JPH0525896B2 - - Google Patents

Description

[Detailed description of the invention]

(Technical Field) The present invention relates to a method for producing a novel thermoplastic resin composition having excellent impact resistance and heat resistance. (Prior art) Impact-resistant resins such as ABS resin and high-impact polystyrene are usually obtained by graft polymerizing styrene, acrylonitrile, methyl methacrylate, and other monomers to rubber components.
The composition and structure of the graft copolymer, the rubber content, the polymerization method, etc. greatly influence the physical properties of the final composition. In particular, when graft polymerizing rubber components using emulsion polymerization, it is a widely known fact that the particle size of the base rubber component controls the impact resistance and processability of the final composition. The larger the size, the better the impact resistance and processability of the resulting resin. Therefore, attempts have been made to make the rubber particle size as large as possible, and various proposals have been made so far. The present applicant has also previously discovered that diene rubber or acrylic rubber can be enlarged with a copolymer latex consisting of an unsaturated acid monomer and an alkyl acrylate, and in the presence of the obtained enlarged rubber latex, styrene, acrylonitrile, etc. We proposed a resin composition with good impact resistance obtained by polymerizing a monomer containing at least one selected from the group consisting of Thermoplastic resin containing α-methylstyrene and α-methylstyrene as essential components ()
and the butadiene rubber (A) and α-
The present invention was completed by discovering that a thermoplastic resin composition having excellent impact resistance and high heat resistance can be obtained by blending the methylstyrene units in an amount within a specific range. (Object of the invention) The present invention provides a method for producing a thermoplastic resin composition having excellent impact resistance and heat resistance. (Structure of the Invention) The present invention is produced from 100 to 50% by weight of 1,3-butadiene and 0 to 50% by weight (total amount: 100% by weight) of a monomer having a CH ₂ =C group copolymerizable therewith. Acid group-containing monomer 3 to 100 parts by weight (as solid content) of small particle diameter rubber (A) latex with a pH of 7 or more
30% by weight, 97-35% by weight of at least one alkyl acrylate whose alkyl group has 1-12 carbon atoms, and 0-48% by weight of at least one monovinyl monomer copolymerizable with these (total amount 100% by weight) Acid group-containing copolymer (B) latex obtained from 0.1
~5 parts by weight (as solid content) and 0.05 inorganic electrolyte
from the group consisting of styrene, α-methylstyrene, acrylonitrile and methyl methacrylate in the presence of 7 to 70 parts by weight (as solids) of a thickened rubber latex having a particle size of at least 0.2 μ obtained by adding ~4 parts by weight of Copolymerizable with 30 to 100% by weight of at least one selected monomer
At least one monomer having a CH ₂ =C group 0
Graft copolymer () obtained by polymerizing 93 to 30 parts by weight of a grafting monomer consisting of ~70% by weight
The thermoplastic resin () obtained by polymerizing 70% by weight or more of α-methylstyrene and 30% by weight or less of at least one monomer having a CH ₂ =C group copolymerizable with the butadiene-based A thermal product with excellent impact resistance and heat resistance, which is blended so that the rubber (A) is 3 to 40% by weight of the total composition and the α-methylstyrene unit is 10 to 75% by weight of the total composition. This is a method for producing a plastic resin composition. The rubber component (A) in the present invention contains 100 to 50% by weight of 1,3-butadiene and CH ₂ copolymerizable therewith.
= 0 to 50% by weight of monomers having C groups (total amount
100% by weight) and 1,
3-polybutadiene or a copolymer containing 50% or more of 1,3-butadiene, such as butadiene-styrene, butadiene-vinyltoluene copolymer, butadiene-aromatic vinyl compound copolymer, butadiene-acrylonitrile copolymers, butadiene-alkyl acrylate copolymers, such as butadiene-methacrylonitrile copolymers, butadiene-methyl acrylate, butadiene-ethyl acrylate, butadiene-butyl acrylate, butadiene-2-ethylhexyl acrylate copolymers, butadiene -Methyl methacrylate, butadiene-alkyl methacrylate copolymers such as butadiene-ethyl methacrylate copolymers, etc., and also terpolymers containing 50% or more of butadiene.
