U.S. patent application number 10/047686 was filed with the patent office on 2003-05-08 for colored thermoplastic resin compositions for laser welding, specific neutral anthraquinone dyes as colorants therefor, and molded product therefrom.
Invention is credited to Hatase, Yoshiteru, Hayashi, Ryuichi, Koshida, Reiko, Sumi, Hiroyuki.
Application Number | 20030088076 10/047686 |
Document ID | / |
Family ID | 22935738 |
Filed Date | 2003-05-08 |
United States Patent
Application |
20030088076 |
Kind Code |
A1 |
Koshida, Reiko ; et
al. |
May 8, 2003 |
Colored thermoplastic resin compositions for laser welding,
specific neutral anthraquinone dyes as colorants therefor, and
molded product therefrom
Abstract
Thermoplastic resin compositions suitable for laser welding are
disclosed, which include a mixture of neutral anthraquinone blue
dye with other red dye to absorb visible light with wavelength less
than 700 nm and transmit a laser beam with wavelength at 800 nm to
1200 nm and to enhance weldability.
Inventors: |
Koshida, Reiko; (Utsunomiya,
JP) ; Hatase, Yoshiteru; (Osaka, JP) ;
Hayashi, Ryuichi; (Tokyo, JP) ; Sumi, Hiroyuki;
(Tochigi-ken, 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: |
22935738 |
Appl. No.: |
10/047686 |
Filed: |
November 13, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60247647 |
Nov 13, 2000 |
|
|
|
Current U.S.
Class: |
534/653 |
Current CPC
Class: |
B29K 2995/0073 20130101;
B29C 66/7315 20130101; B29K 2995/0022 20130101; B29C 65/1674
20130101; B29C 65/8238 20130101; B29C 66/43 20130101; B29C 66/73921
20130101; C08K 5/0041 20130101; C08K 5/3467 20130101; B29C 66/836
20130101; B29K 2995/0027 20130101; B29C 66/1282 20130101; B29C
66/73321 20130101; B29C 65/1635 20130101; B29C 66/7212 20130101;
B29C 66/73362 20130101; B29K 2309/08 20130101; C08K 5/3437
20130101; B29C 65/16 20130101; B29C 65/1616 20130101; B23K 26/009
20130101; B29K 2995/0089 20130101; B29C 66/71 20130101; B29C
65/8207 20130101; B29K 2101/12 20130101; B29C 66/73361 20130101;
B29K 2995/002 20130101; B29K 2105/06 20130101; B29C 65/8215
20130101; B23K 26/18 20130101; B29C 65/1677 20130101; B29C 66/12841
20130101; B29C 65/1654 20130101; B29C 66/14 20130101; C08K 5/17
20130101; B29C 66/7212 20130101; B29K 2307/04 20130101; B29C 66/71
20130101; B29K 2077/00 20130101; B29C 66/7212 20130101; B29K
2309/08 20130101; B29C 66/71 20130101; B29K 2067/003 20130101; B29C
66/71 20130101; B29K 2067/006 20130101; B29C 66/71 20130101; B29K
2067/00 20130101 |
Class at
Publication: |
534/653 |
International
Class: |
C09B 056/00 |
Claims
1. A thermoplastic resin composition for laser welding comprising:
1) thermoplastic resin; and, 2) a laser beam transmitting black
colorant comprising neutral anthraquinone dye of formula [I] or
[II]wherein formula [I] is 19wherein R.sup.55 and R.sup.58, which
may be the same or different, are independently selected from alkyl
groups having 1 to 18 carbon atoms; and R.sup.56 and R.sup.59,
which may be the same or different, are independently selected from
the group consisting of alkyl, aryl, alkenyl, alkoxy, amino,
N-alkylamide, N-arylamide, acyl, acylamide, alkoxycarbonyl,
hydroxy, and carboxy groups and halogen atom; and R.sup.57 and
R.sup.60, 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, acyl, acylamide, carboxy,
alkoxycarbonyl, and hydroxy groups and halogen atom, and wherein
formula [II] is 20wherein R.sup.61, R.sup.62, R.sup.63, and R64,
which may be the same or different, are independently selected from
the group consisting of H, alkyl, alkenyl, aryl, alkoxy, amino,
N-alkylamide, N-arylaminde, acyl, acylamide, carboxy,
alkoxycarbonyl, hydroxy group, halogen atom, formula [II-a], and
P.sup.1 is NR.sup.66 or CO, wherein R.sup.66 is H, alkyl, or aryl
groups. formula [II-a] is: 21wherein p.sup.2 is NH or NHCO;
R.sup.65 is H, alkyl, aryl, alkoxy, amino, hydroxy, or halogen
atom.
2. The composition of claim 1 wherein the thermoplastic resin is
polyamide or polyester.
3. The composition of claim 1 further comprising a second dye mixed
with said neutral anthraquinone dye to produce said black
colorant.
4. The composition of claim 3 wherein said second dye is selected
from the group consisting of perinone dyes, monoazo complex dyes,
and anthraquinone dyes.
5. The composition of claim 1 further comprising reinforcing
agent.
6. A transparent article formed from the composition of claim
1.
7. An article formed by laser welding opaque articles with the
transparent article of claim 5.
8. A black colorant suitable for being mixed with a thermoplastic
resin and for laser welding, comprising a mixture of neutral
anthraquinone dye of formula [I] or [II] which imparts color of
blue, absorbs visible light with wavelength less than 700 mn and
transmit a laser beam with wavelength at 800 nm to 1200 nm in
infra-red region with at least one other red dye which transmits
the laser beam with wavelength at 800 nm to 1200 nm in infra-red
region. 22wherein R.sup.55 and R.sup.58, which may be the same or
different, are independently selected from alkyl groups having 1 to
18 carbon atoms; and R.sup.56 and R.sup.59, which may be the same
or different, are independently selected from the group consisting
of alkyl, aryl, alkenyl, alkoxy, amino, N-alkylamide, N-arylamide,
acyl, acylamide, alkoxycarbonyl, hydroxy, and carboxy groups and
halogen atom; and R.sup.57 and R.sup.60, 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,
acyl, acylamide, carboxy, alkoxycarbonyl, and hydroxy groups and
halogen atom, and 23wherein R.sup.61, R.sup.62, R.sup.63, and
R.sup.64, which may be the same or different, are independently
selected from the group consisting of H, alkyl, alkenyl, aryl,
alkoxy, amino, N-alkylamide, N-arylaminde, acyl, acylamide,
carboxy, alkoxycarbonyl, hydroxy group, halogen atom, formula
[II-a], and P.sup.1 is NR.sup.66 or CO, wherein R.sup.66 is H,
alkyl, or aryl groups. formula [II-a] is: 24wherein p.sup.2 is NH
or NHCO; R.sup.65 is H, alkyl, aryl, alkoxy, amino, hydroxy, or
halogen atom.
Description
[0001] This application claims the benefit of U.S. Provisional
Application No.60/247,647, filed Nov. 13, 2000.
FIELD OF THE INVENTION
[0002] The instant invention relates to thermoplastic resin
compositions with specific anthraquinone dyes. More particularly,
the inventions relates to such compositions having improved laser
weldability.
BACKGROUND OF THE INVENTION
[0003] It is known in the art to join together two articles of
resins (and respectively opaque and transparent) by positioning
them in contact with each other, transmitting a predetermined
amount of laser beam focusing 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 ofjoining plastic parts.
[0004] 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.
[0005] 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 and
pigments such as carbon black to cause them to offer a
substantially homogenous visual impression even after welding.
