Method of bonding vulcanized rubber to resin

A composite composed of vulcanized rubber and thermoplastic resin which adheres tightly to the rubber can be obtained by treating the surface of the vulcanized rubber with at least one of halogen, halogen generating compound and halogenoid, and bonding melted polyamide resin, polyester resin, styrene series resin or acrylic resin to the above treated rubber surface region by the injection or extrusion molding.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a method of bonding vulcanized rubber to 
resin. 2. Description of the Prior Art 
Among recently developed various thermoplastic resins, resins called as 
engineering plastics are known. These resins are polyamide resin, 
polyester resin, polycarbonate resin, polyacetal resin, polysulfone resin, 
silicone resin, polyphenylene oxide resin, polyimide resin, ABS resin, 
methacrylic resin and the like, and many of them are excellent in 
mechanical strength, heat resistance, creep resistance, chemical 
resistance, electrical property, dimensional stability and the like, and 
can be widely used in place of metals, such as iron, zinc, aluminum and 
the like, under various use conditions. 
In general, industrial rubber products are composites composed of rubber 
and metal; rubber and plastics; and rubber and inorganic substance, but 
major part of the rubber products are composites composed of rubber and 
metal. However, in recent industrial rubber products, the rubber-metal 
composite tends to be replaced by a rubber-resin composite. Industrial 
rubber composites are now required to have a light weight, excellent 
corrosion resistance, chemical resistance, wear resistance and electrical 
property, and a low friction coefficient. 
When the composites of rubber and plastics are produced, the rubber must be 
tightly bonded to the plastics. In the conventional method for bonding 
rubber to plastics, a chlorine-containing adhesive is applied on the 
surface of a resin molded article obtained by the extrusion molding and 
the resin molded article is bonded to an unvulcanized rubber through the 
adhesive layer by vulcanization. However, this method of bonding resin 
molded article to rubber through vulcanization has the following 
drawbacks. That is, the adhesion strength between the resin molded article 
and the rubber lowers or the resin molded article cracks due to the 
repeating cooling and heating cycles or to the heat aging during the 
vulcanization step, and further the adhesion strength varies depending 
upon the kind of the resin. Moreover, when thermoplastic resins having a 
low melting point are used among thermoplastic resins, the resin molded 
article deforms due to the high temperature and pressure during the 
vulcanization. 
SUMMARY OF THE INVENTION 
In order to obviate the above described drawbacks, the inventors have made 
various investigations with respect to treating agents for the surface of 
a vulcanized rubber in a method of bonding a vulcanized rubber to a resin. 
The surface of the vulcanized rubber is treated with a treating agent to 
form a treated rubber surface region, and a previously melted polyamide 
resin, polyester resin, styrene series resin or acrylic resin is bonded to 
the above treated rubber surface region through an injection molding or 
extrusion molding. The inventors found a method of bonding tightly the 
vulcanized rubber to the resin to produce rubber products having a high 
dimensional accuracy, and accomplished the present invention. 
That is, the feature of the present invention is a method of bonding 
vulcanized rubber to resin, comprising treating the surface of a 
vulcanized rubber with at least one member selected from the group 
consisting of halogen, halogen generating compound and halogenoid to form 
a treated rubber surface region, and bonding a heated and melted resin 
selected from the group consisting of polyamide resin, polyester resin, 
styrene series resin and acrylic resin to the above treated rubber surface 
region by the injection or extrusion molding. 
According to the present invention, a vulcanized rubber having an optional 
shape is previously prepared, the rubber is treated with at least one of 
halogen, halogen generating compound and halogenoid at the surface to be 
bonded to a resin, the thus treated vulcanized rubber is placed in a metal 
mold, and the above described specifically limited resin previously heated 
and melted is bonded to the above treated rubber surface region by 
injection or extrusion molding to produce a composite composed of the 
rubber and the resin bonded tightly thereto at the interface. Moreover, in 
the present invention, vulcanized rubber is treated with a solution or the 
like at the surface to be bonded to resin without subjecting the surface 
to mechanical treatment, such as buffing by means of emery paper, grinder 
and the like, and therefore composites having a precise and complicated 
shape can be produced.

