JPS63270755A - Thermoplastic resin composition of good residence heat stability - Google Patents

Abstract

PURPOSE:To make it possible to improve the residence heat stability, by using a specified rubber-containing resin graft product in a composition comprising a copolymer having imide groups as side chains, a rubber-containing resin graft product and a polycarbonate and/or polyester resin. CONSTITUTION:The following components A-D are mixed together: [A] 10-85wt.% specified copolymer having imide groups as side chains, [B] 10-80wt.% graft copolymer obtained by emulsion-polymerizing 20-95pts.wt. graft polymerization monomer mixture comprising an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer copolymerizable therewith with 5-80pts.wt. acrylic rubberlike polymer obtained by emulsion-polymerizing a monomer mixture comprising 1-13C alkyl acrylate, a vinyl monomer copolymerizable therewith and a crosslinking compound with the aid of an organic sulfonate, [C] 5-70wt.% polycarbonate and/or polyester and [D] 0-80wt.% copolymer comprising an aromatic vinyl monomer, a vinyl cyanide monomer, etc.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a thermoplastic resin composition having excellent heat resistance and retention heat stability. It can be preferably used for office equipment parts, heating appliances, etc.

(Prior art and problems) Resin compositions with a good balance of heat resistance and impact resistance, which are composed of copolymers having imide groups in side chains, rubber-containing resin grafts, and polycarbonate and/or polyester resins, have been known for some time. (Japanese Unexamined Patent Publication No. 57-125241).

However, the better the heat resistance of this type of composition, the higher the molding temperature (the higher the molding temperature), so if it remains in the cylinder of the molding machine, it will deteriorate in an extremely short period of time, resulting in a marked decrease in the impact strength of the molded product, coloring, and It exhibits so-called poor retention thermal stability phenomena such as occurrence of flash.

Attempts to improve the retention thermal stability of this type of composition have already been reported (Japanese Patent Application Laid-Open No. 62-25148). By adding an organic carboxylic acid (anhydride), etc., thermal deterioration of the polycarbonate component is mainly suppressed, and the residence thermal stability of the composition is considerably improved. However, when considering the molding cycle of an actual machine, further improvement is desired.

(Means for Solving the Problems) Therefore, the inventor of the present invention conducted extensive research and found that in the composition described above, the rubber-containing resin grafted material was ``an acrylic resin obtained by emulsion polymerization using an organic sulfonate. We have discovered that retention heat stability can be significantly improved by using a "resin graft product obtained by emulsion graft polymerization of a resin using an organic sulfonate" for rubber, and have arrived at the present invention.

That is, the present invention contains component A: 35 to 80% by weight of aromatic vinyl monomer residues, 20 to 65% by weight of unsaturated dicarboxylic acid imide derivative residues,
10 to 85% by weight of a copolymer containing 0 to 30% by weight of vinyl monomer residues other than these and 0 to 30% by weight of a rubbery polymer, and component B: acrylic having an alkyl group having 1 to 13 carbon atoms. 60 to 99.99% by weight of an acid alkyl ester, 0 to 40% by weight of a vinyl monomer copolymerizable with the same, and 0.01 to 0.01% of a crosslinkable compound having two or more carbon-carbon unsaturated bonds in one molecule. Acrylic rubber-like polymer obtained by emulsion polymerization of a monomer mixture consisting of 20% by weight using 0.01 to 1.0 parts by weight of an organic sulfonate per 100 parts by weight of this mixture. monomers for graft polymerization consisting of 40 to 90% by weight of aromatic vinyl monomers, 0 to 40% by weight of vinyl cyanide monomers, and 0 to 40% by weight of vinyl monomers copolymerizable with these. 20 to 95 parts by weight of the monomer mixture, and 0.01 to 95 parts by weight per 100 parts by weight of the monomer mixture.
10 to 80% by weight of a graft copolymer obtained by emulsion polymerization using 1 part by weight of an organic sulfonate; Component C: 5 to 80% by weight of one or more polymers selected from polycanibonates and/or polyesters; 70% by weight, component D: a copolymer consisting of 40 to 90% by weight of aromatic vinyl monomers, 0 to 40% by weight of vinyl cyanide monomers, and 0 to 40% by weight of vinyl monomers copolymerizable with these. Polymer 0-8
This is a heat-resistant thermoplastic resin composition with excellent residence heat stability, characterized by containing a resin consisting of 0% by weight.