[0006] Other illustrations of the laser welding of compositions are
found in the 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 industries and
other applications. However, carbon black and nigrosine can not
transmit a laser beam with a main wavelength in infra-red region
(1200 nm to 800 nm), such as Nd:YAG laser and a diode laser which
are of wide use in industries.
[0007] Surprisingly, it has now been found that thermoplastic resin
compositions both black in appearance can be used for laser-welded
molded articles, and both for 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.
[0008] The object of the present invention is to offer a
thermoplastic resin composition capable of offering moldings which
appear in black, offer excellent thermal resistance, and are
transparent to a laser beam, in particular to the near-infrared
light region. A further object of the invention is to provide
select anthraquinone blue dyes which offer minimal discoloration
during molding and in high temperature applications. A feature of
the invention is the compositions herein can provide a
substantially homogenous visual black impression of transparent and
opaque articles that appears in black and absorbs the laser beam
largely by containing black dyes, welded together by the laser
beam, and possess excellent and balanced heat-resistance and
mechanical properties as required in automotive parts,
electric/electronic components, mechanical components, and many
other applications. The aforementioned objects, features and
advantages will become better understood upon having reference to
the following description of the invention herein.
SUMMARY OF THE INVENTION
[0009] This invention relates to an improved thermoplastic resin
compositions for laser welding comprised of thermoplastic resin and
a black colorant comprising at least neutral anthraquinone dye
which imparts color of blue, absorbs visible light with wave length
less than 700 nm and transmits a laser beam with wavelength at 800
nm to 1200 nm. In addition to said neutral anthraquinone dye, other
red dye which transmit the laser beam with wavelength at 800 nm to
1200 nm in infra-red region, such as perinone dyes or monoazo
complex dyes can be present at predetermined weight ratio.
[0010] The present invention, which allows the sated objective to
be attained, concerns a thermoplastic resin composition for laser
welding comprising:
[0011] 1) thermoplastic resin; and,
[0012] 2) a laser beam transmitting black colorant comprising
neutral anthraquinone dye of formula [I] or [II]
[0013] wherein formula [I] is 1
[0014] wherein R.sup.55 and R.sup.58 , which may be the same or
different, are independently selected from alkyl groups having 1 to
18 carbon atoms; and R56 and R.sup.59, which may be the same or
different, are independently selected from the group consisting of
alkyl, aryl, alkenyl, alkoxy, amino, N-alkylamide, N-arylamide,
acyl, acylamide, alkoxycarbonyl, hydroxy, and carboxy groups and
halogen atom; and R.sup.57 and R.sup.60, 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,
acyl, acylamide, carboxy, alkoxycarbonyl, and hydroxy groups and
halogen atom,
[0015] and wherein formula [II] is 2
[0016] wherein R.sup.61, R.sup.62, R.sup.63, and R.sup.64, which
may be the same or different, are independently selected from the
group consisting of H, alkyl, alkenyl, aryl, alkoxy, amino,
N-alkylamide, N-arylaminde, acyl, acylamide, carboxy,
alkoxycarbonyl, hydroxy group, halogen atom, formula [II-a], and
P.sup.1 is NR or CO, wherein R.sup.66 is H, alkyl, or aryl
groups.
[0017] formula [II-a] is: 3
[0018] wherein p.sup.2 is NH or NHCO; R.sup.65 is H, alkyl, aryl,
alkoxy, amino, hydroxy, or halogen atom.
[0019] With these components, thermoplastic resin compositions for
laser welding offer improvements in moldability, solubility in the
thermoplastic resin, bleeding and blooming-resistance, transparency
to wavelengths of a laser beam at 800 nm to 1200 nm and resistance
to chemicals. Another advantage is that the composition provides
the greater color value to produce the black colorant because of
the said neutral anthraquinone dye of formula [I] or [II] as a
major component of said colorant and higher heat resistance.
Therefore, the compositions of the present invention comprising the
black colorant comprising at least said neutral anthraquinone dye
as the major component are extremely suitable for thermoplastic
resins which requiring melt temperature higher than 300.degree. C.
during molding operation.
[0020] The compositions of the invention may also contain other
yellow dyes in addition to the mixture of anthraquinone dyes with
red dyes as one of components of black dyes used as a colorant of
the composition, preferably anthraquinone yellow dyes.
[0021] The actual amount of respective dyes which are useful in the
practice of the invention will depend upon kind of thermoplastic
resins blended with the dyes, the desired colors, the desired depth
of shade and thickness of molded articles of the composition of the
invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The invention will be better understood upon having
reference to the drawings herein.
[0023] FIG. 1 is a view of the articles in contact with and with a
laser beam applied thereto; and
[0024] FIG. 2 is identical to FIG. 1, but with the articles of the
same color.
[0025] FIG. 3 illustrates a shape and dimensions of a test piece
creating a notch in the test piece (60 mm.times.18 mm).
[0026] FIG. 4 is a perspective view of test pieces of FIG. 3
disposed close to each other for a laser welding test and
relationship between the test pieces and laser beam.
[0027] FIG. 5 illustrates a shape and dimensions of a test piece
creating a notch in the test piece (80 mm.times.40 mm).
[0028] FIG. 6 is a perspective view of test pieces of FIG. 5
disposed close to each other for a laser welding test and
relationship between the test pieces and laser beam
DETAILED DESCRIPTION OF THE INVENTION
[0029] Examples of the anthraquinone dyes of Formulas [I] and [II]
having the above-mentioned properties used as the main component
forming the black dye contained in the composition of the invention
are listed in Tables 1 and 2 respectively.
1TABLE1 Pro. Ex. No R.sup.55 R.sup.56 R.sup.57 R.sup.58, R.sup.59
R.sup.60 I-1 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 H I-2 CH.sub.3
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 I-3 CH.sub.3
C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 C.sub.2H.sub.5
C.sub.2H.sub.5 I-4 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3
C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 I-5 C.sub.2H.sub.5
C.sub.2H.sub.5 H C.sub.2H.sub.5 C.sub.2H.sub.5 H I-6 CH.sub.3
C.sub.12H.sub.25 H CH.sub.3 C.sub.12H.sub.25 H I-7 CH.sub.3
OCH.sub.3 H CH.sub.3 OCH.sub.3 H I-8 CH.sub.3 CH.sub.3 Cl CH.sub.3
CH.sub.3 Cl I-9 CH.sub.3 CH.sub.3 C.sub.4H.sub.9 CH.sub.3 CH.sub.3
C.sub.4H.sub.9 I-10 CH.sub.3 CH.sub.3 OH CH.sub.3 CH.sub.3 OH Pro.
Ex. No. = Product Example Number
[0030]
2 TABLE2 Pro. Ex. No P.sup.1 R.sup.61 R.sup.62 R.sup.63 R.sup.64
II-1 NH OH H OH H II-2 NH Cl H Cl H II-3 NH H Br H Br II-4 NH
CH.sub.3 CH.sub.3 H H II-5 NCH.sub.3 H H H H II-6 NH NH.sub.2 H
NH.sub.2 H II-7 NH H H H H II-8 NH OH H H H II-9 NH anilino H
anilino H II-10 NH benzamide H benzamide H II-11 CO
NHC.sub.4H.sub.9 H NHC.sub.4H.sub.9 H II-12 CO NH.sub.2 H NH.sub.2
H Pro. Ex. No. = Product Example Number
[0031] The above mentioned formula dyes offer superior color value
when forming the black color, as well as high heat resistance.
[0032] Various additional dyes (like red, orange, and yellow dye
forming black color) in the composition of the invention are
reviewed below.
