JPS63221155A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent impact resistance, weld strength and moldability, by adding two specific components to a compsn. consisting of an ABS resin and an arom. polycarbonate resin. CONSTITUTION:10-90wt.% ABS resin (a) obtd. from diene rubber, a vinyl cyanide monomer, an arom. vinyl monomer and optionally, other copolymerizable monomer, is blended with 90-10wt.% arom. polycarbonate resin (b) to obtain a compsn. 1-20pts.wt. polymethacrylate resin (c) and/or polyglutarimide (c) which is a polymer having a cyclic imide unit of formula [wherein R1, R2 and R3 are each H, a 1-20C (substd.) alkyl or aryl] and 0.5-20 pts.wt. MBS resin (d) obtd. by grafting an alkyl unsaturated carboxylate and an arom. vinyl monomer onto diene rubber and/or acrylate graft copolymer (d) obtd. by grafting a vinyl compd. onto a copolymer obtd. from an alkyl acrylate and a polyfunctional polymerizable monomer having a conjugated diene type double bond, are added to 100pts.wt. said composition.

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention particularly relates to a thermoplastic resin composition that has excellent impact resistance and queld strength, and is also excellent in moldability.

<Prior art> Aromatic polycarbonate resin is an engineering plastic with excellent impact resistance, heat resistance, and electrical properties, and is used for various purposes, but it has problems such as high molding temperature and poor fluidity. It has the disadvantage that the 1-meter impact strength is highly dependent on the thickness.

Therefore, attempts have been made to blend polycarbonate with ABS resin (acrylonitrile-butadiene rubber-styrene copolymer) or MBS resin (methyl methacrylate-butadiene rubber-styrene copolymer) to cover these drawbacks (especially Kosho 38-1522
Publication No. 5, Special Publication No. 39-71, Special Publication No. 42-i1
Publication No. 496).

On the other hand, aromatic polycarbonate resin, polymethacrylic acid ester resin (hereinafter abbreviated as PMMA resin) and AB
Compositions made of S resin are also known (Japanese Unexamined Patent Publication No. 49-1
32143). This compensates for the shortcomings of the aromatic polycarbonate resin and PIVIM A resin, which are the impact resistance and delamination phenomenon.

<Problems to be Solved by the Invention> In recent years, ABS-based resin compositions (aromatic polycarbonate) have been increasingly used for large molded products such as automobile parts, but welds occur during molding. The problem is that the strength at the weld portion is extremely poor.

Various proposals have been made to solve this problem.

For example, AH5@PC resin, IVI BS resin (JP-A-58-59258), polyester elastomer (JP-A-60-219250), acrylic ester graft co-electrolyte (JP-A-61-1999) 72054
), unsaturated dicarboxylic acid-modified olefins (JP-A-58-167645), polyolefins (JP-A-58-45251), 5T-BD block coordinating bodies (JP-A-58-59259) ) etc. are added.

However, although improvements have been recognized in all of these, the weld strength is still insufficient.

Means for Solving the Problems> As a result of intensive studies by the present inventors to solve the above-mentioned problems, we found that aromatic polycarbonate resin and ABSel
We have discovered that by adding a small amount of PMMA resin and MBS resin to a composition consisting of oil, moldability is even better than before, and especially impact resistance and weld strength are improved, and we have arrived at the present invention.

That is, the present invention provides (4) 1 to 20 parts by weight of a polymethacrylic acid ester resin and/or a polyglutarimide to 100 parts by weight of a composition consisting of 10 to 9% by weight of an ABS resin; The present invention provides a thermoplastic resin composition characterized in that 0.5 to 20 parts of an acrylic acid ester-based graft copolymer is melt-kneaded.

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

(A) ABS resin used in the present invention includes (a) diene rubber, (c) vinyl cyanide, 1. P → aromatic vinyl monomer and (if necessary) other copolymerizable monomers, and the total amount of the monomers is (a) a graft copolymer obtained by graft copolymerizing with diene rubber. or a part of the monomer; (a) a resin composition of a graft copolymer graft copolymerized to a diene rubber and a copolymer copolymerized with the remaining monomers;

Examples of the diene rubber (a) used in the present invention include polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, polyisoprene rubber, etc. The above can be used together. Particularly preferably, polybutadiene rubber and/or styrene-butadiene copolymer rubber is used.

(Example) Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred. Examples of the e→aromatic hinyl monomer include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, and vinyltoluene, with styrene and/or α-methylstyrene being particularly preferred.

