U.S. patent application number 14/302633 was filed with the patent office on 2014-10-02 for copier/printer exterior part using halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate.
This patent application is currently assigned to SHANGHAI KUMHOSUNNY PLASTICS CO., LTD.. The applicant listed for this patent is Lei GAO, Ryuji KITANI, Qiang LI, Wenqiang LI, Minghua LUO, Yasuharu SAITA, Minqi XIN. Invention is credited to Lei GAO, Ryuji KITANI, Qiang LI, Wenqiang LI, Minghua LUO, Yasuharu SAITA, Minqi XIN.
Application Number | 20140296383 14/302633 |
Document ID | / |
Family ID | 47598706 |
Filed Date | 2014-10-02 |
United States Patent
Application |
20140296383 |
Kind Code |
A1 |
XIN; Minqi ; et al. |
October 2, 2014 |
COPIER/PRINTER EXTERIOR PART USING HALOGEN-FREE FLAME-RETARDANT
RESIN COMPOSITION INCLUDING RECYCLED POLYCARBONATE AND RECYCLED
POLYETHYLENE TEREPHTHALATE
Abstract
A copier/printer exterior part uses a halogen-free
flame-retardant resin composition. The halogen-free flame-retardant
resin composition includes 5 wt % to 50 wt % of unused
polycarbonate, 20 wt % to 63 wt % of recycled polycarbonate 5 wt %
to 35 wt % of recycled polyethylene terephthalate, 0.2 wt % to 2 wt
% of a styrene-acrylonitrile-glycidyl methacrylate terpolymer, 5 wt
% to 15 wt % of a toughener, 10 wt % to 20 wt % of a flame
retardant, 0.1 wt % to 0.8 wt % of a flame-retardant antidrip
agent, 0.1 wt % to 1 wt % of an antioxidant, and 0.1 wt % to 2 wt %
of a lubricant. The styrene-acrylonitrile-glycidyl methacrylate
terpolymer includes 1 wt % to 5 wt % of glycidyl methacrylate and
20 wt % to 33 wt % of acrylonitrile.
Inventors: |
XIN; Minqi; (SHANGHAI,
CN) ; LUO; Minghua; (SHANGHAI, CN) ; LI;
Wenqiang; (SHANGHAI, CN) ; GAO; Lei;
(SHANGHAI, CN) ; LI; Qiang; (SHANGHAI, CN)
; KITANI; Ryuji; (Tokyo, JP) ; SAITA;
Yasuharu; (Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
XIN; Minqi
LUO; Minghua
LI; Wenqiang
GAO; Lei
LI; Qiang
KITANI; Ryuji
SAITA; Yasuharu |
SHANGHAI
SHANGHAI
SHANGHAI
SHANGHAI
SHANGHAI
Tokyo
Tokyo |
|
CN
CN
CN
CN
CN
JP
JP |
|
|
Assignee: |
SHANGHAI KUMHOSUNNY PLASTICS CO.,
LTD.
Shanghai
CN
KONICA MINOLTA BUSINESS TECHNOLOGIES, INC.
Tokyo
JP
|
Family ID: |
47598706 |
Appl. No.: |
14/302633 |
Filed: |
June 12, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13743934 |
Jan 17, 2013 |
|
|
|
14302633 |
|
|
|
|
Current U.S.
Class: |
523/435 ;
523/437 |
Current CPC
Class: |
C08K 5/521 20130101;
C08L 69/00 20130101; C08L 69/00 20130101; C08L 2205/02 20130101;
C08L 69/00 20130101; C08L 69/00 20130101; C08K 5/0066 20130101;
C08L 25/14 20130101; C08L 67/02 20130101; C08L 51/00 20130101; C08L
25/12 20130101; C08L 67/02 20130101; C08L 37/00 20130101; C08L
51/00 20130101; C08L 25/12 20130101; C08K 5/0066 20130101; C08L
25/14 20130101; C08L 51/00 20130101; C08K 5/0066 20130101; C08L
69/00 20130101; C08L 67/02 20130101; C08L 67/02 20130101; C08L
69/00 20130101 |
Class at
Publication: |
523/435 ;
523/437 |
International
Class: |
C08L 69/00 20060101
C08L069/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 18, 2012 |
CN |
201210016861.X |
Claims
1. A method for producing a copier/printer exterior part from a
chlorine-free and bromine-free flame-retardant resin composition
comprising: 5 wt % to 50 wt % of unused polycarbonate; 20 wt % to
63 wt % of recycled polycarbonate; 5 wt % to 35 wt % of recycled
polyethylene terephthalate; 0.2 wt % to 2 wt % of a
styrene-acrylonitrile-glycidyl methacrylate terpolymer; the
styrene-acrylonitrile-glycidyl methacrylate terpolymer includes 1
wt. % to 5 wt. % of glycidyl methacrylate and 20 wt. % to 33 wt. %
of acrylonitrile, 5 wt % to 15 wt % of a toughener; 10 wt % to 20
wt % of a flame retardant; 0.1 wt % to 0.8 wt % of a
flame-retardant antidrip agent; 0.1 wt % to 1 wt % of an
antioxidant; and 0.1 wt % to 2 wt % of a lubricant, the method
comprising obtaining materials of the resin composition; mixing the
recycled polyethylene terephthalate material and the
styrene-acrylonitrile-glycidyl methacrylate terpolymer material in
a mixer so as to make a first mixture; extruding the first mixture
in a screw extruder so as to produce a base grain; mixing the base
grain and the remaining materials in a mixer so as to make a second
mixture; extruding the second mixture in a screw extruder so as to
produce a final grain as the chlorine free and bromine-free
flame-retardant resin composition; and manufacturing the
copier/printer exterior part from the final grain.
2. The method according to claim 1, wherein the
styrene-acrylonitrile-glycidyl methacrylate terpolymer includes 1
wt % to 5 wt % of glycidyl methacrylate and 27 wt % to 30 wt % of
acrylonitrile.
3. The method according to claim 1, herein the unused polycarbonate
is bisphenol A aromatic polycarbonate having a weight average
molecular weight of 10000 to 40000.
4. The method according to claim 1, wherein the recycled
polycarbonate is bisphenol A aromatic polycarbonate having a weight
average molecular weight of 10000 to 40000.
5. The method according to claim 1, wherein the recycled
polyethylene terephthalate has a viscosity of 0065 dl/g to 0.9
dl/g.
6. The method according to claim 1, wherein the toughener is at
least one of a core-shell structured acrylate system toughener, a
core-shell structured acrylate silicone rubber system toughener, a
core-shell structured styrene system toughener, a
long-chain-containing toughener, and a reactive terpolymer
toughener.
7. The method according to claim 6, wherein the toughener is at
least one of a core-shell structured acrylate system toughener and
a core-shell structured acrylate-silicone rubber system
toughener.
8. The method according to claim 6, wherein the core-shell
structured acrylate system toughener is a methyl
methacrylate-butadiene-styrene copolymer, an
acrylonitrile-butadiene-acrylate copolymer, or a methyl
methacrylate-butyl methacrylate copolymer, the core-shell
structured acrylate-silicone rubber system toughener is a methyl
methacrylate-silicone rubber copolymer, the core-shell structured
styrene system toughener is an acrylonitrile-styrene-butadiene
terpolymer, the long-chain-containing toughener is an
ethylene-methyl acrylate copolymer or an ethylene-butyl acrylate
copolymer, and the reactive terpolymer toughener is an
ethylene-methyl acrylate-glycidyl methacrylate copolymer or an
ethylene-butyl acrylate-glycidyl methacrylate copolymer.
