U.S. patent application number 13/984206 was filed with the patent office on 2013-12-19 for polyorganosiloxane latex, graft copolymer using the same, thermoplastic resin composition, and molded body.
This patent application is currently assigned to UMG ABS, LTD.. The applicant listed for this patent is Toshihiro Kasai, Hidemichi Kouno, Shigenari Takeda, Ayaka Wakita. Invention is credited to Toshihiro Kasai, Hidemichi Kouno, Shigenari Takeda, Ayaka Wakita.
Application Number | 20130338311 13/984206 |
Document ID | / |
Family ID | 46638697 |
Filed Date | 2013-12-19 |
United States Patent
Application |
20130338311 |
Kind Code |
A1 |
Wakita; Ayaka ; et
al. |
December 19, 2013 |
POLYORGANOSILOXANE LATEX, GRAFT COPOLYMER USING THE SAME,
THERMOPLASTIC RESIN COMPOSITION, AND MOLDED BODY
Abstract
A variety of molded bodies having high weatherability, impact
resistance, designability, and the like, and a polyorganosiloxane
latex and a graft copolymer used as the raw material therefor are
provided. A polyorganosiloxane latex having a mass average particle
diameter (Dw) of a polyorganosiloxane particle of 100 to 200 nm,
and a ratio of the mass average particle diameter (Dw) to a number
average particle diameter (Dn) (Dw/Dn) of 1.0 to 1.7. A
polyorganosiloxane-containing vinyl-based copolymer (g) obtained by
polymerizing one or more vinyl-based monomers in the presence of
the latex. A graft copolymer (G) obtained by graft polymerizing one
or more vinyl-based monomers in the presence of the copolymer. A
thermoplastic resin composition including the graft copolymer (Ga)
and a thermoplastic resin (Ha) except for the graft copolymer (Ga).
A molded body obtained by molding the resin composition. A lamp
housing for vehicle lighting including the molded body obtained by
molding the composition.
Inventors: |
Wakita; Ayaka; (Hiroshima,
JP) ; Kasai; Toshihiro; (Hiroshima, JP) ;
Kouno; Hidemichi; (Yamaguchi, JP) ; Takeda;
Shigenari; (Yamaguchi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Wakita; Ayaka
Kasai; Toshihiro
Kouno; Hidemichi
Takeda; Shigenari |
Hiroshima
Hiroshima
Yamaguchi
Yamaguchi |
|
JP
JP
JP
JP |
|
|
Assignee: |
UMG ABS, LTD.
Tokyo
JP
MITSUBISHI RAYON CO., LTD.
Tokyo
JP
|
Family ID: |
46638697 |
Appl. No.: |
13/984206 |
Filed: |
February 9, 2012 |
PCT Filed: |
February 9, 2012 |
PCT NO: |
PCT/JP2012/052914 |
371 Date: |
September 9, 2013 |
Current U.S.
Class: |
524/801 ;
428/402; 525/451; 525/63 |
Current CPC
Class: |
C08F 290/068 20130101;
C08L 83/06 20130101; C08G 77/42 20130101; C08L 83/10 20130101; C08F
290/068 20130101; C08L 51/00 20130101; C08F 290/068 20130101; C08L
2201/52 20130101; C08K 3/20 20130101; C08L 25/12 20130101; C08L
51/085 20130101; C08G 77/20 20130101; C08L 2205/03 20130101; F21S
43/26 20180101; C08F 283/124 20130101; C08F 220/06 20130101; C08F
222/1006 20130101; C08F 220/18 20130101; C08F 220/40 20130101; Y10T
428/2982 20150115; C08F 290/068 20130101; C08F 290/068 20130101;
C08L 83/04 20130101; F21S 41/28 20180101; F21S 45/10 20180101 |
Class at
Publication: |
524/801 ;
428/402; 525/451; 525/63 |
International
Class: |
C08L 83/10 20060101
C08L083/10; C08K 3/20 20060101 C08K003/20; C08G 77/42 20060101
C08G077/42 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 9, 2011 |
JP |
2011-026088 |
Claims
1. A polyorganosiloxane latex, wherein a mass average particle
diameter (Dw) of a polyorganosiloxane particle is 100 to 200 nm,
and wherein a ratio (Dw/Dn) of the mass average particle diameter
(Dw) to a number average particle diameter (Dn) of the particle is
1.0 to 1.7.
2. The polyorganosiloxane latex according to claim 1, wherein a
standard deviation of the mass average particle diameter (Dw) of
the polyorganosiloxane particle is 0 to 80.
3. The polyorganosiloxane latex according to claim 1, wherein a
proportion of the polyorganosiloxane particle having a particle
diameter less than 50 nm is 5% by mass or less based on the total
amount of the particle, and wherein a proportion of the
polyorganosiloxane particle having a particle diameter of 300 nm or
more is 20% by mass or less based on the total amount of the
particle.
4. A polyorganosiloxane-containing vinyl-based copolymer obtained
by polymerizing one or more vinyl-based monomers in the presence of
the polyorganosiloxane latex according to claim 1.
5. The polyorganosiloxane-containing vinyl-based copolymer
according to claim 4, wherein a mass average particle diameter (Dw)
of a particle in the polyorganosiloxane-containing vinyl-based
copolymer is 110 nm to 800 nm, and a ratio (Dw/Dn) of the mass
average particle diameter (Dw) to a number average particle
diameter (Dn) of the particle is 1.0 to 2.0.
6. The polyorganosiloxane-containing vinyl-based copolymer
according to claim 4, wherein the vinyl-based monomer is an acrylic
acid ester.
7. A graft copolymer (G) obtained by graft polymerizing one or more
vinyl-based monomers in the presence of the
polyorganosiloxane-containing vinyl-based copolymer according to
claim 4.
8. The graft copolymer (G) according to claim 7, wherein a molded
body obtained by molding the following composition exhibits the
following performance (1) and (2) when evaluated under the
following measurement conditions: (1) a Charpy impact strength at
23.degree. C. is 6 kJ/m.sup.2 or more, and (2) a diffuse
reflectance is 5% or less; test piece production conditions of: (a)
33 parts by mass of a graft copolymer (Ga), (b) 9 parts by mass of
an acrylonitrile-styrene copolymer comprising 25% by mass of an
acrylonitrile unit and 75% by mass of a styrene unit and having a
reduced viscosity (.eta.sp/c) of 0.40 dL/g in an
N,N-dimethylformamide solution of 0.2 g/dL at 25.degree. C., (c) 9
parts by mass of an acrylonitrile-styrene copolymer comprising 28%
by mass of an acrylonitrile unit and 72% by mass of a styrene unit
and having a reduced viscosity of 0.62 dL/g in an
N,N-dimethylformamide solution of 0.2 g/dL at 25.degree. C., (d) 50
parts by mass of an acrylonitrile-styrene-N-phenylmaleimide
copolymer comprising 22% by mass of an acrylonitrile unit, 55% by
mass of a styrene unit, and 23% by mass of an N-phenylmaleimide
unit and having a reduced viscosity of 0.40 dL/g in an
N,N-dimethylformamide solution of 0.2 g/dL at 25.degree. C., (e)
0.5 parts by mass of ethylenebisstearylamide, (f) 0.03 parts by
mass of silicone oil, and (g) 0.05 parts by mass of carbon black;
wherein the seven materials (a) to (g) above are blended and
kneaded using a volatilizing extruder whose barrel is heated to a
temperature of 260.degree. C. to obtain pellets; the pellets are
molded using a 4-ounce injection molding machine in conditions of a
cylinder temperature of 260.degree. C. and a mold temperature of
60.degree. C. to obtain a test piece 1 with a length of 80 mm, a
width of 10 mm and a thickness of 4 mm; and a plate-like molded
body 2 a length of 100 mm, a width of 100 mm and a thickness of 2
mm is obtained in the same manner as above in conditions of a
cylinder temperature of 260.degree. C., a mold temperature of
60.degree. C., and an injection rate of 5 g/sec; Charpy impact
strength measurement conditions of: measurement is conducted on a
V-notched test piece 1 that is left under a 23.degree. C.
atmosphere for 12 hours or more by a method according to ISO 179;
diffuse reflectance measurement conditions of: a 50 nm aluminum
film is formed through a direct deposition on the surface of the
molded body 2 by a vacuum deposition method in conditions of a
degree of vacuum of 6.0.times.10.sup.-3 Pa and a film forming rate
of 10 angstroms/sec; and a diffuse reflectance (%) of the obtained
molded body is measured using a reflectance meter.
9. The graft copolymer (Ga) according to claim 8, comprising 5 to
25% by mass of polyorganosiloxane based on 100% by mass of a
polyorganosiloxane-containing vinyl-based copolymer, wherein a
mixture of a vinyl cyanide-based monomer and an aromatic
vinyl-based monomer is graft polymerized with the
polyorganosiloxane-containing vinyl-based copolymer, wherein the
polyorganosiloxane-containing vinyl-based copolymer has a mass
average particle diameter (Dw) of 120 to 200 nm, wherein a
proportion of a particle having a particle diameter of 100 nm or
less is 15% by mass or less based on the total amount of the
particle, and wherein a proportion of the particle having a
particle diameter of 400 nm or more is 1% by mass or less based on
the total amount of the particle.
10. The graft copolymer (Ga) according to claim 9, wherein the
polyorganosiloxane contains 0.5 to 5 parts by mass of a component
derived from a siloxane-based crosslinking agent based on 100 parts
by mass of the organosiloxane.
11. A thermoplastic resin composition (Ia) comprising the graft
copolymer (Ga) according to claim 8, and a thermoplastic resin (Ha)
except for the graft copolymer (Ga).
12. The thermoplastic resin composition (Ia) according to claim 11,
wherein the thermoplastic resin (Ha) is a copolymer comprising 0 to
40% by mass of a vinyl cyanide-based monomer unit, 40 to 80% by
mass of an aromatic vinyl-based monomer unit, and 0 to 60% by mass
of another monomer unit whose monomer is copolymerizable with these
monomers.
13. A molded body obtained by molding the thermoplastic resin
composition (Ia) according to claim 11.
14. A lamp housing for vehicle lighting comprising a molded body
obtained by molding the thermoplastic resin composition (Ia)
according to claim 11.
15. The graft copolymer (G) according to claim 7, wherein a molded
body obtained by molding the following composition exhibits the
following performance (1) and (2) when evaluated under the
following measurement conditions: (1) L* is 24 or less, and (2) a
Charpy impact strength at -30.degree. C. is 6 kJ/m.sup.2 or more;
test piece production conditions of: (a) 42 parts by mass of a
graft copolymer (Gb), (b) 58 parts by mass of an
acrylonitrile-styrene copolymer comprising 34% by mass of an
acrylonitrile unit and 66% by mass of a styrene unit and having a
reduced viscosity (.eta.sp/c) of 0.62 dL/g in an
N,N-dimethylformamide solution of 0.2 g/dL at 25.degree. C., (c)
0.3 parts by mass of ethylenebisstearylamide, and (d) 0.5 parts by
mass of carbon black; wherein the four materials (a) to (d) above
are blended and kneaded using a volatilizing extruder whose barrel
is heated to a temperature of 230.degree. C. to obtain pellets; the
pellets are molded using a 4-ounce injection molding machine in
conditions of a cylinder temperature of 230.degree. C. and a mold
temperature of 60.degree. C. to obtain a test piece 3 with a length
of 80 mm, a width of 10 mm and a thickness of 4 mm and a tensile
test piece 4 a length of 170 mm, a width of 20 mm and a thickness
of 4 mm; Charpy impact strength measurement conditions of:
measurement is conducted on a V-notched test piece 3 that is left
under a -30.degree. C. atmosphere for 12 hours or more by a method
according to ISO 179; L*measurement conditions of: L* is measured
for the tensile test piece 4 using a spectrophotometer on a side
opposite to a gate.
16. The graft copolymer (Gb) according to claim 15, comprising 15
to 80% by mass of polyorganosiloxane based on 100% by mass of a
polyorganosiloxane-containing vinyl-based copolymer, wherein a
mixture of a vinyl cyanide-based monomer and an aromatic
vinyl-based monomer is graft polymerized with the
polyorganosiloxane-containing vinyl-based copolymer, wherein the
polyorganosiloxane-containing vinyl-based copolymer has a mass
average particle diameter (Dw) of 110 to 250 nm, wherein a
proportion of a particle having a particle diameter less than 100
nm is 20% by mass or less based on the total amount of the
particle, and wherein a proportion of the particle diameter of 300
nm or more is 20% by mass or less based on the total amount of the
particle.
17. The graft copolymer (Gb) according to claim 16, wherein the
polyorganosiloxane contains 0.5 to 3 parts by mass of a component
derived from a siloxane-based crosslinking agent based on 100 parts
by mass of the organosiloxane.
18. A thermoplastic resin composition (Ib) comprising the graft
copolymer (Gb) according to claim 15 and a thermoplastic resin (Hb)
except for the graft copolymer (Gb).
19. The thermoplastic resin composition (Ib) according to claim 18,
wherein the thermoplastic resin (Hb) is a copolymer comprising 0 to
40% by mass of a vinyl cyanide-based monomer unit, 40 to 80% by
mass of an aromatic vinyl-based monomer unit, and 0 to 60% by mass
of another vinyl-based monomer unit whose monomer is
copolymerizable with these monomers.
20. A molded body obtained by molding the thermoplastic resin
composition (Ib) according to claim 18.
21. A method of producing a polyorganosiloxane latex, the method
comprising a step of dropping an emulsion (B) comprising
organosiloxane, an emulsifier, and water into a water-based medium
(A) comprising water, an organic acid catalyst, and an inorganic
acid catalyst; and a step of performing polymerization, wherein a
total amount of the organic acid catalyst and the emulsifier is 0.5
to 6 parts by mass based on 100 parts by mass of the
organosiloxane, wherein the pH of the water-based medium (A)
measured at 25.degree. C. is within the range of 0 to 1.2, and
wherein the dropping rate of the emulsion (B) is a rate such that
an amount of organosiloxane to be fed is 0.5 [parts by mass/min] or
less when a total amount of organosiloxane to be used is 100 parts
by mass.
Description
TECHNICAL FIELD
[0001] The present invention relates to a polyorganosiloxane latex,
a graft copolymer using the polyorganosiloxane latex, a
thermoplastic resin composition, and a molded body.
BACKGROUND ART
[0002] Polyorganosiloxane latexes are widely used as raw materials
for resin additives, fiber treatment agents, mold release agents,
cosmetics, antifoaming agents, additives for a coating material,
and the like. Various methods have been proposed as the method of
producing a polyorganosiloxane latex. For example, Patent
Literature 1 and Patent Literature 2 describe polyorganosiloxane
latexes obtained by emulsion polymerizing organosiloxane in an
aqueous medium.
[0003] Polyorganosiloxane in a latex exhibits different properties
depending on the particle diameter. When a polyorganosiloxane latex
is used as a raw material for resin additives, fiber treatment
agents, mold release agents, cosmetics, antifoaming agents,
additives for a coating material, and the like, a
polyorganosiloxane latex having the particle diameter optimal to
the application is required in order to exhibit the performance
which each of these target products requires. Thus,
polyorganosiloxane having a controlled particle diameter and
particle diameter distribution is useful.
[0004] For polyorganosiloxane contained in the latexes produced by
the methods described in these Patent Literatures, the mass average
particle diameter (Dw) is 150 to 800 nm, particle diameter
distribution (Dw/Dn) expressed as a ratio of the mass average
particle diameter (Dw) to the number average particle diameter (Dn)
is 1.2 or less (Patent Literature 1), the number average particle
diameter is 100 nm or less, and the standard deviation of the
particle diameter is 70 nm or less (Patent Literature 2) as
described in these Patent Literatures. Unfortunately, the methods
described in these Patent Literatures actually have difficulties to
obtain polyorganosiloxane having the mass average particle diameter
of 100 nm to 200 nm and Dw/Dn of 1.7 or less.
[0005] Automobile lights such as a taillight, a brake light, and a
headlight for automobiles mainly include a lens made of a
transparent resin such as a polymethyl methacrylate (PMMA) resin
and a polycarbonate (PC) resin and a housing that supports the
lens. Among these, the housing is partially exposed to the sunlight
outdoors. For this reason, the housing formed of a material having
high weatherability has been desired in these days.
[0006] In production of the automobile light in the related art,
the lens is bonded to the housing with a hot-melt adhesive, and
integrated. To increase productivity, recently, the lens is bonded
to the housing by a vibration welding method in some cases. Here,
the vibration welding method is a welding method utilizing
frictional heat in which in the state where the periphery end of
the lens is pressed against the periphery end of the housing,
vibration having a amplitude of 0.5 mm to 2.0 mm and the number of
vibration of 200 Hz to 300 Hz is applied to generate frictional
heat between the lens and the housing; thereby, the lens and the
housing are fused, bonded, and integrated. In such a vibration
welding method, the finished bonded portion of the lens and the
housing needs to have a good appearance.
[0007] For the material for vibration welding, a thermoplastic
resin composition containing a graft copolymer containing a
composite rubber-based polymer consisting of polyorganosiloxane
including vinyl polymerizable functional group-containing siloxane
and alkyl (meth)acrylate rubber is disclosed.
[0008] A thermoplastic resin molded body for automobile parts and
casings for a variety of electrical appliances may be subjected to
a plating surface treatment for forming a metallic film made of a
material such as copper, chromium, and nickel on the surface of the
molded body to enhance designability and other functionalities.
Moreover, a metallization treatment for forming a metallic film of
aluminum, chromium, or the like (thickness of several dozen
nanometers to several hundred nanometers) may be performed on the
surface of the thermoplastic resin molded body by a vacuum
deposition method, a sputtering method, or the like.
