JP3405478B2 - Thermoplastic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent heat resistance, impact resistance, chemical resistance, dimensional stability and moldability. More specifically, a copolymer containing an unsaturated dicarboxylic acid anhydride monomer residue and an unsaturated dicarboxylic acid imide monomer residue in a specific ratio, a specific graft copolymer, a polyamide resin, and a specific The present invention relates to a thermoplastic resin composition containing an ethylene-α-olefin elastomer having an unsaturated dicarboxylic acid and / or an anhydride group thereof at a ratio as an essential component. The thermoplastic resin composition of the present invention can be preferably used for automobile parts, electric / electronic parts, office equipment parts, heat appliances, tableware, refrigerator parts, bath parts, shower parts, water purifier parts, toilet seats and the like.

[0002]

2. Description of the Related Art Conventionally, a method for producing a copolymer having an unsaturated dicarboxylic acid imide derivative residue has been known (US Pat. No. 3,840,499, US Pat. No. 39).
9907). However, although the copolymer having an unsaturated dicarboxylic acid imide derivative residue is excellent in heat resistance and dimensional stability, there is a problem that impact resistance, chemical resistance and moldability are poor.

Therefore, a resin composition in which an ABS resin is blended with a copolymer having an unsaturated dicarboxylic acid imide derivative residue to improve impact resistance is also known (US Pat. No. 3,642,949, US). Japanese Patent No. 3652726, Japanese Unexamined Patent Publication No. 57-98536, Japanese Unexamined Patent Publication No. 57-
No. 125241). However, the resin composition obtained by blending these ABS resins has a drawback that the chemical resistance is not sufficient, although the impact resistance is improved.

Further, for the purpose of improving the chemical resistance of a copolymer having an unsaturated dicarboxylic acid imide derivative residue, a resin composition prepared by blending a polyamide resin with this copolymer has also been proposed (Japanese Patent Laid-Open Publication No. Sho. 58-71952, JP-A-63-17949, JP-A-3-277648, and JP-A-1-215843). By blending a polyamide resin, chemical resistance can be improved, but various problems have occurred.

For example, in JP-A-58-71952, although this resin composition has excellent chemical resistance, the compatibility between the blended resins is not sufficient and there is a drawback that peeling occurs in a molded product. . In addition, the amount of polyamide resin is 20
Impact resistance improves when it exceeds 20% by weight, but 20% by weight
If it becomes less than the following, impact resistance and chemical resistance will be extremely lowered. Further, an example in which an ABS resin is added to improve impact resistance is described in the examples. This is when the amount of polyamide resin exceeds 20% by weight, and when the amount is 20% by weight or less, ABS is used. Even if a resin is added, the impact resistance is low and it is not suitable for practical use.

Further, Japanese Patent Laid-Open No. 63-17949 proposes a resin composition comprising a copolymer having an unsaturated dicarboxylic acid imide derivative residue, a polyamide resin, and a graft copolymer. In this resin composition, when the content of the polyamide resin is large, the impact resistance is improved but the dimensional stability is lowered, and when the content of the polyamide resin is small, the dimensional stability is improved, but the impact resistance and the There is a drawback that the chemical properties are lowered.

Further, in JP-A-3-277648, in order to improve the compatibility of the copolymer having an unsaturated dicarboxylic acid imide derivative residue with a resin composition of a polyamide resin, an unsaturated dicarboxylic acid imide derivative residue is used. There has been proposed a resin composition comprising a group-containing polymer and an unsaturated dicarboxylic acid anhydride monomer residue as the copolymer, and the copolymer and a polyamide resin. Although the compatibility of this resin composition is greatly improved, since the polyamide resin content is 30% by weight or more, there is a drawback that the dimensional stability is poor. Further, when the amount of polyamide resin of this resin composition is less than 30% by weight, impact resistance is significantly lowered.