9. The method according to claim 1, wherein the flame retardant is
a phosphate flame retardant.
10. The method according to claim 9, wherein the phosphate flame
retardant is at least one of a monophosphate flame retardant and an
oligophosphate flame retardant.
11. The method according to claim 10, wherein the monophosphate
flame retardant is trimethyl phosphate, triethyl phosphate,
triphenyl phosphate, dimethylphenyl phosphate, tributyl phosphate,
or xylyl diphenyl phosphate, and the oligophosphate flame retardant
is resorcinol bis(diphenyl phosphate), bisphenol A his (diphenyl
phosphate), or diphenyl pentaerythritol diphosphate.
12. The method according to claim 1, wherein the antioxidant is at
least one of a hindered phenol system antioxidant and a phosphite
system antioxidant.
13. The method according to claim 12, wherein the hindered phenol
system antioxidant is triethylene glycol
bis[.beta.-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate],
pentaerythritol
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], or
n-octadecyl-.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
and the phosphite system antioxidant is
tris(2,4-di-tert-butylphenyl)phosphite or
bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite.
14. The method according to claim 1, wherein the lubricant is at
least one of fatty acid salt, fatty acid amide, a silane polymer,
solid paraffin, liquid paraffin, calcium stearate, zinc stearate,
octadecanamide, silicone powder, methylene bis(octadecanamide), and
N,N'-ethylene bis(octadecanamide).
15. The method according to copier/printer exterior part according
to claim 1, wherein the flame-retardant antidrip agent is a
polytetrafluoroethylene system flame-retardant antidrip agent.
16. The method according to claim 1, comprising: 20.2 wt. % to 3245
wt. % of the unused polycarbonate, 20.2 wt. % to 32.5 wt. % of the
recycled polycarbonate, 10 wt. % to 30 wt. % of the recycled
polyethylene terephthalate, and 0.4 wt. % to 1.4 wt. % of the
styrene-acrylonitrile-glycidyl methacrylate terpolymer.
Description
[0001] This is a Continuation of U.S. application Ser. No.
13/743,934 filed Jan. 17, 2013, which claimed the priority of
Chinese Application No. 201210016861.X filed Jan. 18, 2012, the
priority of both applications is claimed and both applications are
incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a composition and use of
the composition, and, in particular, relates to a halogen-free
flame-retardant resin composition including recycled polycarbonate
and recycled polyethylene terephthalate and a copier/printer
exterior part using the resin composition.
[0004] 2. Description of the Related Art
[0005] With continuous and rapid development of the plastic
industry, plastic products have been widely used. At the same time,
however, plastic waste has increased, and a huge amount of energy
sources has been wasted. Accordingly, collection and reuse of
plastic waste has attracted more attention than before.
[0006] Plastic materials are chemicals derived from petroleum. It
is well known that petroleum is a lifeline for the industries of
the present age and a natural source which cannot be reproduced.
According to statics of a related organization, plastic waste
generated by one medium-sized city per year can cover plastic
materials demanded by 20 small and medium-sized plastics companies
per year. Hence, reuse of plastics can be regarded as reuse of
petroleum. By melting and granulating plastic waste, supply-demand
imbalance in plastic materials can be reduced, and a national
budget for petroleum import can be drastically cut.
[0007] Polycarbonate (PC) has excellent impact resistance, heat
resistance, dimensional stability, electric insulation and the
like, is nontoxic, and has low water absorbency. Accordingly, PC
can be used in a wide range of temperatures. In addition, because
PC has high light transmittance of 90%, it is named "transparent
metal", and used instead of copper or other colored metals in
various fields, such as the electrical and electronic industry, the
automobile industry, the mechanical industry, the optical industry,
and the pharmaceutical industry. In recent years, consumption of PC
has rapidly and continuously increased, and unavoidably, a large
amount of PC waste has been generated. PC waste is an important
recycled source, and it is necessary to properly process PC waste
so as to reduce influence of PC waste on environments. Collection
and reuse of PC waste contribute to economic and social benefits
significantly. Examples of PC waste to be collected include PC used
in buckets, dies, and optical disks.
[0008] According to data by PCI (PET Packaging, Resin &
Recycling Ltd), in 2008, production capacity of polyethylene
terephthalate (PET) in the world reached 67 million tons, and
output thereof was 61 million tons. Meanwhile, several million tons
of PET waste, which is generated by consumption of a large amount
of PET, is generated every years. If PET waste is not sufficiently
used, a large amount of resources is wasted. Nowadays, recycled PET
is mainly used in fibers, sheets, and bottles for containing
nonfood, and used in some plastic bottles, monofilaments, and the
like. However, the application range of recycled PET is relatively
narrow in the engineering plastic field. In particular, application
thereof in the plastic alloy field is hardly reported.
[0009] In U.S. Pat. No. 7,462,649, there is disclosed decomposing a
PET bottle or the like, and performing repolymerization by ester
interchange, so as to realize production of a bottle from a
bottle.
[0010] Furthermore, in Chinese Patent Application Laid Open
Publication No. 101338070, there is disclosed preparing a
composition containing flame-retardant PC and a polyester resin,
which are denaturalized by an epoxy group-containing rubber
modified aromatic vinyl copolymer resin, but not, disclosed using a
recycled material.
[0011] Engineering PET has low viscosity/toughness in general, and
recycled PET has lower viscosity/toughness. Hence, unless the
viscosity/toughness is increased, the application range of recycled
PET is not widened. Furthermore, influence of low molecular weights
and wide distribution of molecular weights of recycled PET on
performance thereof is more than that of recycled PC on performance
thereof, and hence a composition including recycled PET and a
product using the composition are unstable in performance, and
difficult to obtain stable mechanical performance. Consequently,
the application range of recycled PET is somewhat limited.
[0012] Therefore, development of a halogen-free flame-retardant
resin composition including recycled PET and recycled PC and a
product using the resin composition has an important meaning in
terms of environmental protection and practical application.
BRIEF SUMMARY OF THE INVENTION
[0013] The present invention is made in view of the circumstances,
and objects of the present invention include providing a
halogen-free flame-retardant resin composition including recycled
polycarbonate and recycled polyethylene terephthalate and a
copier/printer exterior part using the resin composition, each of
which can realize cycle use (recycling) of polycarbonate and
polyethylene terephthalate, and prevent stability of mechanical
performance of materials (components) of the resin composition from
decreasing.