[0009] In the latter metallization treatment, to enhance the
brightness of the molded body, an undercoat layer is usually formed
by coating or plasma polymerization in advance before performing
metallization treatment. Further, to protect the metallic film
obtained by metallization treatment, a top coat layer composed of a
silicon-based material or the like is usually formed.
[0010] Thus, conventional metallization treatment needs many steps,
a dedicated apparatus, and an expensive treatment agent, while the
so-called "direct deposition method" eliminating the step for
forming the undercoat layer is used these days. The designability
of the molded body obtained by the direct deposition method easily
changes according to the kind of resin materials and the state of
the surface of the molded body. For this reason, one of important
problems is to stably maintain a beautiful bright appearance of the
surface without fogging.
[0011] For the resin material suitable for the direct deposition,
Patent Literature 3 discloses a thermoplastic resin containing a
rubber-containing graft copolymer prepared by graft polymerizing a
vinyl-based monomer with a rubber-based polymer having specific
particle diameter distribution. Moreover, Patent Literature 3
discloses a thermoplastic resin composition in which the mass
average particle diameter of the rubber-based polymer and the
proportion of the component (% by mass) have a specific
relationship.
[0012] Meanwhile, automobile members tend to be lighter these days.
For this reason, the automobile members need to have higher
physical properties such as impact resistance than ever. In
addition to high heat resistance, the level of a demand for a
beautiful bright appearance has been increased year after year.
Unfortunately, the thermoplastic resin composition disclosed in
Patent Literature 3 cannot sufficiently meet the recent demand for
high brightness and impact resistance.
[0013] Further, recent thermoplastic resin compositions used for
vehicle members and construction members need high mechanical
strength under a low temperature. Efforts have been made so far to
improve the surface appearance and impact resistance of the molded
article made from a composite rubber-based graft copolymer prepared
from a polyorganosiloxane rubber and an acrylic rubber in
combination and the performance of impact resistance. For example,
Patent Literature 4 discloses a thermoplastic resin composition
comprising a polyorganosiloxane/acrylic composite rubber-based
graft copolymer in which the average particle diameter is 10 to 70
nm and the proportion of particles having a particle diameter more
than 100 nm is 20% or less based on the total particle volume. Such
a resin composition, however, cannot achieve the performance that
sufficiently meets the recent demand.
CITATION LIST
Patent Literature
[0014] Patent Literature 1: JP2007-321066A [0015] Patent Literature
2: JP05-194740A [0016] Patent Literature 3: JP2003-128868A [0017]
Patent Literature 4: JP06-25492A
SUMMARY OF INVENTION
Technical Problem
[0018] An object of the present invention is to provide a variety
of molded bodies (in particular, automobile parts, casings for a
variety of electrical appliances, construction members and the
like) having high weatherability, impact resistance, designability
and the like; and a polyorganosiloxane latex and a graft copolymer
as raw materials for these molded bodies.
Solution to Problem
[0019] The problems above are solved by aspects [1] to [24]
according to the present invention below.
[1] A polyorganosiloxane latex, wherein a mass average particle
diameter (Dw) of a polyorganosiloxane particle is 100 to 200 nm,
and wherein a ratio (Dw/Dn) of the mass average particle diameter
(Dw) to a number average particle diameter (Dn) of the particle is
1.0 to 1.7. [2] The polyorganosiloxane latex according to [1],
wherein a standard deviation of the mass average particle diameter
(Dw) of the polyorganosiloxane particle is 0 to 80. [3] The
polyorganosiloxane latex according to [1] or [2], wherein a
proportion of the polyorganosiloxane particle having a particle
diameter less than 50 nm is 5% by mass or less based on the total
amount of the particle, and wherein a proportion of the
polyorganosiloxane particle having a particle diameter of 300 nm or
more is 20% by mass or less based on the total amount of the
particle. [4] A polyorganosiloxane-containing vinyl-based copolymer
obtained by polymerizing one or more vinyl-based monomers in the
presence of the polyorganosiloxane latex according to any one of
[1] to [3]. [5] The polyorganosiloxane-containing vinyl-based
copolymer according to [4], wherein a mass average particle
diameter (Dw) of a particle in the polyorganosiloxane-containing
vinyl-based copolymer is 110 nm to 800 nm, and a ratio (Dw/Dn) of
the mass average particle diameter (Dw) to a number average
particle diameter (Dn) of the particle is 1.0 to 2.0. [6] The
polyorganosiloxane-containing vinyl-based copolymer according to
[4] or [5], wherein the vinyl-based monomer is an acrylic acid
ester. [7] A graft copolymer (G) obtained by graft polymerizing one
or more vinyl-based monomers in the presence of the
polyorganosiloxane-containing vinyl-based copolymer according to
any one of [1] to [4]. [8] The graft copolymer (G) according to
[7], wherein a molded body obtained by molding the following
composition exhibits the following performance (1) and (2) when
evaluated under the following measurement conditions:
[0020] (1) a Charpy impact strength at 23.degree. C. is 6
kJ/m.sup.2 or more, and
[0021] (2) a diffuse reflectance is 5% or less.
<Test Piece Production Condition>
[0022] (a) 33 parts by mass of a graft copolymer (Ga),
[0023] (b) 9 parts by mass of an acrylonitrile.cndot.styrene
copolymer including 25% by mass of an acrylonitrile unit and 75% by
mass of a styrene unit and having a reduced viscosity (.eta.sp/c)
of 0.40 dL/g in an N,N-dimethylformamide solution of 0.2 g/dL at
25.degree. C.,
[0024] (c) 9 parts by mass of an acrylonitrile-styrene copolymer
including 28% by mass of an acrylonitrile unit and 72% by mass of a
styrene unit and having a reduced viscosity of 0.62 dL/g in an
N,N-dimethylformamide solution of 0.2 g/dL at 25.degree. C.,
[0025] (d) 50 parts by mass of an
acrylonitrile-styrene-N-phenylmaleimide copolymer including 22% by
mass of an acrylonitrile unit, 55% by mass of a styrene unit, and
23% by mass of an N-phenylmaleimide unit and having a reduced
viscosity of 0.66 dL/g in an N,N-dimethylformamide solution of 0.2
g/dL at 25.degree. C.,
[0026] (e) 0.5 parts by mass of ethylenebisstearylamide,
[0027] (f) 0.03 parts by mass of silicone oil, and
[0028] (g) 0.05 parts by mass of carbon black.
[0029] These seven materials (a) to (g) above are blended, and
kneaded using a volatilizing extruder (TEX-30.alpha. made by The
Japan Steel Works, Ltd.) whose barrel is heated to a temperature of
260.degree. C. to obtain pellets; the pellets are molded using a
4-ounce injection molding machine (made by The Japan Steel Works,
Ltd.) in conditions of a cylinder temperature of 260.degree. C. and
a mold temperature of 60.degree. C. to obtain a test piece 1 (a
length of 80 mm, a width of 10 mm and a thickness of 4 mm); and a
plate-like molded body 2 (a length of 100 mm, a width of 100 mm and
a thickness of 2 mm) is obtained in the same manner as above in
conditions of a cylinder temperature of 260.degree. C., a mold
temperature of 60.degree. C., and an injection rate of 5 g/sec.
<Charpy Impact Strength Measurement Condition>
[0030] Measurement is conducted on a V-notched test piece 1 that is
left under a 23.degree. C. atmosphere for 12 hours or more by a
method according to ISO 179.
<Diffuse Reflectance Measurement Condition>
[0031] A 50 nm aluminum film is formed (direct deposition) on the
surface of the molded body 2 by a vacuum deposition method
(VPC-1100 made by ULVAC-PHI, Inc.) in conditions of a degree of
vacuum of 6.0.times.10.sup.-3 Pa and a film forming rate of 10
angstroms/sec; and a diffuse reflectance (%) of the obtained molded
body is measured using a reflectance meter (TR-1100AD made by Tokyo
Denshoku Co., Ltd.).
[9] The graft copolymer (Ga) according to [8], comprising 5 to 25%
by mass of polyorganosiloxane based on 100% by mass of a
polyorganosiloxane-containing vinyl-based copolymer, wherein a
mixture of a vinyl cyanide-based monomer and an aromatic
vinyl-based monomer is graft polymerized with the
polyorganosiloxane-containing vinyl-based copolymer, wherein the
polyorganosiloxane-containing vinyl-based copolymer has a mass
average particle diameter (Dw) of 120 to 200 nm, wherein a
proportion of a particle having a particle diameter of 100 nm or
less is 15% by mass or less of a total amount of the particle, and
wherein a proportion of the particle having a particle diameter of
400 nm or more is 1% by mass or less of the total amount of the
particle. [10] The graft copolymer (Ga) according to [8] or [9],
wherein the polyorganosiloxane contains 0.5 to 5 parts by mass of a
component derived from a siloxane-based crosslinking agent based on
100 parts by mass of the organosiloxane. [11] A thermoplastic resin
composition (Ia) including the graft copolymer (Ga) according to
any one of [8] to [10], and a thermoplastic resin (Ha) except for
the graft copolymer (Ga). [12] The thermoplastic resin composition
(Ia) according to [11], wherein the thermoplastic resin (Ha) is a
copolymer including 0 to 40% by mass of a vinyl cyanide-based
monomer unit, 40 to 80% by mass of an aromatic vinyl-based monomer
unit, and 0 to 60% by mass of another monomer unit whose monomer is
copolymerizable with these monomers. [13] A molded body obtained by
molding the thermoplastic resin composition (Ia) according to [11]
or [12]. [14] A lamp housing for vehicle lighting including a
molded body obtained by molding the thermoplastic resin composition
(Ia) according to [11] or [12]. [15] The graft copolymer (G)
according to [7], wherein a molded body obtained by molding the
following composition exhibits the following performance (1) and
(2) when evaluated under the following measurement conditions:
[0032] (1) L* is 24 or less, and
[0033] (2) a Charpy impact strength at -30.degree. C. is 6
kJ/m.sup.2 or more.
<Test Piece Production Condition>
[0034] (a) 42 parts by mass of a graft copolymer (Gb),
[0035] (b) 58 parts by mass of an acrylonitrile-styrene copolymer
including 34% by mass of an acrylonitrile unit and 66% by mass of a
styrene unit and having a reduced viscosity (.eta.sp/c) of 0.62
dL/g in an N,N-dimethylformamide solution of 0.2 g/dL at 25.degree.
C.,
[0036] (c) 0.3 parts by mass of ethylenebisstearylamide, and
[0037] (d) 0.5 parts by mass of carbon black.
[0038] These four materials (a) to (d) above are blended, and
kneaded using a volatilizing extruder (made by Ikegai Corp.,
PCM-30) whose barrel is heated to a temperature of 230.degree. C.
to obtain pellets; the pellets are molded using a 4-ounce injection
molding machine (made by The Japan Steel Works, Ltd.) in conditions
of a cylinder temperature of 230.degree. C. and a mold temperature
of 60.degree. C. to obtain a test piece 3 (length of 80 mm, width
of 10 mm, and thickness of 4 mm) and a tensile test piece 4 (length
of 170 mm, width of 20 mm, and thickness of 4 mm).
<Charpy Impact Strength Measurement Condition>
[0039] Measurement is conducted on a V-notched test piece 3 that is
left under a -30.degree. C. atmosphere for 12 hours or more by a
method according to ISO 179.
<L* Measurement Condition>
[0040] L* is measured for the tensile test piece 4 using a
spectrophotometer CM-508D made by Konica Minolta Sensing, Inc. on a
side opposite to a gate.
[16] The graft copolymer (Gb) according to [15], comprising 15 to
80% by mass of polyorganosiloxane based on 100% by mass of a
polyorganosiloxane-containing vinyl-based copolymer, wherein a
mixture of a vinyl cyanide-based monomer and an aromatic
vinyl-based monomer is graft polymerized with the
polyorganosiloxane-containing vinyl-based copolymer, wherein the
polyorganosiloxane-containing vinyl-based copolymer has a mass
average particle diameter (Dw) of 110 to 250 nm, wherein a
proportion of a particle having a particle diameter less than 100
nm is 20% by mass or less based on the total amount of the
particle, and wherein a proportion of the particle having a
particle diameter of 300 nm or more is 20% by mass or less based on
the total amount of the particle. [17] The graft copolymer (Gb)
according to [15] or [16], wherein the polyorganosiloxane contains
0.5 to 3 parts by mass of a component derived from a siloxane-based
crosslinking agent based on 100 parts by mass of organosiloxane.
[18] A thermoplastic resin composition (Ib) including the graft
copolymer (Gb) according to any one of [15] to [17] and a
thermoplastic resin (Hb) except for the graft copolymer (Gb). [19]
The thermoplastic resin composition (Ib) according to [18], wherein
the thermoplastic resin (Hb) is a copolymer including 0 to 40% by
mass of a vinyl cyanide-based monomer unit, 40 to 80% by mass of an
aromatic vinyl-based monomer unit, and 0 to 60% by mass of another
vinyl-based monomer unit whose monomer is copolymerizable with
these monomers. [20] A molded body obtained by molding the
thermoplastic resin composition (Ib) according to [18] or [19].
[21] A method of producing a polyorganosiloxane latex, the method
comprising a step of dropping an emulsion (B) comprising
organosiloxane, an emulsifier, and water into a water-based medium
(A) comprising water, an organic acid catalyst, and an inorganic
acid catalyst; and a step of performing polymerization, wherein a
total amount of the organic acid catalyst and the emulsifier is 0.5
to 6 parts by mass based on 100 parts by mass of the
organosiloxane, wherein the pH of the water-based medium (A)
measured at 25.degree. C. is within the range of 0 to 1.2, and
wherein the dropping rate of the emulsion (B) is a rate such that
an amount of organosiloxane to be fed is 0.5 [parts by mass/min] or
less when a total amount of organosiloxane to be used is 100 parts
by mass. [22] The method according to [21], wherein the total
amount of the organic acid catalyst and the emulsifier is 0.5 to 6
parts by mass based on 100 parts by mass of organosiloxane, and the
pH of the water-based medium (A) measured at 25.degree. C. is
within the range of 0 to 1.0. [23] The method according to [21] or
[22], wherein the dropping rate of the emulsion (B) is a rate such
that the rate of organosiloxane to be fed is 0.5 parts by mass/min
or less. [24] The method according to [22] or [23], wherein the
organic acid catalyst contains at least one or more selected from
the group consisting of aliphatic sulfonic acids,
aliphatic-substituted benzenesulfonic acids, and
aliphatic-substituted naphthalenesulfonic acids.
Advantageous Effects of Invention
[0041] The present invention provides a variety of molded bodies
(in particular, automobile parts, casings for a variety of
electrical appliances, construction members and the like) having
high weatherability, impact resistance, designability and the like;
and a polyorganosiloxane latex and a graft copolymer as raw
materials for these molded bodies.
DESCRIPTION OF EMBODIMENTS
[Polyorganosiloxane Latex]
[0042] In the polyorganosiloxane latex according to the present
invention, the mass average particle diameter (Dw) of the
polyorganosiloxane particle is 100 to 200 nm, and the ratio (Dw/Dn)
of the mass average particle diameter (Dw) to the number average
particle diameter (Dn) is 1.0 to 1.7. Since Dw and Dw/Dn are in
these ranges, the molded body comprising a blend of the
polyorganosiloxane-containing vinyl-based copolymer and the graft
copolymer exhibits high brightness, color developability, and
impact resistance. Dw is preferably 100 to 190 nm. Dw/Dn is
preferably 1.0 to 1.3.
[0043] In the polyorganosiloxane latex, the standard deviation in
the mass average particle diameter (Dw) of the polyorganosiloxane
particle is preferably 0 to 80.
[0044] In the polyorganosiloxane particle in the polyorganosiloxane
latex, preferably, the proportion of the particle having a particle
diameter less than 50 nm is 5% by mass or less based on the total
amount of the particle, and the proportion of the particle having a
particle diameter of 300 nm or more is 20% by mass or less based on
the total amount of the particle.
[0045] The polyorganosiloxane latex according to the present
invention is produced, for example, by dropping an emulsion (B)
including organosiloxane, an emulsifier, and water into a
water-based medium (A) including water, an organic acid catalyst,
and an inorganic acid catalyst, and performing polymerization. For
a specific production condition, for example, the total amount of
the organic acid catalyst and the emulsifier is 0.5 to 6 parts by
mass based on 100 parts by mass of organosiloxane, the pH of the
water-based medium (A) measured at 25.degree. C. is within the
range of 0 to 1.2, and the dropping rate of the emulsion (B) is a
rate such that the amount of organosiloxane to be fed is 0.5 [parts
by mass/min] or less when a total amount of organosiloxane to be
used is 100 parts by mass.
[0046] The total amount of the organic acid catalyst and the
emulsifier is preferably 0.8 to 6 parts by mass based on 100 parts
by mass of organosiloxane. The pH of the water-based medium (A)
measured at 25.degree. C. is preferably within the range of 0.1 to
1.2, and preferably within the range of 0.5 to 1.2.
[0047] The water-based medium (A) used in the method of producing a
polyorganosiloxane latex includes water, an organic acid catalyst,
and an inorganic acid catalyst. Deionized water can be used for
water above. The amount of water to be contained in the water-based
medium (A) is preferably 60 to 300 parts by mass, and more
preferably 60 to 100 parts by mass based on 100 parts by mass of
organosiloxane contained in the emulsion (B) described later. When
the amount of water to be contained in the water-based medium (A)
is 60 parts by mass or more, increase in the viscosity of the latex
to be obtained can be suppressed, and handling of the latex becomes
easy. When the amount of water to be contained in the water-based
medium (A) is 300 parts by mass or less, production with high
productivity is enabled, and reduction in the concentration of the
solid content in the latex to be obtained can be suppressed.
