JPS6086149A - Thermoplastic resin composition with excellent heat resistance and impact resistance - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin having excellent heat resistance and impact resistance. The present invention relates to a thermoplastic resin composition having excellent heat resistance and impact resistance and comprising a copolymer obtained by polymerizing the above and a multistage structured acrylic elastic body.

As a method for obtaining a thermoplastic resin with excellent heat resistance and impact resistance using this method, a graft copolymer obtained by graft copolymerizing styrene or acrylonitrile to a diene rubber,
A method of completely mixing a terpolymer consisting of α-methylstyrene, methyl methacrylate, and acrylonitrile (JP-A-57-70143 @), or a method of mixing a polycarbonate resin and a diene rubber (q! J Publication No. 38-15225) and the like have been proposed. However, with these methods, it is difficult to balance heat resistance and impact resistance, and in the case of mixtures of polycarbonate and diene rubber, flow processability is significantly reduced. The reality is that no material has yet been developed that has impact resistance.

As a result of intensive studies on heat-resistant and impact-resistant thermoplastic resin compositions with excellent flow processability, the present inventors found that a resin composition of a polymer having a specific composition and structure was found to be suitable for the intended purpose. We have found that this can be achieved satisfactorily and have arrived at the present invention.

The gist of the present invention is that methyl methacrylate 40
~89 superimposed parts, α-methylstyrene 1-20 superimposed parts,
5-20ml styrene 1% and maleic anhydride 5-20ml
2! (a copolymer obtained by polymerizing a monomer mixture consisting of i% [131 to 99% by weight and 2 to 1
A total of 100 parts by weight of 50 to 70 parts by weight of an acrylic alkyl ester having 0 12 atoms and 50 to 50 parts by weight of an aromatic vinyl compound, and a polyfunctional crosslinking having one or more allyl groups in the molecule. A mixture of the aromatic vinyl compound and the polyfunctional crosslinking monomer is emulsion polymerized using 0.1 to 5 parts by weight of the polyfunctional monomer, and then an alkyl acrylate is added in the presence of the obtained polymer latex. A mixture of an ester and a polyfunctional crosslinking monomer is polymerized to form an acrylic elastic body, and 40 to 80 parts by weight of this elastic body is mixed with 50 to 80% of methyl methacrylate and 70 to 70% of an aromatic vinyl compound. 20% by weight and total proportion of monomers 60-20
A thermoplastic resin composition having excellent heat resistance and impact resistance, consisting of a multi-stage structure acrylic copolymer [■] obtained by polymerizing the entire strip individually in an amount of 1 to 99% by weight.

The composition of the present invention is characterized by the above-mentioned methyl methacrylate, α
- Copolymer of methylstyrene, styrene and maleic anhydride [■] and multistage acrylic copolymer [I []g
Due to the synergistic effect with the components, it is possible to exhibit excellent, well-balanced properties in heat resistance, impact resistance, and flow processability.

The copolymer C1) in the present invention is methyl methacrylate 40
~89 Mm %, α-methylstyrene 1-20 M, methyl ref 5-20 M, maleic anhydride 5-20
It is a product obtained by polymerizing a monomer mixture consisting of a heavy polycarbonate, and has the effect of imparting heat resistance and flow processability to the final resin composition. In addition, the proportions of the constituent units of methyl methacrylate, α-methylstyrene, styrene, and maleic anhydride in the copolymer [■] are determined by the heat resistance, weather resistance, polymerization rate, and flow processability of the copolymer [I]. If any monomer component is outside the above range, problems such as poor heat resistance, poor weather resistance, and extremely poor productivity will occur. The blending ratio of the copolymer [13] is 1 to 991% by weight, preferably 10 to 90% by weight, in the total resin composition. If it is less than 1% by weight, heat resistance and flow processability are poor; If it exceeds 99% by weight, impact resistance S
There is a tendency for the sex to be inferior.

Copolymer CD can be produced by a commonly used polymerization method such as bulk polymerization or solution polymerization using the above monomer mixture using a radical polymerization initiator. If necessary, it is also possible to add other monomer units that can be copolymerized under 10% by weight as the 4th X component. It has the effect of imparting impact resistance to the resin composition, and contains 1 to 99% by weight of the entire resin composition, more preferably 1% by weight.
0 to 90 weight percent, and less than 1 weight percent of the overlapped portion, the impact resistance is poor, and if it exceeds 99 weight percent, the heat resistance is poor, both of which are not desirable.

Most of the invention! One of the key features is the structure of the multi-stage acrylic copolymer [■]. There is also a multi-stage structure in which styrene and styrene are individually polymerized.