[0014] In order to achieve at least one of the objects, according
to an aspect of the present invention, there is provided a
copier/printer exterior part using a halogen-free flame-retardant
resin composition including: 5 wt % to 50 wt % of unused
polycarbonate; 20 wt % to 63 wt % of recycled polycarbonate; 5 wt %
to 35 wt % of recycled polyethylene terephthalate; 0.2 wt. % to 2
wt % of a styrene-acrylonitrile-glycidyl methacrylate terpolymer; 5
wt % to 15 wt % of a toughener; 10 wt % to 20 wt % of a flame
retardant; 0.1 wt % to 0.8 wt. % of a flame-retardant antidrip
agent; 0.1 wt % to wt % of an antioxidant; and 0.1 wt % to 2 wt %
of a lubricant, wherein the styrene-acrylonitrile-glycidyl
methacrylate terpolymer includes 1 wt % to 5 wt % of glycidyl
methacrylate and 20 wt % to 33 wt % of acrylonitrile.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0015] The present invention is fully understood from the detailed
description given hereinafter and the accompanying drawings, which
are given by way of illustration only, and thus are not intended to
limit the present invention, wherein:
[0016] FIG. 1 shows external appearance of a copier using an
exterior part in accordance with an example of the present
invention; and
[0017] FIG. 2 is a perspective view of the exterior part (outside
dimensions: length of 500 mm, width of 600 mm, and thickness of 2.5
mm) using a resin composition in accordance with an example of the
present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0018] In the following, the present invention is described in
detail by using examples. The examples are given for a person
skilled in the art only to more easily understand the present
invention. Hence the present invention is not limited to the
example, and can be variously modified without departing from the
scope of the present invention.
[0019] An exterior part for a copier or a printer (a copier/printer
exterior part 1 shown in FIG. 2) of the present invention is used
in a scanner which reads an original document, a copier which
prints the original document read by the scanner, a printer or a
facsimile apparatus which prints image data inputted from an
external apparatus, or a multifunctional machine called MFP (Multi
Function Peripheral) which has these functions. The copier/printer
exterior part 1 of the present invention is used for exterior parts
G1 to G9 of a copier shown in FIG. 1, for example. The
copier/printer exterior part 1 is provided with pin side gates 2 as
shown in FIG. 2.
[0020] In the following, an "unused" component indicates that the
component has not been used yet, and a "recycled" component
indicates that the component has been used before. That is, for
example, "unused polycarbonate (PC)" indicates that the PC has not
been used, and "recycled polycarbonate (PC)" indicates that the PC
has been used before. These are well known by a person skilled in
the art,
1. Examples 1 to 10 and Comparative Examples 1 to 16
1.1 Explanation of Components
[0021] Component A-1: unused PC having a weight average molecular
weight of 25000, produced by HONAM Petrochemical Corp.
[0022] Component A2: unused PC having a weight average molecular
weight of 21000, produced by HONAM Petrochemical Corp.
[0023] Component A-3: recycled PC having a weight average molecular
weight of 24000, on the market
[0024] Component B-1: recycled PET derived from PET bottles/sheets
for drinks, and having a viscosity of 0.8 dl/g, on the market
[0025] Component B-2: unused PET having a viscosity of 1.0 dug,
produced by Jinshan Petrochemical Company
[0026] Component C-1: styrene-acrylonitrile-glycidyl methacrylate
terpolymer containing 8 wt % glycidyl methacrylate and 28 wt %
acrylonitrile
[0027] Component C-2: styrene-acrylonitrile-glycidyl methacrylate
terpolymer containing 5 wt % glycidyl methacrylate and 28 wt %
acrylonitrile
[0028] Component C-3: styrene-acrylonitrile-glycidyl methacrylate
terpolymer containing 2 wt % glycidyl methacrylate and 28 wt %
acrylonitrile
[0029] Component C-3a: styrene-acrylonitrile-glycidyl methacrylate
terpolymer containing 2 wt % glycidyl methacrylate and 35 wt %
acrylonitrile
[0030] Component C-3b styrene-acrylonitrile-glycidyl methacrylate
terpolymer containing 2 wt % glycidyl methacrylate and 30 wt %
acrylonitrile
[0031] Component C-3c: styrene-acrylonitrile-glycidyl methacrylate
terpolymer containing 2 wt % glycidyl methacrylate and 27 wt %
acrylonitrile
[0032] Component C-3d: styrene-acrylonitrile-glycidyl methacrylate
terpolymer containing 2 wt % glycidyl methacrylate and 20 wt %
acrylonitrile
[0033] Component C-3e: styrene-acrylonitrile-glycidyl methacrylate
terpolymer containing 2 wt glycidyl methacrylate and 15 wt %
acrylonitrile
[0034] Component C-4: styrene-acrylonitrile-glycidyl methacrylate
terpolymer containing 1 wt % glycidyl methacrylate and 28 wt %
acrylonitrile
[0035] Component C-5: styrene-acrylonitrile-glycidyl methacrylate
terpolymer containing 0.5 wt % glycidyl methacrylate and 28 wt %
acrylonitrile
[0036] Component D-1: MBS EM-500, produced by LG Electronics
[0037] Component D-2: acrylic acid-silicone rubber system
toughener, S-2001, produced by Mitsubishi Rayon Co., Ltd.
[0038] Component D-3: acrylonitrile-butadiene-styrene copolymer
toughener containing 54 wt % butadiene, 34 wt % styrene and 12 wt %
acrylonitrile, produced by Korea Kumho Petrochemical Co., Ltd.
[0039] Component E: flame retardant, BDP, produced by Great Lakes
Chemical Corporation
[0040] Component P: flame-retardant antidrip agent, AS-coated
polytetrafluoroethylene system flame-retardant antidrip agent
containing 50 wt % polytetrafluoroethylene, on the market
[0041] Component G: processing aid containing, for example,
ethylenebisstearamide (lubricant), IRGAFOS.RTM. 168 (phosphite
(phosphoric acid ester) system antioxidant), IRGANOX.RTM. 1076
(hindered phenol system antioxidant), and DOW CORNING.RTM. MB-50
(lubricant), and having a weight ratio of ethylenebisstearamide,
IRGAFOS.RTM. 168, IRGANOX.RTM. 1076 anal DOW CORNING.RTM. M-50
being 2:2:1:1
1.2 Measuring Method of Mechanical Performance
[0042] Notched Izod Impact Strength: measured in accordance with
ASTM-D256 standard
[0043] MI (Melt Index): measured in accordance with ASTM-D1238
standard
[0044] FR (Flame Resistance): measured in accordance with UL 94
standard
1.3 Preparation Method of Examples 1-10 and Comparative Examples
1-16
(1) Examples 1 to 10
[0045] Each of Examples 1 to 10 provided a halogen-free
flame-retardant resin composition including recycled PC and
recycled PET.
[0046] The preparation method of the halogen-free flame-retardant
resin composition of each of Examples 1 to 10 included the
following steps of:
[0047] a) obtaining materials of the halogen-free flame-retardant
resin composition in accordance with the components and their
contents (wt %) shown in TABLE 1;
[0048] b) of the materials obtained at Step (a), sufficiently
mixing a recycled PET material and a styrene-acrylonitrile-glycidyl
methacrylate terpolymer material in a mixer so as to make a first
mixture, taking out the first mixture from the mixer, and placing
the first mixture in a screw extruder to extrude the first mixture
so as to produce a base grain (a first step in a two-step method as
a processing method); and
[0049] c) sufficiently mixing the base grain and the remaining
materials in the mixer so as to make a second mixture, taking out
the second mixture from the mixer, and placing the second mixture
in the screw extruder to extrude the second mixture so as to
produce a final grain as the halogen-free flame-retardant resin
composition (pellet) (a second step in the two-step method as the
processing method).