These can be easily obtained by commonly known emulsion polymerization. There are no particular restrictions on catalysts, emulsifiers, etc.
Its particle size is 0.04-0.2μ. Enlargement of rubber particles can be achieved simply by adding the acid group-containing copolymer latex to this synthetic rubber latex, but it is necessary that the synthetic rubber latex has a pH of 7 or higher. For example, polybutyl acrylate rubber latex polymerized with sodium octylsulfosuccinate as an emulsifier and potassium persulfate as a catalyst has a pH of 2 to 3, but even if an acid group-containing copolymer latex is added to this latex, no No hypertrophy occurs. However, if a small amount of alkali such as potassium hydroxide is added to raise the pH to 7 or higher, a rubber with a large particle size can be easily obtained. The acid group-containing copolymer used for enlarging the synthetic rubber in the present invention must be in the form of latex, and is composed of a specific acid group-containing monomer and alkyl acrylate. This is an essential condition, and if necessary, a monovinyl monomer copolymerizable with these can also be copolymerized. Examples of the acid group-containing monomer constituting the acid group-containing copolymer include acrylic acid, methacrylic acid, itaconic acid, and crotonic acid.
Or used in combination. The content of the acid group-containing monomer in the acid group-containing copolymer is 3 to 30% by weight. If it is less than 3% by weight, the enlargement ability is small;
If it exceeds 1μ by weight, the enlargement ability is too strong.
This is undesirable because it generates particles that exceed . In addition to the above, cinnamic acid, maleic anhydride, butenetricarboxylic acid, etc. may be used as acid group-containing monomers or monomers similar thereto, but their use is not practical due to their low enlargement ability. In addition, the alkyl acrylate having an alkyl group having 1 to 12 carbon atoms constituting the acid group-containing copolymer alone,
Alternatively, they can be used as a mixture, and the satisfactory effect of the present invention can be obtained when the content in the acid group-containing copolymer is 97 to 35% by weight. Other copolymerizable monovinyl monomers that may be used if necessary to form the acid group-containing copolymer (B) include unsaturated aromatic compounds such as styrene, α-methylstyrene, and vinyltoluene; acrylonitrile, and methacrylonitrile; Examples include unsaturated nitrile compounds such as nitrile; alkyl (meth)acrylates in which the alkyl has 1 to 12 carbon atoms; these may be used alone or in combination. Acid group-containing copolymer
The content of the other copolymerizable monovinyl monomer in (B) is 0 to 48% by weight, and if it exceeds 48% by weight, the effects of the present invention will not be achieved. When producing the acid group-containing copolymer used in the present invention, it is preferable to use an anionic surfactant as an emulsifier, but a nonionic surfactant may also be used. In carrying out the present invention, the acid group-containing copolymer is used in the form of a latex, and its particle size greatly affects its enlargement ability, and preferably the average particle size is in the range of 0.05 to 0.2μ. are used. If it is smaller than 0.05μ, its enlargement ability will be significantly reduced, and if it is larger than 0.2μ, the rubber particle size will become too large after enlargement, resulting in instability and agglomeration when graft polymerization is continued. It becomes easier. The particle size of the enlarged rubber obtained by this method is 0.2 to 1 μm. By adding this acid group-containing copolymer to synthetic rubber latex in the form of latex, enlargement of the synthetic rubber can be achieved, but at this time, by simultaneously adding an inorganic electrolyte, the particle size of the synthetic rubber can be extremely efficiently increased. , and stably enlarges. The amount of acid group-containing copolymer latex added is 0.1 per 100 parts by weight (solid content) of synthetic rubber latex.
~5 parts by weight (as solids), particularly preferably 0.5
~3 parts by weight. In addition, the amount of inorganic electrolyte added is 0.05 to 4 per 100 parts by weight (as solid content) of synthetic rubber latex.