The resin composition of the present invention may consist only of component A, component B, and component C, but it may further contain an aromatic vinyl copolymer as component D in an amount of 80% by weight or less. However, since the excellent properties of the thermoplastic resin of the present invention are not deteriorated, it has the advantage that a large amount of an inexpensive aromatic vinyl copolymer can be blended.

First, component A will be explained.

The aromatic vinyl monomer residues constituting the copolymer include styrene monomers and their substituted products such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, among which styrene is particularly preferred.

The unsaturated dicarboxylic acid imide derivative residue contained in the copolymer is an imide monomer such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-naphthylmaleimide, etc. The anhydride of an unsaturated dicarboxylic acid such as maleic acid, itaconic acid, citraconic acid, or aconitic acid (among these, the anhydride of maleic acid is particularly preferred) An imide derivative may be obtained by copolymerizing and then reacting with ammonia and/or a primary amine.

Examples of primary amines used in the imidization reaction include alkyl amines such as methylamine, ethylamine, butylamine, and cyclohexylamine, and aromatic amines such as chloro- or bromo-substituted alkyl amines, aniline, tolylamine, and naphthylamine, and chloro- or bromo-substituted alkyl amines. Examples include halogen-substituted aromatic amines such as substituted aniline.

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

Further, a catalyst may be present during imidization, and for example, a tertiary amine or the like is preferably used.

The temperature of the imidization reaction is about 80°C to 350°C, preferably 100 to 300°C. If the temperature is lower than 80°C, the reaction rate is slow and the reaction takes a long time, which is not practical. On the other hand, if the temperature exceeds 350°C, the physical properties will deteriorate due to thermal decomposition of the polymer. Further, the amount of ammonia and/or primary amine to be reacted is preferably 0.8 molar equivalent or more based on the unsaturated dicarboxylic anhydride group. If it is less than 0.8 molar equivalent, a large amount of acid anhydride groups will be present in the imidized polymer, resulting in decreased thermal stability and hot water resistance, which is not preferable.

Vinyl monomer residues other than aromatic vinyl monomer residues and unsaturated dicarboxylic acid imide derivative residues are combined with aromatic vinyl monomer and unsaturated dicarboxylic acid anhydride and/or unsaturated dicarboxylic acid imide. A group (monomer residue) is added to the polymerized vinyl monomer.

Vinyl monomers copolymerizable with aromatic vinyl monomers and unsaturated dicarboxylic acid anhydrides and/or unsaturated dicarboxylic acid imides include vinyl cyanide monomers such as acrylonitrinopemethacrylonitrile and α-chloroacrylonitrile. acrylic acid alkyl ester monomers having an alkyl group having 1 to 13 carbon atoms, methacrylic acid alkyl ester monomers having an alkyl group having 1 to 4 carbon atoms, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid. Acrylic acid amide, methacrylic acid amide, etc. Among these, acrylonitrile, methacrylic acid alkyl ester,
Monomers such as acrylic acid and methacrylic acid are preferred.

Examples of rubbery polymers include butadiene polymers, copolymers of butadiene and copolymerizable vinyl monomers, and ethylene-
Propylene copolymers, block copolymers of butadiene and aromatic vinyl, acrylic acid alkyl ester polymers, and copolymers of acrylic acid alkyl esters and vinyl monomers copolymerizable therewith are used. Considering the deterioration of the final composition obtained by retention in the molding machine, ethylene-propylene copolymers and acrylic acid alkyl ester copolymers are particularly preferred. However, if the final physical property balance (thermal deterioration resistance and impact resistance) is considered, a butadiene copolymer can also be fully used.

Aromatic vinyl monomer residues contained in component A are 35 to 8
If it is less than 35% by weight, the moldability and dimensional stability, which are characteristics of aromatic vinyl compounds, will be impaired.

In addition, the unsaturated dicarboxylic acid imide derivative residue is contained in the component A in an amount of 20 to 65% by weight, and if it is less than 20% by weight, the heat resistance of the final composition will be insufficient;
If it exceeds this, the copolymer will become brittle and its moldability will also deteriorate significantly.

Vinyl monomer residues and rubber-like polymers other than aromatic vinyl monomer residues and unsaturated dicarboxylic acid imide derivative residues are
Each of them can be used in an amount not exceeding 30% by weight in component A, but if it exceeds 30% by weight, it is unfavorable in terms of heat resistance and moldability.

Next, component B will be explained.

