JPS6058451A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:The titled composition, obtained by incorporating a modified vinyl polymer prepared by polymerizing a vinyl monomer in the presence of a special chain transfer agent and an initiator with a specific polyolefin, and having improved impact resistance and weather resistance and further high productivity. CONSTITUTION:A thermoplastic resin composition obtained by incorporating (A) a modified vinyl polymer prepared by polymerizing (ii) a vinyl monomer, preferably styrene, selected from aromatic vinyl monomers, vinyl cyanide monomers and (meth)acrylic acid ester based monomers in the presence of (i) a chain transfer agent, preferably beta-mercatoethylamine, and/or an initiator having functional groups selected from amino groups, substituted amino groups and mineral acid salts thereof with (B) a modified polyolefin having functional groups selected from carboxylic acid groups, metallic base thereof and acid anhydride groups. The amounts of the respective components are as follows; 30-99pts.wt. component (A), 70-1pts.wt. component (B) and further 100pts.wt. total of the components (A) and (B).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition that has excellent mechanical properties such as impact resistance and weather resistance, and has good productivity.

Acrylonitrile-butadiene-styrene terpolymer (ABS) resin and methyl methacrylate-butadiene-styrene terpolymer (MBS) resin are used in a wide range of fields as representative impact-resistant resins. However, it has a serious drawback of poor weather resistance because the diene rubber that is the base rubber easily deteriorates. Various studies have been carried out to improve this drawback and to obtain thermoplastic resins with excellent impact resistance and weather resistance. For example, (1) ethylene-propylene-nonconjugated diene as a base rubber terpolymer (EPDM)
A method using rubber and (2) a method using an acrylic acid ester rubbery polymer have been proposed. However, in the above method (1), since a bulk polymerization method or a solution polymerization method is employed, there are problems such as not being able to obtain a polymer with a high rubber content and the removal of the solvent being complicated. Further, since the method (2) above employs an emulsion polymerization method, there are problems such as difficulty in controlling the particle size of the rubbery polymer and a complicated polymer recovery process. Therefore, the above-mentioned conventional method has several problems in the manufacturing process, the productivity is poor, and the impact resistance of the thermoplastic resin obtained is still insufficient.

Therefore, the present inventors conducted extensive studies with the aim of solving the problems of the conventional method and obtaining a thermoplastic resin with excellent impact resistance and weather resistance, as well as good productivity. Mixing a specific modified vinyl polymer polymerized using a chain transfer agent and/or initiator having a functional group such as an amino group with a specific modified polyolefin having a functional group such as an amino group in a specific ratio. It has been discovered that a resin composition exhibiting excellent effects and meeting the above objectives can be obtained, and the present invention has been achieved.

Specifically, the present invention provides (A) (a) a chain transfer agent having at least one functional group selected from the group consisting of an amino group, a substituted amino group, and a mineral acid salt thereof in the molecule;
or (b) aromatic vinyl monomer in the presence of an initiator,
At least 1i selected from the group consisting of vinyl cyanide monomers and (meth)acrylic acid ester monomers
and (B) a modified vinyl polymer obtained by polymerizing a vinyl monomer of (A) is 30-99
parts by weight, (B) is 70 to 1 part by weight, and (A) and (B)
The present invention provides a thermoplastic resin composition in which the total amount of the components is 100 parts by weight.

The thermoplastic resin composition of the present invention does not require a graft polymerization process as in the conventional method and can be obtained as a simple blend compound, so various problems in the manufacturing process are solved and productivity is good. Furthermore, in the present invention, the modified vinyl polymer (A) usually has a functional group such as an amino group at the end of the polymer chain, while the modified polyolefin (B) has a functional group such as a carboxylic acid group or an acid anhydride group. So.

The affinity between the two is significantly improved, and a resin composition having both sufficient impact resistance and weather resistance can be obtained.

What is the modified vinyl-based polymer (A) used in the present invention? (a) Chain transfer having at least one functional group selected from the group consisting of amino groups, substituted amino groups, and mineral acid salts thereof in the molecule. In the presence of an agent and/or an initiator, at least one selected from the group consisting of (b) an aromatic vinyl spinning wheel, a vinyl cyanide monomer, and a (meth)acrylic acid ester monomer. It is a vinyl polymer obtained by polymerizing vinyl monomers.