[0048] For the organic acid catalyst, sulfonic acids such as
aliphatic sulfonic acids, aliphatic-substituted benzenesulfonic
acids, and aliphatic-substituted naphthalenesulfonic acids are
preferable. Aliphatic-substituted benzenesulfonic acids are more
preferable because of their significant action to stabilize an
organosiloxane latex. An aliphatic substituent for the
aliphatic-substituted benzenesulfonic acids is preferably an alkyl
group having 9 to 20 carbon atoms, and more preferably an n-dodecyl
group having 12 carbon atoms.
[0049] Examples of the inorganic acid catalyst include mineral
acids such as sulfuric acid, hydrochloric acid, and nitric acid.
Among these, sulfuric acid is preferable. These may be used alone
or in combination.
[0050] The amounts of these catalysts to be used are adjusted such
that the pH at 25.degree. C. of the water-based medium (A) falls
within the range of 0 to 1.2 because the pH of the water-based
medium (A) is an important factor to determine the particle
diameter of polyorganosiloxane to be obtained. By adjusting the pH
of the water-based medium (A) in the above range,
polyorganosiloxane having a narrow particle diameter distribution
can be obtained. The pH at 25.degree. C. of the water-based medium
(A) is preferably in the range of 0.5 to 1.2 because adjustment is
easy.
[0051] The pH of the water-based medium (A) is an important factor
to determine the particle diameter of polyorganosiloxane for the
following reason. Organosiloxane existing in oil droplets of the
emulsion (B) contacts with the acid catalyst to form silanol.
Silanol dissolves in the aqueous phase, comes to a micelle of the
organic acid catalyst and the emulsifier, and condensation reaction
occurs. This reaction progresses simultaneously with the
condensation reaction of organosiloxane in oil droplets. When the
pH of the water-based medium (A) is sufficiently low, the
generation rate of silanol becomes faster, the condensation
reaction by silanol is accelerated, and the rate of the
condensation reaction of organosiloxane in oil droplets becomes
relatively slower. As a result, polyorganosiloxane having a narrow
particle diameter distribution is formed. Meanwhile, when the pH of
the water-based medium (A) is more than 1.2, the generation rate of
silanol becomes slower, and progression of the condensation
reaction of organosiloxane in oil droplets cannot be neglected. As
a result, the particle diameter of polyorganosiloxane to be
obtained is larger, and the particle diameter distribution is
wider. By controlling the pH of the water-based medium (A) in the
above range, polyorganosiloxane having a narrow particle diameter
distribution can be obtained.
[0052] Such a pH of the water-based medium (A) can be adjusted by
adjusting the contents of the organic acid catalyst and the
inorganic acid catalyst. Here, the value of the pH to be used is a
value obtained by measuring the water-based medium (A) at
25.degree. C. with a pH meter (Model PH82: made by Yokogawa
Electric Corporation) and correcting the measured value at pHs of
4.01 and 6.86 by two-point calibration.
[0053] The content of the organic acid catalyst in the water-based
medium (A) is preferably 0.1 to 5.5% by mass, and more preferably
0.1 to 2.5% by mass. The content of the inorganic acid catalyst in
the water-based medium (A) is preferably 0.5 to 2.0% by mass, and
more preferably 1.3 to 2.0% by mass from the viewpoint of
preventing decomposition, coloring, and the like of a resin by the
inorganic acid catalyst remaining in the latex when an additive or
the like for a resin is synthesized using the latex to be obtained
as a raw material. The values of these contents are based on 100%
by mass of the water-based medium (A). The water-based medium (A)
can be obtained by properly mixing and stirring these
components.
[0054] The emulsion (B) includes organosiloxane, an emulsifier, and
water. For organosiloxane, both linear organosiloxanes and cyclic
organosiloxanes can be used. Cyclic organosiloxanes are preferable
because they have high polymerization stability and a high
polymerization rate. For cyclic organosiloxanes, those having a 3-
to 7-membered ring are preferable. Examples thereof can include
hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
trimethyltriphenylcyclotrisiloxane,
tetramethyltetraphenylcyclotetrasiloxane, and
octaphenylcyclotetrasiloxane. These may be used alone or in
combination.
[0055] For the above organosiloxanes, commercially available
products such as DMC made by Shin-Etsu Chemical Co., Ltd. can be
used.
[0056] For the emulsifier used for the emulsion (B), anionic
emulsifiers or nonionic emulsifiers are preferable. Examples of the
anionic emulsifiers include sodium alkylbenzene sulfonate, sodium
alkyldiphenyl ether disulfonate, sodium alkyl sulfate, sodium
polyoxyethylene alkyl sulfate, and sodium polyoxyethylene
nonylphenyl ether sulfate.
[0057] Examples of the nonionic emulsifiers include polyoxyethylene
alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene
distyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether,
polyoxyethylene polyoxypropylene glycol and the like. These
emulsifiers may be used alone or in combination.
[0058] The content of the emulsifier in the emulsion (B) needs to
be such an amount that organosiloxane can be dispersed in fine oil
droplets, the fine oil droplets can adequately contact with the
organic acid catalyst contained in the water-based medium (A), and
generation of silanol can be promoted. For the content of the
emulsifier, the total amount of the emulsifier and the organic acid
catalyst contained in the water-based medium (A) is in the range of
0.5 to 6 parts by mass based on 100 parts by mass of
organosiloxane. When the content of the organic acid catalyst is
reduced, the content of the emulsifier is competitively increased
in order to adjust the total amount of these components within the
range of 0.5 to 6 parts by mass. When the total amount of these
components is 0.5 parts by mass or more based on 100 parts by mass
of organosiloxane, the mass average particle diameter of the
polyorganosiloxane to be obtained can be controlled to be 200 nm or
less, and the particle diameter distribution can be narrowed. When
the total amount of these components is 6 parts by mass or less
based on 100 parts by mass of organosiloxane, the mass average
particle diameter of the polyorganosiloxane to be obtained is 100
nm or more, and the particle diameter distribution is narrowed. The
total amount of these components is preferably 0.8 to 6 parts by
mass, and more preferably 0.8 to 3 parts by mass based on 100 parts
by mass of organosiloxane.
[0059] Further, preferably, the amount of the organic acid catalyst
is 0.3 to 5.5 parts by mass and the amount of the emulsifier is 0.5
to 5.7 parts by mass based on 100 parts by mass of
organosiloxane.
[0060] For water used for the emulsion (B), deionized water can be
used. The content of water in the emulsion (B) is preferably 10
times or less the mass of organosiloxane. When the content of water
is 10 times or less the mass of organosiloxane, reduction in the
concentration of polyorganosiloxane in the latex to be obtained can
be suppressed. When a vinyl monomer is added to the
polyorganosiloxane latex having a proper value of the concentration
of polyorganosiloxane and graft polymerization is performed, a
graft copolymer can be synthesized efficiently by one stage
polymerization. When the polyorganosiloxane latex to be obtained is
used as a coating material, increase in the drying time of the
coating film can be suppressed.
[0061] The emulsion (B) can contain a siloxane-based crosslinking
agent and/or a siloxane-based grafting agent. For these
crosslinking agents and grafting agents, those having a siloxy
group are preferable. By using the siloxane-based crosslinking
agent, polyorganosiloxane having a crosslinking structure can be
obtained. Examples of the siloxane-based crosslinking agent include
trifunctional or tetrafunctional silane-based crosslinking agents
such as trimethoxymethylsilane, triethoxyphenylsilane,
tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and
tetrabutoxysilane. Among these, tetrafunctional crosslinking agents
are preferable, and tetraethoxysilane is more preferable. The
content of the crosslinking agent is preferably 0.1 to 30 parts by
mass, more preferably 0.5 to 5 parts by mass, and most preferably
0.5 to 3 parts by mass based on 100 parts by mass of
organosiloxane.
[0062] The siloxane-based grafting agent has a siloxy group and a
functional group which is polymerizable with a vinyl monomer. By
using a siloxane-based grafting agent, polyorganosiloxane having a
vinyl monomer and a functional group which is polymerizable with
the vinyl monomer can be obtained. For this reason, a vinyl monomer
can be grafted to the polyorganosiloxane thus obtained by radical
polymerization. Examples of the siloxane-based grafting agent
include siloxane represented by formula (I).
RSiR.sup.1.sub.n(OR.sup.2).sub.(3-n) (I)
[0063] In formula (I), R.sup.1 represents a methyl group, an ethyl
group, a propyl group, or a phenyl group; R.sup.2 represents an
organic group in an alkoxy group, and examples thereof include a
methyl group, an ethyl group, a propyl group, or a phenyl group; n
represents 0, 1, or 2; R represents a group represented by formulas
(I-1) to (I-4).
CH.sub.2.dbd.C(R.sup.3)--COO--(CH.sub.2).sub.p-- (I-1)
CH.sub.2.dbd.C(R.sup.4)--C.sub.6H.sub.4-- (I-2)
CH.sub.2.dbd.CH-- (I-3)
HS--(CH.sub.2).sub.p-- (I-4)
[0064] In these formulas, R.sup.3 and R.sup.4 each represents
hydrogen or a methyl group, and p represents an integer of 1 to
6.
[0065] Examples of the functional group represented by formula
(I-1) include a methacryloyloxyalkyl group. Examples of siloxane
having this group include
.beta.-methacryloyloxyethyldimethoxymethylsilane,
.gamma.-methacryloyloxypropylmethoxydimethylsilane,
.gamma.-methacryloyloxypropyldimethoxymethylsilane,
.gamma.-methacryloyloxypropyltrimethoxysilane,
.gamma.-methacryloyloxypropylethoxydiethylsilane,
.gamma.-methacryloyloxypropyldiethoxymethylsilane, and
.delta.-methacryloyloxybutyldiethoxymethylsilane.
[0066] Examples of the functional group represented by formula
(I-2) include a vinylphenyl group and the like. Examples of
siloxane having this group include
vinylphenylethyldimethoxysilane.
[0067] Examples of siloxane having the functional group represented
by formula (I-3) include vinyltrimethoxysilane and
vinyltriethoxysilane.
[0068] Examples of the functional group represented by formula
(I-4) include a mercaptoalkyl group. Examples of siloxane having
this group include .gamma.-mercaptopropyldimethyoxymethylsilane,
.gamma.-mercaptopropylmethoxydimethylsilane,
.gamma.-mercaptopropyldiethoxymethylsilane,
.gamma.-mercaptopropylethoxydimethylsilane, and
.gamma.-mercaptopropyltrimethoxysilane.
[0069] These siloxane-based grafting agents may be used alone or in
combination.
[0070] The content of the siloxane-based grafting agent is
preferably 0.05 to 20 parts by mass based on 100 parts by mass of
organosiloxane. The siloxane-based crosslinking agent and the
siloxane-based grafting agent are preferably used in combination.
0.5 to 5 parts by mass of the siloxane-based crosslinking agent and
0.05 to 5 parts by mass of the siloxane-based grafting agent are
preferably used in combination based on 100 parts by mass of
organosiloxane.
[0071] Further, the emulsion (B) may contain a siloxane oligomer
having a terminal blocking group if necessary. The siloxane
oligomer having a terminal blocking group refers to a siloxane
oligomer that has an alkyl group or the like at the terminal of the
organosiloxane oligomer, and terminates polymerization of
polyorganosiloxane.
[0072] Examples of the siloxane oligomer having a terminal blocking
group include hexamethyldisiloxane,
1,3-bis(3-glycidoxypropyl)tetramethyldisiloxane,
1,3-bis(3-aminopropyl)tetramethyldisiloxane, and
methoxytrimethylsilane.
[0073] The emulsion (B) can be prepared by an emulsion method of
mixing organosiloxane, the emulsifier, and water described above,
and stirring the mixture such that a shear force is applied
thereto. For the stirrer, typical stirring apparatuses having a
stirring blade and a tank can be used. Preferably, a high pressure
emulsifying apparatus can be used. The high pressure emulsifying
apparatus is an apparatus that stirs a raw material mixture at a
high pressure, and emulsifies the mixture by applying a shear
force. Examples thereof include a homogenizer. By using such a high
pressure emulsifying apparatus, a stable emulsion can efficiently
be generated.
[0074] The thus-obtained emulsion (B) is dropped into the
water-based medium (A). Thereby, a polyorganosiloxane latex can be
obtained. The temperature of the water-based medium (A) is
preferably 60 to 100.degree. C., and more preferably 80.degree. C.
or more. When the temperature of the water-based medium (A) is
60.degree. C. or more, the acid catalyst can sufficiently
dissociate, and contact with organosiloxane to generate silanol
effectively. When the temperature of the water-based medium (A) is
100.degree. C. or less, a high pressure polymerization facility is
unnecessary.
[0075] When the total amount of organosiloxane to be used is 100
parts by mass, the dropping rate of the emulsion (B) is preferably
a rate such that the amount of organosiloxane to be fed is 0.5
[parts by mass/min] or less, and more preferably 0.3 [parts by
mass/min] or less. When the amount of organosiloxane to be fed is
0.5 [parts by mass/min] or less, generation of silanol can be
accelerated, and progression of the condensation reaction of
organosiloxane in a micelle containing no acid catalyst can be
suppressed. As a result, polyorganosiloxane having a narrow
particle diameter distribution is obtained.
[0076] When the total amount of organosiloxane to be used is 100
parts by mass, the dropping rate of the emulsion (B) is preferably
a rate such that the amount of organosiloxane to be fed is 0.05
[parts by mass/min] or more, and more preferably 0.08 [parts by
mass/min] or more. When the amount of organosiloxane to be fed is
0.05 [parts by mass/min] or more, reduction in productivity can be
suppressed.
[0077] The emulsion (B) is preferably dropped at a temperature of
60 to 100.degree. C. for 3 to 34 hours. This operation can
efficiently progress the reaction.
[0078] After dropping of the emulsion (B) is completed, further,
heating is preferably performed. Heating can be performed for 2 to
50 hours, for example. By heating after dropping, silanol derived
from organosiloxane can almost completely be reacted.
[0079] Further, because the crosslinking reaction between silanol
progresses at a temperature of 30.degree. C. or less, the
temperature of 30.degree. C. or less can be kept for approximately
5 to 100 hours in order to increase the crosslinked density of
polyorganosiloxane.
[0080] The condensation reaction for polyorganosiloxane can be
terminated by neutralizing the latex with an alkaline substance
such as sodium hydroxide, potassium hydroxide, and an aqueous
ammonia solution to a pH of 6 to 8.
[0081] The thus-obtained polyorganosiloxane has a mass average
particle diameter (Dw) in the range of 100 to 200 nm and a narrow
particle diameter distribution at Dw/Dn of 1.7 or less. By
adjusting the total amount of the organic acid catalyst and the
emulsifier in the range of 0.8 to 6 parts by mass based on 100
parts by mass of organosiloxane, the mass average particle diameter
of polyorganosiloxane can be adjusted to have a desired value in
the range of 100 to 200 nm.
[0082] For the particle diameter of polyorganosiloxane, a value
obtained by measurement by the following method can be used. The
polyorganosiloxane latex is diluted with deionized water to have a
concentration of approximately 3%, and the obtained product is used
as a sample. The particle diameter is measured using a CHDF2000
type particle size distribution analyzer made by MATEC Instrument
Companies, Inc., U.S.A.
[0083] The measurement can be performed on the standard condition
recommended by MATEC Instrument Companies, Inc. as below:
[0084] cartridge: dedicated capillary cartridge for separating
particles (trade name; C-202),
[0085] carrier solution: dedicated carrier solution (trade name;
2XGR500),
[0086] solution properties of the carrier solution: almost
neutral,
[0087] flow rate of the carrier solution: 1.4 ml/min,
[0088] pressure of the carrier solution: approximately 4,000 psi
(2,600 kPa),
[0089] measurement temperature: 35.degree. C.,
[0090] amount of the sample to be used: 0.1 ml.
[0091] Among monodisperse polystyrenes made by Duke Scientific
Corporation, U.S.A. and having a known particle diameter, those
having 12 different particle diameters in total in the range of 40
to 800 nm are used as the standard particle diameter substance.
[0092] To improve mechanical stability, an emulsifier may be added
to the polyorganosiloxane latex obtained by the above method if
necessary. The same anionic emulsifiers and nonionic emulsifiers as
those listed above are preferable.
[0093] The amount of the emulsifier to be added is preferably 0.05
to 10 parts by mass based on 100 parts by mass of organosiloxane.
When the amount is 0.05 parts by mass or more, the mechanical
stability of the latex is improved. When the amount is 10 parts by
mass or less, occurrence of coloring can be suppressed in the
additive for a resin obtained using the polyorganosiloxane latex as
a raw material.
[0094] The polyorganosiloxane latex according to the present
invention is suitably used as a raw material for an impact strength
modifier for a resin. The polyorganosiloxane latex according to the
present invention is suitable for a variety of applications such as
a variety of cosmetics such as hair cosmetics, skin cosmetics, and
make-up cosmetics; lustering agents and surface protecting agents
for automobiles, furniture, leather products, and the like; surface
treatment agents for improving lubrication of weather strips and
the like; fiber treatment agents for cloths, curtains, bedcloths,
and the like; antifoaming agents used for waste water treatments
and production of foods.
[0095] The impact strength modifier for a resin using the
polyorganosiloxane latex according to the present invention is, in
particular, useful because a material having a narrow particle
diameter distribution and a good balance between impact strength
and the surface appearance can be provided.
[Polyorganosiloxane-Containing Vinyl-Based Copolymer]
[0096] The polyorganosiloxane-containing vinyl-based copolymer
according to the present invention is a copolymer obtained by
polymerizing one or more vinyl-based monomers in the presence of
the polyorganosiloxane latex wherein the mass average particle
diameter (Dw) is 100 to 200 nm and wherein the ratio (Dw/Dn) of the
mass average particle diameter (Dw) to the number average particle
diameter (Dn) is 1.0 to 1.7.
