U.S. patent application number 10/053074 was filed with the patent office on 2003-03-06 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 | 20030045618 10/053074 |
Document ID | / |
Family ID | 22935738 |
Filed Date | 2003-03-06 |
United States Patent
Application |
20030045618 |
Kind Code |
A1 |
Koshida, Reiko ; et
al. |
March 6, 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 dyes
and at least one other red dye to absorb and transmit select
regions of visible light 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.: |
10/053074 |
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: |
524/358 ;
524/495 |
Current CPC
Class: |
B29C 65/16 20130101;
B29C 66/836 20130101; B29C 66/73361 20130101; B29C 65/1616
20130101; B29C 66/43 20130101; B29C 66/12841 20130101; B29K
2995/0073 20130101; B29C 66/7315 20130101; B29K 2995/0089 20130101;
B29C 65/1677 20130101; B29C 65/8215 20130101; B29C 66/73321
20130101; B29K 2995/0022 20130101; B29C 66/73362 20130101; B23K
26/18 20130101; C08K 5/3437 20130101; B29K 2309/08 20130101; B29C
66/1282 20130101; B29K 2995/002 20130101; B29K 2101/12 20130101;
C08K 5/3467 20130101; B29C 66/14 20130101; B29C 65/8207 20130101;
C08K 5/0041 20130101; B29C 66/71 20130101; B29C 66/7212 20130101;
B29C 66/73921 20130101; B29K 2105/06 20130101; C08K 5/17 20130101;
B29C 65/1635 20130101; B29C 65/8238 20130101; B29K 2995/0027
20130101; B23K 26/009 20130101; B29C 65/1654 20130101; B29C 65/1674
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: |
524/358 ;
524/495 |
International
Class: |
C08K 003/04; C08K
005/08 |
Claims
1. A thermoplastic resin composition for laser welding comprising:
1) thermoplastic resin; and, 2) a laser transmitting black colorant
comprising a mixture of a) neutral anthraquinone dye which imparts
colors of blue, violet or green, absorbs visible light with
wavelength less than 700 nm and transmits a laser beam with
wavelength at 800 nm to 1200 nm in the infra-red region with b) at
least one other red dye which transmits with a wavelength at 800 nm
to 1200 nm in infra-red region.
2. The composition of claim 1 wherein said colorant comprises a
mixture of said neutral anthraquinone blue dyes with said red dyes
and further other yellow dyes.
3. The composition of claim 1 wherein said thermoplastic resin is
polyamide or polyester.
4. The composition of any of claims 1-3 wherein said red 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 laser-transmitting article formed from the composition of
claim 1.
7. An article formed by laser welding a laser-absorbing article
with the laser-transmitting article of claim 6.
8. A laser-transmitting black colorant suitable for being mixed
with a thermoplastic resin applied to a laser welding comprising a
mixture of a) neutral anthraquinone dye which imparts colors of
blue, violet or green, 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 b) at least other red dye which
transmits the laser beam with wavelength at 800 nm to 1200 nm in
infra-red region.
9. The colorant of claim 8 comprising said mixture of neutral
anthraquinone blue dyes with red dyes and further yellow dyes.
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 present 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 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 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 .mu.m), 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, and 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 application, is achieved by including a specific weight
percentage of black dyes.
[0007] The object of the present invention is to offer a
thermoplastic resin composition capable of offering moldings which
appear in black, are transparent to a laser beam, in particular to
the near-infrared light region. 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
[0008] There is disclosed and claimed herein thermoplastic resin
compositions for laser welding comprising a laser transmitting
black colorant comprising a mixture of a) neutral anthraquinone
dyes which impart colors of blue, violet or green, absorb visible
light with a wavelength at less than 700 nm in the visible light
region and transmit a laser beam with a wavelength at 800 nm to
1200 nm in the infra-red region with b) at least one other red dye
which transmits the laser beam with a wavelength at 800 nm to 1200
nm in the infra-red region. As red dyes, perinone dyes, monoazo
complex dyes or disazo dyes may be used.