(a) Chain transfer agent and initiator used in the present invention are represented by the following formula (I), where R1 represents hydrogen, mef/L/ group, or ethyl group, and R2 represents hydrogen and has 1 to 12 carbon atoms. an alkyl group of
It represents an alkanoic μ group having 2 to 12 carbon atoms, a phenyl group having 6 to 12 carbon atoms, a cycloalkyl group having t and 6 to 12 carbon atoms, or derivatives thereof. ) has at least one functional group selected from the group consisting of amino groups, substituted amino groups, and mineral acid salts thereof, and specific examples of chain transfer agents include mercaptomethylamine,
β-Mercaptoethylamine N-(β-Mercaptoethyl A/) - N-methifleamine, N-(β-MercaptoethylA/)
)-N-ethylamine, N-(β
-Mercaptoethyl/l/) -N-Phenyl
Amine, N-(β-)rucabuto
ethyl)-N-cyclohexylamine, binu(4
-AminobueneI) Disalrefide, Bis-(2-
Examples of the initiator include aminophenyl) disulfide, bis-(6-amitupheni/L/) disulfide, p-mercaptoniline, 0-mercaptoniline, m-mercaptoniline, and their hydrochlorides. is α, σl-azobis(n-amino-σ, γ-dimethiμ
valeronitrile), σ,α′-azobis(lo-mefl
Amino α. 7゛-dimethyl/<L/roni)lyl,
σ (1/-azobis(1-ethylamino-d1γ-dimethylbalonitrile), α,σ′-azobis(γ-propylamino-d,7-dimethylparellonitrile), α
, a/-azobis-(γ-dimethylamino/-d.r-dimethylvaleronitrile α, α′-azobis-(γ-diethyl-reamin-α,-dimethylvaleronitrile), a
, αI-azobis-(7-dipropylamino-σ, 7-
cyclonitrile) and p-aminobency!
Examples include peroxide. Among these, those having an amino group or its hydrochloride are preferable, and particularly as chain transfer agents, β-mercaptoethylamine, 1-mercaptopropylaminetoethylamine hydrochloride, γ-mercaptopropylamine hydrochloride and bis-(4-amino phenyl)disulfide, and α,ge′-azobis(γ) as an initiator.
-Amino-α,γ-dimethylvaleronitrile The transfer agent and the initiator may be used alone as a chain transfer agent or an initiator alone, or may be used in combination with a chain transfer agent and an initiator.

The vinyl monomers used in the present invention include styrene, σ-methylnutyrene, vinyltoluene-methylstyrene, O-methylstyrene, m-methylstyrene, t-butylstyrene, p-chlorostyrene, and O-chlorostyrene. V
Nio J: Aromatic vinyl monomers such as aaa styrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and methyl methacrylate;
(From the group consisting of methanoacrylic acid ester monomers, such as ethyl aryl acid, methyl aryl acid, ethyl aryl acid, and butyl acrylic acid) At least one selected vinyl monomer, particularly styrene, d-methylstyrene, p-.

Methylstyrene, t-butylstyrene, acrylonitrile and methyl methacrylate are preferred, and one or more of these may be used in combination.

There are no particular restrictions on the method of polymerizing the modified vinyl polymer (A) (the polymerization can be carried out by commonly known methods, such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and bulk-suspension polymerization). Polymerization is carried out by a method such as a method, but it is particularly preferably carried out by a bulk polymerization method or a bulk-suspension polymerization method. The chain transfer agent and the initiator having a functional group such as an amino group are usually selected based on the degree of polymerization, polymerization rate, and amount of functional groups. Total amount is 0,01
It is added in an amount of up to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight. In addition to the above-mentioned chain transfer agents and initiators, t-dodecyl mercaptan ordinary chain transfer agents or ordinary initiators such as benzoyl peroxide or α,σ'-azobisisobutyronitrile are used in combination, if necessary. You can also do that. In addition to the vinyl monomer (2), a vinyl monomer having a functional group such as an amino group such as p-aminostyrene or allylamine may be used in conjunction with the sunset view within a range that does not impair the effects of the present invention. - Phenylmaleimide, acenaphthalate, and other vinyl monomers can also be used in combination.