[0033] The perinone dyes which are mixed with the above-mentioned
anthraquinone dyes for use as a black colorant comprised in the
composition of the invention are known products of formula [III].
4
[0034] The perinone dyes which are mixed with the anthraquinone to
produce a black dye may be used alone or in combination
thereof.
[0035] Preferred perinone dyes used in the composition of the
invention when solubility and / or dispersion in the resin are
considered, are those of formula [IV], 5
[0036] wherein P and Q, which may be the same or different, are
independently constituent units which can be represented by the
following formula [IV-a] to [IV-c]. R.sup.14 to R.sup.29, which may
be the same or different, are independently an atom or a group
selected from the group consisting of H, halogen atom such as Cl,
Br, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1
to 18 carbon atoms, aralkyl group, aryl group; m.sup.6 is the
number of 1 or 2. 6
[0037] Dyes which belong to the class of perinone dyes listed in
color index are for example C.I.Solvent Orange 60, 78, C.I.Solvent
Red 135, 162, 178, 179, C.I.Violet 29, C.I.Pigment Orange 43,
C.I.Pigment Red 149. If solubility and dispersibility in the resin
are enhanced, solvent type dyes are preferred.
[0038] Examples of the perinone dyes of formula [IV] are
illustrated below in Table 3.
3TABLE3 Pro. Ex. No P Q m.sup.6 IV-1 Formula [IV-b], Formula
[IV-a], 1 R.sup.18 = R.sup.19 = R.sup.20 = R.sup.21 = R.sup.22 =
R.sup.23 = H R.sup.14 = R.sup.15 = R.sup.16 = R.sup.17 = H IV-2
Formula [IV-b], Formula [IV-a], 1 R.sup.18 = R.sup.19 = R.sup.20 =
R.sup.21 = R.sup.22 = R.sup.23 = H R.sup.14 = R.sup.15 = R.sup.16 =
R.sup.17 = Cl IV-3 Formula [IV-b], Formula [IV-c], 1 R.sup.18 =
R.sup.19 = R.sup.20 = R.sup.21 = R.sup.22 = R.sup.23 = H R.sup.24 =
R.sup.25 = R.sup.26 = R.sup.27 = R.sup.28 = R.sup.29 = H IV-4
Formula [IV-a], Formula [IV-b], 1 R.sup.14 = R.sup.15 = R.sup.16 =
R.sup.17 = H R.sup.18 = R.sup.19 = R.sup.20 = R.sup.21 = R.sup.22 =
R.sup.23 = H IV-5 Formula [IV-b], Formula [IV-c], 1 R.sup.18 =
R.sup.19 = R.sup.20 = R.sup.21 = R.sup.22 = R.sup.23 = H R.sup.24 =
R.sup.25 = R.sup.26 = R.sup.27 = R.sup.28 = R.sup.29 = H, R.sup.25
= OC.sub.2H.sub.5 IV-6 Formula [IV-b], Formula [IV-a], 1 R.sup.18 =
R.sup.19 = R.sup.20 = R.sup.21 = R.sup.22 = R.sup.23 = H R.sup.14 =
R.sup.15 = R.sup.17 = H, R.sup.16 = benzoyl IV-7 Formula [IV-b],
Formula [IV-a], 2 R.sup.18 = R.sup.19 = R.sup.20 = R.sup.22 =
R.sup.23 = H, R.sup.21 = C.sub.4H.sub.9 R.sup.14 = R.sup.17 = H
IV-8 Formula [IV-b], Formula [IV-c], 1 R.sup.18 = R.sup.19 =
R.sup.20 = R.sup.21 = R.sup.22 = R.sup.23 = H R.sup.24 = R.sup.26 =
R.sup.27 = R.sup.28 = R.sup.29 = H, R.sup.25 = phenyl IV-9 Formula
[IV-b], Formula [IV-a], 1 R.sup.18 = R.sup.19 = R.sup.20 = R.sup.21
= R.sup.22 = R.sup.23 = H R.sup.15 = R.sup.16 = R.sup.17 = H,
R.sup.14 = Br IV-10 Formula [IV-b], Formula [IV-a], 1 R.sup.18 =
R.sup.19 = R.sup.20 = R.sup.21 = R.sup.22 = R.sup.23 = H R.sup.15 =
R.sup.16 = R.sup.17 = H, R.sup.14 = COOH Pro. Ex. No. = Product
Example Number
[0039] The monoazo complex dyes which are mixed with the
anthraquinone dyes of formula [I] or formula [II] to produce a
black dye for use as colorant comprised in the composition of the
invention, can be represented by formula [V]. 7
[0040] 5n.sup.2- wherein R.sup.30 and R.sup.31, which may be the
same or different, are Cl, SO.sub.2R.sup.32,
SO.sub.2(-R.sup.33)(-R.sup.34), or H; wherein R.sup.33 and
R.sup.34, which may be the same or different, are independently
hydrogen K.sup.2(D).sup.+ atom, linear or branched C1- C4 alkyl;
R.sup.32 is linear or branched C1- C4 alkyl; L.sub.3 and L.sub.4
are independently O or COO; (D).sup.+ is hydrogen ion, cation of
alkali metals, ammonium ion, cations of organic amine including
aliphatic primary, secondary and tertiary amines, or quaternary
ammonium ion; K.sup.2 is an integer; m.sup.2 is 0, 1 or 2; ,
M.sup.2 is selected from metals of ionic valency from 2 to 4 (such
as Zn, Sr, Cr, Al, Ti, Fe, Zr, Ni, Mn, B[boron] and Co), preferably
metal of trivalent metal such as Cu or trivalent metal such as Cr,
Co, Ni, and Al. and B.sup.1 and B.sup.2 are represented by formula
[V-a] or formula [V-b]. 8
[0041] wherein R.sup.35 and R.sup.37, which may be the same of
different, are Cl, SO.sub.2R.sup.32,
SO.sub.2(-R.sup.33)(-R.sup.34), or H; R.sup.33 and R.sup.34, which
may be the same or different, are independently hydrogen atom,
linear or branched C1- C4 alkyl; and R.sup.36 and R.sup.38, which
may be the same or different, are independently hydrogen atom,
linear or branched C1- C18 alkyl, carboxyl, hydroxyl, C1- C18
alkoxy, amino or halogen atoms.
[0042] Suitable cations for use in the above-mentioned monoazo
complex dyes are H.sup.+; cations of alkali metal, ammonium ion,
cations of organic amine including aliphatic primary, secondary and
tertiary amines, quaternary ammonium ion.
[0043] 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.