[0097] The polyorganosiloxane-containing vinyl-based copolymer
(hereinafter, referred to as a "composite polymer (g)" in some
cases) preferably has a mass average particle diameter (Dw) of 110
nm to 800 nm, and the ratio (Dw/Dn) of the mass average particle
diameter (Dw) to the number average particle diameter (Dn) of 1.0
to 2.0.
[0098] A vinyl-based monomer usable to obtain the composite polymer
(g) is not in particular limited, and examples thereof include
(meth)acrylic acid ester-based monomers, aromatic vinyl monomers,
and vinyl cyanide monomers.
[0099] Examples of the (meth)acrylic acid ester-based monomers
include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl
(meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate,
i-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl
(meth)acrylate. Examples of the aromatic vinyl monomers include
styrene, .alpha.-methylstyrene, vinyltoluene, and chlorostyrene.
Examples of the vinyl cyanide monomers include acrylonitrile and
methacrylonitrile. These vinyl-based monomers can be used alone or
in combination. Among these vinyl-based monomers, acrylic acid
ester-based monomers are preferably used.
[0100] For the polymerizable component, a grafting agent and a
crosslinking agent can also be used if necessary. Examples of the
grafting agent or crosslinking agent include polyfunctional
monomers such as allyl methacrylate, triallyl cyanurate, triallyl
isocyanurate, divinylbenzene, ethylene glycol diester
dimethacrylate, propylene glycol diester dimethacrylate,
1,3-butylene glycol diester dimethacrylate, 1,4-butylene glycol
diester dimethacrylate, 1,6-hexane diol diacrylic acid ester, and
triallyl trimellitate. These can be used alone or in
combination.
[0101] The method of producing the composite polymer (g) is not in
particular limited. The composite polymer (g) can be produced, for
example, by an emulsion polymerization method, a suspension
polymerization method, or a micro-suspension polymerization method.
Use of the emulsion polymerization method is preferable. Among
these, a method of emulsion polymerizing one or more vinyl-based
monomers in the presence of the polyorganosiloxane latex to obtain
a latex of the composite polymer (g) is in particular
preferable.
[0102] Examples of a method of adding a vinyl-based monomer to the
polyorganosiloxane latex include a method of adding a vinyl-based
monomer into the polyorganosiloxane latex in a lump sum or
dropwise.
[0103] In production of the latex of the composite polymer (g), an
emulsifier can be added to stabilize the latex and control the
average particle diameter of the composite polymer. The emulsifier
is not in particular limited, and anionic emulsifiers and nonionic
emulsifiers are preferable.
[0104] Examples of the anionic emulsifiers include a variety of
carboxylic acid salts such as sodium sarcosinate, fatty acid
potassium, fatty acid sodium, dipotassium alkenyl succinate, and
rosin acid soap; sulfonic acid salts such as sodium alkylbenzene
sulfonate and sodium diphenylether disulfonate; sulfuric acid salts
such as sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate,
and sodium polyoxyethylene nonylphenyl ether sulfate; and
phosphoric acid salts such as sodium polyoxyethylene alkyl
phosphate and calcium polyoxyethylene alkyl phosphate.
[0105] Examples of the nonionic emulsifiers include polyoxyethylene
alkyl ether, polyoxyethylene distyrenated phenyl ether, and
polyoxyethylene tribenzylphenyl ether. These emulsifiers can be
used alone or in combination.
[0106] By adjusting the amounts of the emulsifier and the
vinyl-based monomer, a composite polymer (g) having Dw of 110 to
800 nm and Dw/Dn of 1.0 to 2.0 can be produced. The amount of the
emulsifier is preferably 0.1 to 20 parts by mass based on 100 parts
by mass of the polyorganosiloxane latex.
[0107] Examples of the polymerization initiator used for
polymerization of the vinyl-based monomer include peroxides,
azo-based initiators, or redox type initiators in combination of an
oxidizing agent with a reducing agent. Among these, the redox type
initiators, in particular, combinations of redox type initiators
using ferrous sulfate, ethylenediaminetetraacetic acid disodium
salt, a reducing agent and peroxide are preferable.
[0108] Examples of the peroxide include organic peroxides such as
diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, cumene
hydroperoxide, and t-butyl hydroperoxide. These can be used alone
or in combination. Examples of the reducing agent include sodium
formaldehyde sulfoxylate, L-ascorbic acid, fructose, dextrose,
sorbose, and inositol. These can be used alone or in
combination.
[0109] For the mass ratio of the polyorganosiloxane and vinyl-based
polymer in the composite polymer (g) (100% by mass), preferably,
polyorganosiloxane is 1.0 to 99.0% by mass and the vinyl-based
polymer is 99.0 to 1.0% by mass. The mass ratio can be calculated
from the mass ratio of polyorganosiloxane to the vinyl-based
monomer, the grafting agent, and the crosslinking agent used in
production of the composite polymer (g).
[0110] The composite polymer (g) can be recovered as a powder from
the latex of the composite polymer (g). The latex of the composite
polymer (g) can be used as a raw material for the graft copolymer
(G) described later.
[0111] When the powder of the composite polymer (g) is recovered
from the latex of the composite polymer (g), one of a spray drying
method and a coagulation method can be used.
[0112] The spray drying method is a method in which the latex of
the composite polymer (g) is sprayed in a dryer in a form of micro
liquid droplets, and these droplets are dried by applying a heated
gas for drying. Examples of a method for generating micro liquid
droplets include a rotary disk method, a pressure nozzle method, a
two-fluid nozzle method, and a pressurized two-fluid nozzle method.
The dryer may have a small volume for use in a laboratory, or a
large volume for industrial use. The temperature of the heated gas
for drying is preferably 200.degree. C. or less, and more
preferably 120 to 180.degree. C. The latexes of two or more
composite polymers (g) individually produced can also be spray
dried together. Further, to improve powder properties such as
blocking during spray drying and bulk specific gravity, optional
component such as silica can also be added to a polymer latex and
spray drying can be performed.
[0113] The coagulation method is a method in which the latex of the
composite polymer (g) is put into very hot water in which calcium
chloride, calcium acetate, aluminum sulfate, or the like is
dissolved; the composite polymer (g) is separated by salting-out
and coagulation; next, the separated wet composite polymer (g) is
dehydrated to reduce the content of water, and recovered; further,
the recovered composite polymer (g) is dried using a squeeze
dehydrator or a hot air dryer.
[0114] Examples of a coagulant used in coagulation of the composite
polymer (g) from the latex include inorganic salts such as aluminum
chloride, aluminum sulfate, sodium sulfate, magnesium sulfate,
sodium nitrate, and calcium acetate and acids such as sulfuric
acid. These coagulants may be used alone or in combination. When
these are used in combination, a combination that does not allow
formation of a water-insoluble salt is required. For example, if
calcium acetate is used in combination with sulfuric acid or a
sodium salt thereof, a water-insoluble calcium salt is formed. This
combination is not preferable.
[0115] The above coagulant is usually used in a form of an aqueous
solution. The concentration of the coagulant aqueous solution is
0.1% by mass or more, and in particular preferably 1% by mass or
more from the viewpoint of stably coagulating and recovering the
composite polymer (g). The concentration of the coagulant aqueous
solution is 20% by mass or less, and in particular preferably 15%
by mass or less from the viewpoint of reducing the amount of the
coagulant remaining in the recovered composite polymer (g) and
thereby suppressing coloring of the molded article. The amount of
the coagulant aqueous solution is not in particular limited. The
amount is 10 parts by mass or more, and preferably 500 parts by
mass or less based on 100 parts by mass of the latex.
[0116] The method of contacting the latex with the coagulant
aqueous solution is not in particular limited. Examples thereof
usually include a method in which while the coagulant aqueous
solution is stirred, the latex is continuously added thereto and
the solution is kept for a predetermined period of time, and a
method in which the coagulant aqueous solution is contacted with
the latex while these materials are continuously charged into a
container having a stirrer at a predetermined ratio; and a mixture
of a flocculated polymer and water is continuously extracted from
the container. The temperature when the latex contacted with the
coagulant aqueous solution is not in particular limited. The
temperature is 30.degree. C. or more, and preferably 100.degree. C.
or less. The time for the contact is not in particular limited.
[0117] The flocculated composite polymer (g) is washed with water
approximately 1 to 100 times the mass thereof. The filtered wet
composite polymer (g) is dried using a fluidized bed dryer, a
squeeze dehydrator, or the like. The temperature and the time for
drying may be properly determined depending on the composite
polymer (g) to be obtained. Without recovering the composite
polymer (g) discharged from a squeeze dehydrator or an extruder,
the composite polymer (g) may directly be sent to an extruder or a
molding machine that produces a resin composition, and may be mixed
with other thermoplastic resins to obtain a molded body.
[Graft Copolymer (G)]
[0118] A graft copolymer (G) according to the present invention is
a graft copolymer obtained by graft polymerizing one or more
vinyl-based monomers in the presence of the
polyorganosiloxane-containing vinyl-based copolymer. A composite
polymer (g) according to the present invention can be used as a raw
material for a graft copolymer (G). Examples of the graft
polymerization method include a method of polymerizing a
vinyl-based monomer (hereinafter, referred to as a "monomer for
grafting" in some cases) in the presence of the latex of the
composite polymer (g). By performing polymerization using the same
method as that in production of the latex of the composite polymer
(g) described above, the latex of the graft copolymer (G) can be
obtained.
[0119] For the monomer for grafting, the same (meth)acrylic acid
ester-based monomers, aromatic vinyl monomers, and vinyl cyanide
monomers as those described in production of the composite polymer
(g) are preferable.
[0120] Examples of the graft polymerization method include a method
in which the monomer for grafting is fed into the latex of the
composite polymer (g), and polymerization is performed at one or
multi stages. Specifically, examples thereof include a batch
polymerization method of feeding the total amount of the monomer
for grafting at one time and a consecutive polymerization method of
feeding the monomer for grafting by continuously dropping the
monomer for grafting (hereinafter, referred to as a "semi-batch
polymerization method"). As an intermediate operation, a method in
which the monomer for grafting is divided into portions having a
small amount, and an operation of "feeding a small amount of the
monomer for grafting and polymerization" is repeated at many stages
can be used. The semi-batch polymerization method is preferable
because the stability during polymerization is high and a latex
having a desired particle diameter and particle diameter
distribution can be obtained.
[0121] Examples of the emulsifier used in graft polymerization
include the same emulsifiers as those described in production of
the composite polymer (g). The anionic emulsifiers and nonionic
emulsifiers are preferable.
[0122] Examples of the polymerization initiator used in the graft
polymerization include the same polymerization initiators used in
production of the composite polymer (g). In particular,
polymerization initiators in combination of ferrous sulfate,
ethylenediaminetetraacetic acid disodium salt, a reducing agent,
and peroxide are preferably used.
[0123] When powders of a graft copolymer (G) is recovered from the
latex of the graft copolymer (G), one of the spray drying method
and the coagulation method can be used similarly in the case of
recovering powders of the composite polymer (g).
[0124] Examples of preferable embodiments of the graft copolymer
(G) according to the present invention include graft copolymers
(Ga) and (Gb) described later. Examples of preferable embodiments
of the composite polymer (g) according to the present invention
include composite polymers (ga) and (gb) described later.
[Graft Copolymer (Ga)]
[0125] A graft copolymer (G) according to the present invention is
preferably a graft copolymer (Ga), wherein a molded body obtained
by molding the following composition exhibits the following
performance (1) and (2) when evaluated under the following
measurement conditions:
[0126] (1) a Charpy impact strength at 23.degree. C. is 6
kJ/m.sup.2 or more, and
[0127] (2) a diffuse reflectance is 5% or less.
<Test Piece Production Condition>
[0128] (a) 33 parts by mass of a graft copolymer (G),
[0129] (b) 9 parts by mass of an acrylonitrile.cndot.styrene
copolymer including 25% by mass of an acrylonitrile unit and 75% by
mass of a styrene unit and having a reduced viscosity (.eta.sp/c)
of 0.40 dL/g in an N,N-dimethylformamide solution of 0.2 g/dL at
25.degree. C.,
[0130] (c) 9 parts by mass of an acrylonitrile-styrene copolymer
including 28% by mass of an acrylonitrile unit and 72% by mass of a
styrene unit and having a reduced viscosity of 0.62 dL/g in an
N,N-dimethylformamide solution of 0.2 g/dL at 25.degree. C.,
[0131] (d) 50 parts by mass of an
acrylonitrile-styrene-N-phenylmaleimide copolymer including 22% by
mass of an acrylonitrile unit, 55% by mass of a styrene unit, and
23% by mass of an N-phenylmaleimide unit and having a reduced
viscosity of 0.66 dL/g in an N,N-dimethylformamide solution of 0.2
g/dL at 25.degree. C.,
[0132] (e) 0.5 parts by mass of ethylenebisstearylamide,
[0133] (f) 0.03 parts by mass of silicone oil, and
[0134] (g) 0.05 parts by mass of carbon black.
[0135] These seven materials (a) to (g) above are blended, and
kneaded using a volatilizing extruder (TEX-30.alpha. made by The
Japan Steel Works, Ltd.) whose barrel is heated to a temperature of
260.degree. C. to obtain pellets. The pellets are molded using a
4-ounce injection molding machine (made by The Japan Steel Works,
Ltd.) in conditions of a cylinder temperature of 260.degree. C. and
a mold temperature of 60.degree. C. to obtain a test piece 1 (a
length of 80 mm, a width of 10 mm and a thickness of 4 mm).
Moreover, a plate-like molded body 2 (a length of 100 mm, a width
of 100 mm and a thickness of 2 mm) is obtained in the same manner
as above in conditions of a cylinder temperature of 260.degree. C.,
a mold temperature of 60.degree. C., and an injection rate of 5
g/sec.
<Charpy Impact Strength Measurement Condition>
[0136] Measurement is conducted on a V-notched test piece 1 that is
left under a 23.degree. C. atmosphere for 12 hours or more by a
method according to ISO 179.
<Diffuse Reflectance Measurement Condition>
[0137] A 50 nm aluminum film is formed (through a direct
deposition) on the surface of the molded body 2 by a vacuum
deposition method (VPC-1100 made by ULVAC-PHI, Inc.) in conditions
of a degree of vacuum of 6.0.times.10.sup.-3 Pa and a film forming
rate of 10 angstroms/sec. A diffuse reflectance (%) of the obtained
molded body is measured using a reflectance meter (TR-1100AD made
by Tokyo Denshoku Co., Ltd.).
[0138] A composite polymer (g) according to the present invention
is preferably a composite polymer (ga) which contains 5 to 25% by
mass of polyorganosiloxane and has a mass average particle diameter
(Dw) of 120 to 200 nm, in which a proportion of the particle having
a particle diameter of 100 nm or less is 15% by mass or less based
on the total amount of the particle, and in which a proportion of
the particle having the particle diameter of 400 nm or more is 1%
by mass or less based on the total amount of the particle. A graft
copolymer (Ga) according to the present invention is preferably a
copolymer obtained by graft polymerizing a mixture of a vinyl
cyanide-based monomer and an aromatic vinyl-based monomer with the
composite polymer (ga).
[0139] A molded body obtained from the graft copolymer (Ga)
preferably has performances as below:
[0140] (1') A Charpy impact strength at 23.degree. C. is 6
kJ/m.sup.2 or more, and 50 kJ/m.sup.2 or less, and
[0141] (2') A diffuse reflectance is 0.1% or more, and 5% or
less.
[0142] The polyorganosiloxane that forms the composite polymer (ga)
preferably contains 0.5 to 5 parts by mass of a component derived
from a siloxane-based crosslinking agent based on 100 parts by mass
of organosiloxane.
[0143] The vinyl-based polymer that forms the composite polymer
(ga) is an acrylic acid ester monomer, or an acrylic acid
ester-based polymer obtained by polymerizing a monomer mixture
containing one or more acrylic acid ester monomers.
[0144] Examples of the acrylic acid ester-based monomers include
methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl
acrylate, and 2-ethylhexyl acrylate. These can be used alone or in
combination. Among these, n-butyl acrylate is preferable because
the molded body obtained from the resin composition has high impact
resistance.
[0145] For the polymerizable component, a grafting agent and a
crosslinking agent can be used if necessary. For the grafting agent
and the crosslinking agent, the same polyfunctional monomers as
those used in production of the composite polymer (g) can be used.
These may be used alone or in combination. The amount of the
grafting agent and crosslinking agent to be added may be properly
determined. From the viewpoint of a good balance between the impact
resistance of the molded body and brightness after direct
deposition, the amount is preferably 0.1 to 5 parts by mass, more
preferably 0.2 to 2 parts by mass, and in particular preferably 0.4
to 1.0 part by mass based on 100 parts by mass of the acrylic acid
ester-based monomer (including a mixture). A smaller amount is
preferable from the viewpoint of impact resistance, and a larger
amount is preferable from the viewpoint of brightness.
[0146] A method of producing the composite polymer (ga) is not in
particular limited. A method of mixing a polyorganosiloxane latex
with an acrylic acid ester-based polymer latex and
heteroaggregating or co-enlarging of particles in the mixture may
be used, or the same method as that used in production of the
composite polymer (g) described above may be used. At this time,
the monomer may be a mixture. Among these, a method of polymerizing
an acrylic acid ester-based monomer in the presence of the
polyorganosiloxane latex is preferable from the viewpoint of the
impact resistance of the molded body, the brightness of the molded
body after direct deposition and appearance of welding portion.
[0147] For the content of the acrylic acid ester-based polymer
derived from polyorganosiloxane and the acrylic acid ester-based
monomer, in the composite polymer (ga), preferably, the content of
polyorganosiloxane is 5 to 25% by mass and the content of acrylic
acid ester-based polymer is 95 to 75% by mass from the viewpoint of
high impact resistance of the molded body and remarkable brightness
of the molded body after direct deposition. The content of
polyorganosiloxane is more preferably 7 to 20% by mass, and in
particular preferably 9 to 16% by mass. As the content of
polyorganosiloxane reduces, impact resistance tends to reduce. As
the content of polyorganosiloxane increases, brightness after
direct deposition tends to reduce.