Part by weight, particularly preferably 0.1 to 1 part by weight, is sufficient, and by adding such a small amount, the synthetic rubber can be enlarged efficiently. As the inorganic electrolyte, neutral inorganic salts such as potassium chloride, sodium chloride, and sodium sulfate can be suitably used. Further, this inorganic electrolyte can be added in advance during the polymerization of the synthetic rubber latex, and the same effect as when added at the time of enlargement is achieved. When carrying out the enlargement treatment of the present invention, it is necessary to maintain the pH of the synthetic rubber latex at 7 or higher. If the pH value is on the acidic side, the enlargement efficiency will be low even if an acid group-containing copolymer latex is added.
The thermoplastic resin which is the object of the present invention cannot be produced advantageously. The pH of this synthetic rubber latex can be adjusted to 7 or higher during polymerization of the synthetic rubber, or
Alternatively, it may be performed separately before the enlargement treatment. In the presence of 7 to 70 parts by weight (solid content) of the enlarged rubber latex subjected to enlargement treatment in this way,
30 to 100% by weight of at least one monomer selected from the group consisting of styrene, α-methylstyrene, acrylonitrile, and methyl methacrylate, and at least one monomer having a CH ₂ =C group copolymerizable with this monomer 0 By polymerizing 93 to 30 parts by weight of the grafting monomer consisting of 70% by weight, the graft copolymer (2) having excellent impact resistance used in the present invention can be obtained. Styrene, α-methylstyrene, acrylonitrile, and methyl methacrylate as grafting monomers may be used alone or in combination as required, and are used in an amount of 30 to 100% by weight based on the total grafting monomers. Monomers having a CH ₂ =C group that can be copolymerized with these monomers include aromatic vinyl compounds such as vinyltoluene; unsaturated nitrile compounds such as methacrylonitrile; and carbon atoms of alkyl groups other than methyl methacrylate. Examples include alkyl (meth)acrylates having a number of 1 to 12, and these can be used alone or in combination, but the amount used is up to 70% by weight of the total grafting monomers, and the amount of grafting monomers It is not preferable to use it alone as a body. Examples of mixtures of monomers for grafting include styrene-acrylonitrile mixtures, styrene-alkyl acrylate mixtures, acrylonitrile-methyl methacrylate, acrylonitrile-α-methylstyrene, methyl methacrylate-alkyl acrylate mixtures, acrylonitrile-alkyl acrylate mixtures, and the like. A monomer mixture of three or more of these monomers can also be used. In this emulsion graft polymerization, commonly known emulsifiers and catalysts are used, and there are no particular restrictions on the type and amount added. When graft polymerizing the enlarged rubber, the graft monomers may be added all at once, or may be added in portions or continuously, or each monomer may be graft polymerized individually in stages. You can let me. Next, examples of monomers having a CH ₂ ═C group that can be copolymerized with α-methylstyrene used in the polymerization of thermoplastic resins () containing α-methylstyrene as an essential component include acrylonitrile, methacrylonitrile, and other monomers. Saturated nitrile compounds; aromatic vinyl compounds such as styrene and vinyltoluene; alkyl (meth)acrylates in which the alkyl group has 1 to 12 carbon atoms, maleic anhydride, etc., and these may be used alone or in mixtures. . Graft polymer thus obtained ()
The butadiene rubber (A) is 3 to 40% by weight of the total composition, and the α-methylstyrene unit is 10 to 75% by weight of the total composition. %, a thermoplastic resin composition with excellent impact resistance and high heat resistance can be obtained. If the content of butadiene-based enlarged rubber in the thermoplastic resin composition of the present invention is less than 3% by weight, the impact resistance will be low and there will be no practical value, and if it exceeds 40% by weight, fluidity and processability will deteriorate. So I don't like it. Moreover, the graft polymer () is not limited to one type, and can be used in combination with one or more other graft copolymers obtained by the method shown in the above-mentioned range. In this case, the rubber content in each graft copolymer does not need to be in the range of 7 to 70% by weight, but the final rubber content after blending with the thermoplastic resin () containing α-methylstyrene as an essential component Preferably, the rubber content in the composition is in the range of 3 to 40% by weight. In the present invention, as a method for blending the graft copolymer () and the thermoplastic resin (), when the thermoplastic resin () is produced by emulsion polymerization, it is possible to blend both in the state of an emulsion. . Other combinations of powders or powders and beads, Henschel mixer, extruder, etc.