The modified polyolefin (B) in the present invention is not particularly limited as long as it has at least one functional group selected from the group consisting of carboxylic acid groups, carboxylic acid metal bases, and acid anhydride radicals, but representative examples are listed below. and ethylene/acrylic μ acid copolymer, ethylene/methacrylic acid copolymer, ethylene/fumaric acid copolymer, ethylene/methacrylic acid/zinc methacrylate copolymer/1%
7/7 Acrylic acid/sodium methacrylate copolymer, ethylene/isobutyl acrylate/methacrylic acid/zinc methacrylate copolymer, ethylene/methyl methacrylate
methacrylic acid/magnesium methacrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/ethyl acrylate/acrylic acid copolymer, ethylene/maleic anhydride copolymer, ethylene/propylene/ Maleic anhydride copolymer, ethylene-g-maleic anhydride copolymer (1g' represents a graft. The same applies hereinafter), ethylene/propylene-g-maleic anhydride copolymer, ethylene/g-maleic anhydride copolymer,
/7' Robylene-g-acrylic acid copolymer, ethylene/1-pudene-g-fumarv copolymer. , :c
Chin/1-hexene-g-icone copolymer.

Ethylene/propylene-g-endovincro (2.

2,1) - 5-hebutene-2,3-dicarboxylic anhydride copolymer, ethylene/propylene/1,4-hexadiene-g-maleic anhydride copolymer, ethylene/propylene/dicyclopentadiene- g-fumarvx polymer, ethylene/furopylene/dicyclopentadiene-g-
Maleic anhydride copolymer, ethylene/propylene 15-
Ethylidene-2-//Leporne-g-maleic anhydride copolymer, ethylene/propylene 15-ethylidene-2
-Norbornene- Vinyl acetate-g-acrylic acid copolymer, etc., but is not limited to these. It is also possible to use two or more of these modified polyolefins in combination.

(E) The modified polyolefin is usually prepared by a known method, for example, Japanese Patent Publication No. 59-6810, Japanese Patent Publication No. 52-4367.
Publication No. 7, Special Publication No. 5716, Special Publication No. 53-
It can be produced by the method disclosed in Japanese Patent Publication No. 19037, Japanese Patent Publication No. 53-41173, Japanese Patent Publication No. 56-9925, and the like. In addition, ethylene ionomer e
Kotsui teha, generally 1 saarin 1, 'hymiran 1,'
Various blades commercially available under the brand name Koboren 1 can be used.

The blending ratio of (A) modified vinyl polymer and (B) modified polyolefin is 30 to 99 parts by weight, particularly preferably 50 to 95 parts by weight, and 70 to 1 part by weight, particularly preferably CB). , 50 to 5 parts by weight, and the total of (A) and (gong) is 100 parts by weight.The blending ratio is for the purpose,
It can be appropriately selected depending on the application and can be set to a desired balance of physical properties. For example, for applications that require relatively high rigidity, a small proportion of CB) modified polyolefin may be mixed, and conversely, for applications that particularly require flexibility and toughness, a high proportion of I) modified polyolefin may be mixed. In addition to (A) a modified vinyl polymer and CB) a modified polyolefin, the resin composition of the present invention contains borinutylene (P
S), styrene/acrylonitrile copolymer (SAN)
, polymethyl styrene/methacrylate (PMMA), nutyrene/methacrylic acid/acrylonitrile copolymer, α-methyl restyrene/acrylonitrile copolymer, α-methylstyrene/styrene/acrylonitrile copolymer, α-methylstyrene/methyl methacrylate/acrylonitrile copolymer By appropriately mixing ordinary vinyl polymers (C) such as p-methylene/renethylene/acrylonitrile copolymer and t-butylstyrene/acrylonitrile copolymer, polyethylene, polypropylene, and ethylene/propylene copolymer. , ethylene/butene-1 copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene 15-ethylidene 2-norhorne copolymer, ethylene/propylene/1,4-hexadiene copolymer, ethylene /Vinyl acetate copolymer, ethylene/
By appropriately mixing polyolefin rubbers such as glopyrene/vinyl acetate copolymer and ethylene/butyl acrylate copolymer, it is also possible to further adjust the physical properties and characteristics to desired ones. ' There are no particular limitations on the method for producing the thermoplastic resin composition of the present invention, and generally known methods can be employed.