(4) There are no particular restrictions on the copolymerization ratio of the ABS resin, but the moldability and impact resistance of the thermoplastic resin composition obtained based on 100 parts by weight of the ABS resin are as follows.
Diene rubber is preferably 5 to 85 parts by weight, particularly 10 to 8 parts by weight.
It is preferably 0 parts by weight, and more preferably 15 to 75 parts by weight. Similarly, the vinyl cyanide monomer (←) is preferably 5 to 50 parts by weight, particularly preferably 7 to 45 parts by weight, and more preferably 8 to 40 parts by weight. e→1 aromatic vinyl monomer is preferably 10 to 90 parts by weight, and 1
It is particularly preferably used in an amount of 3 to 83 parts by weight, and more preferably in a range of 17 to 77 parts by weight.

(4) Regarding the method for producing ABS resin, there are no particular limitations, and commonly known methods such as bulk polymerization, solution polymerization, bulk-suspension polymerization, suspension polymerization, and emulsion polymerization can be used. It is also possible to obtain the above composition by blending separately copolymerized resins.

The aromatic polycarbonate resin used in the present invention is
There are no particular limitations, and those produced by commonly known methods, such as those obtained from bisphenol A and phosgene and those obtained from bisphenol A and diphenyl carbonate, can be used.

The Ω polymethacrylate resin used in the present invention is
There are no particular restrictions, and polymerization methods include bulk, solution, suspension,
Those produced by either emulsion polymerization or combination polymerization thereof can be used.

The 0 polyglutarimide used in the present invention is represented by the following formula (1)
It is a polymer or copolymer containing a cyclic imide unit represented by

R8 In the formula, R, R, and R each represent hydrogen or a substituted or unsubstituted alkyl group or aryl group having 1 to 20 carbon atoms.

Any polyglutarimide having any chemical structure can be applied to the present invention as long as it contains the above cyclic imide unit, but usually R and R1 in the above cyclic imide unit are hydrogen or a methyl group. , R3 is hydrogen, methyl group, ethyl group, propyl group, butyl group or phenyl group.

The method for producing polyglutarimide is not particularly limited, but for example, polymethyl methacrylate described in JP-A-52-63989 is reacted with ammonia or a primary amine such as methylamine or ethylamine in an extruder. Methods that form glutarimide rings are useful.

ΩMBS [fat] used in the present invention is a graft copolymer obtained by graft polymerizing an unsaturated carbonaceous alkyl ester monomer and an aromatic vinyl monomer to a diene rubber.

The diene rubber content in the IVIBs resin is not particularly limited, but is preferably 5 to 70% by weight. Furthermore, the copolymerization ratio of unsaturated carboxylic acid alkyl ester and aromatic vinyl in MBS resin is not particularly limited, but 20 to 80% by weight of unsaturated carboxylic acid alkyl ester
: Preferably, the aromatic vinyl content is 80 to 20% by weight.

The diene rubber constituting the MBS resin includes polybutadiene, butadiene-styrene copolymer, butadiene-styrene copolymer,
Although acrylonitrile copolymers and the like can be used, polybutadiene and butadiene-styrene copolymers are particularly preferred.

As the unsaturated carboxylic acid alkyl ester, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, etc. can be used, but methyl methacrylate is particularly preferred. . As the aromatic vinyl, styrene, α-methylstyrene, dimethylstyrene, vinyltoluene, etc. can be used, but styrene and α-methylstyrene are particularly preferred.

One or more types of these diene rubbers, unsaturated carboxylic acid alkyl esters, and aromatic vinyls can be used.

The manufacturing methods for MBS resin are usually emulsion method, suspension polymerization method, bulk polymerization method, and dissolution method. e! Emulsion-suspension polymerization method, bulk-suspension polymerization method, etc. are used.

The acrylic acid ester graft copolymer, which is the zero component of the present invention, is a polyfunctional polymer having a conjugated diene type dilinear bond represented by an alkyl ester of acrylic acid having 2 to 12 carbon atoms in an alkyl group and butadiene. It refers to a graft copolymer obtained by graft polymerizing one or more vinyl compounds as an essential component to a rubbery copolymer obtained by copolymerizing a rubbery copolymer with a rubber monomer as an essential component. As a polyfunctional polymerizable monomer with a conjugated diene-based di-I bond,
In addition to the above-mentioned butadiene, 1-methyl-2-vinyl-
4,6-hebutadien-1-ol, 7-methyl-3-
Examples include methylene-1,6-octadiene and 1,3,7-octatriene. In addition, when copolymerizing an alkyl ester of acrylic acid with a polyfunctional polymerizable monomer having a conjugated diene type double bond, an aromatic vinyl compound represented by styrene or methyl methacrylate may be used depending on the desired P. As appropriate from among methacrylic acid esters represented by methacrylic acid esters, vinyl cyanide compounds represented by acrylonitrile, vinyl ether compounds represented by methyl vinyl ether, halogenated vinyl compounds represented by vinyl chloride, and vinyl ester compounds represented by vinyl acetate. A selected monofunctional polymerizable monomer and a crosslinking agent represented by ethylene dimethacrylate and divinylbenzene are appropriately selected and used. Vinyl compounds used in graft polymerization include methacrylic acid esters represented by methyl methacrylate, aromatic vinyl compounds represented by styrene, vinyl cyanide compounds represented by acrylonitrile, and halogenated vinyl compounds represented by vinyl chloride. Examples include polymerizable monomers selected from the group consisting of: two or more of these monomers may be used in combination. Furthermore, the above-mentioned crosslinking agent may be used in combination during graft polymerization.