The rubber component in component B is mainly composed of an acrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms, preferably methyl acrylate, ethyl acrylate, butyl acrylate, or 2-ethyl-hexyl acrylate. Vinyl or vinylidene monomers copolymerizable with, for example, styrenic monomers such as styrene, α-methylstyrene, and vinyltoluene, vinyl cyanide monomers such as acrylonitrile and α-chloroacrylonitrile, and carbon atoms of 1 to 1. Meccrylic acid alkyl ester monomer having 4 alkyl groups, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amide, methacrylic acid amide, N,N'-dimethylacrylamide, vinyl norbornene, etc. by 40 weight It is also possible to copolymerize within a range not exceeding %. If it exceeds 40% by weight, the properties of the rubber such as rubber elasticity may be impaired, which is not preferable.

In an uncrosslinked state, acrylic rubber is susceptible to deformation during molding and processing, which can lead to deterioration of physical properties. Therefore, during polymerization of rubber, two or more >C=
C<A crosslinkable compound having an unsaturated bond is added to carry out crosslinking simultaneously with polymerization.

Examples of such crosslinking compounds include diacrylate compounds such as divinylbenzene, ethylene glycol diacrylate, diethylene glycol diacrylate, and triethylene glycol diacrylate; Triacrylate compounds, dimethacrylate compounds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate; diaryl compounds such as diaryl phthalate and diaryl maleate; unsaturated aryl carboxylates such as aryl acrylate and aryl methacrylate. , dicyclopentadiene, ethylidenenorbornene, vinylnorbornene, norbornadiene, triallyl cyanurate, triallyl isocyanurate, and the like. The amount of these crosslinking compounds used should be within the range of 20% by weight, preferably 10% by weight, in the rubber; if it exceeds 20% by weight, the rubber elasticity will be significantly reduced.

Further, if it is less than 0.01% by weight, sufficient crosslinking effect cannot be obtained.

The preferred rubber particle size in the composition is a weight average particle size of 0.
．． 05 to 5μ, more preferably 0.1 to 2μ.

If it is less than 0.05μ, the resulting resin composition will have insufficient impact resistance and the molded product will have a noticeable pearl-like pattern, and if it exceeds 5μ, the surface gloss of the molded product will decrease. From the viewpoint of controlling the rubber particle size, emulsion polymerization is most suitable for rubber polymerization, and a desired particle size can be obtained by a known seed polymerization method.

In the present invention, the rubber is produced by emulsion polymerization using an organic sulfonate as an emulsifier.

Examples of preferred organic sulfonates include aliphatic sulfonates such as sodium (or potassium) lauryl sulfate, alkyl group-substituted aromatic sulfonic acids such as sodium (or potassium) dodecylbenzenesulfonate, and sodium laurylnaphthalenesulfonate. salt, sodium (or potassium) dioctyl sulfosuccinate, general formula RO
Examples include higher alcohol sulfate salts represented by 3O3Na (R(K) is an alkyl group), alkyldiphenyl ether disulfoether sulfates represented by the general formula, and polyoxyethylene alkylphenyl ether sulfates represented by the general formula. The amount used is 0.01 to 1.0 per 100 parts by weight of the monomer mixture to be polymerized.
Part by weight is preferably 0.05 to 0.8 part by weight. 0.
If it is less than 160 parts by weight, the emulsified state will become unstable during polymerization, and if it exceeds 160 parts by weight, the amount of emulsifier residue in the final composition will increase, which is unfavorable in terms of heat resistance and thermal stability.

In addition, these organic sulfonate emulsifiers include nonionic ones such as polyoxyethylene alkyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene alkylphenyl ether, oxyethylene/oxypropylene block copolymer, and polyoxyethylene (sorbitan) fatty acid ester. There is no problem even if a type emulsifier is used in combination.

Polymerization initiators that can be used in the emulsion polymerization method include benzoyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, hydrogen peroxide, and peroxide (IJ).
peroxide catalysts such as ammonium persulfate, potassium persulfate, azo catalysts such as azobisisobutyronitrile and reducing agents such as formaldehyde sulfoxylate, L-ascorbic acid, glucose, ferrous sulfate, Examples include redox catalysts in combination with metal salts such as cobalt chloride, chelating agents such as pyrophosphoric acid or disodium ethylenediaminetetraacetate, and the like.

Among these, potassium persulfate, etc. may significantly lower the pH in the polymerization system due to decomposition, so sodium acetate, sodium carbonate, and sodium hydrogen carbonate are used as buffering agents to prevent demulsification and corrosion of the polymerization equipment. It is preferable to add a small amount of a salt of a weak acid such as The polymerization temperature is 3
The temperature is preferably about 0 to 100°C, particularly about 40 to 80°C.