The mixture is kneaded and blended using various equipment such as a Banbury mixer or heated rolls. Note that an antioxidant, a lubricant, a coloring agent, a filler, etc. can be added to the resin composition of the present invention, if necessary. (Example) The present invention will be specifically described below with reference to Examples. In the examples, "parts" and "%" mean "parts by weight" and "% by weight," respectively. The evaluation methods for various physical properties were as follows. Impact strength: Izod impact strength (ASTM D256
by. ) Melt index: According to ASTM D 1238 (200°C, 5 kg load) Vikatsu softening temperature: According to ISO R-306. Example 1 [Synthesis of base rubber (A-1)] 1,3-butadiene 66 parts Butyl acrylate 9 Styrene 25 Diisopropylbenzene hydroperoxide
0.2〃 Potassium oleate 1.0〃 Potassium rosinate 1.0 parts Sodium pyrophosphate 0.5〃 Ferrous sulfate 0.005〃 Dextrose 0.3〃 Water 200〃 According to the above composition, autoclave 100 at 50℃
Polymerized with Polymerization was almost completed in 9 hours, and the conversion rate was
A rubber latex with a particle size of 97%, a particle size of 0.08μ, and a pH of 9.0 was obtained. [Synthesis of acid group-containing copolymer for enlargement (B-1) latex] n-butyl acrylate 85 parts methacrylic acid 15〃 Potassium oleate 2〃 Sodium dioctyl sulfosuccinate 1〃 Cumene hydroperoxide 0.4〃 Sodium formaldehyde sulfoxylate
0.3 〃 Water 200 〃 Polymerization was carried out at 70°C for 4 hours in a separate polymerization apparatus according to the above composition. The conversion rate was 98%, and a latex with a pH of 6.1 and an average particle size of 0.08μ was obtained. [Preparation of enlarged rubber latex] Base rubber latex (A-1) 100 parts (solid content)
1.5 parts (solid content) of (B-1) latex and 0.4 parts of Na ₂ SO ₄ as an inorganic electrolyte were added over 5 seconds with stirring, and stirring was continued for 30 minutes to obtain an enlarged rubber latex with an average particle size of 0.32μ. . Using this enlarged rubber latex, graft polymerization was immediately carried out according to the following composition to synthesize a graft copolymer. [Synthesis of graft copolymer (G-1)] Enlarged rubber (solid content) 60 parts styrene 28〃 Acrylonitrile 12〃 Cumene hydroperoxide 0.16〃 Sodium formaldehyde sulfoxylate
0.1〃 Potassium oleate 1.0〃 Water 200〃 (Polymerization conditions: 70℃, 4 hours) To the obtained polymer latex, 2 parts of butylated hydroxytoluene and 0.5 parts of dilaurylthiopropionate were added as antioxidants to give a 5% It was coagulated with an aqueous sulfuric acid solution, washed and dried to obtain a white powder. [Evaluation of physical properties of final composition] 33 parts of the above graft copolymer (G-1) and acrylonitrile/α-methylstyrene = 30/70 (%)
Blend 67 parts of thermoplastic resin powder separately produced by emulsion polymerization using a monomer mixture of It was pelletized using an extruder. Using this pellet, various test specimens were prepared by injection molding and various physical properties were evaluated. These results are shown in Table 1. Comparative Example 1 The base rubber (A-1) was directly graft-polymerized according to the recipe (G-1) without enlarging it. The same resin composition as in Example 1 was obtained for the obtained graft copolymer, and the same evaluation was performed. The results are also shown in Table 1. Comparative Example 2 [Synthesis of base rubber latex (A-2)] 1,3-butadiene 66 parts Butyl acrylate 9〃 Styrene 25〃 Potassium persulfate 0.3〃 Dodecylmercaptan 0.4〃 Potassium oleate 0.5〃 Disproportionated potassium rosinate 0.5〃 Water 50〃 Charge the mixture with the above composition into a 100 autoclave, start polymerization under stirring at 60℃ and 80rpm,
When the polymerization conversion rate reaches 30%, increase the stirring speed.