[0050] The mechanical performance of each obtained pellet was
examined. The result is shown in TABLE 1.
(2) Comparative Examples 1, 2, 8 and 9
[0051] Each of Comparative Examples 1, 2, 8 and 9 provided a
halogen-free flame-retardant resin composition including recycled
PC and recycled PET.
[0052] The preparation method of the halogen-free flame-retardant
resin composition of each of Comparative Examples 1, 2, 8 and 9
included the following steps of:
[0053] a) obtaining materials of the halogen-free flame-retardant
resin composition in accordance with the components and their
contents (wt %) shown in TABLE 2; and
[0054] b) sufficiently mixing the materials in a mixer so as to
make a mixture, taking out the mixture from the mixer, and placing
the mixture in a screw extruder to extrude the mixture so as to
produce a grain as the halogen-free flame-retardant resin
composition (pellet) (a one-step method as the processing
method).
[0055] The mechanical performance of each obtained pellet was
examined. The result is shown in TABLE 2.
(3) Comparative Examples 3 to 7 and 10
[0056] Each of Comparative Examples 3 to 7 and 10 provided a
halogen-free flame-retardant resin composition including recycled
PC and recycled PET
[0057] The preparation method of the halogen-free flame-retardant
resin composition of each of Comparative Examples 3 to 7 and 10
included the following steps of:
[0058] a) obtaining materials of the halogen-free flame-retardant
resin composition in accordance with the components and their
contents (wt %) shown in TABLE 2;
[0059] b) of the materials obtained at Step (a), sufficiently
mixing a recycled PET material and a styrene-acrylonitrile-glycidyl
methacrylate terpolymer material in a mixer so as to make a first
mixture, taking out the first mixture from the mixer, and placing
the first mixture in a screw extruder to extrude the first mixture
so as to produce a base grain (the first step in the two-step
method as the processing method); and
[0060] c) sufficiently mixing the base grain and the remaining
materials in the mixer so as to make a second mixture, taking out
the second mixture from the mixer, and placing the second mixture
in the screw extruder to extrude the second mixture so as to
produce a final grain as the halogen-free flame-retardant resin
composition (pellet) (the second step in the two-step method as the
processing method).
[0061] The mechanical performance of each obtained pellet was
examined. The result is shown in TABLE 2,
(4) Comparative Examples 11 to 16
[0062] Each of Comparative Examples 11 to 1$ provided a
halogen-free flame-retardant resin composition including recycled
PC and recycled PET.
[0063] The preparation method of the halogen-free flame-retardant
resin composition of each of Comparative Examples 11 to 16 included
the following steps of:
[0064] a) obtaining materials of the halogen-free flame-retardant
resin composition in accordance with the components and their
contents (wt %) shown in TABLE 3;
[0065] b) of the materials obtained at Step (a), sufficiently
mixing a recycled PET material and a styrene-acrylonitrile-glycidyl
methacrylate terpolymer material in a mixer so as to make a first
mixture, taking out the first mixture from the mixer, and placing
the first mixture in a screw extruder to extrude the first mixture
so as to produce a base grain (the first step in the two-step
method as the Processing method); and
[0066] c) sufficiently mixing the base grain and the remaining
materials in the mixer so as to make a second mixture, taking out
the second mixture from the mixer, and placing the second mixture
in the screw extruder to extrude the second mixture so as to
produce a final grain as the halogen-free flame-retardant resin
composition (pellet) (the second step in the two-step method as the
processing method).
[0067] The mechanical performance of each obtained pellet was
examined. The result is shown in TABLE 3.
1.4 Conclusion obtained from Examples 1 to 10 and Comparative
Examples 1 to 16
[0068] 1.4.1 It is preferable that the
styrene-acrylonitrile-glycidyl methacrylate terpolymer contain 1 wt
% to 5 wt % glycidyl methacrylate and 27 wt % to 30 wt %
acrylonitrile. (1) When Example 1 was compared with Comparative
Examples 3 and 4, as shown in TABLE 1 and TABLE 2, the notched Izod
impact strength ("impact strength" hereinafter) of Comparative
Examples 3 and 4 was significantly lower than that of Example 1.
The difference between Example 1 and Comparative Examples 3 and 4
was the component C. That is, Example 1, Comparative Example 3 and
Comparative Example 4 used the components C-3, C-1 and C-5,
respectively. Each of the components C-3, C-1 and C-5 was a
styrene-acrylonitrile-glycidyl methacrylate terpolymer containing
28 wt % acrylonitrile. However, the components C-3 (Example 1) C-1
(Comparative Example 3) and C-5 (Comparative Example 4) contained 2
wt %, 5 wt % and 0.5 wt % glycidyl methacrylate, respectively.
Therefore, it is indicated that the halogen-free flame-retardant
resin composition which contains the styrene-acrylonitrile-glycidyl
methacrylate terpolymer containing 2 wt % glycidyl methacrylate is
excellent in mechanical performance. (2) When Example 1 was
compared with Examples 5 and 6, as shown in TABLE 1, the impact
strength of Examples 1, 5 and 6 was high. Examples 1, 5 and 6 used
the components C-3, C-2 and C-4, respectively. Each of the
components C-3, C-2 and C-4 was a styrene-acrylonitrile-glycidyl
methacrylate terpolymer containing 28 wt % acrylonitrile. However,
the components C-3 (Example 1), C-2 (Example 5) and C-4 (Example 6)
contained 2 wt %, 5 wt % and 1 wt % glycidyl methacrylate,
respectively. Therefore, it is preferable that the component,
namely, the styrene-acrylonitrile-glycidyl methacrylate terpolymer,
contain 1 wt % to 5 wt % glycidyl methacrylate. (3) When Example 1
was compared with Comparative Examples 11, 12, 13, 14 and 15, as
shown in TABLE 1 and TABLE 3, the impact strength of Example 1 was
high, and the impact strength of Comparative Examples 12 and 13 was
relatively high too. The difference between Example 1 and
Comparative Examples 11, 12, 13, 14 and 15 was the content (wt %)
of acrylonitrile in the styrene-acrylonitrile-glycidyl methacrylate
terpolymer (component C-3, C-3a, C-3b, C-3c, C-3d or C-3e). The
contents of acrylonitrile of the components C-3 (Example 1), C-3a
(Comparative Example 11), C-3b (Comparative Example 12), C-3c
(Comparative Example 13), C-3d (Comparative Example 14) and C-3e
(Comparative Example 15) were 28 wt %, 35 wt %, 30 wt %, 27 wt %,
20 wt % and 15 wt %, respectively. Therefore, it is preferable that
the component, namely, the styrene-acrylonitrile-glycidyl
methacrylate terpolymer, contain 27 wt % to 30 wt
acrylonitrile.
[0069] In conclusion, when a styrene-acrylonitrile-glycidyl
methacrylate terpolymer is used in the halogen-free flame-retardant
resin composition, it is preferable that the terpolymer contain 1
wt % to 5 wt % glycidyl methacrylate and 27 wt % to 30 wt %
acrylonitrile.