[0044] Examples of the monoazo complex dyes of formula [V], wherein
B.sup.1 and B.sup.2 are of the formula [V-a] are below and in Table
4. 9
4TABLE4 Pro. Ex. No R.sup.30 R.sup.31 R.sup.35 R.sup.36 M.sup.2
L.sub.3 L.sub.4 m.sup.2 K.sup.2(D).sup.+ V-1 H H H H Cr COO COO 1
H.sup.+ V-2 Cl Cl SO.sub.2NH.sub.2 H Cr O O 1 H.sup.+ V-3
SO.sub.2NH.sub.2 SO.sub.2NH.sub.2 SO.sub.2NH.sub.2 H Cr O O 1
H.sup.+ V-4 Cl Cl SO.sub.2NH.sub.2 H Co O O 1 H.sup.+ V-5
SO.sub.2NH.sub.2 SO.sub.2NH.sub.2 H H Ni O O 1 H.sup.+ V-6 H H
SO.sub.2NH.sub.2 H Cu COO COO 1 H.sup.+ V-7 H H H H Cr COO COO 1
C.sub.4H.sub.9CH(C.sub.2H.sub.5)OC.sub.3H.sub.6N.sup.+H.sub.3 V-8
Cl Cl SO.sub.2NH.sub.2 H Cu O O 1
C.sub.12H.sub.25N.sup.+H.sub.2(CH.sub.2- CH.sub.2O).sub.2H V-9 Cl
Cl SO.sub.2NH.sub.2 H Cr O O 1 Na.sup.+ V-10 Cl SO.sub.2NH.sub.2 H
Cl Co O O 1 H.sup.+ Pro. Ex. No. = Product Example Number
[0045] Examples of the monoazo complex dyes of formula [V], wherein
B.sup.1 and B.sup.2 are of the formula [V-b] are below and in Table
5. 10
5TABLE5 Pro. Ex. No R.sup.30 R.sup.31 R.sup.35 R.sup.36 M.sup.2
L.sub.3 L.sub.4 m.sup.2 K.sup.2(D).sup.+ V-11 SO.sub.2NH.sub.2
SO.sub.2NH.sub.2 H H Co O O 1 H.sup.+ V-12 H H SO.sub.2NH.sub.2 H
Cr COO COO 1 H.sup.+ V-13 Cl Cl H H Co O O 1
C.sub.4H.sub.9CH(C.sub.2H.sub.5)OC- .sub.3H.sub.6N.sup.+H.sub.3
V-14 SO.sub.2NH.sub.2 SO.sub.2NH.sub.2 SO.sub.2NH.sub.2 H Cr O O 1
NH.sub.4.sup.+ V-15 Cl Cl SO.sub.2NH.sub.2 H Co COO COO 1 H.sup.+
V-16 H H SO.sub.2NH.sub.2 H Co COO COO 1 H.sup.+ Pro. Ex. No. =
Product Example Number
[0046] We can obtain a black colorant having superior heat
resistance by combining specific neutral anthraquinone dyes with
the above mentioned monoazo complex red dyes or yellow dyes.
[0047] The above mentioned monoazo complex dyes offer superior heat
resistance.
[0048] The anthrapyridone dyes which are mixed with the
anthraquinone dyes of formula [I] or formula [II] to produce a
black dye for use as colorants of the invention, can be represented
by formula [VI], 11
[0049] wherein R.sup.67 to R.sup.71, 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, or formula [VI-a]; and
at least one of R.sup.67 to R.sup.74 is of sulfonyl; wherein
P.sup.3 is C--R.sup.72 or N; R.sup.72 is H, alkyl, aryl, alkoxy,
benzoyl, or benzyl; wherein (G).sup.s+ represents ammonium ion or a
cation derived from organic amine compounds or a basic dye; wherein
s is 1 or 2, m.sup.5 is an integer from 1 to 4 and K.sup.5 is the
ratio of m.sup.5/s; 12
[0050] and further wherein P.sup.4 is O or NH, and R.sup.73 to
R.sup.75, 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, acylamido, acyl-N-alkylamide, carboxyl,
alkoxycarbonyl, or sulfonyl.
[0051] Suitable amines for use in producing the above-mentioned
anthrapyridone dyes in dyestuffs include aliphatic amine, alicyclic
amine, alkoxyalkyl amine, amine having alkanol, diamine, amine of
guanidine derivatives, and aromatic amine.
[0052] Examples of the anthrapyridone dyes of formula [VI] are
given below in Table 6.
6TABLE 6 Pro. Ex. No R.sup.67, R.sup.68, R.sup.69, R.sup.70,
R.sup.71 P.sup.3 K.sup.5(G).sup..SIGMA.+ VI-1 R.sup.68 = R.sup.69 =
R.sup.71 = H, R.sup.67 = CH.sub.3, R.sup.70 = formula [VI-a], CH
H.sub.3N.sup.+(CH.sub.2).sub.6NH.sub.2 Formula [VI-a]: P.sup.4 =
NH, R.sup.73 = SO.sub.3.sup.-, R.sup.74 = R.sup.75 = H VI-2
R.sup.68 = R.sup.69 = R.sup.71 = H, R.sup.67 = CH.sub.3, R.sup.70 =
formula [VI-a], CH (CH.sub.3).sub.3N.sup.+C.sub.12H.- sub.25
Formula [VI-a]: P.sup.4 = NH, R.sup.73 = SO.sub.3.sup.-, R.sup.74 =
R.sup.75 = H VI-3 R.sup.68 = R.sup.69 = R.sup.71 = H, R.sup.67 =
CH.sub.3, R.sup.70 = formula [VI-a], CH
C.sub.2H.sub.5OC.sub.3H.sub.6N.sup.+H.sub.3 Formula [VI-a]: P.sup.4
= NH, R.sup.73 = SO.sub.3.sup.-, R.sub.74 = R.sub.75 = H VI-4
R.sup.68 = R.sup.69 = R.sup.71 = H, R.sup.67 = CH.sub.3, R.sup.70 =
formula [VI-a], CH C.sub.4H.sub.9N.sup.+H.sub.3 Formula [VI-a]:
P.sup.4 = NH, R.sup.73 = SO.sub.3.sup.-, R.sub.74 = CH.sub.3,
R.sub.75 = H VI-5 R.sup.68 = R.sup.69 = R.sup.71 = H, R.sup.67 =
CH.sub.3, R.sup.70 = formula [VI-a], CH N-trimethyl-N-benzyl
Formula [VI-a]: P.sup.4 = NH, R.sup.73 = SO.sub.3.sup.-, R.sub.74 =
CH.sub.3, R.sub.75 = H Anmmonium VI-6 R.sup.68 = R.sup.69 =
R.sup.71 = H, R.sup.67 = CH.sub.3, R.sup.70 = formula [VI-a], CH
2(CH.sub.3).sub.4N.sup.+ Formula [VI-a]: P.sup.4 = NH, R.sup.73 =
R.sup.74 = SO.sub.3.sup.-, R.sup.75 = H VI-7 R.sup.68 = R.sup.69 =
R.sup.71 = H, R.sup.67 = CH.sub.3, R.sup.70 = formula [VI-a], CH
C.sub.12H.sub.25N.sup.+H.sub.2(CH.sub.2CH.sub.2O).sub.2H Formula
[VI-a]: P.sub.4 = NH, R.sup.73SO.sub.3.sup.-, R.sup.74=
C.sub.4H.sub.9, R.sub.75 = H VI-8 R.sup.68 = R.sup.69 = R.sup.71 =
H, R.sup.67 = CH.sub.3, R.sup.70 = formula [VI-a], CH
N-trimethyl-N-benzyl Formula [VI-a]: P.sub.4 = NH, R.sup.73 =
SO.sub.3.sup.-, R.sup.74 = Cl, R.sup.75 = H Anmmonium VI-9 R.sup.68
= R.sup.69 = R.sup.71 = H, R.sup.67 = CH.sub.3, R.sup.70 = formula
[VI-a], N C.sub.2H.sub.5OC.sub.3H- .sub.6N.sup.+H.sub.3 Formula
[VI-a]: P.sup.4 = NH, R.sup.73 = SO .sub.3.sup.-, R.sup.74 =
CH.sub.3, R.sup.75 = H VI-10 R.sup.68 = R.sup.69 = R.sup.71 = H,
R.sup.67 = CH.sub.3, R.sup.70 = formula [VI-a], N
C.sub.12H.sub.25N.sup.+H.sub.3 Formula [VI-a]: P.sup.4 = NH,
R.sup.73 = SO.sub.3.sup.-, R.sup.74 = C.sub.8H.sub.17, R.sup.75 = H
VI-11 R.sup.68 = R.sup.69 = R.sup.71 = H, R.sup.67 = H, R.sup.70 =
formula [VI-a], C--C.sub.4H.sub.9 Bis(p-methylphenyl) Formula VI-a:
P.sup.4 = NH, R.sup.73 = SO.sub.3.sup.-, R.sup.74 = R.sup.75 =
CH.sub.3 guanidine anmmonium VI-12 R.sup.67 = R.sup.69 = R.sup.71 =
H, R.sup.68 = formula [VI-a] - 1, C-benzoyl
(CH.sub.3).sub.3N.sup.+C.s- ub.12H.sub.25 R.sup.70 = formula [VI-a]