In component B, among the monomer mixture for graft polymerization to be graft-polymerized to rubber, the aromatic vinyl monomers include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene. and substituted monomers thereof, and among these, styrene and α-methylstyrene are particularly preferred. Examples of vinyl cyanide monomers include acrylonitrinope, methacrylonitrinope, α-chloroacrylonitrile, and the like, with acrylonitrile being particularly preferred. Vinyl monomers that can be copolymerized with these include acrylic acid alkyl esters having an alkyl group having 1 to 13 carbon atoms, methacrylic acid alkyl esters having an alkyl group having 1 to 4 carbon atoms, acrylic acid, methacrylic acid. Examples include vinylcarboxylic acid monomers such as acrylic acid amide, methacrylic acid amide, N-alkyl substituted maleimide, N-aromatic substituted maleimide, and the like. The amount of these graft polymerization monomer mixtures used is 2 to 80 parts by weight of rubber.
The amount is 0 to 95 parts by weight, and if it is less than 20 parts by weight, the molded product obtained will have poor moldability and surface appearance, and will also have low rigidity. Also, 95
If the amount exceeds parts by weight, the impact resistance will be insufficient. The proportion of the aromatic vinyl monomer in the monomer mixture is 40 to 90% by weight, but if it is less than 40 parts by weight, the moldability and dimensional stability of the resulting molded product will be impaired. or,
The proportion of the vinyl cyanide monomer in the monomer mixture is from 0 to 40% by weight, but if it exceeds 40% by weight, the moldability deteriorates, which is not preferable.

The organic sulfonate used as an emulsifier in graft polymerization is exactly the same as in rubber polymerization.
The amount used and the reason for limiting the amount are also the same.

Addition methods for the monomer mixture for graft polymerization include bulk addition,
Although there are methods such as partial addition and continuous partial addition of all the monomers for graft polymerization, continuous partial addition is most preferable in order to effectively carry out graft copolymerization to the rubbery polymer. The polymerization temperature is preferably about 30 to 80°C, particularly about 50 to 75°C. Further, the polymerization initiator used is the same as in the case of rubber polymerization.

In addition, in carrying out graft polymerization to rubber in the present invention, sulfur compounds such as normal decyl mercaptan, dodecyl mercaptan, nonyl mercaptan, xanthogen disulfide, terpene, tetrahydronaphthalene, and carbonized 9,10-dihydro anthracene are used. Chain transfer agents such as hydrogen compounds may also be used.

Next, the C component will be explained.

Polycarbonates that can be used as component C include bisphenol A, (4,4'-dihydroxydiphenyl)
ether and 2. 2-(4,4'-dihydroxy-3.5.3',5'-tetrobromodiphenyl) A polymer having a carbonate bond synthesized from bisphere-1-als such as propane and phosgene or diphenyl carbonate, Furthermore, copolycarbonates (homobond copolymers) made from different bisphenols or other bonds of carbonate bonds, such as ester bonds,
Modified polycarbonate resins such as heterobond copolymers having urethane bonds or siloxane bonds in the main chain can also be used.

Polyesters that can be used as component C include dicarboxylic acids such as terephthalic acid, adipic acid, sebacic acid, isophthalic acid, naphthalene dicarboxylic acid, and 1°4-cyclohexanedicarboxylic acid, or diethyl terephthalate, dimethinopetrephthalate, and 1. , dicarboxylic acid derivatives such as dimethyl 4-cyclohexanedicarboxylate, ethylene glycol, 1,3-propylene diol,
■It is a polymer with ester bonds that is synthesized from 4-butanediol and diol compounds such as poly(detramethylene oxide) glycol, and it is also made from different dicarboxylic acids, their derivatives, and different diol compounds. Copolyesters can be used as well.

The composition of the present invention contains at least one kind of polymer selected from these polycarbonates and polyesters as an essential component, but may of course contain two or more kinds of polymers.

Next, the D component will be explained.

The aromatic vinyl monomers used in component D include styrene monomers and substituted products thereof such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene. Among these, styrene and α-methylstyrene are particularly preferred. ``Vinyl cyanide monomers include acrylonitrile, methachloronitrile, α-chloroacrylonitrile, etc. Among these, acrylonitrile is particularly preferred.

Vinyl monomers that can be copolymerized with these have 1 to 1 carbon atoms.
acrylic acid ester monomer having 13 alkyl groups,
Methacrylic acid ester monomers having an alkyl group having 1 to 4 carbon atoms, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amide, methacrylic acid amide,
Examples include acenaphthylene, N-vinylcarbazole, N-alkyl substituted maleimide, N-aromatic substituted maleimide, and the like.