DESCRIPTION OF THE PREFERRED EMBODIMENT 
The present invention will be explained in more detail. 
As the rubber component of the vulcanized rubbers to be used in the present 
invention, there can be used natural rubber (NR) and synthetic rubber 
having carbon-carbon double bonds in the structural formula alone or in 
admixture of at least two of the rubbers. The synthetic rubbers include 
polyisoprene rubber (IR), polybutadiene rubber (BR), polychloroprene 
rubber and the like, which are homopolymers of conjugated diene compounds, 
such as isoprene, butadiene, chloroprene and the like; styrene-butadiene 
copolymer rubber (SBR), vinylpyridine-butadiene-styrene copolymer rubber, 
acrylonitrile-butadiene copolymer rubber, acrylic acid-butadiene copolymer 
rubber, methacrylic acid-butadiene copolymer rubber, methyl 
acrylate-butadiene copolymer rubber, methyl methacrylate-butadiene 
copolymer rubber and the like, which are copolymers of the above described 
conjufated diene compounds with vinyl compounds, such as styrene, 
acrylonitrile, vinylpyridiene, acrylic acid, methacrylic acid, alkyl 
arcylates, alkyl methacrylates and the like; copolymers of olefins, such 
as ethylene, propylene, isobutylene and the like, with diene compounds, 
for example, isobutylene-isoprene copolymer rubber (IIR); copolymers 
(EPDM) of olefins with nonconjugated diene, for example, 
ethylene-propylene-cyclopentadiene terpolymer, 
ethylene-propylene-5-ethyldiene-2-norbornane terpolymer, 
ethylene-propylene-1,4-hexadiene terpolymer; polyalkenamer obtained by the 
ring opening polymerization of cycloolefin, for example, polypentanamer; 
rubber obtained by the ring opening polymerization of oxirane ring, for 
example, sulfur-vulcanizable polyepichlorohydrin rubber and polypropylene 
oxide rubber; and the like. The rubber components of the vulcanized rubber 
of the present invention further include halogenides of the above 
described rubbers, for example, chlorinated isobutylene-isoprene copolymer 
rubber (Cl-IIR), broninated isobutylene-isoprene copolymer rubber 
(Br-IIR), polynorbornane rubber and the like. 
The vulcanized rubber to be used in the present invention is obtained in 
the following manner. The above described rubber is fully kneaded together 
with fillers, such as carbon black, silica, calcium carbonate, calcium 
sulfate, clay, diatomaceous earth, mica and the like; softeners, such as 
mineral oil, vegetable oil, synthetic plasticizer and the like; 
vulcanization accelerators, such as stearic acid and the like; 
antioxidant, crosslinking agent and promoter and the like in a kneader, 
and the resulting homogeneous mixture is vulcanized under a proper 
vulcanization condition. 
The vulcanized rubbers to be used in the present invention include not only 
vulcanized rubbers obtained by the commonly known and most important 
sulfur vulcanization, but also all vulcanized rubbers obtained by the 
thiurum vulcanization, peroxide vulcanization, quinoide vulcanization, 
resin vulcanization, metal salt vulcanization, metal oxide vulcanization, 
polyamine vulcanization, radiation vulcanization, hexamethylenetetramine 
vulcanization and the like. 
The halogens to be used in the treatment of the vulcanized rubber surface 
include chlorine, bromine and iodine. These halogens are used in the form 
of molecule and an aqueous solution thereof. The halogen generating 
compounds include hypochlorous acid and hypobromous acid, and are used as 
such or in the form of an aqueous solution thereof. 
The halogenoids include halogenated isocyanate, N-monohaloalkylurethane, 
N,N-dihaloalkylurethane, N,N-dihaloarylsulfonamide, sulfur halide, 
sulfenyl halide, halomethyl ether, thiocyanogen, iodine azide, bromine 
azide, iodine chloride, iodine bromide, trichloroacetic acid iodide, 
acetic acid bromide, iodine nitrate, alkyl hypohalite, alkyl 
thionylchloride, aryl thionylchloride, nitrosyl chloride, nitrosyl 
bromide, halogenated isocyanuric acid, halogenated methylhydantoin and the 
like. 
