DE2039022B2 - THERMOPLASTIC MOLDING COMPOUND - Google Patents

Description

(II) 0.01 to 3% by weight of a polyorganosiloxane.

2. Composition according to claim 1, characterized in that the polymer mixture (I) by polymerization with continuous or batchwise addition of part of the monomer mixture (B) in Presence of the butadiene rubber (A) to form a mixture (I ') and then Polymerization of the remaining monomer mixture (B) has been obtained in the presence of the mixture (P) is.

3. Composition according to claim 1, characterized in that the mixture (I) by polymerization under continuous or batch addition of at least 5 parts by weight of the monomer mixture (B) to the butadiene rubber (A) to produce a mixture (I ') and then through Mixing of the mixture (Γ) with a terpolymer (C), which is obtained by separate polymerization of the remaining monomer mixture (B) obtained s5 has been made.

4. Composition according to claim 3, characterized in that the Tcrpolymcre (C) by continuous Adding the remaining monomer mixture (B) to water, which contains an emulsifier in amounts of the <«> Critical micelle concentration up to 1.5% by weight. based on the remainder of the monomer mixture (B).

5. Composition according to claim 1, characterized in that the polyorganosiloxane has a viscosity of f> 5 Has 10 to 30 centistokes.

The invention relates to a thermoplastic molding composition or resin composition with high transparency and Impact strength

It is known to produce impact-resistant resins with high transparency by graft polymerization of diene-containing polymer latexes with methyl methacrylate or a mixture containing monomers copolymerizable with methyl methacrylate. These resins have a relatively high transparency when they are molded under suitable conditions; however, the transparency varies greatly depending on the molding conditions. For example, the resins have a significantly poorer transparency when the temperature of the mold and the injection pressure are low, so that they can practically no longer be addressed as transparent resins. The usual impact-resistant resins with a sufficiently high transparency could therefore only be produced under certain molding conditions.

FR-PS 14 47 638 describes thermoplastic compositions based on a butadiene polymer ren and a polymer mixture of styrene, methyl methacrylate and acrylonitrile, with at least 80 Parts by weight of the above three monomers (based on 100 parts by weight of the butadiene polymer) 'in Presence of a latex of the butadiene polymer having an average particle diameter of 0.3 to 0.6 μπι are polymerized and the remainder of the above three monomers is added in polymerizable form. Even if you however, a polyorganosiloxane is added to a graft copolymer obtained by polymerizing one Mixture of styrene, methyl methacrylate t: nd acrylonitrile in the presence of a butadiene rubber latex according to the known processes, no increase in impact strength can be observed, the turbidity of the product depends noticeably on the processing conditions.

The main purpose of the invention is to create impact-resistant resins whose transparency does not deteriorate when molded under any conditions.

Other objects and advantages of the invention will appear from the description below.

The invention relates to a thermoplastic molding composition based on a polymer mixture a butadiene rubber and a polymer mixture of styrene, methyl methacrylate and acrylonitrile, wherein at least a portion of the total of these three monomers in the presence of the butadiene rubber an average particle diameter of about 0.3 μm was polymerized, the molding compound is characterized by:

(I) 97 to 99.99% by weight of a polymer mixture the end

(A) 10 parts by weight of a butadiene rubber made from polybutadiene or a styrene-butadiene rubber with at least 60% by weight butadiene with an average particle diameter (based on weight) from 0.20 to 0.35 μm, a particle diameter distribution in the range from 0.05 to 1.5 μm and a degree of swelling of at least 10 and

(B) 15 to 190 parts by weight of a terpolymer obtained by polymerizing a monomer mixture of 30 to 65% by weight of styrene, 15 to 68 % by weight of methyl methacrylate and 2 to 20% by weight

Wt .-% acrylonitrile was obtained, wherein at least 5 parts of the monomer mixture in the presence of component (A) were polymerized by being continuously or batch of component (A) were added, and

(II) 0.01 to 3% by weight of a polyorganosiloxane.

The resin composition according to the invention has high surface hardness as well as high toughness and shows excellent flowability at the time of molding; The main property of the mass is that it always gives a molded article with excellent transparency under arbitrarily selected molding conditions, i.e. a molded article with excellent transparency is always obtained, regardless of the mold or cylinder temperature during extrusion or the temperature of the metal mold , the injection speed or the cylinder temperature can be selected during injection molding. The usual resins of this type do not have this property.