In producing the acrylic acid ester-based graft copolymer, the polyfunctional polymerizable monomer having a conjugated diene type double bond is contained in the copolymer with the alkyl ester of acrylic acid in an amount of 0.1-10%. It is used in an amount accounting for 1% by weight.

Typical examples include acrylic esters (e.g. tf,
n-2 thyl acrylate, 2-ethylhexyl acrylate), butadiene, a small amount of crosslinking agent (e.g., ethylene dimethacrylate, divinylbenzene), and optionally a methacrylic acid ester (e.g., methyl methacrylate) are emulsified according to a conventional method. A graft copolymer obtained by copolymerizing by a polymerization method, adding a vinyl compound appropriately selected from styrene, methyl methacrylate, acrylonitrile, vinyl chloride, etc. as a graft component monomer to the obtained latex, and performing graft polymerization according to a conventional method. Coalescence; acrylic ester (e.g. n-butyl acrylate, 2
-ethylhexyl acrylate) and compounds having a non-conjugated double bond in addition to a conjugated diene type double bond in one molecule (e.g. l-vinyl-2-vinyl-4,6-hebutadien-1-ol) and, if desired, an ester of methacrylic acid by a conventional method, a graft component monomer is added to the obtained latex, and the graft component is graft-polymerized according to a conventional method to obtain a graft copolymer.

These graft polymerizations may be carried out in one stage, or may be carried out in multiple stages by changing the components of the graft component monomer in multiple stages. Although a typical production example is shown using emulsion polymerization, the desired acrylic ester graft copolymer can also be produced using other known polymerization methods. Of course.

As such an acrylic ester graft copolymer,
Chemical industry by prefecture (product name rHIA-15 from the east, rHI
A-28J Al-Iha rf (resin commercially available as IA-30J) is preferably used.

The mixing ratio of the above (4) ABS resin and (4) aromatic polycarbonate resin is (4) 10 to 90%, preferably 20 to 90%.
ω) 90 to 10% by weight preferably 80% by weight
It is 0 to 20% by weight. If the ABS resin is less than 10% by weight, the desired improvement in impact resistance and moldability cannot be obtained;
Further, if the aromatic polycarbonate resin is less than 10% by weight, heat resistance will be impaired, which is not preferable.

In addition, Ω polymethacrylic acid ester resin and polyglutarimide are used in an amount of 1 to 20 parts by weight per 100 parts of the total weight of (A) ABS resin and (B) aromatic polycarbonate resin, and if it is less than 2i parts, the weld strength is improved. Not done. Moreover, if it exceeds 20 parts by weight, the impact resistance will deteriorate, which is not preferable.

Furthermore, 0.5 to 20 parts by weight of ([)MBS resin and/or acrylic acid ester graft copolymer are used. If it is less than 0.5 parts, the effect of improving weld strength cannot be obtained, and if it exceeds 20 parts by weight, heat resistance will be poor, and moreover, if it is 70-
This is undesirable as it may leave marks.

The content of diene rubber in the resin composition of the present invention is not particularly limited, but in order to maintain high impact resistance and rigidity, the content is 3 to 50%.
Weight percentages are preferably used.

There are no particular limitations on the method for producing the thermoplastic resin composition of the present invention, and for example, (4) aromatic polycarbonate resin with ABS resin, (C) polymethacrylate resin and/or ([) MBS [fat or / and acrylic acid ester graft copolymer are melt-kneaded using a Banbury Mixer 1 single-screw extruder, two-wheel extruder, etc. to produce a product.

In addition, the thermoplastic resin composition of the present invention may be added with a usual hindered phenol-based surfactant, phosphorus-based antioxidant, and iodine-based antioxidant to improve thermal stability.
A lubricant can be added to improve melt fluidity. In addition, mineral oil, fibrous reinforcing agents such as glass fibers, inorganic fillers, colorants, pigments, ultraviolet absorbers, and the like may be added depending on the purpose.