Among the above described treating agents, the use of halogenoids, 
particularly the use of halogenated isocyanate, N,N-dihaloalkylurethane, 
N,N-dihaloarylsulfonamide, alkyl hypohalite, halogenated isocyanuric acid, 
halogenated methylhydantoin and the like is suitable for attaining the 
object of the present invention in view of the performance, treating 
processability and safety treatment. 
The halogenoids are concretely iodine isocyanate, 
N,N-dichloroethylurethane, N,N-dibromoethylurethane, 
N,N-dichloropropylurethane, N,N-dibromopropylurethane, 
N,N-dichlorodibenzylurethane, N,N-dibromobenzylurethane, 
N,N-dichloro-p-toluenesulfonamide, N,N-dibromotoluenesulfonamide, 
N,N-dichlorobenzenesulfonamide, N,N-dibromobenzenesulfonamide, 
tertiary-butyl hypohalite, trichloroisocyanuric acid, dichloroisocyanuric 
acid, dibromo-dimethylhydantoin, dichloro-dimethylhydantoin, 
dichloro-methyl-isobutylhydantoin, dichloro-methylhexylhydantoin and the 
like. 
When the vulcanized rubber surface is treated with the halogenoid in the 
present invention, the halogenoid is dissolved in a proper solvent and 
used in a concentration of 0.1-20% by weight, preferably, 1-15% by weight. 
As the solvent, mention may be made of halogenated hydrocarbons, such as 
carbon tetrachloride, chloroform, dichloromethane and the like; aromatic 
hydrocarbons, such as benzene, nitrobenzene, halogenated benzene, toluene, 
xylene and the like; chain or cyclic ethers, such as dimethyl ether, 
diethyl ether, tetrahydrofuran (THF), dioxane and the like; esters, such 
as ethyl acetate and the like; aliphatic hydroxarbons, such as pentane, 
hexane, heptane, octane, cyclohexane and the like; ketones, such as 
acetone, cyclohexanone, methyl ethyl ketone and the like; alcohols, such 
as tertiary butyl alcohol and the like. Among them, tetrahydrofuran, 
dioxane, acetone, benzene, toluene, carbon tetrachloride, chloroform, 
methyl ethyl ketone and ethyl acetate are preferably used. 
As a method of forming a treated rubber surface region by treating a rubber 
surface with the above described treating agent, any industrial technique 
capable of making the rubber surface in contact with the treating agent 
can be adopted. This includes brushing, spraying, dipping and the like. 
The resin to be bonded to the vulcanized rubber in the present invention is 
selected from polyamide resin, polyester resin, styrene series resin and 
acrylic resin. 
As the polyamide resin, there can be used nylon-6, nylon-11, nylon-12, 
nylon-66, nylon-610 and their copolymers and blends, and their modified 
polymers obtained by modifying a part of the functional groups of the 
polyamides. 
As the polyester resin, there can advantageously be used polyethylene 
terephthalate, polybutylene terephthalate and their copolymers and blends, 
and their modified polymers obtained by modifying a part of the functional 
groups of the polyesters. Of course, other polyester resins can be used as 
well. 
As the styrene series resin, there can be used polystyrene resin, styrene 
copolymer resins, such as ethylene propylene nonconjugated 
diene-styrene-acrylonitrile copolymer resin (EPSAN resin), 
acrylonitrile-acrylic-styrene copolymer resin (AAS resin), 
acrylonitrile-styrene copolymer resin (AS resin), 
acrylonitrile-butadiene-styrene copolymer resin (ABS resin), 
butadiene-methyl methacrylate copolymer resin (MBS resin) and the like, 
and blends thereof, and their modified polymers obtained by modifying a 
part of the functional groups or carbon-carbon double bonds of the 
polystyrene or styrene copolymers. 