When the polymerization conversion rate exceeds 50%, the stirring speed was changed to 100 r.pm, and then an aqueous solution of 1.0 part of potassium oleate, 1.0 part of disproportionated potassium rosinate, and 15 parts of water was added to the polymerization system. added intermittently. 45
The polymerization was almost completed in a few hours, and a rubber latex with a polymerization conversion rate of 97.5%, a particle size of 0.28μ, and a pH of 8.9 was obtained. This rubber latex was directly graft-polymerized according to the recipe (G-1) without enlarging it. The same resin composition as in Example 1 was obtained for the obtained graft copolymer, and the same evaluation was performed. The obtained results are also shown in Table 1.

[Table] As is clear from Table 1, by blending a graft copolymer obtained using rubber enlarged with an acid group-containing copolymer latex with a thermoplastic resin containing α-methylstyrene as an essential component. ,
It can be seen that even if they have the same heat resistance, the impact strength is better developed. Examples 2 to 4 Using the latex for rubber enlargement (B-1) used in Example 1, various synthetic rubber latexes (particles) were prepared by adding the respective amounts shown in Table 2 per 100 parts (solid content) of base rubber. Electrolyte (diameter 0.06~0.1μ)
The monomers shown in _{Table 2} were graft-polymerized in the presence of 45 parts of these enlarged rubbers to obtain graft copolymers (G-2), (G-3),
(G-4) was obtained. Using these graft copolymers, the same formulation as described in the [Product evaluation of final composition] section of Example 1 was carried out, and the content of butadiene rubber and α-methylstyrene units in the total resin composition was adjusted to 15% each. A thermoplastic resin composition having a concentration of 47% and 47% was prepared and the same evaluation was carried out. These results are shown in Table 2.

[Synthesis of graft copolymer (G-5)]

Thickened rubber (solid content) 40 parts Styrene 22〃 Acrylonitrile 20〃 α-methylstyrene 18〃 Cumene hydroperoxide 0.24〃 Sodium formaldehyde sulfoxylate
0.15〃 Potassium oleate 1.3.〃 Water 200〃 (Polymerization conditions: 70°C, 6 hours) Thermoplastic material containing 38 parts of this graft copolymer (G-5) and α-methylstyrene used in Example 1 as essential components 62 parts of resin powder were blended, the contents of butadiene rubber and α-methylstyrene units in the total composition were set to 15% and 50%, respectively, and pelletized using an extruder. Using this pellet, various test specimens were prepared by injection molding and various physical properties were evaluated.
These results are shown in Table 3. Comparative Example 3 Using the enlarged rubber latex obtained in Example 1,
Graft copolymers (G-6) and (G-7) were synthesized by performing graft polymerization according to the following compositions. [Synthesis of graft copolymer (G-6)] Thickened rubber (solid content) 20 parts styrene 57〃 Acrylonitrile 23〃 Cumene hydroperoxide 0.32〃 Sodium formaldehyde sulfoxylate
0.2〃 Potassium oleate 2.0〃 Water 200〃 (Polymerization conditions 70℃, 6 hours) [Synthesis of graft copolymer (G-7)] Thickened rubber (solid content) 15 parts styrene 9〃 Acrylonitrile 25〃 α-Methyl Styrene 51 Cumene hydroperoxide 0.45 Sodium formaldehyde sulfoxylate
0.28 parts Potassium oleate 2.8〃 Water 200〃 (Polymerization conditions 70℃, 8 hours) 60 parts of the above graft polymer (G-6) (solid content)
(G-7) and 20 parts (solid content) are latex blended, and as antioxidants, 2 parts of butylated hydroxytoluene and 0.5 parts of dilaurylthiopropinate are added to this latex blend.