- 2, Formula [VI-a]-1: P.sup.4 = O, R.sup.73 = SO.sub.3.sup.-,
R.sup.74 = C.sub.13H.sub.27, R.sup.75 = H Formula [VI-a]-2: P.sup.4
= NH, R.sup.73 = SO.sub.3.sup.-, R.sup.74 = R.sup.75 = CH.sub.3
VI-13 R.sup.67 = R.sup.69 = R.sup.71 = H, R.sup.68 = formula [VI-a]
- 1, C-benzoyl N-trimethyl-N-benzyl R.sup.70 = formula [VI-a] - 2,
anmmonium Formula [VI-a]- 1: P.sup.4 = O, R.sup.73 =
SO.sub.3.sup.-, R.sup.74 = CH.sub.3, R.sup.75 = H Formula [VI-a]-2:
P.sup.4 = NH,R.sup.73 = SO.sub.3.sup.-, R.sup.74 = R.sup.75 =
CH.sub.3 VI-14 R.sup.68 = R.sup.69 = R.sup.71 = H, R.sup.67 =
CH.sub.3, R.sup.70 = formula [VI-a], C-benzoyl
(C.sub.4H.sub.9).sub.4N.su- p.+ Formula [VI-a]: P.sup.4O,
R.sup.73SO.sub.3.sup.-, R.sup.74 = R.sup.75 = H VI-15 R.sup.68 =
R.sup.69 = R.sup.71 = H, R.sup.67 = CH.sub.3, R.sup.70 = formula
[VI-a], CH N-trimethyl-N-benzyl Formula [VI-a]: P.sup.4 = NH,
R.sup.73 = SO.sub.3.sup.-, R.sup.74 = R.sup.75 = H anmmonium VI-16
R.sup.68 = R.sup.69 = R.sup.71 = H, R.sup.67 = CH.sub.3, R.sup.70 =
formula [VT-a], CH H.sub.3N.sup.+(CH.sub.2).sub.6NH.sub.2 Formula
[VI-a]: P.sup.4 = NH, R.sup.73 = SO.sub.3.sup.-, R.sup.74 =
CH.sub.3, R.sup.75 = H VI-17 R.sup.68 = R.sup.69 = R.sup.71 = H,
R.sup.67 = CH.sub.3, R.sup.70 = formula [VI-a], N
Diphenyilguanidine Formula [VI-a]: P.sup.4 = NH, R.sup.73 =
SO.sub.3.sup.-, R.sup.74 = C.sub.8H.sub.17, R.sup.75 = H anmmonium
Pro. Ex. No. = Product Example Number
[0053] The anthraquinone dyes which absorb less than 500 nm and
have colors such as yellow, orange and red, can be mixed with the
neutral anthraquinone to produce black colors are described in the
COLOR INDEX below.
[0054] Red dyes:
[0055] C.I. Solvent Red 52, 57, 111, 114, 136, 137, 138, 139, 143,
144, 145, 146, 147,
148,149,150,151,152,155,156,168,169,170,171,172,177,181,19-
0,191,194, 199,200,201.
[0056] Orange dyes:
[0057] C.I. Solvent Orange 35, 55, 64, 65, 66, 68, 69, 71, 77, 86,
87, 163.
[0058] Yellow dyes:
[0059] C.I. Solvent Yellow 100, 109, 117, 125, 156, 158, 163 or
C.I. Vat Yellow 1, 2, 3.
[0060] Compositions suitable to produce the black dyes are reviewed
immediately below.
Example 1
Black Dye
[0061] The neutral anthraquinone dye of the formula [I-2]: perinone
red dye of the formula [IV-3]: anthraquinone yellow dye of the
following formula [a] in a weight ratio of 5:3:2. 13
Example 2
Black Dye
[0062] The neutral anthraquinone dye of the formula [I-3]: perinone
red dye of the formula [IV-3]: anthraquinone yellow dye of the
following formula [a] in a weight ratio of 5:4:1.
Example 3
Black Dye
[0063] The neutral anthraquinone dye of the formula [II-9]:
perinone red dye of the formula [IV-2]: anthraquinone yellow dye of
the formula [a] in a weight ratio of 6:3:1.
Example 4
Black Dye
[0064] The neutral anthraquinone dye of the formula [II-3]:
perinone red dye of the formula [IV-3]: anthraquinone yellow dye of
the following formula [b] in a weight ratio of 3:2:1. 14
Example 5
Black Dye
[0065] The neutral anthraquinone dye of the formula [I-4]: monoazo
complex dye of the formula [V-2]: anthraquinone yellow dye of the
formula [a] in a weight ratio of 6:2:1.
Example 6
Black Dye
[0066] The neutral anthraquinone dye of the formula [I-5]: monoazo
complex dye of the formula [V-3]: anthraquinone yellow dye of the
formula [b] in a weight ratio of 5:2:1.
Example 7
Black Dye
[0067] The neutral anthraquinone dye of the formula [II-4]: monoazo
complex dye of the formula [V-2]: anthraquinone yellow dye of the
formula [a] in a weight ratio of 5:3:2.
Example 8
Black Dye
[0068] The neutral anthraquinone dye of the formula [I-1]:
anthrapyridone dye of the formula [VI-5]: anthraquinone yellow dye
of the following formula [a] in a weight ratio of 5:4:1.
Example 9
Black Dye
[0069] The neutral anthraquinone dye of the formula [I-2]:
anthrapyridone dye of the formula [VI-2]: monoazo complex dye of
the formula [V-16]: in a weight ratio of 5:3:1.
Example 10
Black Dye
[0070] The neutral anthraquinone dye of the formula [II-4]: monoazo
complex dye of the formula [V-2]: anthraquinone yellow dye of the
formula [b] in a weight ratio of 6:3:1. The resins utilized as the
molded resins for laser welding may be any resin as long as they
are thermoplastic resins. Polyamide resins and polyester resins are
preferred from the point of view of heat-resistance and
transmitting property, although other thermoplastic resins
including polycarbonate resins can be used as well, alone, in
combination with each other, or in combination with those
preferable resins above.
[0071] Several examples of polyamide resins suitable for use in the
present invention include condensation products of dicarboxylic
acids and diamines, condensation products of aminocarboxylic acids
and ring-opening polymerization products of cyclic lactams.
Examples of dicarboxylic acids useful in this application include
adipic acid, azelaic acid, sebacic acid, dodecanedioic acid,
isophthalic acid and terephthalic acid. Examples of suitable
diamines include tetramethylene diaamine, 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. As an example of aminocarboxylic acid, 11-aminododecanoic
acid can be used. Examples of useful cyclic lactams include
caprolactam and laurolactam. Specific examples of condensation
products and ring-opening polymerization products include 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 MXD-6), polyhexamethylene
terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon
6I) and polynonamethylene terephthalamide (nylon 9T), and
copolymers and mixtures of these polymers. Examples of useful
copolymers include nylon 6/66, nylon 66/61, nylon 61/6T and nylon
66/6T.