1.4.2 It is preferable that the halogen-free flame-retardant resin
composition contain 0.2 wt % to 2 wt %
styrene-acrylonitrile-glycidyl methacrylate terpolymer.
[0070] When Examples 1, 7 and 8 were compared with each other, as
shown in TABLE 1, "Example 8>Example 1>Example 7" was true in
impact strength.
[0071] The difference between Examples 1, 7 and 8 was the content
of the component C-3. The contents of the component C-3 of Examples
1, 7 and 8 were 0.4 wt %, 0.2 wt % and 2 wt %, respectively.
[0072] When Comparative Examples 6 and 7 were compared with each
other, as shown in TABLE 2, the impact strength of Comparative
Example 6 was significantly lower than that of Comparative Example
7. When Comparative Example 7 and Example 6 were compared with each
other, as shown in TABLE 2 and TABLE 1, the impact strength of
Comparative Example 7 was almost the same as that of Example 8.
However, the melt index of Comparative Example 7 was lower than
that of Example 8. That is, the melt index decreased as the content
of the styrene-acrylonitrile-glycidyl methacrylate terpolymer
increased.
[0073] Furthermore, when Comparative Examples 1 and 2 were compared
with each other, as shown in TABLE 2, "Comparative Example
2>Comparative Example 1" was true in impact strength. This
indicates that the styrene-acrylonitrile-glycidyl methacrylate
terpolymer is very important in the halogen-free flame-retardant
resin composition, and can ensure impact strength to some extent.
In addition, when the content of the styrene-acrylonitrile-glycidyl
methacrylate terpolymer was less than 0.2 wt %, the
styrene-acrylonitrile-glycidyl methacrylate terpolymer did not
exert the favorable influence on the impact strength much. On the
other hand, when the content thereof was more than 2 wt %, the
impact strength did not improve any more, but the liquidity still
decreased.
[0074] In conclusion, it is preferable that the halogen-free
flame-retardant resin composition contain 0.2 wt. % to 2 wt %
styrene-acrylonitrile-glycidyl methacrylate terpolymer.
1.4.3 It is preferable that the halogen-free flame-retardant resin
composition is prepared by using the two-step method as the
processing method.
[0075] When Examples 1, 9 and 10 were compared with Comparative
Examples 1, 8 and 9, as shown in TABLE 1 and TABLE 2, the impact
strength of Examples 1, 9 and 10 was higher than that of
Comparative Examples 1, 8 and 9. This is because, as the processing
method, Examples 1, 9 and 10 used the two-step method while
Comparative Examples 1, 8 and 9 used the one-step method. This
indicates that the composition prepared by using the two-step
method as the processing method is excellent in impact strength)
and indicates that it is important to increase the viscosity of
recycled PET in advance in order to stabilize physical property
thereof
1.4.4 It is preferable that the halogen-free flame-retardant resin
composition contains less than 30 wt % recycled PET.
[0076] When Examples 1, 9 and 10 were compared with Comparative
Examples 1, 8, and 9, as shown in TABLE 1 and TABLE 2, the higher
the content of recycled PET was, the lower the impact strength was.
In addition, when the content of recycled PET was 30 wt % (or
more), the flame resistance became poor.
[0077] Furthermore, when Example 10 was compared with Comparative
Example 10, as shown in TABLE 1 and TABLE 2, the impact strength of
Comparative Example 10 was significantly lower than that of Example
10. The difference between Example 10 and Comparative Example 10
was the content of recycled PET. This indicates that, if the
halogen-free flame-retardant resin composition contains more than
30 wt recycled PET, the impact strength significantly decreases,
and may exert a bad influence on the composition in terms of
practical application.
[0078] In conclusion, it is preferable that, in terms of impact
strength and flame resistance, the halogen-free flame-retardant
resin composition contain less than 30 wt % recycled PET.
1.4.5 The styrene-acrylonitrile-glycidyl methacrylate terpolymer is
effective not only in increasing the viscosity of PET (recycled
PET), but also in preventing ester interchange of the PET, by
blocking the ends of the PET.
[0079] When Example 1 was compared with Comparative Example 16, as
shown in TABLE 1 and TABLE 3, "Example 1>Comparative Example 16"
was true in impact strength. The difference between Example 1 and
Comparative Example 16 was PET. Example 1 used recycled PET, and
the recycled PET had been processed by the component C-3, while
Comparative Example 16 used unused PET having a high viscosity.
This indicates that even if unused PET is used as PET in the
halogen-free flame-retardant resin composition, physical property
of the PET (the composite, by extension) varies, and indicates that
the styrene-acrylonitrile-glycidyl methacrylate terpolymer is
effective not only in increasing the viscosity of PET (recycled
PET), but also in preventing ester interchange of the PET, by
blocking the ends of the PET.
1.4.6 Influence of the content of recycled PC on the impact
strength can be controlled.
[0080] When Example 1 was compared with Example 4, as shown in
TABLE 1, the impact strength of Example 1 was almost the same as
that of Example 4 This indicates that the influence of the content
of recycled PC on the impact strength can be controlled.
1.4.7 The core-shell structured acrylate (acrylic ester) system
toughener and the core-shell, structured acrylate (acrylic
ester)-silicone rubber system toughener are relatively effective in
toughening the halogen-free flame-retardant resin composition.
[0081] When Examples 1, 2 and 3 were compared with each other, as
shown in TABLE 1, the impact strength thereof was almost the same.
The difference between Examples 1, 2 and 3 was the toughener.
Examples 1, 2 and 3 used, as the toughener, the components D1, D2
and D3, which is a mixture of the components D1 and D2,
respectively. This indicates that both the core-shell structured
acrylate system toughener and the core-shell structured
acrylate-silicone rubber system toughener are relatively effective
in toughening the composition.