Further, JP-A 1-215843 discloses a copolymer having an unsaturated dicarboxylic acid imide derivative residue, a polyamide resin, and an ethylene-α-olefin having an unsaturated dicarboxylic acid and / or its anhydride. A resin composition composed of a system elastomer copolymer has been proposed. This resin composition has very good impact resistance, heat resistance and chemical resistance, but the polyamide resin is 30% by weight.
From the above, there is a drawback that the dimensional stability is poor. Further, if the amount of polyamide resin of this resin composition is less than 30% by weight, the impact resistance is significantly lowered and it is difficult to actually use it.

Further, it has been known that a polyamide resin and a resin composition containing a polyamide resin are generally excellent in chemical resistance. However, when the amount of the polyamide resin in the resin composition is large, dimensional stability due to water absorption is obtained. Deteriorates, so that poor fitting, warpage and deformation are likely to occur during the assembly of molded products, and when the amount of polyamide resin is small, the dimensional stability due to moisture absorption is improved, but the chemical resistance is low and the impact resistance is low. There is a drawback to decrease. When the amount of the polyamide resin is small, it may be possible to add a rubber-like polymer such as SBR or MBS in order to improve the impact resistance, but in reality, the impact resistance improving effect was poor.

[0010]

As described above, the present invention provides a resin composition using a copolymer having an unsaturated dicarboxylic acid imide derivative residue, which has high heat resistance, high impact resistance, and high resistance to impact. A resin composition excellent in chemical properties and dimensional stability has not yet been obtained, and under the present circumstances, there is a strong demand for development of a high-performance resin composition having these properties. Therefore, they have arrived as a result of intensive research aimed at providing a resin composition having these high performances.

[0011]

The inventors of the present invention have earnestly studied for the purpose of developing a resin having high heat resistance, high impact resistance, chemical resistance and dimensional stability. Copolymers having unsaturated dicarboxylic acid anhydride monomer residues and unsaturated dicarboxylic acid imide monomer residues, graft copolymers, polyamide resins, and unsaturated dicarboxylic acids and / or their anhydrides in specific proportions It was found that the above object can be achieved when an ethylene-α-olefin elastomer copolymer having a physical group is used as an essential component and blended in a specific ratio, and the present invention has reached the thermoplastic resin composition of the present invention.

That is, in the present invention, the component (A): aromatic vinyl monomer residue 40 to 80% by weight, unsaturated dicarboxylic acid anhydride monomer residue 20% by weight or less (however, 0 is not included). , Unsaturated dicarboxylic acid imide derivative residue 10% by weight
5 to 50% by weight of a maleimide-based copolymer consisting of 0 to 20% by weight and a vinyl monomer residue copolymerizable with the above, and (B) component: an aromatic vinyl monomer residue 0 to 50% by weight of a vinyl-based copolymer comprising 60 to 80% by weight, 20 to 40% by weight of vinyl cyanide monomer residues, and 0 to 20% by weight of vinyl monomer residues copolymerizable therewith Component (C): 50 to 80% by weight of an aromatic vinyl monomer, 20 to 40% by weight of a vinyl cyanide monomer, and 35 to 65 parts by weight of a rubbery polymer, and a vinyl monomer copolymerizable therewith. Monomer mixture 35-65 consisting of 0-30% by weight
Graft copolymers having 5 parts by weight graft polymerized 10-5
Ethylene-α having 0% by weight, (D) component: 3 to 20% by weight of polyamide resin, and (E) component: 5% by weight or less of unsaturated dicarboxylic acid and / or its anhydride (excluding 0). -Olefin-based elastomer copolymer 2-12
Weight of Ri Do from the weight%, and component (D) and (E) component
The ratio is (E) / (D) = 30/70 to 60/40
That is a thermoplastic resin composition.

The greatest feature of the thermoplastic resin composition of the present invention is that the polyamide resin is 20% by weight or less, but the chemical resistance, heat resistance, impact resistance, dimensional stability and moldability are very excellent. That is the point.

First, the maleimide copolymer as the component (A) contained in the thermoplastic resin composition of the present invention will be described. As the aromatic vinyl monomer constituting the component (A), styrene, α-methylstyrene, vinyltoluene,
Examples thereof include styrene-based monomers such as t-butylstyrene and chlorostyrene, and among these, styrene is particularly preferable.

Examples of the unsaturated dicarboxylic acid imide derivative include maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-naphthylmaleimide and glutarimide.