The proportion of aromatic vinyl monomer in component D is 40 to 9.
0% by weight, and that of the weighted vinyl monomer is 0 to 40% by weight, but the reason for limiting the range in this way is to take into account the compatibility with component A, component B, and component C. be.

Any known polymerization method can be employed for the polymerization, such as suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, and precipitation polymerization of the produced polymer in a nonsolvent.

The blending ratio of each component of A, B, C, and D is 10 to 10% for A component.
85% by weight, preferably 15-80% by weight, component B is 10%
~80 parts by weight, preferably 20 to 70% by weight, C component is 5
~70 parts by weight, preferably 10 to 60% by weight, D component is 0
It ranges from 80% by weight, preferably from 0 to 60% by weight.

If the proportion of component A is less than 10 parts by weight, heat resistance will be insufficient,
If it exceeds 85 parts by weight, impact strength decreases. If the proportion of component B is less than 10% by weight, the impact strength will be insufficient, and the
If it exceeds % by weight, the heat resistance and fluidity will be greatly reduced.

If the proportion of C component is less than 5 parts by weight, either the falling weight impact strength or fluidity will be impaired, and if it exceeds 70 parts by weight, there will be disadvantages such as a decrease in hot water resistance and large changes in mechanical properties and dimensions due to moisture absorption. Hail! In addition, fluidity is improved by including component D, but if it exceeds 80% by weight,
This is not preferred because it has the disadvantage of reduced heat resistance and impact strength.

From the composition of the present invention, a resin with a good balance of various physical properties such as heat resistance, impact resistance, and moldability, and excellent retention heat stability in a molding machine can be obtained. This is due to the following reasons. Conceivable.

In the first place, the sources of the impact strength of the composition according to the present invention are the rubber component in the rubber-containing resin graft (ie, component B) and the polycarbonate and/or polyester resin (ie, component C). In the present invention, the rubber in component B, which is one of the sources of strength development, is acrylic rubber, which is less susceptible to thermal deterioration than polybutadiene rubber or the like. (However, this alone does not provide the excellent retention thermal stability seen in the present invention.) However, in order to control the rubber particle size, rubber-containing resin grafts are produced by emulsion polymerization using rubber obtained by emulsion polymerization. It is often obtained by graft polymerization. In this case, fatty acid soaps such as potassium stearate are often and commonly used as emulsifiers, and rubber-containing resin grafts such as CaCA2, A[C
Because it is recovered by salting out with fs, Igs[], etc.
A large amount of metal remains in the form of fatty acid salts (poorly soluble or insoluble in water). It is known that the thermal decomposition of polycarbonate is accelerated by metals (``Plastic Course (5) Polycarbonate Resin'', Nikkan Kogyo Shimbunsha (1969)), and in compositions similar to the present invention, the amount of such residual metals can be reduced. The key point is how to reduce or inactivate it.

The organic sulfonate used as an emulsifier in the present invention can achieve the same emulsifying power with a smaller amount than fatty acid soap, so less metal remains in the rubber-containing resin graft in the form of emulsifier residue after salting out ( Alternatively, the metal may be inactivated), thereby minimizing thermal decomposition of the polycarbonate, which is another source of strength in the composition.
Although the above considerations are considered to be valid, the effect of imparting retention thermal stability to the composition was far greater than initially expected.

The composition of the present invention contains a resin obtained by mixing component A, component B, and component C with component D as necessary, but there is no particular restriction on the mixing method, and known means can be used. Examples of such means include a Banbury mixer, a Henschel mixer, a tumbler mixer, a mixing roll, and a single-screw or twin-screw extruder. As for the mixing form, there are methods of obtaining the composition by ordinary melt mixing, melt kneading at various stages using master pellets, etc., and blending in a solution.

Furthermore, the composition of the present invention may further contain organic (estenopite) phosphorous acid (acid ()phosphorous ester) and organic carboxylic acid (anhydride) shown in JP-A No. 62-25148. Resins such as polyether sulfone, polyether ketone, and polyphenylene sulfide, stabilizers, flame retardants, plasticizers, lubricants, antistatic agents, ultraviolet absorbers, colorants, and talc, silica, clay, mica, glass fiber, and calcium carbonate. It is also possible to add electrically conductive fillers and conductive substances such as carbon fibers and silver powder.