The multistage structure acrylic copolymer [■] used in the heat-resistant and impact-resistant resin composition of the present invention is an aromatic vinyl compound and a polyfunctional crosslinkable monomer having one or more allyl groups in the molecule. The entire production of the acrylic elastomer is carried out by subjecting the mixture of acrylic acid alkyl ester and the above-mentioned polyfunctional crosslinking monomer to total polymerization in the presence of the resulting polymer. do. The aromatic vinyl compounds used here include styrene, focabinyltoluene, 'α-methylstyrene, chlorostyrene, bromostyrene, etc.

Acrylic acid alkyl esters include those having 2 to 10 carbon atoms in the alkyl group, such as ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, n acrylate. -octyl, 2-ethylhexyl acrylate, etc. are used.

The polyfunctional crosslinking monomer contains 1g per molecule! It is necessary to contain allyl groups of A or more in order to completely improve the heat resistance and impact resistance of the final composition.

Examples of the polyfunctional crosslinking agent having one or more allyl groups in the molecule include triallyl cyanurate, triallyl incyanurate, allyl methacrylate, allyl sorbate, allyl acrylate, allyl cinnamate, diallyl itaconate, Diallyl phthalate and the like are used, with allyl methacrylate and triallyl cyanurate being particularly preferred. Divinylbenzene without allyl group, acrylic rtl't
Diacrylic esters or dimethacrylic esters, which are esters of methacrylic acid and polyhydric alcohol, have a small impact resistance improvement effect, so they can be used in combination with other allyl group-containing crosslinking agents, but they cannot be used alone. It cannot be used. The reason for this is not clear, but crosslinking agents such as dimethacrylic acid esters work effectively for crosslinking the styrene phase, but the two-layer structure rubber obtained by polymerizing with the addition of all acrylic acid esters Since the degree of swelling is high, it is thought that sufficient crosslinking has not occurred as a two-layer structure rubber. Also, when graft polymerizing methyl methacrylate and aromatic vinyl compounds to two-layer rubber, the type of cross-linking agent has a large effect, and two-layer rubber using a polyfunctional cross-linking agent that does not support allyl groups is sufficient. Possibly because no grafting reaction occurs, the effect of improving @ bonding resistance is poor. The amount of the polyfunctional crosslinking agent used is [
The amount is 11 to 5 parts by weight. If the amount is too small, the crosslinking efficiency will be poor, and if it is too large, the elasticity of the elastic body will be impaired and it will become brittle, making it impossible to impart impact resistance to the thermoplastic resin composition.

In the composition of the acrylic elastomer, the greater the amount of acrylic acid alkyl ester, the more advantageous the impact strength of the resulting thermoplastic resin composition, but the worse its heat resistance.

On the other hand, when the aromatic vinyl compound is used as a predominant amount, the heat resistance of the thermoplastic resin composition becomes good, but the impact strength becomes weak.

In order to obtain a thermoplastic resin composition with a good balance between heat resistance and impact resistance, the composition of the acrylic elastomer should be 50 to 70% by weight of an acrylic acid alkyl ester and 50 to 30% by weight of an aromatic vinyl compound. It is necessary to keep the area within the designated area. Even in this range, an elastic body obtained by simply random copolymerizing an acrylic acid alkyl ester and an aromatic vinyl compound, or an elastomer obtained by first polymerizing the acrylic acid alkyl ester as a core, and then forming an aromatic vinyl compound as an outer shell. If the elastic body tone obtained by polymerization is used, the impact resistance of the resin composition will not be improved.

The multistage structure acrylic copolymer CID can be obtained by graft polymerizing all 60 to 20 parts by weight of the monomer components in the presence of 40 to 80 parts by weight (as solid content) of the acrylic elastomer. If the amount of the graft copolymer is less than 40 parts by weight, the effect of improving the impact strength of the thermoplastic resin composition is small, and if the amount of the elastic body exceeds 80 parts by weight, the heat resistance of the thermoplastic resin composition will be extremely poor. The strength of opposition also decreases.

As the aromatic vinyl compound used for this purpose, in addition to styrene, α-haze-substituted styrene, nuclear-substituted styrene, and derivatives thereof such as vinyltoluene, α-methylstyrene, chlorostyrene, etc. are used.

In the first grafting, the entire amount of each monomer is added at once, continuously or discontinuously, thereby allowing the polymerization to proceed. If a mixture of methyl methacrylate and an aromatic vinyl compound is simultaneously added and graft polymerized, the impact resistance of the thermoplastic resin composition decreases.

The graft polymerization can be carried out subsequent to the production of the elastomer or in a separate reactor with or without the addition of an initiator, polymerization regulator, crosslinking agent, etc.