[0072] A wide range of common polyester molding compositions useful
for blending with colorants in the practice of the present
invention are known 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, prcpylene glycol, butanediol,
hexanediol, neopentyl glycol, cyclohexanediol, and bisphenol A.
Preferred polyesters include polyethylene terephtalate (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
compnents like trimesic acid, trimellitic acid, pyromellitic acid,
glycerol, and pentaerythritol which have more than 3 functional
groups. Additional other polymers including polycarbonate can also
be presented, provided that the essential characteristics of the
composition of the present invention are not substantially
altered.
[0073] A black colorant useful in the composition of the invention
preferably comprises a mixture of neutral anthraquinone dye which
imparts colors of blue, absorbs visible light with wavelength less
than 700 nm and transmits a laser beam with wavelength at 800 nm to
1200 nm in infra-red region with at least other red dyes which
transmit the laser beam with wavelength at 800 nm to 1200 nm in
infra-red region, such as perinone dyes or monoazo complex dyes, at
predetermined weight ratios.
[0074] The black colorant containing the neutral anthraquinone dye
is present in amounts 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. The amount of the
above-mentioned dye mixture may be determined by applications
requiring different properties associated with the laser
welding.
[0075] 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
beads, glass flakes, talc, kaolin, wollastonite, silica, calcium
carbonate, pottassium titanate and mica. Preferable among them is
glass fiber. Glass fibers suitable for use in the present invention
are those generally used as reinforcing agents for thermoplastic
resins and thermosetting resins.
[0076] 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.
[0077] Typically, additive compounds can include flame retardants,
impact modifiers, viscosity modifiers, heat resistance improvers,
lubricants, antioxidants and UV-and other stabilizers. The
polyamide resin composition of the present invention may have such
additive compounds in such amounts that they do not harm its
characteristic properties.
[0078] In the present invention, there is provided thermoplastic
resin compositions suitable for laser welding, which prepare
transparent articles for laser beam to achieve welding together
with the opaque article for laser beam. Suitable opaque articles
and its compositions are described for example in DE-A-4432081.
[0079] Having reference to the drawings herein, FIG. 1 is an
illustration of a conventional 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 article 3 that have absorbed the laser energy is melted and
pressed with the surface of the first article 2 to weld them
together. As shown in FIG. 2, two thermoplastic components 5 and 6
must have different transmission and absorption coefficients and it
is difficult to weld at surface 8 two articles having the same
color. In FIG. 2 the laser beam 1 is applied to the surface 7 of
the component 5.
[0080] In FIGS. 3 and 5 herein, there is shown a lower test piece
10 used in the laser welding test of these examples. The noted
dimensions creates a notch in the test piece 10. The upper test
piece 9 is of the same construction and dimensions. In FIGS. 4 and
6, there is shown the joinder of the 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.
EXAMPLES
[0081] The present invention is illustrated by the following
examples and comparative examples.
Example A
[0082] Unreinforced nylon 6 ZYTEL.RTM. pellets (available from El
DuPont de Nemours & Co. under the name ZYTEL.RTM. 7301) was
dried at 120.degree. C. for more than 8 h using a drying apparatus,
and weighed according to the following formulation.
7 Nylon 6 400 g Anthraquinone blue dye of the following formula
[I-2] 0.40 g Perinone red dye of the following formula [IV-3] 0.24
g Anthraquinone yellow dye of the following formula [a] 0.16 g
[0083] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0084] For this and all other testing involving this particular
grade of nylon, A homogeneous, black experimental piece
(48.times.86.times.3 (mm)) having excellent appearance and surface
gloss with no color unevenness was obtained after the
aforementioned resulting mixture was injection molded by a usual
method at 250.degree. C. cylinder temperature and 60.degree. C.
molding temperature using an injection molding machine (Product of
Kawaguchi Tekko Co., trade name: K50-C). The experimental piece
obtained after keeping in an injection molding machine for 15
minutes was fadeless.
Example B
[0085]
8 Nylon 6 (same as Example A) 400 g Anthraquinone blue dye of the
following formula [I-4] 0.36 g Perinone red dye of the following
formula [IV-3] 0.28 g Anthraquinone yellow dye of the following
formula [b] 0.16 g
[0086] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0087] Test pieces were prepared and tested as described for
Example A, above, and the results are reported in Table 7, below.
The experimental piece obtained after keeping in an injection
molding machine for 15 minutes was fadeless.
9 Comparative Example C Nylon 6 (same as Example A) 400 g
Anthraquinone violet dye of the following formula [c] 0.68 g
Quinopthalone yellow dye of the following formula [d] 0.12 g
[0088] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0089] Test pieces were prepared and tested as described for
Example A, above, and the results are reported in Table 7, below.
The experimental piece obtained after keeping in an injection
molding machine for 15 minutes was faded and uneven. 15
10 Comparative Example D Nylon 6 (same as Example A) 400 g
Anthraquinone green dye of the following formula [e] 0.48 g
Anthraquinone red dye of the following formula [f] 0.32 g
[0090] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0091] Test pieces were prepared and tested as described for
Example A, above, and the results are reported in Table 7, below.
The experimental piece obtained after keeping in an injection
molding machine for 15 minutes was faded and uneven. 16
11 Comparative Example E Nylon (same as Example A) 400 g
Anthraquinone green dye of the following formula [e] 0.48 g Disazo
red dye of the following formula [g] 0.32 g
[0092] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0093] Test pieces were prepared and tested as described for
Example A, above, and the results are reported in Table 7, below.
The experimental piece obtained after keeping in an injection
molding machine for 15 minutes was faded and uneven.
12 formula [g]: 17 Comparative Example F Nylon 6 (same as Example
A) 400 g Anthraquinone blue dye of the following formula [h] 0.53 g
Perinone red dye of the following formula [IV-3] 0.18 g
Anthraquinone yellow dye of the following formula [a] 0.09 g
[0094] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0095] Test pieces were prepared and tested as described for
Example A, above, and the results are reported in Table 7, below.
The experimental piece obtained after keeping in an injection
molding machine for 15 minutes was faded and uneven. 18
13 TABLE7 Comparative Comparative Comparative Comparative Example A
Example B Example C Example D Example E Example F Transmission TA
0.96 0.97 0.90 0.95 0.95 0.95 TB 1.00 1.02 0.85 0.86 0.94 0.97 OD
2.42 2.42 2.45 2.42 2.42 2.39 Thermal Resistance .DELTA.E 0.46 0.38
1.73 1.55 1.62 1.86 Moisture Resistance .DELTA.E 0.75 0.68 1.08
1.56 2.73 1.14 TG/DTA Exothermic peak(.degree. C.)/ 363.3/ 359.1/
320.9/ 369.7/ 367.2/ 327.4/ Endothermic peak(.degree. C.) none none
179.5 154.6 196.2 102.4
[0096] This testing demonstrates that thermal and moisture
resisitance showed no deterioration in Examples A and B.
Particularly, Examples A and B have no endothemic peak in TG/DAT
analysis. This means that even if the composition such as Examples
A and B are kept in an injection molding machine for a time(for
instance, 15 minutes), the experimental piece obtained by molding
has property not to fade. On the other hand, Comparative Examples
C, D, E and F having endothemic peak in less than Nylon 6 melting
point have great possibility to fade after molding in that same
way. The bigger an injection molding machine is, more important
heat keeping property in it is.