(Examples) Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited to the following Examples unless the gist of the invention is exceeded. In addition, both parts and % in the examples are IT.
Expressed as a standard.

Experimental Example 1 (Synthesis of Component A) 60 parts of styrene and 50 parts of methyl ethyl ketone were placed in an autoclave equipped with a stirrer, and after purging the system with nitrogen gas, the temperature was raised to 85°C, and 40 parts of maleic anhydride was added.
A solution of 0.15 parts of benzoyl peroxide and 180 parts of methyl ethyl ketone was added continuously over 8 hours. The temperature was maintained at 85° C. for an additional 4 hours after the addition. A portion of the reaction solution was sampled and unreacted monomers were determined by gas chromatography. As a result, the polymerization rate was 97.2% for styrene and 99.3% for maleic anhydride. To the copolymer solution obtained here, 38 parts of aniline equivalent to maleic anhydride and 0 parts of triethylamine were added.
．． 3 parts were added and reacted at 150°C for 8 hours. 200 parts of methyl ethyl ketone was added to the reaction solution, cooled to room temperature, poured into 3000 parts of vigorously stirred methanol, precipitated, filtered, and dried to obtain an imidized copolymer. According to MR analysis of C-13 part, the conversion rate of acid anhydride group to imide group was 99.
It was 1%. This imidized polymer was a copolymer containing 54.2% of N-phenylmaleimide units as an unsaturated dicarboxylic acid imide derivative, and was designated as Polymer (2).

Experimental Example 2 (Synthesis of Δ component) In the same autoclave as in Experimental Example 1, 60 parts of styrene,
After charging 70 parts of methyl ethyl ketone and 15 parts of JSR acrylic rubber AR-101 cut into small pieces and stirring at room temperature overnight to dissolve the acrylic rubber AR-101, the inside of the system was replaced with nitrogen gas and the temperature was raised to 85. The temperature was raised to ℃. 40 parts of maleic anhydride and 0.08 parts of benzoyl peroxide
A solution of 0.08 parts of azobisisobutyronitrile and 160 parts of methyl ethyl ketone was added continuously over 8 hours. From this point on, exactly the same operations as in Experimental Example 1 were performed. Polymerization rate: 96.5% styrene, 9% maleic anhydride
It was 9.7%. The conversion rate of acid anhydride groups to imide groups was 98.9%. This imidized copolymer was a copolymer containing 48.7% of N-phenylmaleimide units as an unsaturated dicarboxylic acid imide derivative, and was designated as Polymer (2).

Experimental Example 3 (Synthesis of Δ component) In the same autoclave as in Experimental Example 1, 55 parts of styrene,
Aniline 3 of Experimental Example 1 was prepared by adding 5 parts of acrylonitrile.
The same procedure as in Experimental Example 1 was performed except that 8 parts of aniline were replaced with 32 parts of aniline and 2 parts of methylamine. The polymerization rate was 98.2% for styrene, 95.7% for acrylonitrile, and 99.8% for maleic anhydride. The conversion rate of acid anhydride groups to imide groups was 97.9%. This imidized polymer contains 53.6% of N-phenylmaleimide and N-methylmaleimide units as unsaturated dicarboxylic acid imide derivatives.
This is a copolymer containing the following, and this is designated as Polymer ①.

(1) Polymerization of goto (first stage of seeds) 200 ml of ion-exchanged pure water in an autoclave equipped with a stirrer
1 part, 2.0 parts of sodium acetate, and 0.5 part of sodium dodecylbenzenesulfonate, and heated to 70°C with stirring.
After the temperature was raised to 0.15 parts of potassium persulfate, a mixture of 100 parts of butyl acrylate, 2 parts of divinylbenzene, and 0.2 parts of triallyl isocyanurate was continuously added over 4 hours.

After the addition, stirring was continued for an additional 3 hours at 70°C. The polymerization rate of butyl acrylate was 99.6%.

The weight average particle size of the rubber latex synthesized here was determined to be 0.10 μm using a calibration curve showing the relationship between absorbance and weight average particle size using polystyrene latex with a known weight average particle size. Further, when the latex was observed using an electron microscope, the particle diameter was found to be almost uniform. The rubber latex obtained here is called Lx-〇.