[0009] Using these components, thermoplastic resin compositions for
laser welding can be obtained having improvements in moldability,
solubility in the thermoplastic resin, bleeding- and
blooming-resistance as well as transparency to wavelength of a
laser beam at 800 nm to 1200 nm and resistance to chemicals.
[0010] 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 are used.
[0011] 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. For instance, in the case of coloring the articles,
whether thin or thick, the amount of dyes is adjusted while paying
attention to the transmission properties. The actual amount used
depends on the kind of dyes used, as will be appreciated by those
having skill in this field.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The invention will be better understood upon having
reference to the drawings herein.
[0013] FIG. 1 is a view of the articles in contact and with a laser
beam applied thereto; and
[0014] FIG. 2 is identical to FIG. 1, but with articles of the same
color.
[0015] FIG. 3 is illustrates a shape and dimensions of the test
piece for the laser welding test.
[0016] FIG. 4 is a perspective view of test pieces disposed close
to each other for a laser welding test and relationship the test
piece and laser beam.
[0017] FIG. 5 is illustrates a shape and dimensions of the test
piece for the laser welding test.
[0018] FIG. 6 is a perspective view of test pieces disposed close
to each other for a laser welding test and relationship the test
piece and laser beam.
DETAILED DESCRIPTION OF THE INVENTION
[0019] A black colorant of the compositions of the invention
comprises a mixture of neutral anthraquinone dyes which impart
colors of blue, violet or green, absorb less than 700 nm in the
visible light region and transmit at 800 nm to 1200 nm in the
infra-red region, combined with at least other red dyes which
transmit at 800 nm to 1200 nm in infra-red region, such as perinone
dyes, monoazo complex dyes or disazo dyes, at predetermined weight
ratios. The weight ratios depend on colorant combination.
[0020] There are many examples of combinations of mixed dyes useful
in this invention. For instance, the combination of blue dye, red
dye and yellow dye; the combination of green dye, red dye and
yellow dye; the combination of blue dye, green dye and red dye and
yellow dye; and the combination of green dye, violet dye and yellow
dye can be used.
[0021] The neutral anthraquinone dye described above which can be a
component of the black dyes in the invention may be selected from
the group consisting of the following dyes described in the Color
Index below in Table 1.
[0022] Generally, the dyes which exhibit blue, violet and green
colorant can be main components to produce the black dyes. Neutral
anthraquinone dye imparting blue, violet or green is a major
component of the resulting black colorant by being mixed with red
and then yellow dyes.
1TABLE 1 Anthraquinone green dye: C.I. Solvent Green, 3, 5, 6, 7,
19, 20, 22, 23, 24, 25, 26, 28, 29 Anthraquinone blue dyes: C.I.
Solvent Blue 11, 12, 13, 14, 16, 17, 18, 19, 20, 21, 35, 36, 40,
41, 45, 58, 59, 63, 65, 68, 69, 74, 76, 78, 79, 80, 82, 83, 84, 85,
86, 87, 90, 91, 92, 93, 94, 95, 96, 97, 98, 101, 102, 103, 104,
105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 116, 119, 120,
121, 122, 123, 126, 128, 130, 132, 134, 136, 139 and C.I. Vat Blue
4, 6, 11, 12, 13, 14. Anthraquinone violet dyes: C.I. Solvent
Violet 11, 12, 13, 14, 15, 26, 28, 30, 31, 33, 34, 36, 37, 38, 40,
41, 42.
[0023] Examples of the neutral anthraquinone dyes having the
above-mentioned properties and used as the main component for the
formation of the black dye contained in the composition of the
invention can be represented by the following formula [I] (and
illustrated in Table 2 below) or formula [II-a] or formula
[I-b].