As the acrylic resin, there can be used polyacrylic acid resin, 
polymethacrylic acid resin, polyacrylamide resin, polyacrylonitrile resin, 
and their copolymers and blends, and their modified polymers obtained by 
modifying a part of the functional groups of the acrylic polymers. 
The above described resins can be mixed with inorganic fillers, such as 
glass fibers, calcium carbonate, talc and the like, coloring agent, 
ultraviolet ray absorber and the like, which are commonly added to 
plastics. 
Further, the above described resins can be mixed with other thermoplastic 
resins in order to improve the processability and adhesion of the resins. 
The above described resins are bonded to the treated surface region of a 
vulcanized rubber in the following manner. A previously melted resin is 
injected or extruded on the treated rubber surface region, and the 
resulting assembly is cooled to cure the resins. 
The following examples are given for the purpose of illustration of this 
invention and are not intended as limitations thereof. 
EXAMPLE 1 
A rubber composition having a compounding recipe shown in the following 
Table 1 was vulcanized under a condition shown in Table 1 to produce a 
vulcanized rubber. From the vulcanized rubber were cut out rubber pieces 2 
for test pieces shown in FIGS. 1a and 1b, which would be used for the 
90.degree. peeling test described in ASTM D429, Method B, and conical 
rubber pieces 2 for test pieces shown in FIGS. 2a and 2b, which would be 
used for the tensile test described in ASTM D429, Method C. In FIGS. 1a, 
1b and 2a, 2b, the numeral 1 represents resin and the unit of the 
dimension of the test pieces is mm. 
As rubber surface treating solutions, acetone solutions containing 2, 5, 10 
or 20% by weight of each halogenoid of DCTS 
(N,N-dichloro-p-toluenesulfonamide) and TCCA (trichloroisocyanuric acid) 
were prepared, and each of the acetone solutions was applied by means of a 
brush to the vulcanized rubber pieces 2 shown in FIGS. 1a, 1b, or FIGS. 
2a, 2b at the surface to be adhered to a resin. 
As polyamide resins, nylon-6 (CM 1001 made by Toray Co.), nylon-66 (CM 
3001N made by Toray Co.) and nylon-12 (Daiamid made by Daicel Co.) were 
used, and each of the polyamides was dried for 8 hours under a condition 
of 120.degree. C. and 5 mmHg. 
Then, the above treated vulcanized rubber piece is placed in a metal mold, 
and each of the above described polyamide resins was bonded to the treated 
surface of the rubber piece through an injection molding by means of an 
injection molding machine under an injection condition of 230.degree. C. 
in the case of nylon-6, 250.degree. C. in the case of nylon-66 or 
180.degree. C. in the case of nylon-12 to produce a test piece of a 
composite composed of the rubber and the resin as shown in FIGS. 1a, 1b, 
or 2a, 2b. In FIGS. 1 and 2, the numeral 1 represents the resin, and the 
numeral 2 represents the rubber. 
Then, the test piece shown in FIGS. 1a, 1b or 2a, 2b was subjected to an 
adhesion test according to Method B or Method C in ASTM D429, 
respectively. The obtained results are shown in the following Table 2. It 
can be seen from Table 2 that nontreated vulcanized rubber does not adhere 
to polyamide resin, but vulcanized rubber treated according to the method 
of the present invention adheres tightly to polyamide resin. 