Since it is particularly preferable to produce the multistage structure acrylic copolymer [113] of the present invention by an emulsion polymerization method, it will be explained using an example using the emulsion polymerization method.

After adding deionized water, a polymerization initiator, and an emulsifier to the reaction vessel, the monomer mixture forming the crosslinked polystyrene resin is polymerized, then the monomer mixture forming the crosslinked polyacrylic acid alkyl ester is polymerized, and then Polymerize methyl methacrylate and styrene separately.

Polymerization temperature is 30-120℃ 0-120℃ F50-10
It is 0°C. The polymerization time varies depending on the type and amount of the polymerization initiator and emulsifier, the polymerization temperature, etc., but is usually α5 to 7 hours at each polymerization stage.

The ratio of polymer to water is jlIi active body/water = 1/20 to 1/
1 is preferred.

The polymerization initiator and emulsifier can be added to either or both of the aqueous phase and the monomer phase.

The respective 4-mers in each polymerization stage can be charged all at once or in portions, but a split charging method is preferable from the viewpoint of heat generation during polymerization and the like.

The emulsifier is not particularly limited as long as it is a commonly used emulsifier, but examples include Nagazuchi alkyl carboxylate, sulfosuccinic acid alkyl ester salt, and alkylbenzene sulfonate.

There is no need to particularly limit the type of polymerization initiator, and commonly used inorganic initiators such as persulfates and perborates can be used alone or in combination with sulfite and thiosulfate to initiate redox, or organic initiators can be used. hydroperoxide-ferrous salt,
Redox initiation systems such as organic hydroperoxide-rhydium formaldehyde sulfoxylate, benzoyl peroxide, azobisisobutyronitrile, and the like may also be used.

The polymer latex obtained by the emulsion polymerization method is coagulated and dried by a known method.

The composition of the present invention is composed of a copolymer [1] and a multi-hair structure acrylic copolymer [1], but depending on the purpose of use, it may contain other methacrylic resins, polycarbonate, As resin. , methyl methacrylate-styrene copolymer,
At least one resin [I[1] selected from polystyrene, polyester (polyethylene terephthalate, polybutylene terephthalate), and nylon is contained in the composition.
For example, when extremely good weather resistance is required, methacrylic resins and polyethylene terephthalate resins are suitable, and when flow processability with fc crystallinity is required, Polystyrene, As resin and methyl methacrylate-styrene copolymer are used.

1) In the composition of the present invention, all appropriate stabilizers, lubricants, plasticizers, dyes and pigments, fillers, etc. are added as necessary, and the mixture is mixed in a V-type blender, Henschel mixer, etc., and then mixed. Melt mixing is performed at 150 to 300°C using a roll or screw extruder.

By molding the obtained composition using an extrusion molding machine, an injection molding machine, etc., molded products with excellent heat resistance and impact resistance can be obtained. It is useful for applications such as , electrical parts, etc.

In the following examples, the term "qb" means the entire weight qb.

Examples 1 to 4, Comparative Examples 1 to 6 Production of copolymer [■] Methyl methacrylate 14 kg, α-methylstyrene 1.
0 kg, styrene 2.5 k! ? , maleic anhydride 2
．． To 5! 9 and t-dodecylmercaptan 607 were placed in a SUS reaction vessel equipped with a cooling tube, a thermometer, and a stirring device, heated while stirring, and added 20f of azobisisobutyronitrile at an internal temperature of 75°C. And internal temperature 95
After maintaining the temperature at ℃ for 15 minutes, the mixture was cooled to obtain a partial polymer in the form of a slag.

Bis(
3,5,5-)limethylhexanoyl]peroxide 3001, as a release agent JP-504 (trade name)
After dissolving 2f1 stearic acid monoglyceride as a mold release agent (manufactured by Johoku Chemical Co., Ltd.) during 1oork, the composition was added to several sets of cells formed by two tempered glass plates facing each other at a distance of 6 mm with a polyvinyl chloride gasket interposed therebetween. Inject everything, 80
It was immersed in warm water at ℃ to polymerize and harden. After that, 160℃
The mixture was treated in an air heating oven for 2 hours. After cooling, remove the cell.
A resin plate with a thickness of approximately 6 m was cut and then crushed using a crusher to form a pellet.