TABLE-US-00001 TABLE 1 EXAMPLE EXAM- EXAM- EXAM- EXAM- EXAM- EXAM-
EXAM- EXAM- EXAM- EXAM- PLE 1 PLE 2 PLE 3 PLE 4 PLE 5 PLE 6 PLE 7
PLE 8 PLE 9 PLE 10 COMPONENT 16 16 16 3 16 16 16 15 12.4 10 A-1
COMPONENT 16.5 16.5 16.5 3.5 16.5 16.5 16.5 15.9 13 10.2 A-2
COMPONENT 32.5 32.5 32.5 58.5 32.5 32.5 32.5 32.5 25.4 20.2 A-3
COMPONENT 10 10 10 10 10 10 10 10 20 30 B-1 COMPONENT B-2 COMPONENT
C-1 COMPONENT 0.4 C-2 COMPONENT 0.4 0.4 0.4 0.4 0.2 2 1 1.4 C-3
COMPONENT 0.4 C-4 COMPONENT C-5 COMPONENT 8.9 5 8.9 8.9 8.9 9.1 8.9
11.9 14.8 D-1 COMPONENT 8.9 D-2 COMPONENT 3.9 D-3 COMPONENT 14.4
14.4 14.4 14.4 14.4 14.4 14.4 14.4 14.9 12.4 E COMPONENT 0.3 0.3
0.3 0.3 0.3 0.3 0.3 0.3 0.4 F COMPONENT 1 1 1 1 1 1 1 1 1 1 G
PROCESSING TWO- TWO- TWO- TWO- TWO- TWO- TWO- TWO- TWO- TWO- METHOD
STEP STEP STEP STEP STEP STEP STEP STEP STEP STEP METHOD METHOD
METHOD METHOD METHOD METHOD METHOD METHOD METHOD METHOD NOTCHED
IZOD 532.6 541.6 489.3 527.9 542.1 562.3 356.5 554.4 455.7 334.7
IMPACT STRENGTH [J/m], 1/8 in MI [g/10 min] 27.5 28.2 27.5 28.6
27.8 27.2 28.2 25.2 35.2 41.3 265.degree. C. .times. 2.16 kg FR,
1/16 in V0 V0 V0 V0 V0 V0 V0 V0 V0 V2
TABLE-US-00002 TABLE 2 COMPARATIVE EXAMPLE COMPARATIVE COMPARATIVE
COMPARATIVE COMPARATIVE COMPARATIVE EXAMPLE 1 EXAMPLE 2 EXAMPLE 3
EXAMPLE 4 EXAMPLE 5 COMPONENT 16 16 16 16 32.5 A-1 COMPONENT 16.7
16.5 16.5 16.5 32.5 A-2 COMPONENT 32.7 32.5 32.5 32.5 A-3 COMPONENT
10 10 10 10 10 B-1 COMPONENT B-2 COMPONENT 0.4 C-1 COMPONENT C-2
COMPONENT 0.4 0.4 C-3 COMPONENT C-4 COMPONENT 0.4 C-5 COMPONENT 8.9
8.9 8.9 8.9 8.9 D-1 COMPONENT D-2 COMPONENT D-3 COMPONENT 14.4 14.4
14.4 14.4 144 E COMPONENT 0.3 0.3 0.3 0.3 0.3 F COMPONENT 1 1 1 1 1
G PROCESSING ONE-STEP ONE-STEP TWO-STEP TWO-STEP TWO-STEP METHOD
METHOD METHOD METHOD METHOD METHOD NOTCHED IZOD 138.7 258.7 182.5
212.3 572.6 IMPACT STRENGTH [J/m], 1/8 in MI [g/10 min], 30.6 25.6
28.5 28.9 27.8 265.degree. C. .times. 2.16 kg FR, 1/16 in V0 V0 V0
V0 V0 COMPARATIVE EXAMPLE COMPARATIVE COMPARATIVE COMPARATIVE
COMPARATIVE COMPARATIVE EXAMPLE 6 EXAMPLE 7 EXAMPLE 8 EXAMPLE 9
EXAMPLE 10 COMPONENT 16 15 12.4 10 8.6 A-1 COMPONENT 16.5 15.7 13
10.2 9 A-2 COMPONENT 32.5 32.5 25.4 20.2 17.6 A-3 COMPONENT 10 10
20 30 33 B-1 COMPONENT B-2 COMPONENT C-1 COMPONENT C-2 COMPONENT
0.1 2.2 1 1.4 1.6 C-3 COMPONENT C-4 COMPONENT C-5 COMPONENT 9.2 8.9
11.9 14.8 16.8 D-1 COMPONENT D-2 COMPONENT D-3 COMPONENT 144 14.4
14.9 12.4 12.4 E COMPONENT 0.3 0.3 0.4 F COMPONENT 1 1 1 1 1 G
PROCESSING TWO-STEP TWO-STEP ONE-STEP ONE-STEP TWO-STEP METHOD
METHOD METHOD METHODS METHOD METHOD NOTCHED IZOD 152.1 532.1 95.6
78.6 119.3 IMPACT STRENGTH [J/m], 1/8 in MI [g/10 min], 30.9 24.9
35.6 39.3 43.2 265.degree. C. .times. 2.16 kg FR, 1/16 in V0 V0 V0
V2 V2
TABLE-US-00003 TABLE 3 COMPARATIVE EXAMPLE COMPARATIVE COMPARATIVE
COMPARATIVE COMPARATIVE COMPARATIVE COMPARATIVE EXAMPLE 11 EXAMPLE
12 EXAMPLE 13 EXAMPLE 14 EXAMPLE 14 EXAMPLE 16 COMPONENT 16 16 16
16 16 16 A-1 COMPONENT 16.5 16.5 16.5 16.5 16.5 16.5 A-2 COMPONENT
32.5 32.5 32.5 32.5 32.5 32.5 A-3 COMPONENT 10 10 10 10 10 B-1
COMPONENT 10 B-2 COMPONENT 0.4 C-1 COMPONENT 0.4 C-3a COMPONENT 0.4
C-3b COMPONENT 0.4 C-3c COMPONENT 0.4 C-3d COMPONENT 0.4 C-3e
COMPONENT 8.9 8.9 8.9 8.9 8.9 9.3 D-1 COMPONENT 14.4 14.4 14.4 14.4
14.4 14.4 E COMPONENT 0.3 0.3 0.3 0.3 0.3 0.3 F COMPONENT 1 1 1 1 1
1 G PROCESSING TWO-STEP TWO-STEP TWO-STEP TWO-STEP TWO-STEP
TWO-STEP METHOD METHOD METHOD METHOD METHOD METHOD METHOD NOTCHED
IZOD 334.2 451.1 466.2 241.5 231.5 335.3 IMPACT STRENGTH [J/m], 1/8
in MI [g/10 min], 26.8 27.2 28.1 28.5 28.9 26.5 265.degree. C.
.times. 2.16 kg FR, 1/16 in V0 V0 V0 V0 V0 V0
2. Examples 11 to 14
2.1 Explanation of Components
[0082] Component A-1a: Unused PC, bisphenol A type aromatic
polycarbonate having a weight average molecular weight of 10000
[0083] Component A-2a: Unused PC, bisphenol A type aromatic
polycarbonate having a weight average molecular weight of 40000
[0084] Component A-3a: Recycled PC, bis phenol A type aromatic
polycarbonate having a weight average molecular weight of 10000
[0085] Component A-3b: Recycled PC, bisphenol A type aromatic
polycarbonate having a weight average molecular weight of 40000
[0086] Component B-1a: Recycled PET having a viscosity of 0.65
dl/g, on the market
[0087] Component 13-1b: Recycled PET having a viscosity of 0.90
dl/g, on the market
[0088] Component C-6: styrene-acrylonitrile-glycidyl methacrylate
terpolymer containing 2 wt % glycidyl methacrylate and 33 wt %
acrylonitrile, produced in-house
[0089] Component C-7: styrene-acrylonitrile-glycidyl methacrylate
terpolymer containing 3 wt % glycidyl methacrylate and 20 wt %
acrylonitrile, produced in-house
[0090] Component D-4: ethylene-methyl acrylate copolymer and
ethylene-methyl acrylate-glycidyl methacrylate copolymer having a
weight ratio of ethylene-methyl acrylate copolymer to
ethylene-methyl acrylate-glycidyl methacrylate copolymer being
1:1
[0091] Component D-5; methyl methacrylate-silicone rubber copolymer
and acrylonitrile-butadiene-acrylic ester copolymer having a weight
ratio of methyl methacrylate silicone rubber copolymer to
acrylonitrile-butadiene-acrylate copolymer being 1:1
[0092] Component E-1: resorcinol bis(diphenyl phosphate)
[0093] Component E-2: tri ethyl phosphate and diphenyl
pentaerythritol diphosphate having a weight ratio of
trimethylphosphate to diphenyl pentaerythritol diphosphate being
1:2.