The mixture was coagulated with a 5% aqueous sulfuric acid solution, washed and dried to obtain a white powder. 80 parts of this graph copolymer mixture powder is blended with 20 parts of thermoplastic resin powder separately produced by emulsion polymerization using a monomer mixture of acrylonitrile/styrene/α-methylstyrene = 22/28/50 (%). The contents of butadiene rubber and α-methylstyrene units in the total resin composition were adjusted to 15% and 20%, respectively, and pelletized using an extruder. Using this pellet, various test pieces were prepared by injection molding and various physical properties were evaluated. These results are shown in Table 3. Comparative Example 4 Graft copolymer (G-5) obtained in Example 5 50
part and α-methylstyrene/methyl methacrylate/styrene/maleic anhydride = 20/40/20/20
50 parts of thermoplastic resin powder separately produced by bulk polymerization using a monomer mixture of The mixture was pelletized using an extruder. Using this pellet, various test specimens were prepared by injection molding and various physical properties were evaluated. These results are shown in Table 3.

[Table] (Effects of the Invention) The method for producing a thermoplastic resin composition of the present invention has the following advantages compared to conventionally known methods for producing a thermoplastic resin composition. 1. It is possible to manufacture continuously from rubber polymerization to final resin polymerization. 2 No special equipment is required. 3. Rubber polymerization can be carried out in a short time, resulting in extremely high productivity. 4. Since no specific dispersant or emulsifier is required during rubber enlargement treatment, it is economical and the final resin has good thermal stability. 5. Very little formation of excessive coagulum (coagulum) after rubber enlargement treatment and graft polymerization. 6. By using the acid group-containing copolymer latex according to the present invention, a large particle size synthetic rubber can be easily obtained with a very low acid group-containing monomer content, and therefore has extremely high impact strength and heat resistance. A thermoplastic resin composition with excellent properties can be obtained.

Claims (1)

[Claims] 1 100 to 50% by weight of 1,3-butadiene and a monomer having a CH ₂ =C< group copolymerizable with it 0 to
PH obtained from 50% by weight (total amount 100% by weight)
3 to 30 parts of acid group-containing monomer per 100 parts by weight (as solid content) of small particle diameter rubber (A) latex of 7 or more.
97-35% by weight of at least one alkyl acrylate whose alkyl group has 1-12 carbon atoms and 0-48% by weight of at least one monovinyl monomer copolymerizable with these (total amount 100% by weight); Acid group-containing copolymer (B) latex obtained from 0.1~
5 parts by weight (as solid content) and 0.05 to inorganic electrolyte
selected from the group consisting of styrene, α-methylstyrene, acrylonitrile and methyl methacrylate in the presence of 7 to 70 parts by weight (as solids) of a thickened rubber latex having a particle size of at least 0.2 μ obtained by adding 4 parts by weight of 30 to 100% by weight of at least one monomer copolymerizable with this
At least one monomer having a CH ₂ =C< group 0
Graft copolymer () obtained by polymerizing 93 to 30 parts by weight of a grafting monomer consisting of ~70% by weight
The thermoplastic resin () obtained by polymerizing 70% by weight or more of α-methylstyrene and 30% by weight or less of at least one monomer having a CH ₂ =C< group copolymerizable with the butadiene A product with excellent impact resistance and heat resistance, in which the rubber (A) is blended in an amount of 3 to 40% by weight in the total composition, and the α-methylstyrene unit is in an amount of 10 to 75% by weight in the total composition. A method for producing a thermoplastic resin composition.