JPS60212459A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:The titled composition, consisting of a polycarbonate resin having a specific reduced viscosity and a nonconjugated diene based rubber-reinforced resin having specific melt viscosity characteristics, and having improved weather and impact resistance, moldability and weld strength. CONSTITUTION:A thermoplastic resin composition obtained by incorporating (A) 20-80pts.wt. polycarbonate resin having 0.40-0.55 reduced viscosity in chloroform (25 deg.C) with (B) 80-20pts.wt. nonconjugated diene based rubber-reinforced resin, consisting of (B1) 10-100wt% graft copolymer prepared by grafting one or more compounds selected from the group of aromatic vinyl compounds, e.g. styrene, vinyl cyanide compounds, e.g. acrylonitrile, and alkyl esters of unsaturated carboxylic acids, e.g. methyl acrylate, onto a nonconjugated diene based rubber, e.g. ethylene-propylene copolymer, and (B2) 90-0wt% (co)polymer consisting of one or more compounds, selected from the above-mentioned compound groups, and having 5X10<3>-1X10<5> poises apparent melt viscosity at 10<2>sec<-1> shear rate and 250 deg.C and 1.5X10<3>-1X10<4> poises apparent melt viscosity at 10<3>sec<-1> shear rate and 250 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel thermoplastic resin composition that has excellent weather resistance, impact resistance, moldability, and weld strength.

Conventionally, resins based on polycarbonate resin, ethylene-propylene rubber, acrylate) non-conjugated diene rubber (acrylonitrile-propylene rubber in ethylene, styrene polymer "AES", acrylonitrile-acrylate rubber) have been used. A resin composition that is mixed with a styrene polymer (AAS) and has excellent weather resistance and heat resistance has been proposed. (Tokuko Showa 51 24
540, JP 51-41145° JP 53-653
49).

However, in injection molding, which is the most common molding method for such compositions, it is necessary to change the number of gates and the flow state of the resin depending on the shape and size of the molded product, so the resin always flows in different directions. A so-called "weld part" occurs at the point where the The current situation is difficult.

As a result of extensive research into improving the weld strength of compositions made of such polycarbonate resins and non-conjugated diene rubber reinforced resins, the present inventors have found that polycarbonate resins with specific reduced viscosity and specific melt viscosity characteristics have been developed. It was discovered that by mixing a non-conjugated diene-based rubber-reinforced resin, a composition having excellent weld strength that could not be obtained with conventional polycarbonate resin-non-conjugated diene-based rubber-reinforced resin mixtures was obtained. It has been reached.

That is, the present invention has a reduced viscosity of 0 in chloroform.
40-0.55 polycarbonate resin 20-80
Weather resistance consisting of 80 to 20 parts by weight of a non-conjugated diene rubber reinforced resin, which has an apparent 108 to 1X10' poise at 250°C and 1.5X108 to IXI O' poise at a shear speed of 108 sec. The present invention provides a thermoplastic resin composition that has excellent impact resistance, moldability, and weld strength.

The thermoplastic resin composition of the present invention will be explained in detail below.

Examples of the polycarbonate resin include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like. In general, 2.2
-bis(4-oxyphenyl)alkane, bis(4-
Polymers or copolymers of bisphenols such as oxyphenyl)ether, his(4-oxyphenyl)sulfone, sulfide, or sulfoxide, using bisphenols substituted with halogen depending on the purpose. It is a polymer.

What is important about the polycarbonate resin in the present invention is the viscosity of the polycarbonate resin of ~055. 0
．． If it is less than 40, the impact strength and weld strength of the final composition will be low, and a polycarbonate resin having a value of 0.40 to 0.55 can be obtained by varying the composition and polymerization conditions.

The reduced viscosity in chloroform is determined as follows using an Ostwald viscometer: 0 reduced viscosity −:) sp
(Specific viscosity) / C (concentration) T: Flow time of sample solution Concentration: o, 4y polycarbonate) / 100 ml
ChloroformNext, the non-conjugated diene-based rubber reinforced resin used in the present invention is one type selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, and an unsaturated carboxylic acid alkyl ester compound in a non-conjugated diene-based column. It is a graft polymer obtained by graft polymerizing the above-mentioned compounds, or a mixture of such a graft polymer and a (co)polymer of the above-mentioned compound.

The vine (co)polymer mixed with the graft polymer may be a (co)polymer produced during graft polymerization, or a separately produced (co)polymer.

Non-conjugated diene rubber reinforced resin (co-) with graft polymer
In the case of a mixture with a kraft polymer, from the viewpoint of mechanical properties and processability in the final composition, kraft polymers of 10 to 1
A polymer having a weight ratio of 90 to 0 is particularly preferable, and is preferable from the viewpoints of weld strength, processability, etc. of the final composition. If it is less than 0.50, the weld strength tends to decrease, and if it exceeds 0.10, the processability is poor and the weld strength is also decreased.
It can be obtained by varying the composition and polymerization conditions.