In the resin composition according to the invention, the component (A) of the resin (1) shall be polybutadiene or a styrene-butadiene rubber (hereinafter generally referred to as "butadiene rubber") having an average particle diameter (by weight) of from 0.20 to 0.35 μ, a particle size distribution of about 0.05 to 1.5 μ and a degree of swelling of at least Ό. If a butadiene rubber latex with an average particle diameter (based on weight) of up to 0.20 μ, or with particles that have a diameter of less than 0.05 μ, is usually only obtained with one resin mass a low impact strength. On the other hand, if a butadiene rubber latex having an average particle diameter (by weight) of more than 0.35μ or one containing macro particles larger than 1.5μ in diameter is used, the resulting resin composition has high impact resistance , but shows fog-like cloudiness, ie poor transparency. The formation of such haze is inevitable even if the butadiene rubber has the same refractive index as the terpolymer, so that the resulting composition is practically unusable.

If the degree of swelling of the butadiene rubber latex used is higher than 10, the transparency is reduced and impact strength not impaired; however, if the degree of swelling of the latex is less than 10, the result is a resin composition having a low impact resistance.

The terpolymer (B), which is the other component of the resin (I), must be 2 to 20% by weight of acrylonitrile, 30 to 65% by weight, preferably up to 60% by weight, of styrene and to 15 to 68% by weight. preferably 20 to 60 wt .-%, consist of methyl methacrylate. If the proportion of acrylonitrile is less than 2% by weight, the mass obtained has unsatisfactory mechanical properties; if the proportion of acrylonitrile is greater than 20% by weight, the resulting resin composition is discolored in an undesirable manner. The proportions of styrene and methyl methacrylate are chosen so that the refractive index of the terpolymer comes close to that of butadiene rubber (n "= 1.52 to 1.55).

The resin (I) according to the invention is composed of the above-mentioned butadiene rubber latex (A) and a terpolymer (B) obtained by polymerizing a monomer mixture of acrylonitrile, styrene and methyl methacrylate in the proportions given above (the monomer

The mixture of monomers is hereinafter referred to as the "ternary monomer mixture"). The resin (I) can according to the the following three processes can be produced:

The first process is a grafting process in which 15 to 190 parts by weight of the ternary monomer mixture are added either continuously or batchwise at a temperature of 30 to 95 ° C. to a latex which contains 10 parts by weight of butadiene rubber (as solids); the polymerization is carried out in the presence of a radical polymerization initiator

15, leads to a graft copolymer containing 5 to 40% by weight of butadiene rubber is obtained. The second process is a graft-mixing process in which a graft copolymer _: that is obtained by continuous or batch polymerization of at least 5

20. Parts by weight of the ternary monomer mixture in Presence of a latex containing 10 parts by weight of butadiene rubber was obtained with a terpolymer is mixed, which was obtained separately by polymerizing the ternary monomer mixture.

whereby a resin is obtained which contains 5 bib 40% by weight Contains butadiene rubber.

The third process is a two-step grafting process in which the ternary monomer mixture in the presence of a graft polymer latex which is the intermediate product of the graft blending process. is polymerized; this gives a resin which contains 5 to 40% by weight of butadiene rubber. On the second graft polymerization of the third process, the ternary monomer mixture can either be added continuously, batchwise or all at once.

The graft polymerization in the first and second processes and the graft polymerization the first stage of the third process should be carried out so that the to be graft polymerized ternary monomer mixture either continuously or batchwise over a period of 30 minutes added to the butadiene rubber latex for up to 10 hours and in the presence of a radical polymerization initiator is polymerized. Using this procedure, the transparency is ultimately obtained Molded article almost independent of the molding conditions. In this case, it is desirable that the ternary monomer mixture at a rate of less than 12 parts by weight per hour Polymerization system containing 10 parts by weight of butadiene rubber is added. Will the graft polymerization Carried out in this way, a graft polymer is obtained with a high degree of grafting, the sometimes higher than 50%. On the other hand, if one works in the usual way, adding the entire amount of the ternary monomer mixture of butadiene rubber latex adds at once, the transparency depends of the molded article produced from the graft pile, in particular one according to the The molded article produced by extrusion or injection molding, depending on the molding conditions, and not only when the degree of grafting is low, but also when it is high, including when all the others

f'5 manufacturing conditions according to the invention met became.