(2) Polymerization of rubber (seed second stage) 10 parts of Lx-■ obtained in (1) in terms of solid content, 170 parts of ion-exchanged pure water, 2.0 parts of sodium acetate, 0.0 parts of sodium dodecylbenzenesulfonate. 2 parts were placed in an autoclave equipped with a stirrer, the temperature was raised to 70°C, 0.12 parts of potassium persulfate was added, and a mixture of 100 parts of butyl acrylate and 3 parts of divinylbenzene was continuously added over 6 hours. After the addition, the mixture was further stirred at 70° C. for 3 hours to continue polymerization. The polymerization rate of butyl acrylate is 98.4%,
The particle diameter was 0.22μ, which was a substantially uniform size. The obtained rubber latex is designated as Lx-■.

(3) Polymerization of rubber (3rd stage of seeds) 10 parts of Lx-■ in terms of solid content, 170 parts of ion-exchanged pure water
1 part, 2.0 parts of sodium acetate, and 0.2 part of sodium dodecylbenzenesulfonate were placed in an autoclave equipped with a stirrer, and after raising the temperature to 70°C, 0.10 part of potassium persulfate was added, and 100 parts of butyl acrylate and divinyl were added. A mixture of 2 parts of benzene and 0.4 parts of triallylisocyanurate was added continuously over 6 hours. After the addition, the mixture was kept at 70°C for an additional 3 hours to complete the polymerization. The final polymerization rate of butyl acrylate was 98.8%, and the particle size was almost uniform, with an average particle size of 0.45μ. The obtained rubber latex is designated as Lx-■.

(4) Graft polymerization of LX-■ and Lx-■ to rubber: 40 parts and 6 parts, respectively, in terms of solid content
0 parts, 280 parts of ion-exchanged pure water, 0.5 parts of sodium dodecylbenzenesulfonate, and 2.0 parts of sodium acetate were placed in an autoclave equipped with a stirrer, and after raising the temperature to 50°C,
0.3 parts of sodium formaldehyde sulfoxylate,
Add 0.012 parts of sodium ethylenediaminetetraacetate and 0.006 parts of ferrous sulfate. After this, styrene 7
5 parts acrylonitrile 25L t-dodecyl mercaptan 0.2 parts and t-butyl peroxyacetate 0.2 parts
of the mixture were added continuously over a period of 6 hours. After the addition, 0.1 part of t-butyl peroxyacetate was added, the temperature was raised to 75°C, and stirring was continued for an additional 3 hours. The polymerization rates of styrene and acrylonitrile were determined by gas chromatography, and values of 98.1% and 95.0% were obtained, respectively. The obtained latex was coagulated with calcium chloride, washed with water, and dried to obtain a graft copolymer as a white powder.

This will be referred to as polymer (2).

Experimental Example 5 (Synthesis of Comparative Component B) A graft copolymer was prepared using the same procedure as in Experimental Example 4 (4) except that 0.5 parts of sodium dodecylbenzenesulfonate was replaced with 2.0 parts of potassium stearate. I got it. This will be referred to as polymer (2).

Experimental Example 6 (Synthesis of Comparative Component B) 100 parts of polybutadiene latex (solid content equivalent, weight average particle diameter 0.36μ, gel content 90%) 2.0 parts of potassium stearate, 0 parts of sodium aldehyde sulfoxylate .1 part, disodium ethylenediaminetetraacetate 0.
04 parts, 0.01 part of ferrous sulfate, and 380 parts of water to 50
75 parts of styrene, 25 parts of acrylonitrile, 0.3 parts of t-dodecyl mercaptan, and 0.18 parts of diisopropylbenzene hydroperoxide.
After the addition, the temperature was raised to 75°C and stirring was continued for 3 hours to complete the polymerization. The polymerization rate was 99.5% for styrene and 96.4% for acrylonitrile. A white powdery graft copolymer was recovered in the same manner as in Experimental Example 4 (2).

This will be referred to as polymer (2).

Experimental example? (Synthesis of component D) 70 parts of styrene, 30 parts of acrylonitrile, 0.5 part of sodium dodecylbenzenesulfonate, 0.4 part of t-dodecylmercaptan, and 230 parts of ion-exchanged pure water
The temperature was raised to 0°C, and 0.05 part of potassium persulfate was added to initiate polymerization. Six hours after the start of polymerization, 0.03 part of potassium persulfate was further added, and the temperature was raised to 80° C. and maintained for 3 hours to complete polymerization. Polymerization rate is 97.9
%Met.

The obtained latex was coagulated with calcium chloride, washed with water,
After drying, a white powder copolymer was obtained, which was designated as Polymer ①.