Examples of unsaturated dicarboxylic acid anhydrides include anhydrides such as maleic acid, itaconic acid, citraconic acid and aconitic acid, with maleic anhydride being particularly preferred.

Vinyl monomers copolymerizable with these include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester and butyl acrylic acid ester. Polymer, methyl methacrylate,
Examples thereof include methacrylic acid ester monomers such as ethyl methacrylic acid ester, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amides, methacrylic acid amides, and N-vinylcarbazole. Among these, monomers such as acrylonitrile, acrylic acid ester, methacrylic acid ester, acrylic acid and methacrylic acid are particularly preferable.

In producing the component (A), the first production method is an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide derivative, an unsaturated dicarboxylic acid anhydride monomer and vinyl copolymerizable with these. A method of copolymerizing a monomer mixture, and a second production method is an aromatic vinyl monomer,
After copolymerizing the unsaturated dicarboxylic acid anhydride monomer and the vinyl monomer mixture copolymerizable therewith, the unsaturated dicarboxylic acid anhydride group in the copolymer is converted into ammonia and / or primary Examples thereof include a method of reacting with an amine to convert to an imide group, and a maleimide-based copolymer can be obtained by any method.

In the case of the first production method, bulk-suspension polymerization, solution polymerization and bulk polymerization, and in the case of the second production method, suspension polymerization,
Known polymerization methods such as emulsion polymerization, solution polymerization and bulk polymerization can be used.

The ammonia or primary amine used in the imidization reaction to obtain the maleimide-type copolymer in the second production method may be in either anhydrous or aqueous solution.
Examples of primary amines include alkylamines such as methylamine, ethylamine and cyclohexylamine, and aromatic amines such as aniline, toluidine and naphthylamine.

When the imidization reaction is carried out in a solution state or a suspension state, it is preferable to use an ordinary reaction vessel, for example, an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device is used. May be.

The temperature of the imidization reaction is about 80 to 350 ° C, preferably 100 to 300 ° C. When the temperature is lower than 80 ° C, the reaction rate is slow and the reaction requires a long time, which is not practical. On the other hand, when the temperature exceeds 350 ° C, the physical properties are deteriorated due to thermal decomposition of the polymer. A catalyst may be used during the imidization reaction, and in this case, a tertiary amine such as triethylamine is preferably used.

The aromatic vinyl monomer residue used in the component (A) is 40 to 80% by weight, preferably 43 to 7%.
0 wt% is preferred. If it is less than 40% by weight, the moldability is lowered, and if it exceeds 80% by weight, the heat resistance is lowered.
The unsaturated dicarboxylic acid anhydride monomer residue is 20% by weight (however, 0 is not included) or less, and 0.5 to 15% by weight is particularly preferable. When it is 0% by weight, the compatibility between the component (A) and the polyamide resin is lowered, which not only causes the layer separation of the molded article of the resin composition but also the impact strength and the chemical resistance are lowered. If it exceeds 20% by weight, the reaction with the terminal amino groups in the polyamide resin becomes excessive, and not only the surface appearance is impaired, but also impact resistance and moldability are deteriorated. Further, the unsaturated dicarboxylic acid imide derivative residue is 10% by weight or more and less than 60% by weight, and 25 to 55% by weight is particularly preferable.
If it is less than 10% by weight, the heat resistance is not sufficiently improved, and if it is more than 60% by weight, the impact resistance of the composition is significantly lowered. Further, the vinyl monomer residue copolymerizable with these is 0 to 20.
% By weight, and if it exceeds 20% by weight, the impact resistance decreases.

Next, the vinyl copolymer as the component (B) will be described. Examples of the aromatic vinyl monomer used in the component (B) of the present invention include styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene, and styrene is particularly preferable. preferable. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and the like, and acrylonitrile is particularly preferable.

As the vinyl monomer copolymerizable with these, acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester, butyl acrylic acid ester, etc., methyl methacrylic acid ester, ethyl methacrylic acid ester And other vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amides, methacrylic acid amides, and N-vinylcarbazole. Of these, monomers such as methacrylic acid ester, acrylic acid and methacrylic acid are particularly preferable.