[0148] The mass average particle diameter (Dw) of the composite
polymer (ga) particle is 120 nm to 200 nm from the viewpoint of
high impact resistance of the molded body and remarkable brightness
of the molded body after direct deposition. As the mass average
particle diameter reduces, impact resistance of the molded body
tends to reduce. As the mass average particle diameter increases,
brightness of the molded body after direct deposition tends to
reduce.
[0149] In order to obtain a molded body having a high level
brightness after direct deposition, the proportion of the composite
polymer particle having a particle diameter of 100 nm or less is
preferably 15% by mass or less, more preferably 10% by mass or
less, and still more preferably 5% by mass or less, in 100% by mass
of the composite polymer (ga). From the viewpoint of a molded body
having remarkable brightness after direct deposition, the
proportion of the composite polymer particle having a particle
diameter of 400 nm or more is 1% by mass or less.
[0150] The mass average particle diameters (Dw) of a composite
polymer (ga) and a graft copolymer (G) to be used are a value
measured by the following method. Using a Nanotrac UPA-EX150 made
by NIKKISO CO., LTD., the particle size distribution in the latex
of the composite polymer (ga) and the latex of the graft copolymer
(G) is measured by the dynamic light scattering method. From the
obtained particle size distribution, the mass average particle
diameter, the proportion of the particle having a particle diameter
of 100 nm or less, and the proportion of the particle having a
particle diameter of 400 nm or more are calculated.
[0151] In order to obtain a composite polymer (ga) having a mass
average particle diameter of 120 to 200 nm and a graft copolymer
(G), the particle diameter of polyorganosiloxane may be adjusted.
The mass average particle diameter (Dw) of polyorganosiloxane is
preferably 100 nm to 150 nm, and Dw/Dn is preferably 1.00 to
1.70.
[0152] The monomer for grafting is not in particular limited.
Examples thereof include the same aromatic vinyl-based monomers,
(meth)acrylic acid ester-based monomers, and vinyl cyanide-based
monomers as those used in the case of the composite polymer (g)
described above.
[0153] Examples of the aromatic vinyl-based monomers include
styrene, .alpha.-methylstyrene, and vinyltoluene. Examples of the
(meth)acrylic acid ester-based monomers include methyl
methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, methyl
acrylate, ethyl acrylate, and butyl acrylate. Examples of the vinyl
cyanide-based monomers include acrylonitrile and methacrylonitrile.
These vinyl-based monomers can be used alone or in combination.
Among these, use of the aromatic vinyl-based monomer in combination
with the vinyl cyanide-based monomer is preferable, and use of
styrene in combination with acrylonitrile is in particular
preferable from the viewpoint of high impact resistance of the
molded body.
[0154] When an aromatic vinyl compound is used in combination with
a vinyl cyanide compound, preferably 20 to 40% by mass of the vinyl
cyanide-based monomer and 80 to 60% by mass of the aromatic
vinyl-based monomer are contained, and more preferably 25 to 35% by
mass of the vinyl cyanide-based monomer and 75 to 65% by mass of
the aromatic vinyl-based monomer are contained, in 100% by mass of
a monomer mixture for grafting. As the content of the vinyl
cyanide-based monomer reduces, impact resistance tends to reduce.
As the content increases, fluidity tends to reduce.
[0155] The mass ratio of a composite polymer (ga) to a monomer
mixture for grafting as raw materials is not in particular limited.
From the viewpoint of high impact resistance of the molded body,
high fluidity, and remarkable brightness after direct deposition,
preferably the ratio of the composite polymer (ga) is 20 to 80% by
mass and the ratio of the monomer for grafting is 80 to 20% by
mass, and in particular preferably the ratio of the composite
polymer (ga) is 40 to 70% by mass and the ratio of the monomer for
grafting is 60 to 30% by mass. As the content of the composite
polymer (ga) reduces, impact resistance tends to reduce. As the
content of the composite polymer (ga) increases, brightness after
direct deposition tends to reduce.
[0156] Examples of the graft polymerization method include the same
method as those used in production of the composite polymer (ga)
described above. Among these, emulsion polymerization is suitable.
Examples of the emulsifier include the same as those used in
production of the composite polymer (ga) described above. The
following are preferable from the viewpoint of high stability of
the latex during emulsion polymerization and increase in the
polymerization rate: a variety of carboxylic acid salts such as
sodium sarcosinate, fatty acid potassium, fatty acid sodium,
dipotassium alkenyl succinate, and rosin acid soap; and anionic
emulsifiers such as alkyl sulfuric acid ester, sodium alkylbenzene
sulfonate, and sodium dodecyldiphenyl ether disulfonate. These are
used according to the purpose. Without using an emulsifier during
graft polymerization, the emulsifier used in production of
polyorganosiloxane or the composite polymer (ga) can be used as it
is.
[0157] The emulsifiers listed here are also suitable for
polymerization of the acrylic acid ester-based polymer that forms
the composite polymer (ga).
[0158] Examples of the radical polymerization initiator used in
graft polymerization include the same as the polymerization
initiators used in production of the composite polymer (ga)
described above. In particular, use of ferrous sulfate,
ethylenediaminetetraacetic acid disodium salt, a reducing agent and
peroxide in combination is preferable. The radical polymerization
initiators listed are also suitable in polymerization for the
acrylic acid ester-based polymer that forms the composite polymer
(ga).
[0159] In order to control the graft rate and the molecular weight
of the graft component, for example, a variety of chain transfer
agents such as mercaptan-based compounds, terpene-based compounds,
and .alpha.-methylstyrene dimers can be used. The polymerization
condition is not in particular limited, and can properly be set if
necessary.
[0160] When powders of a graft copolymer (Ga) is recovered from the
latex of the graft copolymer (Ga), one of the spray drying method
and the coagulation method can be used similarly in the case of
recovering the powder of the composite polymer (ga) above. Use of
the coagulation method is preferable.
[0161] A graft copolymer (Ga) according to the present invention
can be used for a thermoplastic resin composition (Ia) by mixing
the graft copolymer (Ga) with a thermoplastic resin (Ha) except for
the graft copolymer (Ga).
[Thermoplastic Resin Composition (Ha)]
[0162] A thermoplastic resin (Ha) is not in particular limited, and
examples thereof include the following: acrylic (Ac) resins such as
PMMA resins; styrene-based resins such as polystyrene (PSt),
acrylonitrile-styrene copolymers (AS resins),
acrylonitrile-.alpha.-methylstyrene copolymers (.alpha.-SAN
resins), styrene-maleic anhydride copolymers,
acrylonitrile-styrene-N-substituted maleimide ternary copolymers,
acrylonitrile-styrene-.alpha.-methylstyrene-N-substituted maleimide
quaternary copolymers, styrene-maleic anhydride-N-substituted
maleimide ternary copolymers, methyl methacrylate-styrene
copolymers (MS resins), and acrylonitrile-styrene-methyl
methacrylate copolymers; PC resins; polyester-based resins such as
polybutylene terephthalate (PBT resins), polyethylene terephthalate
(PET resins), and polyethylene naphthalate (PEN resins); polyvinyl
chloride; modified polyphenylene ether (modified PPE resins); and
polyamides.
[0163] The following can also be used: polyolefins such as
polyethylene and polypropylene; styrene-based elastomers such as
styrene-butadiene-styrene (SBS), styrene-butadiene (SBR),
hydrogenated SBS, and styrene-isoprene-styrene (SIS); a variety of
olefin-based elastomers; a variety of polyester-based elastomers;
polyacetal resins; ethylene-vinyl acetate copolymers; PPS resins;
PES resins; PEEK resins; polyarylate; and liquid crystal polyester
resins.
[0164] These thermoplastic resins (Ha) can be used alone or in
combination. Among these, styrene-based resins are preferable, AS
resins, .alpha.-SAN resins, and copolymers made from vinyl
cyanide-based monomer, aromatic vinyl-based monomer and
N-substituted maleimide are more preferably used, and styrene-based
resins including a copolymer including 0 to 40% by mass of a vinyl
cyanide-based monomer unit, 40 to 80% by mass of an aromatic
vinyl-based monomer unit, and 0 to 60% by mass of another monomer
unit whose monomer is copolymerizable with these monomers, such as
N-substituted maleimide, are still more preferable from the
viewpoint of remarkable brightness after direct deposition, high
impact resistance, high heat plate welding properties, and high
vibration welding properties of the molded body produced from the
thermoplastic resin composition (Ia). For the vinyl cyanide-based
monomer, acrylonitrile is preferable. For the aromatic vinyl-based
monomer, styrene and/or .alpha.-methylstyrene is preferable.
[0165] When an AS resin or .alpha.-SAN resin is used, the
composition in particular preferably includes 20 to 35% by mass of
the vinyl cyanide-based monomer unit, and 65 to 80% by mass of the
aromatic vinyl-based monomer unit. Examples of copolymers made from
vinyl cyanide-based monomer, aromatic vinyl-based monomer and
N-substituted maleimide include acrylonitrile-styrene-N-substituted
maleimide ternary copolymers and
acrylonitrile-styrene-.alpha.-methylstyrene-N-substituted maleimide
quaternary copolymers. When these copolymers made from vinyl
cyanide-based monomer, aromatic vinyl-based monomer and
N-substituted maleimide are used, the composition of the copolymers
in particular preferably includes 0 to 35% by mass of a vinyl
cyanide-based monomer unit, 40 to 70% by mass of an aromatic
vinyl-based monomer unit, and 5 to 60% by mass of an N-substituted
maleimide unit. For the vinyl cyanide-based monomer, acrylonitrile
is preferable. For the aromatic vinyl-based monomer, styrene and/or
.alpha.-methylstyrene is preferable.
[Thermoplastic Resin Composition (Ia)]
[0166] A thermoplastic resin composition (Ia) according to the
present invention is a composition having a graft copolymer (Ga)
and a thermoplastic resin (Ha) blended. For the content in the
thermoplastic resin composition (Ia), preferably, the content of
the graft copolymer (Ga) is 10 to 50% by mass and the content of
the thermoplastic resin (Ha) is 90 to 50% by mass. More preferably,
the content of the graft copolymer (Ga) is 20 to 45% by mass and
the content of the thermoplastic resin (Ha) is 80 to 55% by mass.
By blending the graft copolymer (Ga) with the thermoplastic resin
(Ha) at such mass ratio, the molded body has remarkable brightness
after direct deposition, high impact resistance, high heat plate
welding properties, and high vibration welding properties. As the
content of the graft copolymer (Ga) reduces, impact resistance and
heat plate welding properties tend to reduce. As the content of the
graft copolymer (Ga) increases, brightness after direct deposition
and vibration welding properties tend to reduce.
[0167] In addition to the graft copolymer (Ga) and the
thermoplastic resin (Ha), additives such as dyes, pigments, a
stabilizer, a reinforcing agent, a filler, a flame retardant, a
foaming agent, a lubricant, a plasticizer, an antistatic agent, a
weather proofing agent, and a UV absorber can be blended with the
thermoplastic resin composition (Ia) if necessary.
[0168] The method of preparing the thermoplastic resin composition
(Ia) is not in particular limited. Using a V type blender, a
Henschel mixer, or the like, the graft copolymer (Ga), the
thermoplastic resin (Ha), and a variety of additives to be used if
necessary, are mixed and dispersed. The mixture is melt kneaded
using a kneader such as an extruder, a Banbury mixer, a pressure
kneader, and a roll. Thus, the thermoplastic resin composition (Ia)
can be prepared.
[Molded Body]
[0169] By molding the thermoplastic resin composition (Ia), a
variety of molded bodies are obtained. Examples of the molded body
include the following: vehicle parts, in particular a variety of
exterior parts and interior parts such as front grilles used with
no paint; construction material parts such as wall materials and
window frames; eating utensils; toys; home appliance parts such as
housings of vacuum cleaners, housings of televisions, and housings
of air conditioners; interior members, ship members, and housings
of electrical apparatuses such as housings of communication
apparatuses, housings of notebook type personal computers, housings
of mobile terminals, and housings of liquid crystal projectors.
Among these, a suitable molded body is obtained by the
thermoplastic resin composition (Ia) in the vehicle parts, in
particular, lamp housings, obtained by performing metallization
treatment on the surface of the molded body by the direct
deposition method.
[0170] The molding method is not in particular limited. Known
various molding methods such as an injection molding method, an
extrusion molding method, a blow molding method, a compression
molding method, a calender molding method, and an inflation molding
can be used. Among these, in particular, the injection molding
method is preferable.
[0171] The surface of the molded body according to the present
invention subjected to a primary process by the above variety of
molding methods can be subjected to metallization treatment by a
direct deposition method. Namely, without performing a special
pre-treatment such as formation of an undercoat treatment layer, a
metallic layer of aluminum, chromium, or the like can be formed
directly on the surface of the molded body by a vacuum deposition
method or a sputtering method. The bright surface subjected to
metallization treatment may be left as it is. Further, to protect
the surface against scratches caused by dust or the like, the
surface can be subjected to a top coat treatment to form a
silicon-based coating film or the like.
[0172] According to the thermoplastic resin composition of the
present invention, by using the above configuration, a molded body
having high mechanical strength such as impact resistance and
weatherability, exhibiting a remarkable beautiful bright appearance
after direct deposition, and having high heat plate welding
properties for transparent resins and vibration welding properties
is obtained.
[Lamp Housing for Vehicle Lighting]
[0173] A lamp housing for vehicle lighting is an integrally formed
product which is obtained by bonding a molded body according to the
present invention to a resin lens made of a transparent resin such
as PMMA resins and PC resins by a method such as a heat plate
welding method, a vibration welding method, and a laser welding
method. The surface of the molded body can be subjected to
metallization treatment by a direct deposition method. A necessary
member is optionally mounted on the molded body. The lamp housing
has high mechanical strength such as impact resistance and
weatherability, and a good appearance. The lamp housing according
to the present invention can be suitably used for automobiles and
the like.
[0174] Next, an example of a preferable aspect of the graft
copolymer (G) according to the present invention, that is, a graft
copolymer (Gb) and an example of a preferable aspect of the
composite polymer (g) according to the present invention, that is,
a composite polymer (gb) will be described.
[Graft Copolymer (Gb)]
[0175] A graft copolymer (G) according to the present invention is
preferably a graft copolymer (Gb), wherein a molded body obtained
by molding the following composition exhibits the following
performance (1) and (2) when evaluated under the following
measurement conditions:
[0176] (1) L* is 24 or less, and
[0177] (2) a Charpy impact strength at -30.degree. C. is 6
kJ/m.sup.2 or more.
<Test Piece Production Condition>
[0178] (a) 42 Parts by mass of a graft copolymer (Gb),
[0179] (b) 58 parts by mass of an acrylonitrile-styrene copolymer
including 34% by mass of an acrylonitrile unit and 66% by mass of a
styrene unit and having a reduced viscosity (.eta.sp/c) of 0.62
dL/g in an N,N-dimethylformamide solution of 0.2 g/dL at 25.degree.
C.,
[0180] (c) 0.3 parts by mass of ethylenebisstearylamide, and
[0181] (d) 0.5 parts by mass of carbon black.
[0182] These four materials (a) to (d) above are blended, and
kneaded using a volatilizing extruder (made by Ikegai Corp.,
PCM-30) whose barrel is heated to a temperature of 230.degree. C.
to obtain pellets. The pellets are molded using a 4-ounce injection
molding machine (made by The Japan Steel Works, Ltd.) in conditions
of a cylinder temperature of 230.degree. C. and a mold temperature
of 60.degree. C. to obtain a test piece 3 (a length of 80 mm, a
width of 10 mm and a thickness of 4 mm) and a tensile test piece 4
(a length of 170 mm, a width of 20 mm, a thickness of 4 mm, and a
width of a tensile test portion of 10 mm).
<Charpy Impact Strength Measurement Condition>
[0183] Measurement is conducted on a V-notched test piece 3 that is
left under a -30.degree. C. atmosphere for 12 hours or more by a
method according to ISO 179.
<L* Measurement Condition>
[0184] L* is measured for the tensile test piece 4 using a
spectrophotometer CM-508D made by Konica Minolta Sensing, Inc. on a
side opposite to a gate.
[0185] A composite polymer (g) according to the present invention
is preferably a composite polymer (gb) which contains 15 to 80% by
mass of polyorganosiloxane, and has a mass average particle
diameter of 110 to 250 nm, in which a proportion of the particle
having a particle diameter less than 100 nm is 20% by mass or less
based on the total amount of the particle, and in which a
proportion of the composite polymer particle having a particle
diameter of 300 nm or more is 20% by mass or less based on the
total amount of the particle. A graft copolymer (Gb) according to
the present invention is preferably a copolymer obtained by graft
polymerizing a mixture of a vinyl cyanide-based monomer and an
aromatic vinyl-based monomer with the composite polymer (gb).
[0186] The molded body obtained from the graft copolymer (Gb)
preferably has performances as below:
[0187] (1') L* is 1 or more and 24 or less, and
[0188] (2') a Charpy impact strength at -30.degree. C. is 6
kJ/m.sup.2 or more and 30 kJ/m.sup.2 or less.
[0189] The polyorganosiloxane that forms the composite polymer (gb)
preferably contains 0.5 to 3 parts by mass of the component derived
from a siloxane-based crosslinking agent based on 100 parts by mass
of organosiloxane.
[0190] The vinyl-based polymer that forms the composite polymer
(gb) is an acrylic acid ester-based polymer obtained by
polymerizing an acrylic acid ester monomer or a monomer mixture
containing one or more acrylic acid ester monomers.
[0191] Examples of the acrylic acid ester-based monomers include
the same as those used in production of the composite polymer (ga).
