (in the direction of the arrow) to form
the weld.
9 TABLE 7 Example Example Example Example Example Comp. Comp. I J K
L M Ex. N Ex. O Nylon 6 400 g 400 g 400 g 400 g 400 g 400 g 400 g
Amine salt of 0.67 g 0.64 g 0.6 g 0.53 g 0.40 g 0.80 g
anthraquinone dye [I-21] Monoazo complex black 0.13 g 0.16 g 0.2 g
0.27 g 0.40 g dye [III-1] NUBIAN COMPLEX 0.80 g BLACK G04 Color
Appearance Black Black Black Black Black Blue Black Transmittance
at 940 nm 68% 67% 66% 65% 63% 71% 0.12% (2 mm thick) Laser Weld
Strength (kgf) 162 165 174 166 142 176 -- NUBIAN COMPLEX BLACK G04
(Product name: product of Orient Chemical Industries Ltd): a
mixture of carbon and nigrosine.
* * * * *