The component (B) can also be produced by a usual polymerization method,
For example, a polymerization method such as suspension polymerization, solution polymerization or emulsion polymerization can be adopted.

The aromatic vinyl monomer residue in the component (B) is 60 to 80% by weight, preferably 68 to 78% by weight.
Is. If it is less than 60% by weight, the moldability is lowered, and if it exceeds 80% by weight, the heat resistance is lowered. The vinyl cyanide monomer residue is 20 to 40% by weight, and particularly 22
˜32% by weight is desirable. Less than 20% or 40% by weight
When it exceeds the above range, the compatibility with the component (A) as the thermoplastic resin composition decreases, which causes layer peeling of the composition and a decrease in impact strength.

Next, the graft copolymer of the component (C) of the present invention will be described. The rubber-like polymer used as the component (C) is a butadiene polymer, a copolymer of a vinyl monomer copolymerizable with butadiene, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, and Examples thereof include an acrylic acid ester polymer and a copolymer of an acrylic acid ester and a vinyl monomer copolymerizable with the acrylic acid ester.

Examples of the aromatic vinyl monomer used as the component (C) include styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene, and particularly styrene. Is preferred. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and the like, and acrylonitrile is particularly preferable.

As the vinyl monomer copolymerizable with them, acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester and butyl acrylic acid ester, methyl methacrylic acid ester, ethyl methacrylic acid ester And the like, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amides, methacrylic acid amides, and N-vinylcarbazole, and the like. Monomers such as acid esters, acrylic acid and methacrylic acid are particularly preferred.

Any known polymerization technique can be employed in the production of this graft polymer, for example, aqueous heterogeneous polymerization such as suspension polymerization and emulsion polymerization, bulk polymerization, solution polymerization and a poor solvent for the resulting polymer. Precipitation heterogeneous polymerization, etc., as well as combinations thereof.

The rubber particle size of the graft copolymer is 0.1 to
The range of 0.6 μm is preferable from the viewpoint of impact resistance. When the graft ratio is 20 to 80% and the weight average molecular weight of the ungrafted copolymer is in the range of 50,000 to 200,000, the impact resistance and the moldability are well balanced.

The component (C) is 50 to 80% by weight of an aromatic vinyl monomer in the presence of 35 to 65 parts by weight of a rubber-like polymer,
It is obtained by graft-polymerizing 35 to 65 parts by weight of a monomer mixture consisting of 20 to 40% by weight of a vinyl cyanide monomer and 0 to 30% by weight of a vinyl monomer copolymerizable therewith. In particular, 65 to 70% by weight of an aromatic vinyl monomer, 22 to 32% by weight of a vinyl cyanide monomer, and 3 to 13 % by weight of a vinyl monomer copolymerizable therewith are preferable. If the amount of the aromatic vinyl monomer is less than 50% by weight, the moldability will be lowered, and if it exceeds 80% by weight, the heat resistance will be lowered. Further, if the vinyl cyanide monomer is less than 20% by weight or more than 40% by weight, the compatibility with the component (A) as the thermoplastic resin composition decreases, resulting in delamination and impact strength of the thermoplastic resin composition. It causes a decrease. If the amount of the rubber-like polymer is less than 35 parts by weight, the impact resistance will decrease, and if it exceeds 65 parts by weight, the heat resistance and the moldability will decrease.

In the graft polymerization, it is usually difficult to graft the entire amount of the monomer onto the rubber-like polymer, and an ungrafted copolymer is produced as a by-product. In the present invention, not only the true graft copolymer in which the ungrafted copolymer is positively separated and removed, but also the graft polymerization in which the ungrafted copolymer is contained may be used. It can be handled.

Next, the component (D) polyamide resin of the present invention will be described. Examples of the polyamide resin as the component (D) include nylon-6, nylon-6,6, nylon-4,6, nylon-6,10, nylon-12, nylon-11, etc., which may be used alone or in combination. It can also be used.