These can be used alone or in combination. Among these, n-butyl
acrylate is preferable because the resin composition to be obtained
has high impact resistance.
[0192] In the vinyl-based monomer that forms the composite polymer
(gb), a grafting agent and a crosslinking agent can be used if
necessary. For the grafting agent and the crosslinking agent, the
same polyfunctional monomers as those used in production of the
composite polymer (ga) can be used. These may be used alone or in
combination. The amount of the polyfunctional monomer to be used is
preferably 0.1 to 5 parts by mass, more preferably 0.2 to 2 parts
by mass, and most preferably 0.4 to 1.0 part by mass based on 100
parts by mass of the acrylic acid ester-based monomer. A smaller
amount is preferable from the viewpoint of the impact resistance of
the molded body. A larger amount is preferable from the viewpoint
of an appearance of the surface of the molded body.
[0193] For the method of producing the composite polymer (gb), the
same methods as those used in production of the composite polymer
(ga) can be used.
[0194] For the content ratio of polyorganosiloxane to the acrylic
acid ester-based polymer derived from the acrylic acid ester-based
monomer in the composite polymer (gb), preferably the content of
polyorganosiloxane is 15 to 80% by mass and the content of the
acrylic acid ester-based polymer is 85 to 20% by mass, and more
preferably the content of polyorganosiloxane is 20 to 70% by mass
and the content of the acrylic acid ester-based polymer is 80 to
30% by mass from the viewpoint of high impact resistance of the
resin composition to be obtained, a good appearance of the surface
of the molded body, and high pigment coloring properties of the
molded body. As the content of polyorganosiloxane reduces, impact
resistance tends to reduce. As the content of polyorganosiloxane
increases, the appearance of the surface of the molded body and
pigment coloring properties tend to reduce.
[0195] The mass average particle diameter of the composite polymer
(gb) is preferably 110 to 250 nm, and more preferably 110 to 200 nm
from the viewpoint of high impact resistance of the molded body, a
good appearance of the surface, and high pigment coloring
properties. As the mass average particle diameter reduces, impact
resistance of the molded body tends to reduce. As the mass average
particle diameter increases, the appearance of the surface of the
molded body and pigment coloring properties tend to reduce.
[0196] In the composite polymer (gb), the proportion of the
particle having a particle diameter less than 100 nm is preferably
20% by mass or less, and more preferably 10% by mass or less based
on the total amount of the particle. The proportion of the particle
having a particle diameter of 300 nm or more is preferably 20% by
mass or less, and more preferably 10% by mass or less based on the
total amount of the particle. When the proportion of the particle
having a particle diameter less than 100 nm is excessively large,
the impact resistance of the molded body tends to reduce. When the
proportion of the particle having a particle diameter of 300 nm or
more is 20% by mass or less, the molded body has a good balance
between impact resistance and the appearance of the surface
thereof.
[0197] The mass average particle diameter of the composite polymer
(gb) to be used is a value measured by the same method as that in
the case of the composite polymer (ga).
[0198] In order to obtain a composite polymer (gb) having a mass
average particle diameter of 110 to 250 nm, the particle diameter
of polyorganosiloxane and the amount of the vinyl-based monomer may
be adjusted. Preferably, the mass average particle diameter of
polyorganosiloxane is 100 nm to 200 nm, and Dw/Dn is 1.00 to
1.70.
[0199] Examples of the monomer for grafting include the same as
those used in production of the graft copolymer (Ga) described
above. A monomer mixture of an aromatic vinyl-based monomer and a
vinyl cyanide-based monomer is preferable because the molded body
to be obtained has high impact resistance. In particular, a mixture
of styrene and acrylonitrile is preferable. Moreover, "other
monomers" can be used if necessary for the vinyl-based monomer for
grafting.
[0200] The "other monomers" are monomers copolymerizable with
aromatic vinyl-based monomers, vinyl cyanide-based monomers, and
(meth)acrylic acid ester-based monomers excluding the aromatic
vinyl-based monomers, the vinyl cyanide-based monomer, and the
(meth)acrylic acid ester-based monomers. Examples of the other
monomers include acrylamide, methacrylamide, maleic anhydride, and
N-substituted maleimide. These may be used alone or in combination.
The proportion of the "other monomers" in 100% by mass of the
monomer mixture for grafting is preferably 50% by mass or less,
more preferably 40% by mass or less, and most preferably 20% by
mass or less. If the proportion of the other monomers is the upper
limit or less, impact resistance of the molded body and the
appearance of the surface are well balanced.
[0201] The mass ratio of the composite polymer (gb) as raw
materials to the monomer for grafting is not in particular limited.
Preferably, the ratio of the composite polymer (gb) is 5 to 95% by
mass and the ratio of the monomer for grafting is 95 to 5% by mass,
more preferably the ratio of the composite polymer (gb) is 10 to
90% by mass and the ratio of the monomer for grafting is 90 to 10%
by mass, and most preferably the ratio of the composite polymer
(gb) is 30 to 70% by mass and the monomer for grafting is 70 to 30%
by mass. As the content of the monomer for grafting reduces, the
appearance of the surface of the molded body and pigment coloring
properties tend to reduce. As the content increases, impact
strength of the molded body tends to reduce.
[0202] The graft copolymer (Gb) is preferably produced by emulsion
polymerizing the monomer mixture as above in the presence of the
composite polymer (gb) latex. Examples of the method of
polymerizing the graft copolymer (Gb) include the same method as
that used in production of the graft copolymer (Ga) described
above. Among these, emulsion polymerization is suitable. The same
emulsifier as that used in production of the graft copolymer (Ga)
described above can be used.
[0203] Examples of the polymerization initiator used in graft
polymerization include the same polymerization initiators as those
used in production of the graft copolymer (Ga) described above. In
particular, use of ferrous sulfate, ethylenediaminetetraacetic acid
disodium salt, a reducing agent and peroxide in combination is
preferable.
[0204] When powders of a graft copolymer (Gb) is recovered from the
latex of the graft copolymer (Gb), the same methods as those used
in production of the powder of the graft copolymer (Ga) described
above can be used. One of the spray drying method and the
coagulation method can be used. The coagulation method is
preferable.
[0205] A graft copolymer (Gb) according to the present invention
can be used for a thermoplastic resin composition (Ib) by mixing
the graft copolymer (Gb) with a thermoplastic resin (Hb) except for
the graft copolymer (Gb).
[Thermoplastic Resin (Hb)]
[0206] The thermoplastic resin (Hb) is not in particular limited,
and the same resin as the thermoplastic resin (Ha) can be used.
Among these, MS resins and PMMA resins are preferable for
improvement in the weatherability of the molded body, PC resins are
preferable for improvement in the impact resistance of the molded
body, and PBT resins are preferable for improvement in the
resistance against chemicals of the molded body. For improvement in
the moldability of the thermoplastic resin composition, PET resins
and styrene-based resins are preferable. Modified PPE resins and
polyamides are preferable for improvement in the heat resistance of
the molded body. Styrene-based resins are in particular preferable
for a balance between the impact resistance and molding properties
of the molded body. These thermoplastic resins (Hb) can be used
alone or in combination.
[0207] The styrene-based resin is a resin including an aromatic
vinyl-based monomer as an essential component and obtained by
copolymerizing the aromatic vinyl-based monomer, if necessary, with
other monomers such as a vinyl cyanide-based monomer such as vinyl
cyanide, unsaturated carboxylic acid anhydrides, and N-substituted
maleimide based monomers. These monomers may be used alone or in
combination.
[0208] The styrene-based resin is preferably a resin including 0 to
40% by mass of a vinyl cyanide-based monomer unit, 40 to 80% by
mass of an aromatic vinyl-based monomer unit, and 0 to 60% by mass
of another monomer unit whose monomer is copolymerizable with these
monomers. Specifically, AS resins, .alpha.-SAN resins, and
copolymers made from vinyl cyanide-based monomer, aromatic
vinyl-based monomer and N-substituted phenylmaleimide are in
particular preferable. For the vinyl cyanide-based monomer,
acrylonitrile is preferable. For the aromatic vinyl-based monomer,
styrene and/or .alpha.-methylstyrene is preferable.
[0209] When an AS resin or .alpha.-SAN resin is used, the
composition of the polymer includes preferably 20 to 40% by mass of
a vinyl cyanide-based monomer unit and 60 to 80% by mass of an
aromatic vinyl-based monomer unit, and in particular preferably 25
to 35% by mass of a vinyl cyanide-based monomer unit and 65 to 75%
by mass of an aromatic vinyl-based monomer unit. For the vinyl
cyanide-based monomer, acrylonitrile is preferable. For the
aromatic vinyl-based monomer, styrene and/or .alpha.-methylstyrene
is preferable. Examples of the copolymers made from vinyl
cyanide-based monomer, aromatic vinyl-based monomer and
N-substituted phenylmaleimide include
acrylonitrile-styrene-N-substituted phenylmaleimide ternary
copolymers or
acrylonitrile-styrene-.alpha.-methylstyrene-N-substituted
phenylmaleimide quaternary copolymer. When the copolymer made from
vinyl cyanide-based monomer, aromatic vinyl-based monomer and
N-substituted phenylmaleimide is used, the composition of the
polymer preferably includes 0 to 35% by mass of a vinyl
cyanide-based monomer unit, 40 to 70% by mass of an aromatic
vinyl-based monomer unit, and 5 to 60% by mass of an
N-phenylmaleimide monomer unit.
[0210] If the proportion of the aromatic vinyl-based monomer unit
contained in the styrene-based resin is the lower limit or more,
the thermoplastic resin composition has high molding properties. If
the proportion of the aromatic vinyl-based monomer unit is the
upper limit or less, the molded article has high impact resistance.
If the proportion of the vinyl cyanide-based monomer unit contained
in the styrene-based resin is less than the upper limit, coloring
of the molded body caused by heat can be suppressed. If the
proportion of the vinyl cyanide-based monomer unit is the lower
limit or more, the molded body has high impact resistance.
[Thermoplastic Resin Composition (Ib)]
[0211] The thermoplastic resin composition (Ib) according to the
present invention is a composition comprising a blend of the graft
copolymer (Gb) and the thermoplastic resin (Hb) except for the
graft copolymer (Gb). The amount of the composite polymer (gb)
existing in the thermoplastic resin composition (Ib) is preferably
5 to 50% by mass, more preferably 10 to 40% by mass, and most
preferably 15 to 30% by mass. when the content of the composite
polymer (gb) is 10% by mass or more, the molded body obtained from
the thermoplastic resin composition has high impact resistance.
when the content of the composite polymer component is 40% by mass
or less, the molded body can maintain a good appearance and
fluidity.
[0212] The thermoplastic resin composition (Ib) according to the
present invention may contain a colorant such as pigments and dyes,
a heat stabilizer, a light stabilizer, a reinforcing agent, a
filler, a flame retardant, a foaming agent, a lubricant, a
plasticizer, an antistatic agent, a treatment aid, and the like if
necessary.
[Method of Producing Thermoplastic Resin Composition]
[0213] The thermoplastic resin composition (Ib) according to the
present invention can be produced by the same method as that used
in production of the thermoplastic resin composition (Ia) described
above.
[Molded Body]
[0214] The molded body obtained by molding the thermoplastic resin
composition (Ib) according to the present invention has a good
balance between impact resistance, in particular impact resistance
under a low temperature, rigidity, and the appearance of the
surface, and has high weatherability. For this reason, the molded
body is suitably used in applications of automobile materials,
construction materials, and home appliances used these days. The
molded article formed of the thermoplastic resin composition (Ib)
can be used in various applications. Examples of the molded body
include the same molded bodies as those obtained by molding the
thermoplastic resin composition (Ia).
[0215] Examples of the method of molding a molded body include the
same methods as those used in the case of the thermoplastic resin
composition (Ia) such as an injection molding method, an extrusion
molding method, a blow molding method, a compression molding
method, a calender molding method, and an inflation molding method.
A post treatment such as metallization treatment can be performed
on the molded body.
EXAMPLES
[0216] Hereinafter, the present invention will be specifically
described. Hereinafter, "parts" designate "parts by mass," and "%"
designates "% by mass." A variety of physical properties shown in
Examples were evaluated by the methods shown below.
[1. Solid Content]
[0217] The polyorganosiloxane latex was dried with a hot air dryer
at 180.degree. C. for 30 minutes, and the solid content was
calculated using the following formula.
solid content [%]=(mass of residue after drying at 180.degree. C.
for 30 minutes)/(mass of latex before drying).times.100
[2. Reduced Viscosity]
[0218] Using an N,N-dimethylformamide solution of the thermoplastic
resin Ha or Hb having a concentration of 0.2 [g/dL], the reduced
viscosity of the thermoplastic resin was measured at 25.degree. C.
with an Ubbelohde viscometer.
[3. Melt Volume Rate (MVR)]
[0219] The melt volume rate of the thermoplastic resin composition
Ia or Ib was measured in conditions of a barrel temperature of
220.degree. C. and a load of 98 N by the method according to ISO
1133. The melt volume rate is an index indicating the fluidity of a
thermoplastic resin composition.
[4. Charpy Impact Strength]
[0220] The Charpy impact strength was measured in conditions
described in the section regarding the graft copolymer (Ga) and the
graft copolymer (Gb).
[5. Flexural Modulus, Bending Strength]
[0221] The bending strength and flexural modulus of the
thermoplastic resin composition Ia or Ib was measured at the
measurement temperature of 23.degree. C. and the thickness of a
test piece of 4 mm by a method according to the ISO test method
178.
[6. Deflection Temperature Under Load]
[0222] The deflection temperature under load of the thermoplastic
resin composition Ia or Ib was measured at 1.80 MPa and the
thickness of a test piece of 4 mm by a flat-wise method according
to the ISO test method 75.
[7. Diffuse Reflectance (Brightness)]
[0223] The diffuse reflectance (%) was measured on the condition
described in the section concerned with the graft copolymer (Ga),
and brightness was evaluated. A lower value of the diffuse
reflectance indicates a brighter surface of the molded article.
[8. Vibration Welding Properties]
[0224] A flat plate molded article having a thickness of 2 mm
obtained by injection molding (trapezoidal shape, width of 70 mm,
short side of 110 mm, and long side of 160 mm) was used. As a lens
for evaluation, a sample obtained by molding a PMMA resin (ACRYPET
VH4 made by MITSUBISHI RAYON CO., LTD.) by injection molding into a
3 mm sheet with a rib (trapezoidal shape, width of 70 mm, short
side of 110 mm, and long side of 160 mm; rib: height of 10 mm,
short side of 100 mm, and long side of 150 mm) was used.
[0225] Vibration welding was performed using a BRANSON VIBRATION
WELDER 2407 made by Emerson Japan, Ltd. in conditions of an
amplitude of 1 mm, a pressure of 0.3 MPa, and a sink amount of 1.5
mm. Next, the appearance of the melt portion produced by melting
and bonding during vibration welding was visually observed, and
evaluated according to 4 ranks as below:
[0226] Rank 1: welding fall properties and fluffing properties are
very good in all the peripheries of the welding portion.
[0227] Rank 2: welding fall properties and fluffing properties are
inferior in the range of 0 to less than 10% of all the peripheries
of the welding portion.
[0228] Rank 3: welding fall properties and fluffing properties are
inferior in the range of 10 to less than 40% of all the peripheries
of the welding portion.
[0229] Rank 4: welding fall properties and fluffing properties are
inferior in the range of 40% or more of all the peripheries of the
welding portion.
[0230] In the evaluation criterion, "welding fall properties" means
that the melt portion of the sheet and the rib continues smoothly
as the appearance of the bonding portion, and "fluffing properties"
means the extent of fluffing produced in the melt portion.
Vibration welding properties are excellent when these properties
are good.
[9. Color Developability]
[0231] "L*" was measured in conditions described in the section
concerned with the graft copolymer (Gb). L* having a smaller
numeric value indicates higher color developability.
Example 1
Production of Polyorganosiloxane Latex (L-1)
[0232] 97.5 Parts of a cyclic organosiloxane mixture (a mixture of
a trimer: 5% by mass, a tetramer: 85% by mass, a pentamer: 3%, a
hexamer: 6% by mass, and a heptamer: 1% by mass, made by Shin-Etsu
Chemical Co., Ltd., product name: DMC), 2 parts of
tetraethoxysilane (TEOS), and 0.5 parts of
.gamma.-methacryloyloxypropyldimethoxymethylsilane (DSMA) were
mixed to obtain 100 parts of an organosiloxane mixture. A solution
prepared by dissolving 0.68 parts of sodium dodecylbenzenesulfonate
(DBSNa) in 300 parts of deionized water was added to the
organosiloxane mixture, and stirred with a homomixer at 10,000 rpm
for 2 minutes. Then, the solution was passed through a homogenizer
at a pressure of 20 MPa twice to obtain a stable pre-mixed emulsion
(B-1).
[0233] Meanwhile, 1 part of dodecylbenzenesulfonic acid (DBSH),
1.38 parts of sulfuric acid, and 90 parts of deionized water were
injected into a separable flask equipped with a cooling condenser,
and a water-based medium (A-1) at a pH of 0.84 was prepared at
25.degree. C.
[0234] The water-based medium (A-1) was heated to 90.degree. C. In
this state, the emulsion (B-1) was dropped into the water-based
medium (A-1) at a rate such that the amount of organosiloxane to be
fed was 0.42 parts/min (substantially for 4 hours). After dropping
was completed, the temperature was kept for 2 hours, and then
lowered. Next, the reaction product was kept at room temperature
for 12 hours, and neutralized to a pH of 7.0 with a 10% sodium
hydroxide aqueous solution to obtain a polyorganosiloxane latex
(L-1).
[0235] The solid content and particle diameter of the obtained
polyorganosiloxane latex (L-1) were measured by the methods above.