2TABLE 2 Formula [I]: 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 I-1 R.sup.2 = R.sup.3 =
R.sup.4 = R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.1 =
methylanilino 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 = methylanilino I-3 R.sup.2 =
R.sup.3 = R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.4 =
NH.sub.2, R.sup.1 = anilino I-4 R.sup.2 = R.sup.3 = R.sup.5 =
R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.4 = OCH.sub.3, R.sup.1 =
benzoylamido I-5 R.sup.2 = R.sup.3 = R.sup.6 = R.sup.7 = R.sup.8 =
H, R.sup.4 = R.sup.5 = OH, R.sup.8 = NO.sub.2, R.sup.1 =
ethylanilino 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 = NH.sub.2 I-7 R.sup.2 = R.sup.3 =
R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.4 = NH.sub.2,
R.sup.1 = Cyclohexyl amido I-8 R.sup.2 = R.sup.3 = R.sup.5 =
R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.4 = NH.sub.2, R.sup.1 =
CH.sub.3NH 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 = C.sub.4H.sub.9NH I-10 R.sup.2 =
R.sup.3 = R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.4 =
CH.sub.3NH, R.sup.1 = methylanilino I-11 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 =
C.sub.5H.sub.11NH 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 = methylanilino I-13
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 = methylanilino I-14 R.sup.2 = R.sup.3 = R.sup.4
= R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.1 = R.sup.5 =
methylanilino I-15 R.sup.5 = R.sup.6 = R.sup.7 = R.sup.7 = H,
R.sup.1 = R.sup.4 = NH.sub.2, R.sup.2 = R.sup.3 = phenyloxy I-16
R.sup.3 = R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.1 =
NH.sub.2, R.sup.2 = CH.sub.3, R.sup.4 = methylanilino I-17 R.sup.3
= R.sup.5 = R.sup.6 = R.sup.7 = R.sup.8 = H, R.sup.1 = NH.sub.2,
R.sup.2 = Br, R.sup.4 = methylanilino I-18 R.sup.2 = R.sup.3 =
R.sup.6 = R.sup.7 = H, R.sup.1 = R.sup.4 = HOC.sub.2H.sub.4NH,
R.sup.5 = R.sup.8 = OH Pro. Ex. No. = Product Example Number
[0024] 2
[0025] The perinone dyes which are mixed with the above-mentioned
anthraquinone dyes for use as a black colorant in the compositions
of the invention are known products of formula [III] 3
[0026] The perinone dyes which are mixed with the anthraquinone to
produce a black dye may be used alone or in combination
thereof.
[0027] Preferred perinone dyes used in the composition of the
invention are those of formula [IV], which have practical heat
resistance in molding and good transmittance in main laser beam
wavelength(800 nm to 1200 nm). 4
[0028] 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. 5
[0029] Dyes which belong to the class of perinone dyes listed in
COLOR INDEX are for example,
[0030] 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.
[0031] Examples of the perinone dyes of formula [IV] are
illustrated below in Table 3.
3TABLE 3 Pro. Ex. No. P Q IV-1 Formula [IV-b], Formula [IV-a],
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], 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], 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], 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], 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 = OC.sub.2H.sub.5 IV-6 Formula
[IV-b], Formula [IV-a], 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 2Formula [IV-b], Formula [IV-a], R.sup.18 =
R.sup.19 = R.sup.20 = R.sup.22 = R.sup.23 = H, R.sup.14 = R.sup.17
= H R.sup.21 = C.sub.4H.sub.9 IV-8 Formula [IV-b], Formula [IV-c],
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], 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],
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
[0032] Dyes which belong to monoazo complex dyes that are mixed
with the anthraquinone dyes to produce a black dye for use as
colorants in the composition of the invention, can be represented
by formula [V]. 6
[0033] wherein R.sup.30 and R.sup.31, 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; wherein R.sup.33 and
R.sup.34, which may be the same or different, are independently
hydrogen 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, 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.
[0034] B.sup.1 and B.sup.2 are represented by formula [V-a] or
formula [V-b]. 7
[0035] 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.
[0036] 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, and quaternary ammonium ion.
[0037] Suitable amines for use in producing the above-mentioned
monoazo complex dyes and common in dyestuffs include aliphatic
amines, alicyclic amines, alkoxyalkyl amines, amines having
alkanol, diamine, amines of guanidine derivatives, and aromatic
amines.
[0038] Examples of the monoazo complex dyes of formula [V] wherein
B.sup.1 and B.sup.2 are of the formula [V-a] are indicated as below
formula [V-c]. See also Table 4 illustrating a number of selections
of Formula [V-c].