Next, ethylene-α as the component (E) of the present invention.
-The olefin elastomer will be described. (E)
The ethylene-α-olefin elastomer having an unsaturated dicarboxylic acid and / or its anhydride as a component has a number average molecular weight of 10,000 to 1,000,000.
And an ethylene content of 50 to 80 mol% is preferable. As the α-olefin, propylene, 1-butene, 1-pentene can be used,
Particularly, propylene is preferable.

Further, the unsaturated dicarboxylic acid and / or its anhydride used for modification as the functional group of the component (E) include maleic acid, itaconic acid, citraconic acid, aconitic acid and their acid anhydrides. Maleic anhydride is preferred.

The content of the unsaturated dicarboxylic acid and / or its anhydride is 5% by weight or less (not including 0), preferably 0.5 to 5% by weight. Gel or the like is generated in the plastic resin composition. On the other hand, if it is less than 0.5% by weight, the compatibility between the resins in the thermoplastic resin composition is insufficient, which causes layer peeling, and the chemical resistance and impact strength are not improved. This modified ethylene-α-olefin-based elastomer is disclosed in Japanese Examined Patent Publication No. 445/445.
It can be obtained by using the manufacturing method and the like of Example 1 disclosed in the publication.

In the thermoplastic resin composition of the present invention, the component (A) component, the component (B), the component (C), the component (D) and the component (E) are mixed in a proportion of 5 to 50% by weight of the component (A). ,
(B) component 0 to 50 wt%, (C) component 10 to 50 wt%, (D) component 3 to 20 wt%, and (E) component 2
It is 12% by weight. Preferably, component (A) 10-40
% By weight, 10 to 40% by weight of component (B), 20 of component (C)
˜45% by weight, component (D) 5 to 15% by weight, and component (E) 5 to 10% by weight. If the content of the component (A) is less than 5% by weight, the heat resistance is not sufficient, and if it exceeds 50% by weight, the impact resistance and moldability of the composition are significantly reduced. Further, if the component (B) exceeds 50% by weight, there is a problem that the heat resistance is lowered. When the content of the component (C) is less than 10% by weight, impact resistance is lowered, and when it exceeds 50% by weight, heat resistance and moldability are lowered. If the content of the component (D) is less than 3% by weight, the chemical resistance is insufficient, and if it exceeds 20% by weight, the dimensional stability is deteriorated. If the content of the component (E) is less than 2% by weight, the impact resistance is not sufficient, and if it exceeds 12% by weight, the moldability and heat resistance deteriorate.

The method of mixing the components (A) to (E) to obtain the thermoplastic resin composition of the present invention is not particularly limited, and known means can be used. Examples of the means include a Banbury mixer, a tumbler mixer, a mixing roll, a single-screw or twin-screw extruder, and the like. Examples of the mixing form include ordinary melt mixing, multistage melt mixing using master pellets, and a method of obtaining the composition by blending in a solution. In particular, the component (D) and the component (E) are melt-mixed in advance to form a master pellet, and the remaining (A) to
When mixed with the component (C), chemical resistance, impact resistance and moldability are further improved. This is because the component (E) is incorporated into the component (D) in an island shape, and the component (D) and the component (E)
It is speculated that this is because the sea-island particles composed of the components are more easily dispersed in the matrix resin of the components (A), (B) and (C).

The thermoplastic resin composition of the present invention further comprises an antioxidant, an ultraviolet absorber, a flame retardant, a plasticizer, a lubricant,
It is also possible to add a colorant, an inorganic filler such as talc, silica, clay, mica and calcium carbonate, and a fiber reinforcing agent such as glass fiber and carbon fiber.

The thermoplastic resin composition of the present invention is used in applications requiring heat resistance, impact resistance, chemical resistance, dimensional stability and moldability. For example, door core materials, instrument panel cores, spoilers, pillar sunroof frames, defroster grills, lamp housings, etc. which are automobile parts, electric / electronic device parts, tableware, heat appliances, electric refrigerator parts, toilet seats, microwave oven parts, OA equipment parts It can be suitably used for industrial machine parts and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded. All parts and% in the examples and comparative examples are based on weight unless otherwise specified.