The results are shown in Table 3.
Examples 2 to 23, Comparative Examples 1 and 2, Reference Examples
3 to 5, and Comparative Examples 6 to 8
Production of Polyorganosiloxane Latexes (L-2 to L-30)
[0236] Polyorganosiloxane latexes (L-2 to L-30) were obtained in
the same manner as in Example 1 except that the compositions of the
water-based medium (A) and the emulsion (B), and the dropping rate
of the emulsion (B) in Example 1 were changed as the condition
shown in Table 1 or Table 2. Regarding the obtained
polyorganosiloxane latexes, the particle diameter and the solid
content were measured in the same manner as in Example 1. The
results are shown in Table 3.
Comparative Example 9
Production of Polyorganosiloxane Latex (L-31)
[0237] 97.5 parts of DMC, 2 parts of TEOS, and 0.5 parts of DSMA
were mixed to obtain 100 parts of an organosiloxane mixture. A
solution prepared by dissolving 0.68 parts of DBSNa and 0.68 parts
of DBSH in 200 parts of deionized water was added to the
organosiloxane mixture, and stirred with a homomixer at 10,000 rpm
for 2 minutes. Then, the solution was passed through a homogenizer
at a pressure of 20 MPa twice to obtain a stable pre-mixed emulsion
(B).
[0238] The emulsion (B) was charged into a separable flask equipped
with a cooling condenser, and kept at 85.degree. C. for 6 hours to
produce a polyorganosiloxane latex by polymerization. Next, the
obtained reaction product was kept at room temperature for 12
hours, and neutralized with a 10% sodium hydroxide aqueous solution
to a pH of 7.0. The particle diameter and solid content of the
obtained polyorganosiloxane in the latex were measured. The results
are shown in Table 3.
TABLE-US-00001 TABLE 1 total amount water-based medium (A) of the
organic organic acid inorganic emulsion (B) acid catalyst
polyorgano- deionized catalyst acid catalyst deionized emulsifier
mixture of organosiloxane and the siloxane water DBSH sulfuric acid
water amount composition [part] feed rate emulsifier latex [part]
[part] [part] pH [part] kind [part] DMC/DSMA/TEOS [part/min] [part]
Example 1 L-1 90 1 1.38 0.84 300 DBSNa 0.68 97.5/0.5/2 0.42 1.68
Example 2 L-2 90 1 1.38 0.84 300 DBSNa 0.68 97.5/0.5/2 0.21 1.68
Example 3 L-3 90 5 0.83 0.85 300 DBSNa 0.68 97.5/0.5/2 0.21 5.68
Example 4 L-4 90 3 1.19 0.83 300 DBSNa 0.68 97.5/0.5/2 0.21 3.68
Example 5 L-5 90 2 1.29 0.81 300 DBSNa 0.68 97.5/0.5/2 0.21 2.68
Example 6 L-6 90 0.5 1.40 0.81 300 DBSNa 0.68 97.5/0.5/2 0.21 1.18
Example 7 L-7 90 0.5 1.40 0.81 300 DBSNa 2 97.5/0.5/2 0.21 2.50
Example 8 L-8 90 0.5 1.40 0.81 300 DBSNa 1 97.5/0.5/2 0.21 1.50
Example 9 L-9 90 0.4 1.58 0.82 300 DBSNa 0.68 97.5/0.5/2 0.11 1.08
Example 10 L-10 90 0.3 1.57 0.77 300 DBSNa 0.68 97.5/0.5/2 0.11
0.98 Example 11 L-11 90 1 1.38 0.84 300 A500 1 97.5/0.5/2 0.21 2.00
Example 12 L-12 90 2 1.29 0.84 300 DBSNa 0.68 96/2/2 0.21 2.68
Example 13 L-13 90 2 1.29 0.79 300 DBSNa 0.68 97/2/1 0.21 2.68
Example 14 L-14 90 5 0.83 0.85 300 DBSNa 0.68 98/2/0 0.21 5.68
Example 15 L-15 90 5 0.83 0.85 300 DBSNa 0.68 97/2/1 0.21 5.68
Example 16 L-16 90 5 0.83 0.83 300 DBSNa 0.68 96/2/2 0.21 5.68
Example 17 L-17 90 5 0.83 0.81 300 DBSNa 0.68 94/2/4 0.21 5.68
Example 18 L-18 90 0.5 1.40 0.84 300 DBSNa 0.68 98/2/0 0.21 1.18
Example 19 L-19 90 0.5 1.40 0.84 300 DBSNa 0.68 97/2/1 0.21 1.18
Example 20 L-20 90 2.3 1.29 0.85 300 DBSNa 0.68 96/2/2 0.21 2.98
Example 21 L-21 90 0.5 1.40 0.83 300 DBSNa 0.68 96/2/2 0.21 1.18
Example 22 L-22 90 0.4 1.58 0.81 300 DBSNa 0.68 96/2/2 0.21 1.08
Example 23 L-23 90 0.5 1.40 0.84 300 DBSNa 0.68 94/2/4 0.21
1.18
TABLE-US-00002 TABLE 2 total amount water-based medium (A) of the
organic organic acid inorganic emulsion (B) acid catalyst
polyorgano- deionized catalyst acid catalyst deionized emulsifier
mixture of organosiloxane and the siloxane water DBSH sulfuric acid
water amount composition [part] feed rate emulsifier latex [part]
[part] [part] pH [part] kind [part] DMC/DSMA/TEOS [part/min] [part]
Comparative L-24 90 10 -- 0.86 300 DBSNa 0.68 98/2/0 0.83 10.67 Ex.
1 Comparative L-25 90 2 -- 1.11 300 DBSNa 0.68 97.5/0.5/2 0.83 2.67
Ex. 2 Reference L-26 90 0.1 1.52 0.79 300 DBSNa 0.68 97.5/0.5/2
0.42 0.78 Ex. 3 Reference L-27 90 0.1 1.52 0.79 300 DBSNa 0.68
97.5/0.5/2 0.21 0.78 Ex. 4 Reference L-28 90 0.1 1.52 0.79 300
DBSNa 0.68 97.5/0.5/2 0.11 0.78 Ex 5 Comparative L-29 50 -- -- 6.51
40 DBSH 1 97.5/0.5/2 1.11 1.00 Ex. 6 Comparative L-29-2 50 -- --
6.55 40 DBSH 1 97.5/0.5/2 0.21 1.00 Ex. 7 Comparative L-30 50 0.05
-- 1.35 40 DBSH 1 97.5/0.5/2 1.11 1.05 Ex. 8 Comparative L-31 -- --
-- -- 200 DBSNa 0.68 97.5/0.5/2 -- 1.36 Ex. 9 DBSH 0.68
TABLE-US-00003 TABLE 3 average particle diameter polyorgano Dw
solid siloxane Dw Dn tandard content latex [nm] [nm] Dw/Dn
deviation [%] Example 1 L-1 133 84 1.58 100 17.3 Example 2 L-2 154
145 1.06 47 18.2 Example 3 L-3 100 94 1.06 14 16.4 Example 4 L-4
110 100 1.10 36 17.8 Example 5 L-5 132 118 1.12 25 17.7 Example 6
L-6 159 145 1.10 31 18.0 Example 7 L-7 130 118 1.10 33 16.1 Example
8 L-8 130 124 1.05 17 17.1 Example 9 L-9 172 155 1.11 30 17.4
Example 10 L-10 186 151 1.23 54 16.7 Example 11 L-11 171 134 1.28
169 18.8 Example 12 L-12 132 118 1.12 23 17.3 Example 13 L-13 129
108 1.19 34 17.6 Example 14 L-14 102 94 1.09 14 17.8 Example 15
L-15 108 96 1.06 12 17.6 Example 16 L-16 100 94 1.06 13 17.9
Example 17 L-17 104 99 1.05 12 17.7 Example 18 L-18 184 147 1.25 63
16.6 Example 19 L-19 166 148 1.12 35 17.4 Example 20 L-20 122 96
1.27 41 17.9 Example 21 L-21 154 133 1.16 30 16.9 Example 22 L-22
172 155 1.11 32 17.4 Example 23 L-23 153 135 1.13 35 17.7
Comparative L-24 62 58 1.07 12 19.2 Ex. 1 Comparative L-25 179 104
1.72 39 17.7 Ex. 2 Reference L-26 392 284 1.38 102 17.4 Ex. 3
Reference L-27 402 293 1.37 139 16.5 Ex. 4 Reference L-28 358 334
1.07 97 18.4 Ex. 5 Comparative L-29 470 168 2.80 238 40.0 Ex. 6
Comparative L-29 357 144 2.48 238 40.0 Ex. 7 Comparative L-30 523
138 3.79 231 36.0 Ex. 8 Comparative L-31 254 86 2.95 97 28.3 Ex.
9
[0239] Regarding the polyorganosiloxane latex in Example 1, the pH
of the water-based medium (A) was within the range of 0.1 to 1.2,
and therefore Dw/Dn was 1.58. Namely, the particle diameter
distribution was narrow. Further, as in Example 2, at a slower
feeding rat of the emulsion (B), a polyorganosiloxane latex having
a smaller Dw/Dn of 1.06 and a narrower particle diameter
distribution could be obtained. In Example 3 in which the total
amount of the organic acid catalyst and the emulsifier was changed,
the mass average particle diameter could be reduced while the
narrow particle diameter distribution was kept.
[0240] As in Examples 3 to 10 and 12 to 23, by changing the total
amount of the organic acid catalyst and the emulsifier, a
polyorganosiloxane latex having any mass average particle diameter
and a narrow particle diameter distribution could be obtained.
[0241] In Example 11, polyoxyethylene distyrenated phenylether
(made by Kao Corporation, trade name: EMULGEN A-500) that is a
nonionic emulsifier was used as an emulsifier for the emulsion (B)
instead of DBSNa. Example 11 shows that a polyorganosiloxane latex
having a narrow particle diameter distribution could stably be
produced.
[0242] In Comparative Example 1 in which the total amount of the
organic acid catalyst and the emulsifier was large, the mass
average particle diameter of the polyorganosiloxane latex was less
than 100 nm.
[0243] In Comparative Examples 6 to 8 in which the pH of the
water-based medium (A) was more than 1.2, the mass average particle
diameter of polyorganosiloxane was large, Dw/Dn was large, and the
particle diameter distribution was wide.
[0244] In Comparative Example 9 in which an emulsion (B) was not
dropped, Dw/Dn of the obtained polyorganosiloxane was large and the
particle diameter distribution was wide.
Example 24
Production of Graft Copolymer (Ga-1)
[0245] 7 parts of the polyorganosiloxane latex (L-12) obtained in
Example 12 (in terms of the solid content), 0.7 parts of
dipotassium alkenylsuccinate (made by Kao Corporation, trade name:
LATEMUL ASK, hereinafter, abbreviated to "ASK"), and 197 parts of
deionized water (including water in the polyorganosiloxane latex)
were charged into a separable flask equipped with a cooling
condenser, and mixed. Next, a mixture of 43 parts of n-butyl
acrylate (n-BA), 0.3 parts of allyl methacrylate (AMA), 0.01 parts
of 1,3-butylene dimethacrylate (1,3-BD), and 0.11 parts of t-butyl
hydroperoxide (t-BH) was added into the flask.
[0246] A nitrogen stream was passed through the flask to replace
the internal atmosphere with nitrogen, and the inner temperature
was raised to 60.degree. C. At this point, an aqueous solution
including 0.000075 parts of ferrous sulfate heptahydrate (Fe),
0.000225 parts of ethylenediaminetetraacetic acid disodium salt
(EDTA), 0.2 parts of sodium formaldehyde sulfoxylate (SFS), and 8
parts of deionized water was added to initiate radical
polymerization. Polymerization of the monomer component raised the
temperature of the solution to 78.degree. C. Subsequently, the
temperature was lowered to 75.degree. C., and kept for 30 minutes.
Polymerization of the monomer component was completed to obtain a
latex of a composite polymer (ga-1) consisting of
polyorganosiloxane (L-12) and a polymer of n-BA.
[0247] The composite polymer (ga-1) had a mass average particle
diameter of 182 nm. In 100% by mass of the composite polymer (in
terms of the solid content), the proportion of the composite
polymer particle having a particle diameter of 400 nm or more was
0%, and the proportion of the composite polymer particle having a
particle diameter of 100 nm or less was 0%.
[0248] Further, an aqueous solution including 0.2 parts of ASK,
0.001 parts of Fe, 0.003 parts of EDTA, 0.3 parts of SFS, and 24
parts of deionized water was added to the composite polymer (ga-1)
latex. Next, as a first stage polymerization, a mixed solution of
10 parts of acrylonitrile (AN), 30 parts of styrene (ST), and 0.2
parts of t-BH was dropped over 1 hour to perform polymerization. At
this time, the temperature of the solution was adjusted so as to be
80.degree. C. when dropping was completed. After dropping was
completed, the temperature was lowered to 75.degree. C., and kept
for 20 minutes. Next, as a second stage polymerization, a mixture
including 2.5 parts of AN, 7.5 parts of ST, 0.05 parts of t-BH, and
0.02 parts of n-octylmercaptan (nOM) was dropped over 20 minutes to
perform polymerization. After dropping was completed, the state
where the temperature was 75.degree. C. was kept for 20 minutes.
Then, 0.05 parts of cumene hydroperoxide (CHP) was added, and
further the state where the temperature was 75.degree. C. was kept
for 30 minutes. Then, the temperature was lowered to obtain a latex
of a graft copolymer (Ga-1) in which AN and ST were grafted to the
composite polymer (ga-1).
[0249] Next, 150 parts of a 1% calcium acetate aqueous solution was
heated to 70.degree. C., and 100 parts of the graft copolymer
(Ga-1) latex was gradually dropped into the aqueous solution to
solidify the graft copolymer (Ga-1). A precipitate was dehydrated,
washed, and dried to obtain a white powder of the graft copolymer
(Ga-1).
Examples 25 to 32, and Comparative Examples 10 to 11
Production of Graft Copolymers (Ga-2) to (Ga-11)
[0250] Composite polymers (ga-2) to (ga-11) were obtained in the
same manner as in Example 24 except that the kind and amount of
polyorganosiloxane and the amount of n-BA were changed as the
condition shown in Table 4. Further, graft polymerization was
performed using these composite polymers and AN and ST at the
amounts shown in Table 4 to obtain graft copolymers (Ga-2) to
(Ga-11).
Production Example 1
Production of Thermoplastic Resin (Ha-1)
[0251] Using 25 parts of AN and 75 parts of ST, a
acrylonitrile-styrene copolymer (Ha-1) whose reduced viscosity
measured at 25.degree. C. was 0.40 dL/g was produced in an
N,N-dimethylformamide solution by a known suspension polymerization
method.
Production Examples 2 to 6
Production of Thermoplastic Resins (Ha-2 to Ha-6)
[0252] Thermoplastic resins (Ha-2) to (Ha-6) were produced in the
same manner as in Production Example 1 except that the kind and
amount of the vinyl-based monomer were changed as the condition
shown in Table 5. The measurement results of the reduced viscosity
are shown in Table 5.
TABLE-US-00004 TABLE 4 composition of particle diameter of
composite polymer composition of grafted part mass proportion of
proportion of composite polymer first second average particle
having a particle having a content stage stage particle diameter of
100 nm diameter of 400 nm composite graft kind of POSi/BA of POSi
AN/ST AN/ST diameter or less or more polymer copolymer POSi latex
[part] [%] [part] [part] [nm] [%] [%] Example 24 ga-1 Ga-1 L-12
7/43 14 10/30 2.5/7.5 182 0 0 Example 25 ga-2 Ga-2 L-12 5/45 10
10/30 2.5/7.5 185 3 0 Example 26 ga-3 Ga-3 L-12 7/43 14 12/28 3/7
181 2 0 Example 27 ga-4 Ga-4 L-12 7/43 14 8/32 2/8 185 1.5 0
Example 28 ga-5 Ga-5 L-13 7/43 14 10/30 2.5/7.5 177 0 0 Example 29
ga-6 Ga-6 L-15 7/43 14 10/30 2.5/7.5 128 7.4 0 Example 30 ga-7 Ga-7
L-16 7/43 14 10/30 2.5/7.5 127 1.9 0 Example 31 ga-8 Ga-8 L-17 7/43
14 10/30 2.5/7.5 122 6.8 0 Example 32 ga-9 Ga-9 L-14 7/43 14 10/30
2.5/7.5 130 2.7 0 Comparative ga-10 Ga-10 L-24 1.75/48.25 3.5 10/30
2.5/7.5 150 0 0.9 Ex. 10 Comparative ga-11 Ga-11 L-24 7/43 14 10/30
2.5/7.5 114 22.7 0 Ex. 11 POSi: polyorganosiloxane BA: n-butyl
acrylate AN: acrylonitrile ST: styrene
TABLE-US-00005 TABLE 5 Production thermoplastic composition [part]
.eta. sp/c Example resin (Ha) AN ST PMID .alpha.MS [dL/g] 1 Ha-1 25
75 0.40 2 Ha-2 28 72 0.62 3 Ha-3 34 66 0.48 4 Ha-4 22 55 23 0.66 5
Ha-5 14 53 33 0.68 6 Ha-6 28 24 11 37 0.47 PMID: N-phenylmaleimide
.alpha.MS: .alpha.-methylstyrene
Examples 33 to 47, and Comparative Examples 12 and 13
Production of Thermoplastic Resin Compositions (Ia-1 to Ia-17)
[0253] The graft copolymer and the thermoplastic resin composition
were blended at the composition shown in Table 6, and 0.5 parts of
ethylenebisstearylamide (EBS), 0.03 parts of silicone oil (made by
Dow Corning Toray Co., Ltd., product name: SH-200) as additives,
and 0.05 parts of carbon black #960 (made by Mitsubishi Chemical
Corporation) as a colorant were added, and mixed using a Henschel
mixer. Next, the mixture was fed to a volatilizing extruder (made
by The Japan Steel Works, Ltd., TEX-30a) whose barrel temperature
was heated to 260.degree. C., and kneaded to obtain pellets of a
resin composition. The melt volume rate of the pellets was
measured. Further, the pellets were formed into a test piece for
evaluation using a 4-ounce injection molding machine (made by The
Japan Steel Works, Ltd.) at 220 to 260.degree. C., and the Charpy
impact strength (23.degree. C.), MVR, bending strength, flexural
modulus, deflection temperature under load, diffuse reflectance
(brightness), and vibration welding properties were measured. The
results are shown in Table 6 and Table 7.