4TABLE 4 Formula [V-c]: 8 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
[0039] 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 formula
[V-d]. See also Table 5 illustrating a number of selections of
Formula [V-d].
5TABLE 5 Formula [V-d]: 9 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
[0040] If desired, the anthraquinone dyes which absorb less than
500 nm, but which impart colors of yellow, orange and red may be
mixed with the mixture of neutral anthraquinone dyes with the red
dyes to produce black colorants. For example, one or more
anthraquinone dyes described in the COLOR INDEX below can be
combined with the mixture to produce a black colorant:
[0041] Red Dyes:
[0042] 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, 190, 191, 194, 199, 200, 201.
[0043] Orange Dyes:
[0044] C.I. Solvent Orange 35, 55, 64, 65, 66, 68, 69, 71, 77, 86,
87, 163.
[0045] Yellow Dyes:
[0046] C.I. Solvent Yellow 100, 109, 117, 125, 156, 158, 163 or
C.I. Vat Yellow 1, 2, 3.
[0047] The thermoplastic resins for use in the invented
compositions include polyamides such as polyamide 6(Nylon 6) and
polyamide 6/6(Nylon 6/6), polyester and the like as is commonly
used in making a molded product.
[0048] Preferred thermoplastic resins useful in the practice of
this invention include polyamides, copolymers of amides and/or
other monomers, blends of different polyamides, blends of
polyamides with other thermoplastic polymers and/or blends of the
aforementioned copolymers with a polyamide and/or blends of
different copolymers with or without thermoplastic polymers.
[0049] An example of a suitable polyamide is polyamide 6 or 6/6.
The addition of the mixture of the neutral anthraquinone dyes with
other red dyes in such polyamide resin compositions imparts
substantially and surprisingly increased laser weldability without
decrease of other important properties such as heat-resistance,
chemical-resistance, moldability and mechanical characteristics
such as rigidity and toughness of articles molded therefrom.
Polyamide 6 is especially advantageous because its low rate of
crystallization results in an increased transmission coefficient
for laser beams with particular wavelengths and without adversely
affecting required toughness and warpage. Such compositions are
advantageous in applications such as automobile parts due to their
balanced range of heat-resistance and mechanical properties.
[0050] 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
61) 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.
[0051] 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, propylene 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.
[0052] 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.
[0053] A black colorant of the composition of the invention
comprises a mixture of neutral anthraquinone dyes which impart
colors of blue, violet or green, absorb visible light with
wavelength at less than 700 nm in the visible light region and
transmit a laser beam with wavelength at at 800 nm to 1200 nm in
the infra-red region, combined 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,monoazo complex dyes or
disazo dyes, at predetermined weight ratios.
[0054] The amount of incorporation of the laser-transmitting
colorants in the resin compositions is 0.01-15 weight %, and
preferably 0.05-5 weight %, versus 100 weight % thermoplastic
resin.
[0055] The dye mixture containing the neutral anthraquinone dye 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. The amount of the
above-mentioned dye mixture may be determined by applications
requiring different properties associated with the laser
welding.
[0056] The composition of the present invention may contain an
inorganic filler or reinforcing agent. Suitable examples include
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 is 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.
[0057] 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 from about 5 to
about 100 weight percent, and particularly about 15 to about 85
weight percent.
[0058] One or more optional compounds selected from a wide variety
of materials tailored for different applications of the resin
compositions can be contained in the composition according to the
present invention. Typically, additive compounds can include flame
retardants, impact modifiers, viscosity modifiers, heat resistance
improvers, lubricants, antioxidants and UV-and other stabilizers.
The compositions of the present invention may have such additive
compounds in such amounts that they do not harm their
characteristic properties. These and other additives are used in
accordance with accepted practices as understood by those having
skill in the art.
[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 opaque articles for laser beam absorption. Suitable
opaque articles and their 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 show 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 1 is applied to the surface 7 of component 5.
[0061] 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 create 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 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
[0062] The present invention is illustrated by the following
examples and comparative examples.