[0044]

【Example】

Experimental Example 1 Production of component (A) -1 60 parts of styrene and 100 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, the system was replaced with nitrogen gas, and then the temperature was raised to 85 ° C. to give maleic anhydride 40
Parts and 0.15 parts of benzoyl peroxide in 200 parts of methyl ethyl ketone were continuously added over 8 hours. The temperature was kept at 85 ° C. for a further 3 hours after the addition. To the copolymer solution obtained here, 38 parts of aniline and 0.6 part of triethylamine were added and reacted at 140 ° C. for 7 hours. The reaction solution was supplied to a twin-screw extruder with a vent and devolatilized to obtain a maleimide-based copolymer. From C-13 NMR analysis, the conversion rate of acid anhydride groups to imide groups was 92 mol%. This maleimide copolymer was a copolymer containing 52% of N-phenylmaleimide units as an unsaturated dicarboxylic acid imide derivative, and this was designated as copolymer A-1. The other maleimide copolymers A-2 and A-3 were also prepared in the same manner as in A-1, except that the conversion rate of maleic anhydride group to imide group was adjusted by adjusting the addition amount of aniline. Created.

Experimental Example 2 Preparation of component (A) -2 60 parts of styrene and 100 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, the system was replaced with nitrogen gas, and the temperature was raised to 100 ° C. While maintaining the above value, sufficient stirring was performed. Methyl ethyl ketone 150
Polymerization was carried out while continuously adding 40 parts of N-phenylmaleimide and 0.25 part of benzoyl peroxide dissolved therein in 8 hours. After completion of the polymerization, the reaction liquid was supplied to a twin-screw extruder with a vent, devolatilized and dried to obtain a maleimide-based copolymer. According to C-13 NMR analysis, this copolymer was a copolymer containing 42% of N-phenylmaleimide units as an unsaturated dicarboxylic acid imide derivative. This was designated as copolymer A-4. Table 1 shows the composition analysis results and weight average molecular weights of A-1 to A-4. The weight average molecular weight in Table 1 was determined by using gel permeation chromatography and preparing a calibration curve using polystyrene as the standard molecular weight.

[0046]

[Table 1]

Experimental Example 3 Preparation of component (B) In a reaction can equipped with a stirrer, 70 parts of styrene, 30 parts of acrylonitrile, 2.5 parts of tribasic calcium phosphate, 0.5 part of t-dodecylmercaptan, and 0 benzoyl peroxide. .2 parts and 250 parts of water were charged and the temperature was raised to 70 ° C. to start polymerization. 7 hours after the start of polymerization, the temperature is changed to 75 ° C.
The temperature was raised to and kept for 3 hours to complete the polymerization. Polymerization rate is 97
% Has been reached. The obtained reaction solution is neutralized with hydrochloric acid, dehydrated,
After drying, a white bead-shaped copolymer was obtained. This was designated as copolymer B-1.

Experimental Example 4 Production of component (C) Polybutadiene latex 1 was placed in a reactor equipped with a stirrer.
43 parts (solid content 35% weight average particle size 0.25 μm, gel content 90%), sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.1 part, tetrasodium ethylenediaminetetraacetic acid 0.03
Parts, 0.003 parts of ferrous sulfate, and 150 parts of pure water were charged, the temperature was raised to 50 ° C., and 50 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile, t.
-0.2 parts of dodecyl mercaptan and 0.15 part of kyuumen hydroperoxide were continuously added over 6 hours, and after the addition, the temperature was further raised to 65 ° C and polymerization was performed for 2 hours. Polymerization rate is 97%
Reached After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water and dried to obtain a white powdery graft copolymer. This was designated as copolymer C-1.

Next, in order to measure the graft ratio of C-1 and the molecular weight of the ungrafted copolymer, C-1 was swollen in a methyl ethyl ketone solution, and the ungrafted styrene-acrylonitrile copolymer in the centrifuged supernatant solution was used. When the molecular weight of the polymer was measured by gel permeation chromatography, the weight average molecular weight was 82,000. The composition of the gel component (graft copolymer and polybutadiene rubber) precipitated by centrifugation was analyzed by Kjeldahl nitrogen quantitative analysis and pyrolysis gas chromatography, and the weight% of the graft copolymer was determined from the amounts of styrene and acrylonitrile. The polybutadiene rubber was analyzed by the bromine addition method to determine the weight of the polybutadiene rubber. From the weight% of the graft copolymer thus obtained and the weight of the polybutadiene rubber, the grafting rate was calculated from the following equation 1 and the grafting rate was 33%.