That is, after uniformly mixing (A) modified vinyl polymer and (B) modified polyolefin in the form of pellets, powder, small pieces, etc. using a high-speed stirrer, etc., the mixture is extruded using a single screw or multi-screw with sufficient cross-mixing ability. Various methods can be employed, such as melt-kneading in a machine and melt-kneading using a Banbury mixer or rubber roll machine.

The resin composition of the present invention can be further mixed with other polymers and resins to adjust the desired performance as long as the physical properties are not impaired. For example, ABS resin, MBS@
resin, acrylonitrile-EPDM-styrene terpolymer (AES) resin, polycarbonate, polyamide,
Polybutidine terephthalate, polyethylene terephthalate, and the like may be mixed. Depending on the purpose, reinforcing materials and fillers such as pigments, dyes, glass fibers, metal fibers, metal flakes, and carbon fibers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, and electrostatic charges are also added. Inhibitors, flame retardants, etc. can be added.

Hereinafter, the effects of the present invention will be further explained with reference to Examples and Comparative Examples. Izotsu impact strength is ASTM D256. Tensile yield stress and tensile elongation at break were measured according to AS TMD668. Weather resistance was evaluated by irradiating the notched isot puncture test piece with a Zanshine Weather-Ometer.

Reference Example 1 Production of modified vinyl polymer (A) A mixture having the composition shown in Table 1 was polymerized to produce modified vinyl polymer A.
-1 to A and 6 were manufactured.

Table 1 Chain transfer agent (a) I-Mercaptoethylamine hydrochloride (f) Azobisisobutyronitrile Reference example 2 Modified polyolefin (piece production B-1: Peroxidation of 85% by weight of ethylene and 15% by weight of methacrylic acid) Copolymerization was carried out in the presence of a substance according to the production conditions of high-pressure polyethylene, and zinc acetate was added to the obtained copolymer in an amount capable of neutralizing and ionizing 75% of the methacrylic acid contained therein, and the mixture was heated at 180°C using a Loafremill. Uniformly knead ethylene/methacrylic acid/zinc methacrylate copolymer (ionomer resin) B-
1 was manufactured.

B-2: Copolymerization of 79% by weight of tyrene, 11% by weight of isobutyl V acrylic acid, and methacrylic acid was carried out according to the manufacturing conditions of high-pressure polyethylene, and 72% of the methacrylic acid contained in the obtained copolymer was After adding an amount of zinc acetate that can be neutralized and ionized, the same kneading as B-i was carried out to produce ethylene/isobutyl acrylate/methacrylic acid/methacrylic acid zinc copolymer (ionomer resin) B-2. .

B-6: Ethylene 70-E:) v% and Propylene 6
Ethylene/propylene copolymer 1 consisting of ゜mo/L/%
00 parts by weight, α, α/ dissolved in a small amount of acetone
After adding 0.06 parts by weight of -bis-tert-butylperoxy-p-diisopropylbenzene and 1.0 parts by weight of maleic anhydride.

Ethylene/propylene-g-maleic anhydride copolymer (1g+ represents graft) B-6 was produced by kneading and pelletizing at 230°C using an extruder with a diameter of 40+++ mφ. .

B-4: Ethylene 80 mol% E, 1: Ethylene/propylene copolymer 10 consisting of 20 mol% of hypropylene
After adding 0.1 parts of Sitargy t-butyl peroxide dissolved in a small amount of acetone and 1.0 parts of Acrylic acid to the 0-weight plate part, it was made into a 40 mmφ similar to B-3.
Ethylene/propylene-g-1 acrylic acid copolymer B-4 was produced by kneading and pelletizing at 200° C. using an extruder with a diameter of 1 mm.

B-5: Ethyl V-propylene-5-ethylidene-2-halebornene (EPD) with Mooney viscosity of 60 and iodine value of 12.
M) Terpolymer (ethylene/propylene-68,,5
/31.5 (molar ratio)) 100 parts by weight, di-t-butylene dissolved in a small amount of acetone! Liver oxide 0.
After adding 1 part by weight and 0.5 part by weight of maleic anhydride, 23
By kneading and pelletizing at 0°C, EPDM-g
-Maleic anhydride copolymer B-5 was produced.