Example A
[0063] In this Example, Example B, and Comparative Examples C and
D, 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 the designated dye mixture 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 nm.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. Important results
are shown in Table 6.
[0064] In this Example the dye mixture is anthraquinone blue dye of
C.I. Solvent Blue 97 (0.40 g) combined with perinone red dye
represented by C.I. Solvent Red 179 (0.24 g) and anthraquinone
yellow dye represented by C.I. Solvent Yellow 163 (0.16 g). Good
and uniformly black appearance and surface gloss without color
shading of the specimens were observed.
Example B
[0065] In this Example the dye mixture was anthraquinone blue dye
of C.I. Solvent Blue 101 (0.53 g) combined with perinone red dye
represented by C.I. Solvent Red 179 (0.18 g) and anthraquinone
yellow dye represented by C.I. Solvent Yellow 163 (0.09 g). Good
and uniformly black appearance and surface gloss without color
shading of the specimens were observed.
Comparative Example C
[0066] In this Comparative Example the dye mixture was
anthraquinone violet dye of C.I. Solvent Violet 13 (0.68 g)
combined with quinopthalone yellow dye represented by C.I. Solvent
Yellow 114 (0.12 g). Good and uniformly black appearance and
surface gloss without color shading of the specimens were
observed.
Comparative Example D
[0067] In this Comparative Example the dye mixture was a copper
phthalocyanine blue pigment of C.I. Pigment Blue 15.3 (0.48 g)
combined with perinone red dye represented by C.I. Solvent Red 179
(0.24 g) and anthraquinone yellow dye represented by C.I. Solvent
Yellow 163 (0.08 g). Good and uniformly black appearance and
surface gloss without color shading of the specimens were
observed.
6 TABLE 6 Example Example Comparative Comarative. A B Example C
Example D Transmission TA 0.94 0.94 0.90 0.93 TB 1.04 1.02 0.85
0.41 OD 2.51 2.49 2.45 2.02 Light Resistance 1.08 1.05 1.48 1.06
.DELTA.E Sublimation 8.20 8.19 19.23 5.81 Test .DELTA.E
[0068] This testing demonstrates that Examples A and B showed as
high transmittance as a natural resin at a main wavelength in
infra-red region (800 nm to 1200 nm), compared with Comparative
Example D. And Examples A and B showed low sublimation property,
compared with Comparative Example C. It means that even if
thermoplastic resin colored with Examples A and B is set under
higher temperature as like automobile or electric industry, their
colorant have property not to migrate to other parts.
Example E
[0069] In this Example, Example F, and Comparative Examples G and
H, 400 grams of reinforced polyester pellets (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 30 wt % chopped strand glass fibers 187H
produced by Nippon Electric Glass Co., Ltd. based on a total weight
of the polyester resin composition) were dried under vacuum at
120.degree. C., for more than 8 hours, then mixed with the
designated dye mixture 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.
[0070] In this Example the dye mixture is anthraquinone blue dye of
C.I. Solvent Blue 97 (0.40 g) with perinone red dye represented by
C.I. Solvent Red 179 (0.24 g) and anthraquinone yellow dye
represented by C.I. Solvent Yellow 163 (0.16 g). Good and uniformly
black appearance and surface gloss without color shading of the
specimens were observed.
Example F
[0071] In this Example the dye mixture is anthraquinone blue dye of
C.I. Solvent Blue 101 (0.53 g) with perinone red dye represented by
C.I. Solvent Red 179 (0.18 g) and anthraquinone yellow dye
represented by C.I. Solvent Yellow 163 (0.09 g) Good and uniformly
black appearance and surface gloss without color shading of the
specimens were observed.
Comparative Example G
[0072] In this Example the dye mixture is anthraquinone violet dye
of C.I. Solvent Violet 13 (0.68 g) with quinopthalone yellow dye
represented by C.I. Solvent Yellow 114 (0.12 g) Good and uniformly
black appearance and surface gloss without color shading of the
specimens were observed.