[0050]

[Equation 1]

Experimental Example 5 Modified ethylene-α-olefin-based elastomer copolymer of component (E) Ethylene having a number average molecular weight of 500,000 according to the method described in JP-A-52-49289 (according to Example). It was obtained by grafting 2% of maleic anhydride onto a propylene elastomer copolymer. This was designated as E-1. Further, an ethylene-propylene elastomer copolymer having a number average molecular weight of 500,000 before being modified with maleic anhydride was designated as E-2.

Examples 1 to 6 and Comparative Examples 1 to 7 A-1 to A-as the maleimide copolymers of the component (A)
4, B-1 as a vinyl-based copolymer of the component (B),
C-1 as the graft copolymer of the component (C), D-1 as the polyamide resin of the component (D) and E as the acid-modified ethylene-α-olefin elastomer of the component (E).
-1, and E-2 as an unmodified ethylene-α-olefin-based elastomer were blended in the amount ratios shown in Tables 2 and 3, and the blended product was a co-rotating twin-screw extruder with a devolatilizer of 35 m / m. And extruding at a temperature of 250 ° C.
Pelletized. Using the pellets, an injection molding machine was used to prepare test pieces for measuring physical properties at a molding temperature of 250 ° C.
Various physical properties were measured. The results are shown in Table-2 and Table-3.

The polyamide resin as the component (D) has a relative viscosity of 2.65 obtained by condensation polymerization of ε-caprolactam (concentrated sulfuric acid in the solvent, the concentration is 0.5 g / 100 ml, the temperature is 25 ° C.). Nylon- (value measured by
6 was used. This nylon-6 was designated as D-1.

In Example 6, 60 parts of component (D) and 40 parts of component (E) were extruded at 250 ° C. using a co-rotating twin-screw extruder equipped with a 35 m / m devolatilizer to prepare master pellets. , 15 parts of these pellets are used as the remaining component (A) 2
The mixture was blended with 0 part, 30 parts of the component (B) and 35 parts of the component (C) and further extruded with a twin-screw extruder at a temperature of 250 ° C. to form pellets.

When the morphology of the examples was observed with a transmission electron microscope (ruthenium dyeing, 15,000 times), a nylon resin phase having an ethylene-propylene copolymer incorporated therein was dispersed as a dispersed phase.

[0056]

[Table 2]

[0057]

[Table 3]

Test method for measuring physical properties (1) Heat distortion temperature (HDT): According to ASTM D-648, a 1/4 inch thickness test piece was used and a load of 4.6 kg / c.
Measured in m ² . (2) Izod impact strength: measured according to ASTM-D 256 using a notched test piece having a thickness of 1/4 inch. (3) Melt flow rate (MFR): ASTM D-
According to 6874, it was measured at a temperature of 265 ° C. and a load of 10 kgf. (4) Chemical resistance (critical strain): In order to eliminate the influence of molding strain on the test piece, a test piece shape of 330 × 20 × 2 mm obtained by press-molding pellets at 270 ° C. was used, and a long radius of 248 m.
The critical strain amount after 24 hours at a temperature of 23 ° C. was measured by using a salad oil as a chemical by a 1/4 ellipse method with m and a minor radius of 148 mm. When the critical strain amount is 0.6% or more, it can be judged that the chemical resistance is good. (5) Dimensional stability: ASTM D-638 No. 1 dumbbell was immersed in warm water at 80 ° C. for 24 hours, and the dimensional change in the longitudinal direction of the dumbbell before and after the immersion was measured. Dimensional change rate is 0.5
% Or less was rated as ◯, and more than 0.5% was rated as x.