Reference Example 5 Vinyl polymer (Production of 9) Monomer mixture having the composition shown in Table 2 0.1 part of t-dodecylmercapcan as a chain transfer agent and 0.5 part of azoisobutyronitrile as an initiator was used to produce a normal vinyl polymer (C) containing no amino groups.

(Blank below the wooden page) Table 2 Example 1 The modified vinyl polymer (A) produced in Reference Example 1 and the modified polyolefin (B) produced in Reference Example 2 were mixed in the proportions shown in Table 2, and a vented polymer was prepared. A turret was manufactured by melt mixing and extrusion at a resin temperature of 220° C. using an extruder with a diameter of 40 gφ. Next, a test piece was molded using an injection molding machine at a cylinder temperature of 230°C and a mold temperature of 50°C.
Each physical property was measured.

For Izot impact strength, Weatheroffter 10
Measurements were taken before (a) and after (1) irradiation for 0 hours,
Impact resistance and weather resistance were evaluated simultaneously.

The measurement results are shown in Table 5.

Comparative Example 1 The vinyl polymer (C) produced in Reference Example 3 and the modified polyolefin (B) produced in Reference Example 2 were mixed in the proportions shown in Table 2, and the physical properties were measured in the same manner as in Example 1. did. The results are also shown in Table 2.

Comparative Example 2 The modified vinyl polymer (A) produced in Reference Example 1, the vinyl polymer (C) produced in Reference Example 3, and the following rubbery polymer (D) in the proportions shown in Table 2 Example 1
The physical properties were measured in the same manner as above, and the results are shown in Table 2.

Rubber-like polymer (g) D-1 = Ethylene-propylene copolymer D-2 consisting of 70 mol% of engineered ethylene and 30 mol of oyohypropylene D-2: A-
-”-Ethylene-5-ethylidene with viscosity and iodine value of 12
2-norbornene terpolymer (ethylene/propylene 68.5/31.5 (mole ratio)) The following is clear from the results of Example 1, Comparative Example 1, and Comparative Example 2 (Table 6). . Resin composition of the present invention (melon 1-
No. 14) is an impact-resistant resin with excellent impact strength, tensile yield stress, and tensile elongation at break. In addition, the impact strength hardly decreases even after 100 hours of irradiation with a weatherometer, and it also has weather resistance. On the other hand, if the rubber-like polymer does not have a functional group such as a carboxyl group, impact resistance will not be developed even if the modified vinyl polymer (A) is mixed therein.
~25). In addition, if the vinyl polymer does not have a functional group such as an amino group, impact resistance will not be developed even if the modified polyolefin (B) or rubbery polymer (B) is mixed.
imaginary 15-19 and 26-29).

Example 2 Modified vinyl polymer (A) and modified polyolefin (B)
In addition, a vinyl polymer (c) and a rubbery polymer (D) were mixed in the proportions shown in Table 4, and their physical properties were measured in the same manner as in Example 1. Table 4 shows the blending ratio and measurement results.

As is clear from the results of Example 2 (Table 4), in addition to the modified vinyl polymer (A) and modified polyolefin (B),
A resin composition with even better impact strength and mechanical properties can also be obtained by appropriately mixing an ordinary vinyl polymer (q and/or rubber-like polymer CD).

As explained above, the resin composition of the present invention has excellent mechanical properties such as impact strength and good weather resistance. Furthermore, since it can be manufactured simply by melting and mixing each resin component, productivity is extremely high.

Therefore, by taking advantage of these features, it is expected that it will be applied to various uses in the future.

Patent applicant: Toshi Co., Ltd.

Claims (1)

[Scope of Claims] (A) (a) At least one selected from the group consisting of an amino group, a substituted amine group, and a mineral acid salt thereof in the molecule. Consisting of (b) aromatic vinyl monomer, vinyl cyanide monomer and (meth)acrylate monomer in the presence of a chain transfer agent and/or initiator having one type of functional group a modified vinyl polymer obtained by polymerizing at least one vinyl monomer selected from the group; and CB) at least one member selected from the group consisting of a carboxylic acid group, a carboxylic acid metal base, and an acid anhydride group. A modified polyolefin having a functional group of 60 to 99 parts by weight (A) (7 parts by weight)
1. A thermoplastic resin composition characterized in that it is blended in a proportion of 0 to 1 part by weight and a total of 100 parts by weight (with (A)).