Multi-stage structure acrylic copolymer [Production 1 of 111, Production of acrylic elastomer a] Styrene 4.5 Y (Allyl methacrylate 10 o2 Dialkyl sulfosuccinate sodium salt 40 f Potassium persulfate 309 Water (total) 18 kg 2 ) n-Butyl acrylate 5.5 Y (allyl methacrylate 1002 Potassium persulfate 302 Y) water 1 kg ゛1゛Other than the monomer and crosslinking agent, everything was placed in a SUB 40t autoclave purged with nitrogen according to the above composition 1), and heated at 70°C. A mixture of styrene and allyl methacrylate was added dropwise to the latex over 60 minutes, kept at the same temperature for 1 hour, and then an aqueous solution of potassium persulfate from 2) was added to the latex, and n-butyl acrylate and allyl methacrylate were added dropwise to the latex. The mixture of allyl acids was added dropwise over 60 minutes, and the mixture was kept at the same temperature for 1 hour to complete the polymerization. The conversion rate was 96 inches, and the average particle diameter of the obtained elastic latex was 0.155 μm.

Production of Z multistage structure acrylic copolymer [1B-r A
II N-f i'llf e &;
/ Sho■θλL l -r )7 Methyl methacrylate 1.5kg Styrene 1.5k19 Potassium persulfate 602 Water (total) zokg Other than the monomer, SUS was replaced with nitrogen according to the above recipe.
501 autoclave, and at 70°C, methacrylic dispersion methyl i was added dropwise for 30 minutes, kept at the same temperature for 1 hour, and then styrene was added dropwise for 30 minutes.
The polymerization was completed by holding for a minute. The conversion rate was 96. The average particle diameter of the resulting latex of the grafted copolymer [■] was 0.170 μm.

This latex was then coagulated with a 5% aqueous solution of aluminum chloride under conditions of latex/water-1/2.75°C. The obtained slurry-like white polymer was washed with 30 times as much deionized water, dehydrated, and then dried at 75° C. for 66 hours.

Next, the co-1 compound [13] obtained above, the multi-stage structure acrylic copolymer [■], and other resins [■] were mixed in the proportions shown in Table 1 using a Henschel mixer, and then a screw extrusion method was used. Then, the pellets were made into pellets by IH mixing at a cylinder temperature of 200 to 270° C. and a die temperature of 260° C. This was then injection molded under the following conditions, and the evaluation results shown in Table 1 were obtained from the obtained test pieces.

Injection molding machine: Japan Steel Works Membrane, V-17-65 type screw complete automatic injection molding machine Injection molding conditions Niji cylinder temperature change Injection pressure 700 kg/1W? , mold warm 52℃ test piece size; 110X110X2 (thickness) I+III+7
0 x 12.5 It was produced in exactly the same manner as in Examples 1 to 4, except that the polymer solid content of the elastomer was 4 kg, and the amount of monomer used during production of the graft copolymer was 9 for methyl methacrylate and styrene, and 3 kg for each. . Using that material, a blend was formed in the proportions shown in Table 1. The obtained pellets were evaluated in the same manner as in Examples 1 to 4, and the results shown in Table 1 were obtained.

/ Examples 7 to 11, Comparative Examples 4 to 5 Proportion of copolymer [I] multilayered acrylic copolymer [11] and resin [1■] used in Examples 1 to 4
] as shown in Example 1 and Proportion Table 2, Examples 1 to 4
Evaluation was performed in the same manner as above, and the results shown in Table 2 were obtained.

Claims (1)

[Scope of Claims] 1. Leather body mixture consisting of 40 to 89% by weight of methyl methacrylate, 1 to 20 N parts of α-methylstyrene, 20 to 20 parts by weight of methylene, and 5 to 20 parts by weight of maleic anhydride. Copolymer obtained by total polymerization [I] 1-9931
~99 parts by weight 50 to 70 parts by weight of an acrylic acid alkyl ester having 2 to 10 carbon atoms in the radical and 50 to 30 parts by weight of an aromatic vinyl compound, totaling 100 ffi parts and in the molecule. First, a mixture of an aromatic vinyl compound and a polyfunctional crosslinkable monomer was emulsion polymerized using a 5m piece of a polyfunctional crosslinkable monomer having one or more allyl groups, and then the obtained An acrylic elastomer is produced by polymerizing a mixture of an acrylic acid alkyl ester and a polyfunctional crosslinkable monomer in the presence of a polymer latex, and 40 to 80 parts by weight of this elastomer is added with 30 parts of methyl methacrylate. A multistage structure acrylic copolymer obtained by polymerizing a total of 60 to 20 parts by weight of monomers in the ratio of ~80 overlapped parts and 70 to 20 overlapped parts of the aromatic vinyl compound [ A thermoplastic resin composition having excellent heat resistance and impact resistance, consisting of 1 to 99 N and a weight coefficient. 2 Methacrylic resin, polycarbonate, AS resin,
Thermoplastic material with excellent heat resistance and impact resistance according to claim 1, which is obtained by adding at least one resin selected from methyl methacrylate-styrene copolymer, polystyrene, polyester, and nylon under the weight of i98. Resin composition.