As a method for producing graft polymers and (co)polymers,
Known polymerization methods include emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method, emulsion-bulk polymerization method, emulsion-suspension polymerization method, and bulk-suspension type method.

Non-conjugated diene compounds constituting the non-conjugated diene rubber reinforced resin, ethylene-propylene copolymer, dicyclopentadiene, ethylidene norbornene, 14-hexadiene, 14-cyclohebutane, 15-cyclooctadiene, etc. Ethylene copolymerized with non-conjugated diene
Ethylene-propylene polymers (1) such as propylene-nonconjugated diene copolymers, homopolymers such as methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, and other copolymers such as styrene and acrylonitrile. Examples include acrylic acid ester polymers (11) such as copolymers with compounds, chlorinated polyethylene (110) and ethylene-vinyl acetate copolymers Oψ, and one or more types can be used.Especially ethylene- Propylene polymers are preferred.

Further, examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, methyl-α-methylstyrene, and the like.

Examples of vinyl cyanide compounds include acrylonitrile and metacyclonitrile. Examples of unsaturated carboxylic acid alkyl ester compounds include methyl acrylate,
Examples include ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, and glycidyl acrylate and glycidyl methacrylate having an epoxy group in the molecule.

One or more compounds selected from the above-mentioned compound group are used. In particular, styrene, acrylonitrile,
Preferably, it is one or more selected from the group consisting of methyl methacrylate.

There is no particular restriction on the composition ratio of the non-conjugated diene rubber and the compound in the non-conjugated diene rubber reinforced resin, but from the viewpoint of the physical properties of the final composition, the non-conjugated diene rubber should be 5 to 95% by weight.
It is preferable that the band contains 95 to 5 parts by weight of the compound, and particularly preferably 10 to 50 parts of rubber and 90 to 500 to 50 parts by weight of the compound.

What is important about the non-conjugated diene rubber reinforced resin in the present invention is the melt viscosity characteristics of the non-conjugated diene rubber reinforced resin.

105 voids and a shear rate of 10”5ec-
” and has a poise of 1.5X103 to 1X10'.

If the non-conjugated diene rubber reinforced resin has a higher viscosity than the above conditions, the processability of the final composition will be significantly lowered, and the weld strength will also be lowered. In addition, low-viscosity non-conjugated diene rubber-reinforced resins have a large apparent viscosity difference with polycarbonate resins, and during high-shear injection molding, separation of the strands may occur.
Weld strength is significantly reduced. The non-conjugated diene rubber reinforced resin (It) having such specific melt viscosity characteristics is
It can be obtained by adjusting the composition, polymerization conditions, etc.

Further, within the range of shear rate and apparent melt viscosity of the present invention, the dependence of viscosity on shear rate is not particularly important, but it is better to have less dependence on shear rate.

The thermoplastic resin composition of the present invention comprises 20 to 80 parts by weight of a polycarbonate resin (1) having a specific reduced viscosity and a non-conjugated diene rubber reinforced resin (1) having specific melt viscosity characteristics.
It consists of 1180 to 20 parts by weight. If the polycarbonate resin (1) is less than 20% by weight, heat resistance and processability will be significantly reduced.

Moreover, if it exceeds 80% by weight, weld strength will not be improved and workability will also decrease.

Examples of the mixing method for the polycarbonate resin and the non-conjugated diene rubber reinforced resin include known mixing methods using a Banbury mixer-single-screw extruder, a twin-screw extruder having a kneading block, and the like.

Further, during mixing, it is possible to add known dyes and pigments, stabilizers, plasticizers, antistatic agents, ultraviolet absorbers, lubricants, fillers, etc.

The present invention will be specifically explained below using Examples. A is not limited in any way by these.

Examples and Comparative Examples Table - Based on the formulation shown in IK, the polycarbonate resin and the non-conjugated diene rubber reinforced resin were used.The polycarbonate resin and the non-conjugated diene rubber reinforced resin used are as follows.

0 polycarbonate resin (1) Recarbonate resin ■ and 0.30 polycarbonate ( I am currently creating a resin ■.

0 Non-conjugated diethylene rubber reinforced resin (, ID■ Ethylene-
Propylene-ethylidene norbornene rubber (iodine (d)
Graft polymerization was carried out using 40 parts by weight [i7.5, propylene content 40% by weight], 40 parts by weight of styrene, and 20 parts by weight of acrylonitrile based on a known solution polymerization method. 60 parts by weight of the obtained polymer and 40 parts by weight of a styrene-acrylonitrile copolymer (styrene/acrylonitrile nia 0/30) having an intrinsic viscosity of 0.60 obtained based on a separately known bulk-suspension polymerization method. Mix, 250
℃, melt viscosity at 10'5ec-' is 680×
A resin "AES-1" having a melt viscosity of 10" poise and a melt viscosity of 2.3 x 108 poise at 250 DEG C. and 103 seconds was obtained.