The terpolymer for the second process can be all known per se emulsion, suspension and

Bulk polymerization processes can be obtained. Farther blending of the terpolymer with the goiter polymer can be done by any latex and dry blending process Successea The latexin mixing process, however, gives better results in terms of transparency of the resin composition obtained, so that the terpolymer is preferably obtained by the emulsion polymerization method will be produced. In particular, it is desirable that the ternary monomer mixture continuously contribute a temperature of 30 to 95 ° C over a period of more than 30 minutes in the presence of a Radical polymerization initiator and using an emulsifier is added, the Emulsifier is used in an amount between the critical micelle concentration and 1.5% by weight, based on the weight of the ternary monomer mixture. When using this working method the monomer ratio in the copolymer during the entire polymerization is practically the same as #as the original monomer ratio, and the emulsifier is very small, with the result The transparency of the terpolymer obtained is extremely high. Since the monomer mixture is continuous is added, no block is formed during the polymerization, so that a polymer latex can be obtained with excellent stability. So the above procedure is technically very advanced. Preferably used emulsifiers for this process are anionic Emulsifiers, e.g. B. alkali salts of fatty acids, koiophonium and organosulfuric acid compounds.

When molded, the resin (1) obtained by the above method shows high Transparency, regardless of the form requirements; however, it still has insufficient impact strength, so that 0.01 to 3%, preferably 0.05 to 0.3% of an organosiloxane polymer are added. Is the The proportion of the organosiloxane polymer is less than 0.01%, so no additional effect can be obtained will; if the proportion of this polymer is more than 3%, the transparency of the resin composition obtained becomes higher worsened. The organosiloxane polymer is said to be oily. A polymer with a very low Degree of polymerization and a low viscosity tends to evaporate when the mass at Extrusion is heated. A polymer with a high degree of polymerization becomes cloudy, so that the Transparency of the resin composition obtained is impaired. Therefore, the organosiloxane polymer preferably has a viscosity of IC to 30 centistokes. Organosiloxane polymers which can be used according to the invention are for example polydimethylsiloxane, polydiethylsiloxane, polyphenylmethylsiloxane, etc. polydimethylsiloxane is particularly preferred.

The resin (1) and the oily polysiloxane polymer are usually by means of known devices, z. B. ribbon mixers, Henschel mixers, mixing rollers, Banbury mixers, plastographs or the like. mixed together. But you can also use the Harr (I) in the form of a latex thoroughly with the oily one Mix the organosiloxane polymer (II) and coagulate the resulting mixture, wash, filter and dry.

Usually, the resin composition according to the invention becomes impact resistant without additional treatment Resin compound with a high transparency is used. In some cases, the resin compound is made with a vinyl chloride polymer, z. B. polyvinyl chloride or a copolymer of at least 70% vinyl chloride and Vinyl bromide, vinylidene chloride, vinyl acetate, acrylic acid, Acrylates, methacrylic acid or methacrylates mixed; these additives are used in amounts of 5 to 70%, based on the weight of the polymer, an impact-resistant, transparent or translucent resin that goes out by itself when burned, can be obtained.

In summary, and in particular with regard to the known prior art, the following is held. The molding composition according to the invention has a greatly improved impact strength, the Turbidity does not depend on the processing conditions. Please refer to the comments on the following Table 1 referenced. It is also clear from the following Table 10 and the following comparative examples show that the special composition of the monomer mixture according to the invention increases the impact strength and has a very favorable influence on the dependence of the transparency on the processing conditions. Of the increasing influence of the polyorganosiloxane on the impact strength, which according to the invention together with A special graft mixed polymer is present, can be seen clearly from the following Table 5. A An essential feature of the invention is to be seen in the fact that in the production of the inventions according to the invention Molding compound at least 5 parts by weight of a mixture of styrene, acrylonitrile and methyl methacrylate in Presence of 10 parts by weight (solids) of a butadiene rubber latex with an average Particle diameter of 0.20 to 0.35 µm and a degree of swelling of at least 10 polymerized, the mixture being added continuously or batchwise to the polymerization system. So it is it is essential that at least 5 parts by weight of the monomer mixture are added continuously or in batches polymerized in the presence of 10 parts by weight of the butadiene rubber latex. However, if the amount of the monomer mixture is made smaller than 4 parts by weight, the effect is of the plug and the dependence of the turbidity value on the processing conditions is too small great, as can be seen from the following Table 2, in particular by comparing the following Example 10 with the following comparative examples 10 and 5 to 9 can be found. It is also advantageous that the Monomer mixture with continuous or batch addition of the mixture with grafting polymerize. From a comparison of the following Comparative Example 11 with the following Example 15 and of the following comparative example 12 with the following examples 14 and 16 of the following table 3 it can be seen that the turbidity value - even with a graft yield of more than 59% - very much from the Processing conditions depends, except when the monomer mixture is continuous or batch is admitted. However, the properties of the thermoplastic molding composition according to the invention depend does not depend on the processing conditions.