Comparative Example H
[0073] In this Example the dye mixture is phthalocyanine pigment of
C.I. Pigment blue 15.3 (0.48 g) with perinone red dye represented
by C.I. Solvent Red 179 (0.24 g) and anthraquinone yellow dye
represented by C.I. Solvent Yellow 163 (0.08 g) Good and uniformly
black appearance and surface gloss without color shading of the
specimens were observed.
[0074] The results are set forth in the following Table 7.
7 TABLE 7 Example Example Comparative Comarative E F Example G
Example H Transmission TA 0.93 0.91 0.92 0.93 TB 0.96 0.94 0.89
0.34 OD 1.79 1.85 1.86 1.77 Sublimation 7.44 8.16 19.33 3.86 Test
.DELTA.E
[0075] This testing demonstrates that Examples E and F showed as
high transmittance as a natural color resin at a main wavelength in
infra-red region (800 nm to 1200 nm), compared with Comparative
Example H. And Examples E and F showed low sublimation property,
compared with Comparative Example G. This testing obtained the same
results as Nylon 6.
Test Procedures
[0076] (1) Transmission Properties
[0077] 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 produced 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
and the ratio (TB) of transmission with 940 nm : tarnsmission of
natural resin are determined and compared between the examples.
[0078] (2) Appearance and Surface Gloss
[0079] 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.
[0080] (3) Light Resistance
[0081] 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 conditions. The amount of color fading
and discoloration .DELTA.E between "before" and "after" light
irradiation was determined and mesaured using a colorimeter
(produced by Juki, trade name: JP 7000).
8 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
[0082] The test plate having greater AE are judged to have greater
discoloring and fading.
[0083] (4)Sublimation Test
[0084] The amount of dye sublimation was determined by AE 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 the aforementioned calorimeter.
[0085] The white tape attached on the test plate having greater AE
are judged to have greater sublimation.
Example I
[0086] 5 kg of Nylon 6 Zytel.RTM. 7301 pellets (available from E.I.
DuPont de Nemours and Co.) were dried in a dehumidified dryer set
at 80.degree. C. for more than 4 hours and mixed with a mixture of
anthraquinone green dye of C.I. Solvent Green 3 (6.6 g) with
perinone red dye represented by C.I. Solvent Red 179 (2.3 g) and
anthraquinone yellow dye represented by C.I. Solvent Yellow 163
(1.1 g)
[0087] The dye-mixed pellets above were then molded into the test
pieces of 60 mm.times.18 mm.times.1.5 mm on Sumitomo 75T molding
machine, with cylinder temperature set at 260.degree. C. and mold
temperature at 80.degree..
Example J
[0088] 14 kg of Nylon 6 Zytel.RTM. 7301 pellets (available from
E.I. DuPont de Nemours and Co.), 8.8 grams of CuI, 100 grams of
aluminum distearate, and 6 kg of fiberglass (TP57, available from
Nippon Sheet Glass Co., Ltd.) were mixed and extruded on a
twin-screw extruder (ZSK-40 of Werner & Pfleiderer
Corporation).
[0089] 5 kg of the obtained pellets were dried in a dehumidified
dryer set at 80.degree. C. for more than 4 hours and mixed with a
mixture of anthraquinone green dye of C.I. Solvent Green 3 (6.6 g)
with perinone red dye represented by C.I. Solvent Red 179 (2.3 g)
and anthraquinone yellow dye represented by C.I. Solvent Yellow 163
(1.1 g).
[0090] The dye-mixed pellets above were then molded into the test
pieces according to the ISO3167 on a Toshiba IS 170FIII molding
machine, with cylinder temperature set at 260.degree. C. and mold
temperature at 80.degree. C., and the test pieces of 60 mm.times.18
mm.times.1.5 mm on Sumitomo 75T molding machine, with cylinder
temperature set at 260.degree. C. and mold temperature at
80.degree. C.
Comparative Example K
[0091] 5 kg of Nylon 6 Zytel.RTM. 7301 pellets (available from E.I.
DuPont de Nemours and Co.) were dried in a dehumidified dryer set
at 80.degree. C. for more than 4 hours and mixed with 28grams of
nigrosine dye (Nigrosine Base SAP, Orient Chemical Industries
Ltd.).