<Examples> In order to explain the present invention more specifically, Examples and Comparative Examples will be given below. The resin composition finally obtained was molded by injection molding, and then various physical properties were measured by the following test methods.

Izotsu impact strength ASTM D256-56A
Tensile strength ASTM 0638MF
RJIS K6719 Heat Distortion Temperature ASTM
D648 In addition, parts and % in the examples indicate coulometric parts and coulometric %.

Reference Example 1 1-1 Graft copolymer A-1-A according to the following formulation
-3 and copolymers a-1 to a-3 were prepared.

A-1: Polybutadiene latex (rubber particle size 0.2
5μ, Gen content 80%) 40 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was emulsion polymerized in the presence of 60 parts (in terms of solid content).

The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to prepare a powdery graft copolymer (A-1).

A-2: Polybutadiene latenox 4 used in A-1
Methyl methacrylate in the presence of 0 parts (based on solids) 15
After emulsion polymerizing 60 parts of a monomer mixture consisting of 65% styrene and 20% acrylonitrile, a powdery graft coelectric polymer (A-2) was prepared in the same manner as A-1.

A-3 = Polybutadiene rubber (1 diene' NF35A
After dissolving 20 parts of Asahi Kasei Co., Ltd. in 70 parts of styrene and 10 parts of acrylonitrile, bulk polymerization was performed to prepare a graft copolymer (A-3).

a-1: Copolymer <b, -i) was prepared by copolymerizing 72 parts of styrene and 28 parts of acrylonitrile.

a-2: 72 parts of methyl methacrylate, 24 parts of styrene,
Copolymer (b-2) obtained by copolymerizing 4 parts of acrylonitrile
was prepared.

a-3: 50 parts of styrene, 30 parts of N-phenylmaleimide
part, and 20 parts of acrylonitrile to form copolymer C.
b-3) was prepared.

1-2 A pellet of polyglutarimide polymethyl methacrylate was charged into an extruder together with ammonia, and extrusion was performed at a resin temperature of 280°C while degassing the generated gas from an exhaust port attached to the extruder, and the heat distortion temperature was reached. A polyglutarimide with polymer properties of 140°C was prepared.

Example 1 ABS resins prepared in Reference Example 1-1 (A-1 to A-3
and a-1 to a-'3)) Aromatic polycarbonate resin consisting of biphenol A (Mitsubishi Gas Chemical Co., Ltd. (made of copper, trade name Newpiron S-3000, molecular weight 230
00) and (O polymethacrylic acid ester w fat (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrypera hVH) and the polyglutarimide ([)MBS prepared in Reference Example 1-2)
Resin (manufactured by Kureha Chemical Co., Ltd., product name: BTA N0R)
, acrylic ester-based graft copolymer (Kureha Chemical Co., Ltd.)
(trade name: HIA-28) manufactured by TEN) were mixed at the compounding ratio shown in Table 1, and the resin was heated to 25°C using a 40 mm diameter extruder with a bed/board.
A pellet was produced by melt mixing and extrusion at 0°C. Then, the cylinder temperature was set to 26 by injection molding machine.
A test piece was molded at 0°C and a mold temperature of 70°C, and each physical property was measured. For Comparative Examples, the same operations as in the Examples were performed to measure the physical properties.

The weld strength was determined by measuring the tensile strength and Izotsu a impact strength of the test piece after molding it using a JIS-63011 dumbbell mold with gates on both ends so as to create a felt line in the center of the test piece. .

These results are shown in Table-1.

As is clear from the results shown in Table 1, the resin compositions of the present invention (&1-45) have excellent weld strength and notched isot impact strength, and also have good fluidity and heat distortion temperature. It can be seen that it exhibits well-balanced physical properties.

On the other hand, polycarbonate resin has excellent weld strength, but has poor fluidity and poor moldability. Furthermore, although polycarbonate resin and ABS resin compositions have improved weld strength and moldability, sufficient impact resistance has not been obtained.

<Effects of the Invention> The thermoplastic resin composition of the present invention has particularly excellent @ impact resistance and weld strength, as well as excellent moldability and heat resistance, so it is suitable for use in interior and exterior parts of automobiles.

Patent application Daitoshi Co., Ltd.

Claims (1)

[Claims] Composition 10 consisting of (A) 10-90% by weight of ABS resin and (2) 90-10% by weight of aromatic polycarbonate resin
(C) polymethacrylic acid ester resin and/or polyglutarimide 1 to 20 parts by weight (D
) A thermoplastic resin composition characterized in that 0.5 to 20 parts by weight of an MBS resin and/or an acrylic acid ester graft copolymer are melt-kneaded.