TABLE 1 
______________________________________ 
(parts by weight) 
______________________________________ 
Natural rubber 70 
SBR 1500 30 
Carbon black 50 
Aromatic process oil 
5 
Stearic acid 1.5 
Antioxidant *1 1 
Paraffin wax 1 
Zinc white 5 
Sulfur 2 
Vulcanization accelerator *2 
1 
Vulcanization condition: 160.degree. C. .times. 20 minutes 
______________________________________ 
*1 Nphenyl-Nisopropyl-p-phenylenediamine 
*2 Dibenzothiazyl sulfide 
TABLE 2 
__________________________________________________________________________ 
Halogenoid Not treated 
Poly- DCTS TCCA (Compara- 
amide (N,N-Dichloro-p-toluenesulfonamide) 
(Trichloroisocyanuric 
tive) 
resin 2% 5% 10% 20% 2% 5% 10% 20% example) 
__________________________________________________________________________ 
ASTM D429, 
Nylon-6 
5kg/25mm 
20kg/25mm 
30kg/ 
40kg/ 
21kg/25mm 
37kg/25mm 
45kg/ 
42kg/ 
0kg/25mm 
Method B 
(Toray, 25mm 25mm 25mm 25mm 
CM 1001) 
(25R) (80R) (100R) 
(100R) 
(80R) (100R) 
(100R) 
(100R) 
(R/P) 
Nylon-66 
4kg/25mm 
12kg/25mm 
20kg/ 
29kg/ 
8kg/25mm 
35kg/25mm 
40kg/ 
29kg/ 
0kg/25mm 
(Toray, 25mm 25mm 25mm 25mm 
CM 3001N) 
(25R) (50R) (70R) 
(85R) 
(40R) (100R) 
(100R) 
(100R) 
(R/P) 
Nylon-12 
5kg/25mm 
10kg/25mm 
25kg/ 
30kg/ 
15kg/25mm 
30kg/25mm 
50kg/ 
50kg/ 
1kg/25mm 
(Daicel, 25mm 25mm 25mm 25mm 
Daiamid) 
(20R) (40R) (80R) 
(60R) 
(60R) (100R) 
(100R) 
(100R) 
(R/P) 
ASTM D429, 
Nylon-6 
52kg 76kg 86kg 90kg 87kg 92kg 90kg 90kg 0kg 
Method C 
(Toray, 
CM 1001) 
(80R) (95R) (100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
Nylon-66 
78kg 70kg 86kg 92kg 92kg 62kg 86kg 89kg 0kg 
(Toray, 
CM 3001N) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(80R) (100R) 
(100R) 
(R/P) 
Nylon-12 
58kg 94kg 96kg 99kg 87kg 78kg 78kg 70kg 0kg 
(Daicel, 
Daiamid) 
(80R) (100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
__________________________________________________________________________ 
Note: 
R: Cohesion of rubber is broken (numerical value is % of broken area of 
rubber). 
R/P: Rubber is peeled from plastics at the interface. 
EXAMPLE 2 
Adhesion of polyester resin was evaluated in the same procedure as 
described in Example 1. 
As polyester resins, polyethylene terephthalate (FR-PET, B-3030 made by 
Teijin Co.), polybutylene terephthalate (Tufpet N 1000 made by Mitsubishi 
Rayon Co.), Hitrel 7246 made by DuPont Co. and Pelprene 150B made by 
Toyobo Co. were used. The polyester resins were dried for 8 hours under a 
condition of 120.degree. C. and 5 mmHg. 
Then, test pieces were produced by means of an injection molding machine 
under an injection condition of 265.degree. C. in the case of FR-PET, 
260.degree. C. in the case of Tufpet N 1000, 250.degree. C. in the case of 
Hitrel 7246, and 240.degree. C. in the case of Pelprene 150B. 
The obtained results are shown in the following Table 3. 