[0092] The dye-mixed pellets above were then molded into the test
pieces of 60 mm.times.18 mm.times.1.5 mm on Sumitomo 75T molding
machine, with cylinder temperature set at 260.degree. C. and mold
temperature at 80.degree. C.
[0093] Comparative Example L
[0094] 5 kg of Nylon 6 Zytel.RTM. 7301 pellets (available from E.I.
DuPont de Nemours and Co.) were dried in a dehumidified dryer set
at 80.degree. C. for more than 4 hours and mixed with 5grams of
carbon black and 28grams of nigrosine dye (Nigrosine Base SAP,
Orient Chemical Industries Ltd.).
[0095] The dye-mixed pellets above were then molded into the test
pieces of 60 mm.times.18 mm.times.1.5 mm on Sumitomo 75T molding
machine, with cylinder temperature set at 260.degree. C. and mold
temperature at 80.degree. C.
Comparative Example M
[0096] 14 kg of Nylon 6 Zytel.RTM. 7301 pellets (available from
E.I. DuPont de Nemours and Co.), 8.8 grams of CuI, 100 grams of
aluminum distearate, and 6 kg of fiberglass (TP57, available from
Nippon Sheet Glass Co., Ltd.) were mixed and extruded on the ZSK-40
twin-screw extruder.
[0097] 5 kg of the obtained pellets were dried in a dehumidified
dryer set at 80.degree. C. for more than 4 hours and mixed with 28
grams of nigrosine dye (Nigrosine Base SAP, Orient Chemical
Industries Ltd.).
[0098] The dye-mixed pellets above were then molded into the test
pieces according to the ISO3167 on the Toshiba IS 170FIII molding
machine, with cylinder temperature set at 260.degree. C. and mold
temperature at 80.degree. C., and the test pieces of 60 mm.times.18
mm.times.1.5 mm on the Sumitomo 75T molding machine, with cylinder
temperature set at 260.degree. C. and mold temperature at
80.degree. C.
Comparative Example N
[0099] 14 kg of Nylon 6 Zytel.RTM. 7301 pellets (available from
E.I. DuPont de Nemours and Co.), 8.8 grams of CuI, 100 grams of
aluminum distearate, and 6 kg of fiberglass (TP57, available from
Nippon Sheet Glass Co., Ltd.) were mixed and extruded on the ZSK-40
twin-screw extruder.
[0100] 5 kg of the obtained pellets were dried in a dehumidified
dryer set at 80.degree. C. for more than 4 hours and mixed with 5
grams of carbon black and 28grams of nigrosine dye (Nigrosine Base
SAP, Orient Chemical Industries Ltd.).
[0101] The dye-mixed pellets above were then molded into the test
pieces according to the ISO3167 on the Toshiba IS 170FIII molding
machine, with cylinder temperature set at 260.degree. C. and mold
temperature at 80.degree. C., and the test pieces of 60 mm.times.18
mm.times.1.5 mm on the Sumitomo 75T molding machine, with cylinder
temperature set at 260.degree. C. and mold temperature at
80.degree. C.
[0102] (5) Laser Welding Test
[0103] The 60 mm.times.18 mm.times.1.5 mm test pieces were placed
so that 20 mm of each were overlapped. The overlapped area was
irradiated with a Nd: YAG laser (Olion 510, 1064 nm continuous) set
at 4W with 3 mm diameter for 2 seconds. Welded test pieces were
visually inspected and judged OK when adhesion was formed and NG
when the two test pieces were not adhered and fell apart or when
the surface of transparent part were burnt and damaged, per Table 8
below.
9TABLE 8 Upper test piece Example I Comparative Example K Lower
test piece Comparative Example L Comparative Example L Welding
results Good adhesion OK Could not adhere NG
[0104] The 60 mm.times.18 mm.times.1.5 mm test pieces were placed
so that 20 mm of each be overlapped. The overlapped area was
irradiated with a diode laser (SDL-FD25, 820 nm continuous) set at
4W with 3 mm diameter for 10 seconds. The welded test pieces were
tested for strength on the Autograph (Shimadzu Seisakusho) with 2
mm/min speed. The results are shown in Table 9.