Example G
[0097] Unreinforced polyester (prepared from terephthalic acid and
ethylene glycol the intrinsic viscosity of which is 0.85 when
measured at 25.degree. C. as a 1% solution in a mixed solution of
phenol and dichlorobenzene with the weight ratio of 1/1) was dried
at 120.degree. C. for more than 8 h using a vacuum drying
apparatus, and weighed according to the following formulation.
14 Polyester 400 g Anthraquinone blue dye of the following formula
[II-9] 0.40 g Perinone red dye of the following formula [IV-3] 0.24
g Anthraquinone yellow dye of the following formula [a] 0.16 g
[0098] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0099] For this and all other testing involving this particular
grade of polyester, A homogeneous, black experimental piece
(48.times.86.times.3 (mm)) having excellent appearance and surface
gloss with no color unevenness was obtained after the
aforementioned resulting mixture was injection molded by a usual
method at 290.degree. C. cylinder temperature and 60.degree. C.
molding temperature using an injection molding machine (Product of
Kawaguchi Tekko Co., trade name: K50-C). The experimental piece
obtained after keeping in an injection molding machine for 15
minutes was fadeless.
15 Polyester (same as Example G) 400 g Anthraquinone blue dye of
the following formula [I-2] 0.40 g Perinone red dye of the
following formula [IV-3] 0.24 g Anthraquinone yellow dye of the
following formula [a] 0.16 g
[0100] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0101] Test pieces were prepared and tested as described for
Example G, above, and the results are reported in Table 8, below.
The experimental piece obtained after keeping in an injection
molding machine for 15 minutes was fadeless.
Example I
[0102]
16 Polyester(same as Example G) 400 g Anthraquinone blue dye of the
following formula [I-4] 0.36 g Perinone red dye of the following
formula [IV-3] 0.28 g Anthraquinone yellow dye of the following
formula [b] 0.16 g
[0103] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0104] Test pieces were prepared and tested as described for
Example G, above, and the results are reported in Table 8, below.
The experimental piece obtained after keeping in an injection
molding machine for 15 minutes was fadeless.
17 Comparative Example J Polyester (same as Example G) 400 g
Anthraquinone violet dye of the following formula [c] 0.68 g
Quinopthalone yellow dye of the following formula [d] 0.12 g
[0105] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0106] Test pieces were prepared and tested as described for
Example G, above, and the results are reported in Table 8, below.
The experimental piece obtained after keeping in an injection
molding machine for 15 minutes was faded and uneven.
18 Comparative Example K Polyester (same as Example G) 400 g
Anthraquinone green dye of the following formula [e] 0.48 g
Anthraquinone red dye of the following formula [f] 0.32 g
[0107] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0108] Test pieces were prepared and tested as described for
Example G, above, and the results are reported in Table 8 , below.
The experimental piece obtained after keeping in an injection
molding machine for 15 minutes was faded and uneven.
19 Comparative Example L Polyester (same as Example G) 400 g
Anthraquinone green dye of the following formula [e] 0.48 g Disazo
red dye of the following formula [g] 0.32 g
[0109] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0110] Test pieces were prepared and tested as described for
Example G, above, and the results are reported in Table 8, below.
The experimental piece obtained after keeping in an injection
molding machine for 15 minutes was faded and uneven.
20 Comparative Example M Polyester (same as Example G) 400 g
Anthraquinone blue dye of the following formula [h] 0.53 g Perinone
red dye of the following formula [IV-3] 0.18 g Anthraquinone yellow
dye of the following formula [a] 0.09 g
[0111] The above formula product was agitated and mixed for 1 h in
a stainless steel tumbler.
[0112] Test pieces were prepared and tested as described for
Example G, above, and the results are reported in Table 8, below.
The experimental piece obtained after keeping in an injection
molding machine for 15 minutes was faded and uneven.
21 TABLE8 Comparative Comparative Comparative Comparative Example G
Example H Example I Example J Example K Example L Example M
Transmission TA 0.88 0.93 0.93 0.92 0.93 0.92 0.93 TB 0.85 0.93
0.93 0.89 0.93 0.89 0.96 OD 1.78 1.81 1.80 1.86 1.78 1.85 1.78
Moisture 3.15 3.56 3.30 5.02 4.64 4.48 4.55 Resistance .DELTA.E
Sublimation Test 5.32 9.72 7.07 19.33 12.36 11.97 17.42 .DELTA.E
TG/DTA 532.8/ 363.3/ 359.1/ 320.9/ 369.7/ 367.2/ 327.4/ Exothermic
none none none 179.5 154.6 196.2 102.4 peak(.degree. C.)/
Endothermic peak(.degree. C.)
[0113] This testing demonstrates that moisture resisitance showed
no deterioration in Examples G, H and I. Particularly, Examples G,
H and I showed low sublimation, compared with Comparative J, K, L
and M. Therefore, even if thermoplastic resin composition colored
by Examples G, H or I is put on higher temperature space as like
automobile or electric industry, its colorant have property not to
migrate other parts. And in heat keeping property in an injection
molding machine, the result same as Nylon 6 can be occured.
Test Procedures
[0114] (1) Transmission Properties
[0115] 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 nexr-infrared. The
ratio (TA) of transmission with 940 nm: transmission with 1064 nm
and the ratio (TB) of transmission with 940 nm: tamsmission of
natural resin are determined and compared between the examples.
[0116] (2) Appearance and surface gloss
[0117] 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 plates having higher OD
values are judged to have better surface smoothness and rich in
gloss.
[0118] (3) Thermal Resistance
[0119] The amount of color fading and discoloration .quadrature.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).
[0120] (4) Moisture Resistance
[0121] The amount of color fading and discoloration .quadrature.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 colorimeter (produced by
Juki, trade name: JP 7000).
[0122] (5) TG(Thermogravimetric alalyzers) / DTA (Differential
thermal analyzers)
[0123] TG and DTA of each test colorant powder were measured using
TG / DTA analyzers (prodcued by Seiko Instrument, trade name:SII
EXSTAR 6000) in a heating furnace that air is introduced into at
200 ml / min, of which temperature is raised from 30 to 55.degree.
C. at 10.degree. C./min then when reached to at 550.degree. C. for
28 minutes.
[0124] (6) Sublimation Test
[0125] The amount of dye sublimation was determined by E between
before and after white tape attached on each test plate being
placed and kept in an oven at 140.degree. C. for 3 hours and was
mesaured using a colorimeter (produced by Juki, trade name: JP
7000).
[0126] The white tape attached on the test plate having greater E
are judged to have greater sublimation.
[0127] Example N and comparative Example O and P
[0128] Fiberglass reinforced nylon 6 (Zytel.RTM. 73G30L, available
from E. I. DuPont de Nemours and Co.) and dyes were dry-blended
with the amount described in Table 9. The blended material was
molded into two types of test pieces: one for mechanical
properties, and the other for laser welding. Test pieces for
mechanical properties were molded according to the IS03167 on the
Toshiba IS 170FIII injection molding machine, with cylinder
temperature set at 260.degree. C. and mold temperature at
80.degree. C. Test pieces for laser welding, with dimensions
illustrated as FIG. 3, were molded on the Sumitomo Juki 75T
injection molding machine, with cylinder temperature set at
250.degree. C. and mold temperature set at 80.degree. C.