As is clear from the results shown in Table 2, the compositions of Examples 1 to 6 had a large critical strain with respect to chemicals,
It has excellent chemical resistance, as well as excellent heat resistance, impact resistance, moldability, and dimensional stability.

On the other hand, as shown in Table 3, since the composition of Comparative Example 1 contains no maleimide-based copolymer,
Poor impact resistance, heat resistance, and chemical resistance.

The composition of Comparative Example 2 does not contain a maleic anhydride-modified ethylene-propylene copolymer, and therefore has poor impact resistance and chemical resistance.

The composition of Comparative Example 3 contained a large amount of nylon-6 and had sufficient chemical resistance, but was inferior in dimensional stability.

In the composition of Comparative Example 4, the composition of the maleimide copolymer was outside the scope of the present invention (the maleimide anhydride residue was large in the maleimide copolymer) and the moldability (MFR) was high.
Is extremely inferior.

In the composition of Comparative Example 5, the composition of the maleimide copolymer is outside the scope of the present invention (the maleimide copolymer does not have the amount of unsaturated dicarboxylic acid anhydride residues),
Poor impact resistance and chemical resistance.

The composition of Comparative Example 6 had a maleimide copolymer content outside the range of the present invention, and was inferior in impact resistance and moldability (MFR).

The composition of Comparative Example 7 was prepared by using an unmodified ethylene-propylene elastomer copolymer in place of the modified ethylene-α-olefin elastomer copolymer as the component (E), and was excellent in impact resistance. Inferior.

[0067]

The thermoplastic resin composition of the present invention comprises a specific maleimide-based copolymer, a specific graft copolymer, a vinyl-based copolymer, a polyamide resin, and a modified ethylene-α-olefin-based copolymer. This thermoplastic resin composition, which is made of a polymer, has excellent chemical resistance and also has an excellent balance of physical properties such as impact resistance, heat resistance, moldability, and dimensional stability. The composition of the present invention is used as a material for automobile parts, electric / electronic parts, office equipment parts, heat appliances, tableware, refrigerator parts, bath parts, shower parts, water purifier parts, toilet seats, etc., which are required to have these properties. It can be applied particularly effectively.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP 62-22844 (JP, A) JP 1-318060 (JP, A) JP 2-311545 (JP, A) JP 62- 179546 (JP, A) JP 62-59647 (JP, A) JP 2-132140 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 35/06 C08L 25 / 08 C08L 51/04 C08L 77/00

Claims (2)

(57) [Claims] 1. Component (A): aromatic vinyl monomer residue 4
0 to 80% by weight, unsaturated dicarboxylic acid anhydride monomer residue 20% by weight or less (however, 0 is not included), unsaturated dicarboxylic acid imide derivative residue 10% by weight or more and less than 60% by weight, and these Copolymerizable vinyl monomer residue 0 to
5 to 50% by weight of a maleimide-based copolymer comprising 20% by weight, (B) component: 60 to 80% by weight of an aromatic vinyl monomer residue, 20 to 40% by weight of a vinyl cyanide monomer residue, and 0 to 50% by weight of a vinyl-based copolymer composed of 0 to 20% by weight of a vinyl monomer residue copolymerizable with these, and (C) component: 35 to 65 parts by weight of a rubber-like polymer and an aromatic vinyl monomer. Monomer mixture 35-65 comprising 50 to 80% by weight of a monomer, 20 to 40% by weight of a vinyl cyanide monomer, and 0 to 30% by weight of a vinyl monomer copolymerizable therewith.
Graft copolymers having 5 parts by weight graft polymerized 10-5
Ethylene-α having 0% by weight, (D) component: 3 to 20% by weight of polyamide resin, and (E) component: 5% by weight or less of unsaturated dicarboxylic acid and / or its anhydride (excluding 0). -Olefin-based elastomer copolymer 2-12
Weight of Ri Do from the weight%, and component (D) and (E) component
The thermoplastic resin composition, wherein the ratio is (E) / (D) = 30/70 to 60/40 . 2. A resin composition comprising a component (D) and a component (E) is melt-mixed in advance, and the component (A) and the component (B) are further mixed.
The thermoplastic resin composition according to claim 1, wherein the component and the component (C) are mixed.