The invention is illustrated below with the aid of the examples. In the examples are all Percentages and parts based on weight, the physical properties were determined as follows:

1. Average particle diameter (by weight) and particle diameter distribution the butadiene rubber latex: These values

were determined by measuring the diameter of at least 3000 particles of the latex on the basis of electron micrographs.
2. Gel content and degree of swelling:

Gel content =, ³

Degree of swelling =

- 1

wherein Wi weight of the butadiene rubber used, W ₂ is the weight of the addition of purified toluene and allowing the mixture at 30 ⁰ C over a period of 48 hours swollen butadiene and Wj the weight of the completely dried butadiene rubber with weight W. ₂
3. Graft yield (degree of grafting):

yi
Graft yield = - ■ 100 (%),

wherein Q is the weight fraction of the butadiene used in the graft polymerization; Y the yield; and Is is the ratio between the sum of the amount of free rubber extracted with cyclohexane from the graft polymer washed with methanol, from the amount of the graft polymer, which is insoluble in cyclohexane, with acetone to remove the terpolymer. which does not take part in the grafting reaction, the residue formed, and the amount of the graft polymer before the extraction with cyclohexane.

4. Melt index:

The melt index was determined according to the ASTM-D-238 method, the resin being held at 200 ^° C. for five minutes and then a weight of 21.6 kg being allowed to act.

5. Impact strength:

A sample with that prescribed in ASTM-D-256-54T Size was made in an injection molding machine and used to determine Izod impact strength

6. Total light transmission and haze:

A plate with the dimensions 60 × 100 × 1.7 mm was produced by injection molding at 220 ^° C. and the entire light transmission and cloudiness of the plate were after the mediode ASTM-D-1003 ^ 61 determined

example 1 Styrene 25th Butadkr 75 parts Manufacture of rubber latex A n-dodecyl mercaptan 0.4 parts Nali iuiuseue by dispro portioned rosin 1,2TeHe Cheese sulphate 03 parts Deionized water 80 parts

A mixture with these ingredients was poured into a pressure vessel and the polymerization of this was started at 50 ° C. When a degree of conversion of 30 or 60% was reached, 12.5 parts of water and 0.75 parts of sodium soap became the disproportionated rosin was added to the system, and the polymerization was carried out for a total of 6 hours, whereby a rubber latex A was obtained with a conversion rate of 98%. The rubber latex A thus obtained had an average particle diameter of 0.20 µm, a degree of swelling of 11 and a gel content of 87%. The particle diameter distribution of the rubber latex A was in the range from 0.05 to 1.5 μm.

Production of the graft copolymer latex

Rubber latex A 50 parts

(based on
Solids)

Potassium persulfate 0.25 parts

Water 200 parts

A mixture of the above ingredients was placed in a reactor. After the reactor had been flushed with nitrogen, the mixture was ^{heated to 70 °} C. with stirring, whereupon 50 parts of a mixture of 12% acrylonitrile, 40% styrene and 48% methyl methacrylate were added continuously over a period of 2.5 hours. After the addition, the mixture was left to stand for one hour and then cooled to obtain a graft copolymer latex.

Production of a terpolymer latex

55

60

Acrylonitrile 48 parts Styrene 160 parts Methyl methacrylate 192 parts t-dodecyl mercaptan 2.0 parts Sodium laurate 4.0 parts Potassium persulfate 1.2 parts Deionized water 800 parts

A mixture of the above-mentioned constituents was ^{heated with stirring at 70 °} C., a terpolymer latex being obtained.

Manufacture of the resin mass

Graft copolymer latex

Terpolymer latex 2,6-di-tert-butyl-4-methylphenol Polydhnethylsfloxane (lOCentistokes)

100 parts
400 parts

1.5 parts
0.75 parts

Em mixture of the ingredients listed above was precipitated in 4000 parts of a l% aqueous calcium chloride solution at 90 ⁰ C and then heated to 95 ° C. After washing and drying, the mixture was extruded into pills, which were then injection molded into a resin article.

Example 2 Production of a terpolymer latex

A mixture of 48 parts of acrylonitrile, 160 parts of styrene, 192 parts of methyl methacrylate and 17 parts t-Dodecycaptan was continuously over a

ίο

A reactor containing 1.2 parts of sodium laurate, 1.2 parts of potassium persulfate and 800 parts of water at 70 ^° C. was fed to a reactor over a period of 2.5 hours. The resulting mixture was then allowed to stand for about 30 minutes without further treatment and then cooled to obtain a terpolymer latex. The procedure was then as in Example 1, except that the terpolymer indicated above was used; a resin composition was obtained.