Examples 1 to 8 Polymers ■ to ■ as component A, polymers ■ and C as components
Polycarbonate as an ingredient (Panrai manufactured by Ondai Kasei Co., Ltd.)
K1300W or less (indicated as PC), polystyrene terephthalate (DURANEX 2 manufactured by Polyplastics)
002 (hereinafter referred to as PBT), and polyester elastomer (Pelprene P7 OB manufactured by Toyobo Co., Ltd., hereinafter referred to as TPE)
), Polymer (1) as component D was blended in the ratio shown in Table 1, and pentaerythrityl-tetrakis C3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate 0 .35 parts, triisodecyl phosphite 0.03 parts, monoisopropyl acid phosphate 0.03 parts, trimellitic anhydride 0.06 parts, styrene-maleic anhydride copolymer (Kawayu Chemical SM)
After adding 0.1 part of A resin, molecular weight 2000),
Mixed using a Henschel mixer. Add this mixture to 30
It was extruded into pellets using a screw extruder equipped with a +n+nφ devolatilization device. After molding this pellet with an injection molding machine, physical properties were measured and the results are shown in Table 1.

Comparative Examples 1 to 4 The same formulation (same additives) was carried out according to Table 1 except that component B was replaced with comparative component B (polymer ■, ■) in Example 1, and the evaluation results of physical properties were compared to Table 1. Shown in the table.

The physical properties were measured by the following method.

(1) Vicat softening point load 5 kg, ASTM-D
-1525 (2) Izod impact strength/Notched Izod impact strength ASTM D-256 (3) Retention stability Inside the cylinder of the molding machine (300°C)
After staying for 35 seconds and 300 seconds, molding was performed and changes in Izod strength were observed.

(4) Electron microscopy observation After staining the rubber particles by mixing the sample latex with a 1% uranyl acetate solution at a volume ratio of 1:1, drop it onto a collodion membrane and dry it, then use a transmission electron microscope JEM200CX under accelerating voltage. Observation was made at 100 kV.

(Effect of the invention) In a composition consisting of a copolymer having an imide group in the side chain, a rubber-containing resin graft, and a polycarbonate and/or polyester 1M resin, the rubber-containing resin graft has "
By using a 1-seal fat graft product obtained by emulsion graft polymerization of a resin using an organic sulfonate to acrylic rubber obtained by emulsion polymerization using an organic sulfonate,
It is clear from Table 1 that a thermoplastic resin composition having a good balance of various physical properties such as heat resistance and impact resistance and extremely excellent residence heat stability can be obtained.

Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedural Amendment May 29, 1988 Commissioner of the Patent Office Kuro 1) Mr. Yu Akira ■, Indication of the Case Patent Application No. 104803 of 1988 2, Name of the Invention Retention Thermal Stability Good thermoplastic resin composition 3, relationship with the amended person's case Patent applicant address ■100 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Name (329) Detailed description of the invention in the specification of Denki Kagaku Kogyo Co., Ltd. Explanation Column 5, Contents of Amendment (1) "Polybutylene terephthalate" on page 33, line 19 of the specification is corrected to "polybutylene terephthalate."

Claims (1)

[Scope of Claims] Component A: 35-80% by weight of aromatic vinyl monomer residues, 20-65% by weight of unsaturated dicarboxylic acid imide derivative residues, 0-30% by weight of other vinyl monomer residues. % and 10 to 85% by weight of a copolymer containing 0 to 30% by weight of a rubbery polymer; Component B: 60 to 99.99% by weight of an acrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms; A monomer mixture consisting of 0 to 40% by weight of a copolymerizable vinyl monomer and 0.01 to 20% by weight of a crosslinkable compound having two or more carbon-carbon unsaturated bonds in one molecule is added to this mixture. 5 to 80 parts by weight of an acrylic rubbery polymer obtained by emulsion polymerization using 0.01 to 1.0 parts by weight of an organic sulfonate per 100 parts by weight, and 40 to 90 parts by weight of an aromatic vinyl monomer. 20 to 95 parts by weight of a monomer mixture for graft polymerization consisting of 0 to 40 weight % of a vinyl cyanide monomer and 0 to 40 weight % of a vinyl monomer copolymerizable with these monomers; 10 to 80% by weight of a graft copolymer obtained by emulsion polymerization using 0.01 to 1 part by weight of an organic sulfonate per 100 parts by weight of the mixture, and component C: 1 selected from polycarbonate and/or polyester. Component D: 40 to 90 weight % of aromatic vinyl monomer, 0 to 40 weight % of vinyl cyanide monomer, and 0 vinyl monomer copolymerizable with these. 40% by weight of a copolymer;