■ Ethylene-propylene-ethylidene norbornene rubber (iodine value 8.5, propylene content 43 parts by weight) 5
Graft polymerization was carried out using a known solution polymerization method using 0 parts by weight, 35 parts by weight of styrene, and 15 parts by weight of acrylonitrile. 80 parts by weight of the obtained polymer and an intrinsic viscosity of 1.0 obtained based on a separately known bulk-suspension polymerization method.
Styrene-acrylonitrile copolymer (styrene/
The melt viscosity at 250°C and 102 seconds was 2.0.
×lOr'bois, or) 250℃, 10"sec
Resin "AES-2" having a melt viscosity of 2.8×10' poise at vc was obtained.

(2) Graft polymerization was carried out using 30 parts by weight of acrylic acid butyl ester polymer, 50 parts by weight of styrene, and 20 parts by weight of acrylonitrile based on a known suspension polymerization method. 60 parts by weight of the obtained polymer and 40 parts by weight of a styrene-acrylonitrile copolymer (styrene/acrylonitrile nia 0/30) having an intrinsic viscosity of 0.60 obtained by a known bulk-suspension polymerization method were added separately. The melt viscosity at 250°C and 10'5 ecK is 7.5 x 108 boids, and the melt viscosity at 250°C and 108 sec is 3.
A resin "AAS-1" having a poise of 0.times.10" was obtained.

(2) Graft polymerization was carried out using 40 parts by weight of acrylic acid butyl ester polymer, 40 parts by weight of styrene, and 20 parts by weight of acrylonitrile based on a known suspension polymerization method. 80 parts by weight of the obtained polymer and, separately, 20 parts by weight of a styrene-acrylonitrile copolymer (styrene/acrylonitrile nia 0/30) with an intrinsic viscosity of 1.10 obtained based on a known bulk-suspension polymerization method. Mix, 250℃,
Melt viscosity at 10” 5ee-’ is 2.5X10
The melt viscosity at 250°C and lO'sec is 3.
A resin "AAS-2" having a poise of 5 x 10' was obtained.

■ Chlorinated polyethylene (chlorine content: 30 parts by weight, 40 parts by weight)
parts by weight, 45 parts by weight of styrene and 1 part by weight of acrylonitrile
Graft polymerization was carried out based on a known suspension polymerization method using 5 parts by weight.

55 parts by weight of the obtained polymer and, separately, styrene with an intrinsic viscosity of 0.55 obtained based on a known bulk-suspension polymerization method.
45 parts by weight of an acrylonitrile copolymer (styrene/acrylonitrile = 70/30) was mixed, and the melt viscosity at 250°C and 110"8ee was 7.0X103 HST, and the melt viscosity at 250°C and 108See-' was 3. Resin “AC” which is I x 103 poise
I got 8″.

[Measurement method of weld strength]

Two gates with a gate spacing of 100m+n (each 25x 2
．． Molten resin (260° C.) was injected from a tube (260° C.) to prepare a test piece with a thickness of 150 wm in both length and width.

Place the test piece in a jig (height: 80 mm, inner diameter: 120 mm, outer diameter: 126 mm)
rrrm).

In a cold room adjusted to -30℃, 14 steel balls were dropped into the center of the test piece, and the maximum energy value (
#・cm).

[Measurement method of apparent viscosity and shear rate]

It is calculated by the following formula using a Koka type flow tester manufactured by Takafusa Seisakusho and an orifice (nozzle diameter 0.1 cm, nozzle length LO cm).

Q: Outflow tea/see.

R: Nozzle radius Q, 05cm L: Nozzle length 1.0 cm P: Pressure dyn/c4

Claims (1)

[Claims] 1) Reduced viscosity (25°C, chloroform) 0.40 to 0
．． 55 polycarbonate resin (1) with 20 to 80 parts by weight and an apparent melt viscosity at 250°C at a shear rate of 10'
5 X 10'' to lXl0' poise in sec and 1.5 X 103 to I
Non-conjugated diene rubber reinforced resin with 10' poise (
II) Thermoplastic resin composition consisting of 80 to 20 parts by weight. 2) The non-conjugated diene rubber reinforced resin is obtained by polymerizing a non-conjugated diene rubber with one or more compounds selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, and an unsaturated carboxylic acid alkyl ester compound. A graft polymer consisting of 10 to 100 double bands and a (co)bipolymer consisting of one or more compounds selected from the above compound group 90 to 0.
The thermoplastic resin composition according to claim 1, which is a resin consisting of 0% by weight.