[0094] Component F: flame-retardant antidrip agent, AS-coated
polytetrafluoroethylene system flame-retardant antidrip agent
containing 50 wt % polytetrafluoroethylene, on the market
[0095] Component G-1a: antioxidant,
bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite
[0096] Component G-1b: antioxidant, pentaerythritol
tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and
tris(2,4-di-tert-butylphenyl)phosphite having a weight ratio of
pentaerythritol
tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) to
tris(2,4-ditert-butylphenyl)phosphite being 1:1
[0097] Component G-2a: lubricant, methylenebisstearic acid
amide
[0098] Component G-2b: lubricant, zinc stearate and silane
polymer
2.2 Measuring Method of Mechanical Performance
[0099] Notched Izod Impact Strength: measured in accordance with
ASTM-D256 standard
[0100] MI (Melt Index): measured in accordance with ASTM-D1238
standard
[0101] FR (Flame Resistance): measured in accordance with UL 94
standard
2.3 Preparation Method of Examples 11 to 14
[0102] Each of Examples 11 to 14 provided a halogen-free
flame-retardant resin composition including recycled PC and
recycled PET.
[0103] The preparation method of the halogen-free flame-retardant
resin composition of each of Examples 11 to 14 included the
following steps of:
[0104] a) obtaining materials of the halogen-free flame-retardant
resin composition in accordance with the components and their
contents (wt %) shown in TABLE 4;
[0105] b) of the materials, sufficiently mixing a recycled
polyethylene terephthalate material and a
styrene-acrylonitrile-glycidyl methacrylate terpolymer material in
a mixer so as to make a first mixture, taking out the first mixture
from the mixer, and placing the first mixture in a screw extruder
to extrude the first mixture so as to produce a base grain (the
first step in the two-step method as the processing method);
and
[0106] c) sufficiently mixing the base grain and the remaining
materials in the mixer so as to make a second mixture, taking out
the second mixture from the mixer, and placing the second mixture
in the screw extruder to extrude the second mixture so as to
produce a final grain as the halogen-free flame-retardant resin
composition (pellet) (the second step in the two-step method as the
processing method).
[0107] The mechanical performance of each obtained pellet was
examined. The result is shown in TABLE 4.
2.4 Conclusion Obtained from Examples 11 to 14
[0108] As shown in TABLE 4, the halogen-free flame-retardant resin
compositions, each of which included recycled PC and recycled PET,
prepared as Examples 11 to 14 were, overall, excellent in impact
strength and the like, and also excellent in stability of the
impact strength (mechanical performance)
TABLE-US-00004 TABLE 4 EXAMPLE EXAMPLE 11 EXAMPLE 12 EXAMPLE 13
EXAMPLE 14 UNUSED PC A-1a, 5 A-2a, 50 A-1a, 13 A-2a, 25 RECYCLED PC
A-3a, 63 A-3b, 20 A-3b, 20 A-3a, 37 RECYCLED PET B-1a, 5 B-1b, 7.5
B-1b, 35 B-1a, 15 STYRENE-ACRYLONITRILE- C-6, 1 C-7, 0.5 C-7, 1
C-6, 1 GLYCIDYL METHACRYLATE TERPOLYMER TOUGHENER D-4, 15 D-5, 5
D-5, 8 D-4, 8 FLAME RETARDANT E-1, 10 E-2, 15 E-2, 20 E-1, 12
FLAME-RETARDANT ANTIDRIP AGENT F, 0.8 F, 0.1 F, 0.5 F, 0.5
ANTIOXIDANT G-1a, 0.1 G-1b, 1 G-1b, 0.5 G-1a, 0.5 LUBRICANT G-2a,
0.1 G-2b, 0.9 G-2b, 2 G-2a, 1 PROCESSING METHOD TWO-STEP METHOD
TWO-STEP METHOD TWO-STEP METHOD TWO-STEP METHOD NOTCHED IZOD IMPACT
STRENGTH [J/m], 1/8 in 289.3 614.3 112.1 346.5 MI [g/10 min],
265.degree. C. .times. 216 kg 23.9 19.3 46.5 35.5 FR, 1/16 in N/A
V0 N/A V2
[0109] As described above, in the present invention, recycled PET
and a styrene-acrylonitrile-glycidyl methacrylate terpolymer (a
first mixture) are extruded together to produce a base grain.
Consequently, by glycidyl methacrylate, the viscosity of the
recycled PET is increased, and the ends thereof are blocked.
Accordingly, molecular weights thereof are increased, and
distribution of the molecular weights becomes stable, so that ester
interchange can be controlled. Accordingly, a halogen-free
flame-retardant resin composition including recycled. PC and
recycled PET of the present invention is excellent in impact
strength, has high stability of the impact stretch (mechanical
performance), and reduces costs of a product to which the
composition is applied
3. Manufacturing of Exterior Part
[0110] Each of the obtained pellets (compositions) as Examples 1 to
14 and Comparative Examples 1 to 16 was dried for five hours at
100.degree. C. with a hot-air circulation system dryer. After
dried, the pellet was molded at a cylinder temperature of
250.degree. C. and a die temperature of 80.degree. C. by using an
injection molding machine (J1300E-C5, produced by The Japan Steel
Works, LTD.) to manufacture the copier/printer exterior part 1
shown in FIG. 2. Then, a sample was extracted from the center
thereof. External appearance of each sample was evaluated. The
result is shown in TABLE 5 and TABLE 6.
[0111] The evaluation on the external appearance of each sample,
namely, each product (copier/printer exterior part 1), was
evaluated by visually observing the external appearance of the
sample. The criteria are as follows.
[0112] .circleincircle. (double circle): [0113] There is no problem
or the external appearance.
[0114] .largecircle.(circle): [0115] Burned spots and/or burrs are
slightly seen, but they are not a problem as a product.
[0116] X (cross): [0117] Burned spots and/or burrs are seen, and
they are a problem as a product.
TABLE-US-00005 [0117] TABLE 5 EXAMPLE EXAMPLE EXAMPLE EXAMPLE
EXAMPLE EXAMPLE EXAMPLE EXAMPLE 1 2 3 4 5 6 7 EXTERNAL
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .circleincircle. APPEARANCE
EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE 8 9
10 11 12 13 14 EXTERNAL .circleincircle. .largecircle.
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. APPEARANCE
TABLE-US-00006 TABLE 6 COMPARATIVE EXAMPLE COMPAR- COMPAR- COMPAR-
COMPAR- COMPAR- COMPAR- COMPAR- COMPAR- ATIVE ATIVE ATIVE ATIVE
ATIVE ATIVE ATIVE ATIVE EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM-
EXAM- PLE 1 PLE 2 PLE 3 PLE 4 PLE 5 PLE 6 PLE 7 PLE 8 EXTERNAL
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. X .largecircle. APPEARANCE COMPARATIVE
EXAMPLE COMPAR- COMPAR- COMPAR- COMPAR- COMPAR- COMPAR- COMPAR-
COMPAR- ATIVE ATIVE ATIVE ATIVE ATIVE ATIVE ATIVE ATIVE EXAM- EXAM-
EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- PLE 9 PLE 10 PLE 11 PLE 12 PLEE
13 PLE 14 PLE 15 PLE 16 EXTERNAL .largecircle. X .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. APPEARANCE
[0118] When Examples 1 to 14 were compared with Comparative
Examples 1 to 16, as shown in TABLE 5 and TABLE 6, the
copier/printer exterior parts 1 manufactured by using the
compositions of Examples 1 to 14 were better in external
appearance.