TABLE 3(a) 
__________________________________________________________________________ 
Halogenoid Not treated 
Poly- DCTS TCCA (Compara- 
ester (N,N-Dichloro-p-toluenesulfonamide) 
(Trichloroisocyanuric 
tive) 
resin 2% 5% 10% 20% 2% 5% 10% 20% example) 
__________________________________________________________________________ 
ASTM D429, 12kg/25mm 
--kg/25mm 
36kg/ 
38kg/ 
28kg/ 
--kg/ 
40kg/25mm 
39kg/25mm 
0kg/25mm 
Method B 
PET 25mm 25mm 25mm 25mm 
(FR-PET) 
(50R) (--) (100R) 
(100R) 
(70R) 
(--) (100R) 
(100R) 
(R/P) 
PBT 38kg/25mm 
42kg/25mm 
48kg/ 
45kg/ 
40kg/ 
42kg/ 
41kg/25mm 
32kg/25mm 
0kg/25mm 
(Tufpet 25mm 25mm 25mm 25mm 
N1000) 
(90R) (100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
Copolymer 
39kg/25mm 
50kg/25mm 
46kg/ 
43kg/ 
51kg/ 
42kg/ 
35kg/25mm 
28kg/25mm 
1kg/25mm 
(Hitrel 25mm 25mm 25mm 25mm 
7246) (90R) (100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
Copolymer 
25kg/25mm 
21kg/25mm 
45kg/ 
40kg/ 
48kg/ 
48kg/ 
44kg/25mm 
36kg/25mm 
0kg/25mm 
(Pelprene 25mm 25mm 25mm 25mm 
150B) (70R) (60R) (100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
__________________________________________________________________________ 
TABLE 3(b) 
__________________________________________________________________________ 
Halogenoid Not treated 
Poly- DCTS TCCA (Compara- 
ester (N,N-Dichloro-p-toluenesulfonamide) 
(Trichloroisocyanuric 
tive) 
resin 2% 5% 10% 20% 2% 5% 10% 20% example) 
__________________________________________________________________________ 
ASTM D429, 
PET 98kg 120kg 
109kg 
120kg 
105kg 
129kg 
120kg 
126kg 
0kg 
Method C 
(FR-PET) 
(80R) 
(100R) 
(95R) 
(100R) 
(90R) 
(100R) 
(100R) 
(100R) 
(R/P) 
PBT 112kg 
128kg 
129kg 
129kg 
129kg 
108kg 
110kg 
105kg 
0kg 
(Tufpet 
N1000) (90R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
Copolymer 
108kg 
126kg 
120kg 
115kg 
130kg 
108kg 
102kg 
101kg 
0kg 
(Hitrel 
7246) (95R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
Copolymer 
128kg 
131kg 
105kg 
103kg 
126kg 
108kg 
106kg 
100kg 
0kg 
(Pelprene 
150B) (100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
__________________________________________________________________________ 
EXAMPLE 3 
Adhesion of another polyester resin (polyarylate resin, AX 1500 produced by 
Unichika Co. and called as U polymer) was evaluated in the same procedure 
as described in Example 1. The injection molding was carried out at a 
temperature of 230.degree. C. 
The obtained results are shown in the following Table 4. 
TABLE 4 
__________________________________________________________________________ 
Halogenoid Not treated 
DCTS TCCA (Compara- 
(N,N-Dichloro-p-toluenesulfonamide) 
(Trichloroisocyanuric acid) 
tive 
Method 2% 5% 10% 20% 2% 5% 10% 20% example) 
__________________________________________________________________________ 
ASTM D429, 
15kg/25mm 
18kg/25mm 
50kg/25mm 
48kg/25mm 
10kg/25mm 
46kg/25mm 
52kg/25mm 
49kg/25mm 
0kg/25mm 
Method B 
(R/P) (20R) (100R) 
(100R) 
(20R) (90R) (P) (100R) 
(R/P) 
ASTM D429, 
26kg 69kg 112kg 108kg 48kg 102kg 121kg 105kg 0kg 
Method C 
(R/P) (50R) (100R) 
(100R) 
(40R) (90R) (100R) 
(100R) 
(R/P) 
__________________________________________________________________________ 
Note: 
P: Cohesion of plastics is broken. 
EXAMPLE 4 
Adhesion of styrene series resins was evaluated in the same procedure as 
described in Example 1. 
The kind of used styrene series resins and the injection molding condition 
are as follows. Polystyrene resin (Styron 683 made by Asahi Dow Co.) was 
injection molded at 260.degree. C., acrylonitrile-butadiene-styrene 
copolymer resin (Cevian SER 20 made by Daicel Co.) was injection molded at 
200.degree. C., and glass fiber-reinforced acrylonitrile-styrene copolymer 
resin (Cevian N 080 FS made by Daicel Co.) was injection molded at 
235.degree. C. 
The obtained results are shown in the following Table 5. 