[0254] In Examples 46 and 47, a polycarbonate resin (made by
Mitsubishi Engineering-Plastics Corporation, trade name: Iupilon
S-2000F, hereinafter, abbreviated to "Ha-7") was used as a
thermoplastic resin composition.
[0255] As shown in Examples 33 to 47 in Table 6 and Table 7, the
graft copolymers (Ga-1) to (Ga-9) according to the present
invention can produce a thermoplastic resin having high physical
properties such as impact strength and fluidity, low diffuse
reflectance, remarkable brightness, and high vibration welding
properties. In contrast, in Comparative Example 12, although the
particle diameter of the composite polymer meets the requirement of
Claims, the thermoplastic resin showed reduced brightness because
the mass average particle diameter (Dw) of the polyorganosiloxane
(L-24) was small. In Comparative Example 13, impact strength and
brightness were reduced because the mass average particle diameter
(Dw) of the polyorganosiloxane (L-24) was small and the composite
polymer had a large proportion of the particle having a particle
diameter of 100 nm or less.
TABLE-US-00006 TABLE 6 Example 33 Example 34 Example 35 Example 36
Example 37 Example 38 Example 39 Example 40 thermoplastic resin
Ia-1 Ia-2 Ia-3 Ia-4 Ia-5 Ia-6 Ia-7 Ia-8 composition (Ia) graft
copolymer Ga-1 33 26 40 28 34 (Ga) [part] Ga-2 33 Ga-3 33 Ga-4 33
Ga-5 Ga-6 Ga-7 Ga-8 Ga-9 thermoplastic resin Ha-1 9 9 9 9 (Ha) Ha-2
8 8 8 8 36 22 [part] Ha-3 47 41 Ha-4 50 50 50 50 Ha-5 38 38 Ha-6 25
25 Ha-7 Charpy impact kJ/m.sup.2 9.3 8.8 9.5 8.3 6.0 12.2 7.1 9.6
strength (23.degree. C.) MVR cm.sup.3/10 min 5.1 5.0 4.2 5.5 8.9
4.0 17.0 14.0 bending strength MPa 79 81 80 81 87 70 82 74 flexural
modulus MPa 2470 2500 2510 2530 2710 2200 2750 2490 deflection
.degree. C. 95 95 95 94 96 94 86 85 temperature under load diffuse
reflectance % 3.8 4.3 4.1 4.3 3.5 4.3 3.0 3.0 (brightness)
vibration welding rank 2 2 2 2 2 2 2 2
TABLE-US-00007 TABLE 7 Com- Com- Exam- Exam- parative parative
Example 41 Example 42 Example 43 Example 44 Example 45 ple 46 ple
47 Ex. 12 Ex. 13 thermoplastic resin Ia-9 Ia-10 Ia-11 Ia-12 Ia-13
Ia-14 Ia-15 Ia-16 Ia-17 composition (Ia) graft copolymer (Ga) Ga-1
33 33 [part] Ga-2 Ga-3 Ga-4 Ga-5 33 Ga-6 33 Ga-7 33 Ga-8 33 Ga-9 33
Ga-10 33 Ga-11 33 thermoplastic resin Ha-1 9 9 9 9 9 9 (Ha) Ha-2 29
8 8 8 8 47 27 8 8 [part] Ha-3 Ha-4 50 50 50 50 50 50 Ha-5 38 Ha-6
Ha-7 20 40 Charpy impact kJ/m.sup.2 9.7 7.8 7.5 7.6 7.1 21 50 7.3
5.1 strength (23.degree. C.) MVR cm.sup.3/10 min 5.8 4.5 4.5 4.6
4.4 12.1 7.7 4.8 4.3 bending strength MPa 80 83 82 83 81 71 71 80
84 flexural modulus MPa 2560 2490 2480 2480 2440 2200 1990 2490
2500 deflection temperature .degree. C. 94 93 94 94 94 87 93 95 95
under load diffuse reflectance % 4.3 3.6 3.7 3.7 4.5 3.8 4.4 5.1
5.1 (brightness) vibration welding rank 2 2 2 2 2 2 2 2 2 Ha-7: a
polycarbonate resin (Mitsubishi Engineering-Plastics Corporation,
trade name: Iupilon S-2000F)
Example 48
Production of Graft Copolymer (Gb-1)
[0256] A mixture of 25 parts of the polyorganosiloxane latex (L-12)
obtained in Example 12 (in terms of the solid content), 25 parts of
n-BA, 0.2 parts of AMA, 0.05 parts of 1,3-BD, 0.063 parts of t-BH,
and 208 parts of deionized water (including water in the
polyorganosiloxane latex) was charged into a separable flask
equipped with a cooling condenser. Next, a nitrogen stream was
passed through the flask to replace the atmosphere, and the inner
temperature was raised to 60.degree. C. At this point, an aqueous
solution including 0.00005 parts of Fe, 0.00015 parts of EDTA, 0.12
parts of SFS, and 4 parts of deionized water was added to initiate
polymerization. After the maximum point of the inner temperature
was recognized from heat generated by polymerization of the monomer
component, the temperature was lowered to 65.degree. C., and kept
for 30 minutes. Then, polymerization of the monomer component was
completed to obtain a latex of a composite polymer (gb-1)
consisting of polyorganosiloxane (L-12) and a polymer of n-BA.
Regarding the obtained composite polymer (gb-1), the mass average
particle diameter was 140 nm, the proportion of the composite
polymer particle having a particle diameter less than 100 nm was
7%, and the proportion of the composite polymer particle having a
particle diameter of 300 nm or more was 1.3%.
[0257] Next, an aqueous solution including 0.001 parts of Fe, 0.003
parts of EDTA, 0.3 parts of SFS, 0.55 parts of DBSNa, and 11 parts
of deionized water was added to the composite polymer (gb-1) latex.
Further, while a mixed solution of 12.5 parts of AN, 37.5 parts of
ST, and 0.23 parts of t-BH was dropped over 100 minutes, the
temperature was raised to 80.degree. C. After dropping was
completed, the state where the temperature was 80.degree. C. was
kept for 20 minutes. Then, 0.05 parts of CHP was added, and the
temperature was kept for 30 minutes, and then lowered to obtain a
graft copolymer (Gb-1) latex.
[0258] Meanwhile, 140 parts of an aqueous solution in which 6%
calcium acetate was dissolved was prepared, and heated to
85.degree. C. Next, while the aqueous solution was stirred, the
graft copolymer (Gb-1) latex (100 parts of the solid content) was
gradually dropped into the aqueous solution to solidify the graft
copolymer (Gb-1). Further, the temperature was raised to 95.degree.
C., and kept for 5 minutes. The obtained solidified product was
dehydrated, washed, and dried to obtain a powder of the graft
copolymer (Gb-1).
Examples 49 to 60, and Comparative Examples 14 to 17
Production of Graft Copolymers (Gb-2) to (Gb-17)
[0259] Composite polymers (gb-2) to (gb-17) were obtained in the
same manner as in Example 48 except that the kind and amount of
polyorganosiloxane and the amount of n-BA were changed as the
condition shown in Table 8. Further, using these composite polymers
and AN and ST at the amounts shown in Table 8, graft polymerization
was performed to obtain graft copolymers (Gb-2) to (Gb-17). In
Comparative Example 16, a mixture of 83 parts of (L-24) and 17
parts of (L-31) in terms of the solid content was used as the
polyorganosiloxane latex (L-32). The mass average particle diameter
(Dw) of the polyorganosiloxane (L-32) was 101 nm, the number
average particle diameter (Dn) was 58 nm, and the particle diameter
distribution (Dw/Dn) expressed as the ratio thereof was 1.74.
Production Examples 7 to 9
Production of Thermoplastic Resins (Hb-1) to (Hb-3)
[0260] Using the kind and amount of the vinyl-based monomers shown
in Table 9, copolymers (Hb-1) to (Hb-3) were produced by a known
suspension polymerization method. The reduced viscosity of each
copolymer measured in an N,N-dimethylformamide solution at
25.degree. C. was shown in Table 9.
TABLE-US-00008 TABLE 8 particle diameter of composite polymer
proportion of composition of composition proportion of particle
composite polymer of mass average particle havin a diameter content
grafted part particle having a diameter of 300 nm or composite
graft kind of POSi/BA of POSi AN ST diameter of 100 nm or less more
polymer copolymer POSi latex [part] [%] [part] [part] [nm] [%] [%]
Example 48 gb-1 Gb-1 L-12 25/25 50 12.5 37.5 140 7.0 1.3 Example 49
gb-2 Gb-2 L-12 10/40 20 12.5 37.5 170 0.8 4.9 Example 50 gb-3 Gb-3
L-12 15/35 30 12.5 37.5 160 6.1 6.0 Example 51 gb-4 Gb-4 L-12 20/30
40 12.5 37.5 150 1.1 1.6 Example 52 gb-5 Gb-5 L-12 35/15 70 12.5
37.5 135 12.9 2.0 Example 53 gb-6 Gb-6 L-13 25/25 50 12.5 37.5 140
8.9 0.8 Example 54 gb-7 Gb-7 L-19 25/25 50 12.5 37.5 160 3.4 6.7
Example 55 gb-8 Gb-8 L-20 25/25 50 12.5 37.5 140 11.7 2.1 Example
56 gb-9 Gb-9 L-21 25/25 50 12.5 37.5 160 0.7 2.1 Example 57 gb-10
Gb-10 L-22 25/25 50 12.5 37.5 190 0.0 5.3 Example 58 gb-11 Gb-11
L-23 25/25 50 12.5 37.5 160 4.1 5.0 Example 59 gb-12 Gb-12 L-12
20/30 40 15.0 35.0 150 1.1 1.6 Example 60 gb-13 Gb-13 L-12 24/36 40
12.0 28.0 150 4.3 1.2 Comparative gb-14 Gb-14 L-24 25/25 50 12.5
37.5 70 88.5 0.1 Ex. 14 Comparative gb-15 Gb-15 L-31 25/25 50 12.5
37.5 210 2.6 20.7 Ex. 15 Comparative gb-16 Gb-16 L-32 25/25 50 12.5
37.5 90 66.9 1.9 Ex. 16 Comparative gb-17 Gb-17 L-24 7/43 14 12.5
37.5 90 47.9 0.0 Ex. 17
TABLE-US-00009 TABLE 9 Production thermoplastic composition [part]
.eta. sp/c Example resin (Hb) AN ST PMID [dL/g] 7 Hb - 1 34 66 0.62
8 Hb - 2 29 71 0.61 9 Hb - 3 48 52 0.64
Examples 61 to 78, and Comparative Examples 18 to 22
Production of Thermoplastic Resin Compositions (Ib-1 to Ib-23)
[0261] The graft copolymers (Gb-1) to (Gb-17) and the thermoplastic
resins (Hb-1) to (Hb-3) were blended at the corresponding
composition shown in Tables 10 to 12. Further, 0.3 parts of EBS as
a lubricant and 0.5 parts of carbon black #960 as a colorant were
mixed using a Henschel mixer. Next, the mixture was fed into a
volatilizing twin screw extruder (made by Ikegai Corp., PCM-30)
whose barrel temperature was heated to 230.degree. C., and kneaded
to produce pellets of each of the thermoplastic resin compositions
(Ib-1) to (Ib-23). The melt volume rate of each pellet was
measured.
[0262] The pellets were formed into a test piece for evaluation
with a 4-ounce injection molding machine (made by The Japan Steel
Works, Ltd.) at 230.degree. C. The measurement results of the melt
volume rate, flexural modulus, deflection temperature under load,
Charpy impact strengths at 23.degree. C. and -30.degree. C., and
color developability are shown in Tables 10 to 12. In Table 12, a
polycarbonate resin (made by Mitsubishi Engineering-Plastics
Corporation, trade name: Iupilon S-3000) was used as Hb-4.
[0263] The thermoplastic resin compositions in Examples 61 to 78
using the graft copolymers (Gb-1) to (Gb-13) according to the
present invention could have a good balance between mechanical
strength such as impact strength and flexural modulus, in
particular Charpy impact strength at -30.degree. C., and color
developability. Meanwhile, in Comparative Examples 18, 21, and 22,
the polyorganosiloxane (L-24) and the composite polymers (gb-14)
and (gb-17) had a small mass average particle diameter (Dw), and
the composite polymer had a large proportion of the particle having
a particle diameter of 100 nm or less. For this reason, Charpy
impact strength at -30.degree. C. was low. Further, in Comparative
Example 19, the mass average particle diameter (Dw) of the
polyorganosiloxane (L-31) was large, and the composite polymer had
a large proportion of the particle having a particle diameter of
300 nm or more. For this reason, Charpy impact strength at
-30.degree. C. was low, and color developability was worsened. In
Comparative Example 20, the particle diameter distribution (Dw/Dn)
of the polyorganosiloxane (L-32) was large, and therefore the mass
average particle diameter (Dw) of the composite polymer (gb-16) was
small, and Charpy impact strength at -30.degree. C. was low.
TABLE-US-00010 TABLE 10 Example Example Example 61 62 63 Example 64
Example 65 Example 66 Example 67 Example 68 thermoplastic resin
composition (Ib) Ib-1 Ib-2 Ib-3 Ib-4 Ib-5 Ib-6 Ib-7 Ib-8 graft
copolymer (Gb) kind Gb-1 Gb-2 Gb-3 Gb-4 Gb-5 Gb-6 Gb-7 Gb-8 amount
[part] 42 42 42 42 42 42 42 42 thermoplastic resin (Hb) kind Hb-1
Hb-1 Hb-1 Hb-1 Hb-1 Hb-1 Hb-1 Hb-1 amount [part] 58 58 58 58 58 58
58 58 rubber content % 21 21 21 21 21 21 21 21 MVR cm.sup.3/10 min
11 13 12 13 10 12 12 13 flexural modulus MPa 2180 2210 2230 2240
2240 2250 2150 2230 deflection temperature .degree. C. 82 83 83 83
83 83 81 83 under load Charpy impact 23.degree. C. kJ/m.sup.2 22 21
23 23 16 24 21 22 strength -30.degree. C. 12 8 9 11 9 12 12 11
color developability (L*) 18 19 19 19 19 18 20 18
TABLE-US-00011 TABLE 11 Example Example Example Comparative
Comparative Comparative 69 70 71 Example 72 Example 73 Ex. 18 Ex.
19 Ex. 20 thermoplastic resin composition (Ib) Ib-9 Ib-10 Ib-11
Ib-12 Ib-13 Ib-14 Ib-15 Ib-16 graft copolymer (Gb) kind Gb-9 Gb-10
Gb-11 Gb-12 Gb-13 Gb-14 Gb-15 Gb-16 amount [part] 42 42 42 42 35 42
42 42 thermoplastic resin (Hb) kind Hb-1 Hb-1 Hb-1 Hb-1 Hb-1 Hb-1
Hb-1 Hb-1 amount [part] 58 58 58 58 65 58 58 58 rubber content % 21
21 21 21 21 21 21 21 MVR cm.sup.3/10 min 13 12 12 9 12 10 14 13
flexural modulus MPa 2180 2190 2220 2240 2270 2280 2310 2330
deflection temperature .degree. C. 82 82 83 83 83 83 83 83 under
load Charpy impact 23.degree. C. kJ/m.sup.2 18 18 15 25 24 8 7 13
strength -30.degree. C. 11 11 8 12 11 3 4 5 color developability
(L*) 20 21 19 17 14 13 25 18
TABLE-US-00012 TABLE 12 Example Example Comparative Comparative 74
Example 75 76 Example 77 Example 78 Ex. 21 Ex. 22 thermoplastic
resin composition (Ib) Ib-17 Ib-18 Ib-19 Ib-20 Ib-21 Ib-22 Ib-23
graft copolymer (Gb) kind Gb-4 Gb-4 Gb-4 Gb-4 Gb-4 Gb-17 Gb-17
amount [part] 30 34 38 42 44 42 44 thermoplastic resin (Hb) Hb-1 70
66 62 48 48 [part] Hb-2 37 37 Hb-3 19 19 Hb-4 10 10 rubber content
% 15 17 19 21 22 21 22 MVR cm.sup.3/10 min 17 16 13 8 3 8 3
flexural modulus MPa 2700 2560 2420 2150 2120 2140 2100 deflection
temperature .degree. C. 84 83 83 86 92 86 92 under load Charpy
impact 23.degree. C. kJ/m.sup.2 12 16 21 19 15 17 13 strength
-30.degree. C. 5 6 9 10 6 5 2 color developability (L*) 17 18 19 20
21 17 18 Hb-4: a polycarbonate resin (Mitsubishi
Engineering-Plastics Corporation, trade name: Iupilon S-3000)
INDUSTRIAL APPLICABILITY
[0264] The polyorganosiloxane latex according to the present
invention can be widely used as raw materials for resin additives,
fiber treatment agents, mold release agents, cosmetics, antifoaming
agents, additives for a coating material, and the like. The graft
copolymer obtained using the polyorganosiloxane latex according to
the present invention is in particular useful as raw materials for
resin additives because a thermoplastic resin composition having a
narrow particle distribution and suitable properties for intended
applications can be produced.
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