10TABLE 9 Comparative Upper test piece Example I Example J Example
M Comparative Comparative Comparative Lower test piece Example L
Example N Example N Weld Strength (kgf) 33 34 Could not adhere
NG
[0105] (6) Tensile Properties and Heat Aging
[0106] Tensile strength and elongation were measured according to
ISO527 after molding and after heat aging at 170.degree. C. for
1000 hours. Test piece appearance was also observed. The results
are shown in Table 10.
11 TABLE 10 Exam- Comparative Comparative ple J Example M Example N
After Tensile Strength (Mpa) 190 171 190 Molding Elongation (%) 3.7
3.4 3.8 After Tensile Strength (Mpa) 156 152 169 Aging Elongation
(%) 2.0 2.2 2.4 Appearance Black Dark brown Black
[0107] Examples I and J exhibited good adhesion in laser welding
with an opaque workpiece part for laser beam, being made of
thermoplastic resin containing carbon black. The mechanical
properties after molding and aging showed no deterioration even
when a colorant was added.
Example O and P and Comparative Example Q
[0108] 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 11. 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 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.
[0109] Tensile strength and elongation were measured according to
ISO527 and notched Charpy impact strength was measured according to
ISO179.
[0110] Laser welding was conducted using two of the test pieces
described above, combined as illustrated in FIG. 4. The Example O
and P were used as Upper test piece and the Comparative Example Q
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.
12 TABLE 11 Comp. Example O Example P Ex. Q 73G30L kg 4.9925 4.9925
4.99 C.I. Solvent Blue 87 3.75 g C.I. Solvent Red 179 2.25 g C.I.
Solvent Yellow 163 1.50 g C.I. Solvent Green 3 4.50 g C.I. Solvent
Red 18 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 50W 2.5 m/min Kgf 195 189 -- 5 m/min Kgf 196 177
-- 10 m/min Kgf 115 110 --
Example R and S and Comparative Example T
[0111] Fiberglass reinforced nylon 66 (Zytel.RTM.70G33HS1L,
available from E. I. DuPont de Nemours and Co.) and dyes were
dry-blended with the amount described in the Table 12. 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.
[0112] Tensile strength and elongation were measured according to
ISO527 and notched Charpy impact strength was measured according to
ISO179.
[0113] Laser welding was conducted using two pieces of the test
pieces described above, combined as illustrated in FIG. 4. The
Example R and S were used as Upper test piece and the Comparative
Example T 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.
13 TABLE 12 Comp. Example R Example S Ex. T 70G33HS1L kg 4.9925
4.9925 4.99 C.I. Solvent Blue 97 3.75 g C.I. Solvent Red 179 2.25 g
C.I. Solvent Yellow 163 1.50 g C.I. Solvent Green 3 4.50 g C.I.
Solvent Red 18 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 80W 2.5 m/min kgf 97 75 -- 5 m/min kgf
195 185 -- 10 m/min kgf 194 187 --
Example U and V and Comparative Example W
[0114] Fiberglass reinforced polyester pellet of Example E(dried as
described in Example E) 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.
[0115] Tensile strength and elongation were measured according to
ISO527 and notched Charpy impact strength was measured according to
ISO 179.
[0116] Laser welding was conducted using two pieces of the test
pieces described above, combined as illustrated in FIG. 4. The
Example U and V were used as Upper test piece and the Comparative
Example W 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.
14 TABLE 13 Comp. Example U Example V Ex. W Polyester pellets kg
4.9925 4.9925 4.99 C.I. Solvent Blue 87 3.75 g C.I. Solvent Red 179
2.25 g C.I. Solvent Yellow 163 1.50 g C.I. Solvent Green 3 4.50 g
C.I. Solvent Red 18 3.00 g Carbon black 10 g Tensile strength MPa
135 135 150 Elongation % 4.3 4.0 2.7 Notched Charpy KJ/m.sup.2 13.0
13.0 10.5 Laser Welding at 50W 5 m/min Kgf 150 145 --
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