TABLE 5 
__________________________________________________________________________ 
Halogenoid Not treated 
DCTS TCAA (Compara- 
(N,N-Dichloro-p-toluenesulfonamide) 
(Trichloroisocyanuric 
tive) 
Styrene 
2% 5% 10% 20% 2% 5% 10% 20% example) 
__________________________________________________________________________ 
ASTM D429, 
Polystyrene 
0kg/25mm 
1kg/ 4kg/ 5kg/ 1kg/25mm 
2kg/25mm 
5kg/ 6kg/ 0kg/25mm 
Method B 
resin 25mm 25mm 25mm 25mm 25mm 
(Styron 683) 
(R/P) (R/P) 
(5R) (10R) 
(R/P) (R/P) (10R) 
(10R) 
(R/P) 
ABS resin 
5kg/25mm 
32kg/ 
45kg/ 
40kg/ 
40kg/25mm 
45kg/25mm 
36kg/ 
40kg/ 
0kg/25mm 
(Cevian 25mm 25mm 25mm 25mm 25mm 
SER20) (10R) (90R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
FR-AS resin 
30kg/25mm 
42kg/ 
48kg/ 
42kg/ 
45kg/25mm 
43kg/25mm 
38kg/ 
39kg/ 
0kg/25mm 
(Cevian 25mm 25mm 25mm 25mm 25mm 
N 080FS) 
(85R) (100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
ASTM D429, 
Polystyrene 25kg 50kg 2kg 
Method C 
resin 
(Styron 683) (20R) (30R) (R/P) 
ABS resin 
102kg 128kg 
138kg 
140kg 
139kg 124kg 110kg 
108kg 
5kg 
(Cevian 
SER20) (90R) (100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
FR-AS resin 
124kg 129kg 
136kg 
130kg 
139kg 120kg 111kg 
106kg 
1kg 
(Cevian 
N 080FS) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
__________________________________________________________________________ 
EXAMPLE 5 
Adhesion of acrylic resins was evaluated in the same procedure as described 
in Example 1. 
The kind of used acrylic resins and the injection molding condition are as 
follows. Methacrylic resin (Acrypet MD made by Mitsubishi Rayon Co.) was 
injection molded at 220.degree. C., and a blend (Metamarble made by Teijin 
Co.) of methacrylic resin and polycarbonate resin was injection molded at 
260.degree. C. 
The obtained results are shown in the following Table 6. 
TABLE 6 
__________________________________________________________________________ 
Halogenoid Not treated 
DCTS TCCA (Compara- 
Acrylic (N,N-Dichloro-p-toluenesulfonamide) 
(Trichloroisocyanuric 
tive) 
resin 2% 5% 10% 20% 2% 5% 10% 20% example) 
__________________________________________________________________________ 
ASTM D429, 
Methacrylic 
8kg/25mm 
52kg/ 
48kg/ 
50kg/ 
45kg/ 
53kg/ 
41kg/ 
48kg/25mm 
0kg/25mm 
Method B 
resin 25mm 25mm 25mm 25mm 25mm 25mm 
(Acrypet MD) 
(20R) (100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
Metacrylic 
resin + poly- 
5kg/25mm 
12kg/ 
49kg/ 
42kg/ 
45kg/ 
40kg/ 
42kg/ 
42kg/25mm 
0kg/25mm 
carbonate 25mm 25mm 25mm 25mm 25mm 25mm 
(Metamarble) 
(10R) (25R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
ASTM D429, 
Methacrylic 
96kg 128kg 
138kg 
140kg 
130kg 
124kg 
113kg 
108kg 5kg 
Method C 
resin 
(Acrypet MD) 
(20R) (50R) 
(100R) 
(P) (100R) 
(100R) 
(100R) 
(100R) 
(R/P) 
Metacrylic 
resin + poly- 
68kg 108kg 
120kg 
132kg 
122kg 
128kg 
120kg 
119kg 8kg 
carbonate 
(Metamarble) 
(30R) (80R) 
(100R) 
(100R) 
(80R) 
(100R) 
(100R) 
(100R) 
(R/P) 
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