[0119] According to an aspect of the examples of the present
invention, there is provided a copier/printer exterior part using a
halogen-free flame-retardant resin composition including: 5 wt % to
50 wt % of unused polycarbonate; 20 wt % to 63 wt % of recycled
polycarbonate; 5 wt % to 35 wt % of recycled polyethylene
terephthalate; 0.2 wt 2 wt % of a
styrene-acrylonitrile-glycidylmethacrylateterpolymer; 5 wt % to 15
wt % of a toughener; 10 wt % to 20 wt % of a flame retardant; 0.1
wt % to 0.8 wt % of a flame-retardant antidrip agent; 0.1 wt % to 1
wt % of an antioxidant; and 0.1 wt % to 2 wt % of a lubricant,
wherein the styrene-acrylonitrile-glycidyl methacrylate terpolymer
includes 1 wt % to 5 wt % of glycidyl methacrylate and 20 wt % to
33 wt % of acrylonitrile:
[0120] Preferably, in the copier/printer exterior part, the
styrene-acrylonitrile-glycidyl methacrylate terpolymer includes 1
wt % to 5 wt % of glycidyl methacrylate and 27 wt % to 30 wt % of
acrylonitrile.
[0121] Preferably, in the copier/printer exterior part, the unused
polycarbonate is bisphenol A type aromatic polycarbonate having a
weight average molecular weight of 10000 to 40000.
[0122] Preferably, in the copier/printer exterior part, the
recycled polycarbonate is bisphenol A type aromatic polycarbonate
having a weight average molecular weight of 10000 to 40000.
[0123] Preferably, in the copier/printer exterior part, the
recycled polyethylene terephthalate has a viscosity of 0.65 dl/g to
0.9 dl/g.
[0124] Preferably, in the copier/printer exterior part, the
toughener is at least one of a core-shell structured acrylate
system toughener, a core-shell structured acrylate-silicone rubber
system toughener, a core-shell structured styrene system toughener,
a long-chain type toughener, and a reaction type terpolymer
toughener.
[0125] Preferably, in the copier/printer exterior part, the
toughener is at least one of a core-shell structured acrylate
system toughener and a core-shell structured acrylate-silicone
rubber system toughener.
[0126] Preferably, in the copier/printer exterior part, the
core-shell structured acrylate system toughener is a methyl
methacrylate-butadiene-styrene copolymer, an
acrylonitrile-butadiene-acrylate copolymer, or a methyl
methacrylate-butyl methacrylate copolymer, the core-shell
structured acrylate-silicone rubber system toughener is a methyl
methacrylate-silicone rubber copolymer, the core-shell structured
styrene system toughener is an acrylonitrile-styrene-butadiene
terpolymer, the long chain type toughener is an ethylene-methyl
acrylate copolymer or an ethylene-butyl acrylate copolymer, and the
reaction type terpolymer toughener is an ethylene-methyl
acrylate-glycidyl methacrylate copolymer or an ethylene-butyl
acrylate-glycidyl methacrylate copolymer.
[0127] Preferably, in the copier/printer exterior part, the flame
retardant is a phosphate type flame retardant.
[0128] Preferably, in the copier/printer exterior part, the
phosphate type flame retardant is at least one of a monophosphate
type flame retardant and an oligophosphate type flame
retardant.
[0129] Preferably, in the copier/printer exterior part, the
monophosphate type flame retardant is trimethyl phosphate, triethyl
phosphate, triphenyl phosphate, dimethylphenyl phosphate, tributyl
phosphate, or xylyl diphenyl phosphate, and the oligophosphate type
flame retardant is resorcinol bis(diphenyl phosphate), bisphenol A
bis(diphenyl phosphate), or diphenyl pentaerythritol
diphosphate.
[0130] Preferably, in the copier/printer exterior part, the
antioxidant is at least one of a hindered phenol system antioxidant
and a phosphite system antioxidant.
[0131] Preferably, in the copier/printer exterior part, the
hindered phenol system antioxidant is triethylene glycol
bis[.beta.-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate],
pentaerythritol
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], or
n-octadecyl-.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate,
and the phosphite system antioxidant is
tris(2,4-di-tert-butylphenyl)phosphite or
bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite.
[0132] Preferably, in the copier/printer exterior part, the
lubricant is at least one of fatty acid salt, fatty acid amide a
silane polymer, solid paraffin, liquid paraffin, calcium stearate,
zinc stearate, octadecanamide, silicone powder, methylene
bis(octadecanamide), and N,N'-ethylene bis(octadecanamide).
[0133] Preferably, in the copier/printer exterior part, the
flame-retardant antidrip agent is a polytetrafluoroethylene system
flame-retardant antidrip agent.
[0134] Preferably, in the copier/printer exterior part, the
halogen-free flame-retardant resin composition is obtained by:
obtaining materials of the halogen-free flame-retardant resin
composition; of the materials, sufficiently mixing a recycled
polyethylene terephthalate material and a
styrene-acrylonitrile-glycidyl methacrylate terpolymer material in
a mixer so as to make a first mixture, taking out the first mixture
from the mixer, and placing the first mixture in a screw extruder
to extrude the first mixture so as to produce a base grain; and
sufficiently mixing the base grain and the remaining materials in
the mixer so as to make a second mixture, taking out the second
mixture from the mixer, and placing the second mixture in the screw
extruder to extrude the second mixture so as to produce a final
grain as the halogen-free flame-retardant resin composition.
[0135] According to the present invention, recycled PET and a
styrene-acrylonitrile-glycidyl methacrylate terpolymer, namely, a
first mixture, are extruded to produce a base grain. Consequently,
by glycidyl methacrylate, the viscosity of the recycled PET is
increased, and the ends thereof are blocked. Accordingly, molecular
weights thereof are increased, and distribution of the molecular
weights becomes stable, so that ester interchange can be
controlled. Accordingly, a halogen-free flame-retardant resin
composition including recycled PC and recycled PET of the present
invention is excellent in impact strength, has high stability of
the excellent impact strength (mechanical performance), and reduces
costs of a product to which the composition is applied.
[0136] The halogen-free flame-retardant resin composition of the
present invention can be applied, for example, to household
electric appliance or office automation equipment, so that the
halogen-free flame-retardant composition can replace a halogen-free
frame-retardant polycarbonate/acrylonitrile-butadiene-styrene
(PC/ABS) used in the household electric appliance or the office
automation equipment.
[0137] This application is based upon and claims the benefit of
priority under 35 USC 119 of Chinese Patent Application No.
201210016861.X filed Jan. 18, 2012, the entire disclosure of which,
including the description, claims, drawings, and abstract, is
incorporated herein by reference in its entirety.
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