[0129] Tensile strength and elongation were measured according to
ISO527 and notched Charpy impact strength was measured according to
ISO179. Laser welding was conducted using two of the test pieces
described above, combined as illustrated in FIG. 4. The Example N
and the Comparative Example O were used as Upper test piece and the
Comparative Example P was used as Lower test piece. A diode laser
(wavelength 940 nm, manufactured by Rofin-Sinar Laser GmbH) was
irradiated with laser power at 50W and various speeds, with 3 mm
diameter. Tensile strength of the welded test pieces were measured
on the Autograph (manufactured by Shimazu Seisakusho) by pulling
apart at 5 mm/minute and its maximum load was recorded.
22TABLE 9 Comp. Ex. Comp. Ex. Example N O P 73G30L kg 4.9925 4.9925
4.99 Blue dye formula [I-2] 3.75 g Red dye formula [IV-3] 2.25 g
Yellow dye formula [a] 1.50 g Green dye formula [e] 4.50 g Red dye
formula [g] 3.00 g Carbon black 10 g Tensile strength MPa 174 181
185 Elongation % 3.9 4.2 3.4 Notched Charpy KJ/m.sup.2 12.8 13.3
12.2 Laser Welding at 50 W 2.5 m/min Kgf 195 189 -- 5 m/min Kgf 196
177 -- 10 m/min Kgf 115 110 --
[0130] Example O and Comparative Example R and S
[0131] Fiberglass reinforced nylon 66 (Zytel.RTM. 7OG33HS1L,
available from E. I. DuPont de Nemours and Co.) and dyes were
dry-blended with the amount described in the Table 10. The blended
material was molded into two types of test pieces: one for
mechanical properties, and another for laser welding. Test pieces
for mechanical properties were molded according to the ISO3167 on
the Toshiba IS 170FIII injection molding machine, with cylinder
temperature set at 280.degree. C. and mold temperature at
80.degree. C. Test pieces for laser welding, with dimensions
illustrated in FIG. 3, were molded on the Sumitomo Juki 75T
injection molding machine, with cylinder temperature set at
270.degree. C. and mold temperature set at 80.degree. C.
[0132] Tensile strength and elongation were measured according to
ISO527 and notched Charpy impact strength was measured according to
ISO179. Laser welding was conducted using two pieces of the test
pieces described above, combined as illustrated in FIG. 4. The
Example Q and the Comparative Example R were used as Upper test
piece and the Comparative Example S was used as Lower test piece.
Diode laser (wavelength 940 nm, manufactured by Rofin-Sinar Laser
GmbH) was irradiated with the power at 80W and at various speeds
with 3 mm diameter. Tensile strength of the welded test pieces was
measured on Autograph (manufactured by Shimazu Seisakusho) by
pulling apart at 5 mm/minute and its maximum load was recorded.
23TABLE 10 Comp. Ex. Comp. Ex. Example Q R S 70G33HS1L kg 4.9925
4.9925 4.99 Blue dye formula [I-4] 3.75 g Red dye formula [IV-3]
2.25 g Yellow dye formula [a] 1.50 g Green dye formula [e] 4.50 g
Red dye formula [g] 3.00 g Carbon black 10 g Tensile strength MPa
199 207 207 Elongation % 3.4 3.8 3.2 Notched Charpy kJ/m.sup.2 12.3
13.5 11.9 Laser Welding at 80 W 2.5 m/min kgf 97 75 -- 5 m/min kgf
195 185 -- 10 m/min kgf 194 187 --
[0133] Example T - Example V, Comparative Example W-AA
[0134] Pellets of unreinforced nylon 6 (Zytel-7301, available from
E. I. DuPont de Nemours and Co.) and dyes were dry-blended with the
amount described on the table 11. The blended material was molded
into test pieces for laser welding, with dimension illustrated as
FIG. 5, 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.
[0135] Laser welding was conducted using two pieces of the test
pieces described above, combined as illustrated in FIG. 6. Each
Example from T to V and Comparative Example from W to Z was used as
Upper test piece and Comparative Example AA was used as Lower test
piece. Diode laser (wavelength 940 nm, manufactured by Rofin-Sinar
Laser GmbH) was irradiated at 50W 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.
24TABLE 11 Comp. Example Example Example Comp. Comp. Comp. Comp.
Ex. T U V Ex. W Ex. X Ex. Y Ex. Z AA Nylon 6 400 g 400 g 400 g 400
g 400 g 400 g 400 g 400 g Blue dye formula [I-4] 0.40 g Red dye
formula [IV-3] 0.24 g 0.24 g 0.24 g 0.18 g Yellow dye formula [a]
0.16 g 0.16 g 0.16 g 0.09 g Blue dye formula [II-9] 0.40 g Blue dye
formula [I-2] 0.40 g Violet dye formula [c] 0.68 g Yellow dye
formula [d] 0.12 g Green dye formula [e] 0.48 g 0.48 g Red dye
formula [f] 0.32 g Red dye formula [g] 0.32 g Blue dye formula [h]
0.53 g NUBIAN COMPLEX 0.80 g BLACK G04 Transmittance at 940 nm (2
mm thick) Laser Weld Strength(kgf) 170 151 292 194 195 171 188 --
NUBIAN COMPLEX BLACK G04(Product name: product of Orient Chemical
Industries Ltd): a mixture of carbon and nigrosine.
[0136] Example AB and comparative Example AC-AE
[0137] Fiberglass reinforced polyester (prepared from terephthalic
acid and ethylene glycol the intrinsic viscosity of which is 0.85
when measured at 25.degree. C. as a 1% solution in a mixed solution
of phenol and dichlorobenzene with the weight ratio of 1/1 and
containing 30wt % chopped strand glass fibers 187H produced by
Nippon Electric Glass Co., Ltd. based on a total weight of the
polyester resin composition, and dried as described for xample G )
and dyes were dry-blended with the amount described in Table 13.
The blended material was molded into two types of test pieces: one
for mechanical properties, and the other for laser welding. Test
pieces for mechanical properties were molded according to the
ISO3167 on the Toshiba IS 170FIII injection molding machine, with
cylinder temperature set at 290.degree. C. and mold temperature at
60.degree. C. Test pieces for laser welding, with dimension
illustrated as FIG. 3, were molded on the Sumitomo Juki 75T
injection molding machine, with cylinder temperature set at
280.degree. C. and mold temperature set at 60.degree. C.
[0138] Tensile strength and elongation were measured according to
ISO527 and notched Charpy impact strength was measured according to
ISO179. Laser welding was conducted using two pieces of the test
pieces described above, combined as illustrated in FIG. 4. The
Example AB and the Comparative Example AC-AD were used as Upper
test piece and the Comparative Example AE was used as Lower test
piece. Diode laser (wavelength 940 nm, manufactured by Rofin-Sinar
Laser GmbH) was irradiated with laser power at 50W and regular
speed, with 3 mm diameter. Tensile strength of the welded test
pieces were measured on Autograph (manufactured by Shimazu
Seisakusho) by pulling apart at 5 mm/minute and its maximum load
was recorded.
25TABLE 12 Example AB Comp. Ex. AC Comp. Ex. AD Comp. Ex. AE 73G30L
kg 4.9925 4.9925 4.99 Blue dye formula [I-2] 3.75 g Red dye formula
[IV-3] 2.25 g Yellow dye formula [a] 1.50 g Violet dye formula [c]
6.375 g Yellow dye formula [d] 1.125 g Green dye formula [e] 4.50 g
Red dye formula [g] 3.00 g Carbon black 10 g Tensile strength MPa
135 133 135 150 Elongation % 4.3 4.3 4.0 2.7 Notched Charpy
KJ/m.sup.2 13.0 14.0 13.0 10.5 Laser Welding at 50 W 5 m/min Kgf
150 144 145 --
* * * * *