Example 3

A rubber latex B was prepared in a similar manner to the rubber latex A of Example 1, except that the amounts of the sodium soap, disproportionated rosin and water added at the beginning were 0.9 and 60 parts, respectively, and the polymerization time was 40 hours was discontinued. The degree of conversion was 95%. The rubber latex B thus obtained had an average particle diameter of 0.28 μm, a degree of swelling of 14 and a gel content of 83%. The particle diameter distribution of the latex B was in the range from 0.05 to 1.5 μ. A resin composition was then produced as in Example 1, except that the rubber latex B was used.

Example 4

A resin composition was prepared in the same manner as in Example 2, except that the rubber latex B was used.

Example 5

450 parts of a monomer mixture of 12% acrylonitrile, 40% styrene and 48% methyl methacrylate were mixed with 1 part of t-dodecyl mercaptan and added continuously over a period of 4 hours 70 ° C to 50 parts of rubber latex B, which contained 1.35 parts of potassium persulfate and 4.5 parts of sodium laurate, to give a resin (I).

500 parts of the resin (I) obtained in this way were with 0.75 parts of polydimethylsiloxane (10 centistokes) and 1.5 Parts of 2,6-di-tert-butyl-4-methylphenol were mixed and the resulting mixture was made in the same manner as further treated in Example 1 to obtain a resin composition. '

Example 6

Emc Hroplmischpolymerisat latex was produced in the same way as in Example 1, except that the rubber latex B was used. To 100 parts (based on the solids content) of the latex thus fcergesteflten were added 1.2 parts of potassium persulfate and 4 parts of sodium laurate and 400 parts of a mixture of 12% acrylonitrile, 40% styrene and 48% methyl methacrylate were added to the resulting mixture over a period of 3 hours containing 2 parts of 5-dodecyl mercaptan was added to give a resin (I).

5XX) parts of the resin (I) thus obtained with 0.75 parts of polydimethylsiloxane (10 centistokes) and 13 Parts of 2,6-di-tert-butyl-4-methylphenol mixed and the obtained mixture was made in the same manner as • Further treated according to Example 1, a resin composition being obtained.

Example 7

A rubber latex C was prepared in a manner similar to the rubber latex A according to Example 1, except that the amounts of the sodium soap added at the beginning, the disproportionated rosin and the water were 0.8 and 50 parts, respectively; the polymerization time was 45 hours and the degree of conversion was 93%. The rubber latex C thus obtained had an average particle diameter of 0.35 μm, a degree of swelling of 18 and a gel content of 78%. The particle diameter distribution of the latex C was in the range of 0.05 to 1.5 μ. A resin composition was then prepared following the procedure of Example 1 except that the latex C was used.

Example 8

A resin composition was prepared in the same manner as in Example 2 except that the rubber latex C was used.

Comparative example 1
Manufacture of a rubber latex (a)

Styrene 25 parts Butadiene 75 parts n-dodecyl mercaptan 0.4 parts Sodium soap from dispro portioned rosin 1.0 parts Potassium persulfate 0.3 parts Deionized water 100 parts

, 0 ^ ^'n mixture of the above constituents: - parts was filled into a pressure vessel, and the polymerization of the mixture was set at 50 ⁰ C in motion. After the conversion reached 40%, 25 parts of water containing 2.0 parts of sodium soap of disproportionated rosin was added to the system and the polymerization was continued for a total of 35 hours, with a rubber latex (a) having a conversion of 96% was obtained. The rubber latex (a) thus obtained had an average particle diameter of 0.15 μm, a degree of swelling of 13 and a gel content of 85%. The particle size distribution of the latex (a) was in the range from 0.05 to 1 _; 5μ. A resin composition was then produced as in Example 1, except that the rubber latex (a) was used.

Comparative example 2

A resin composition as prepared according to Example 2 except that the rubber latex (a] was used.

Comparative example 3
Manufacture of a rubber latex (b)
55

Styrene 25 parts Butadiene 75 parts n-dodecyl mercaptan 0.4 parts Sodium soap from dispro portioned rosin 0.7 parts Potassium persulfate 03 parts Deionized water 50 parts

Em mixture of the ingredients listed above was placed in a pressure vessel and the polymerization of the mixture was set at 50 ⁰ C in transition Sehn reaching a degree of conversion before, 30 and 60% were each \ 2J5 parts of water with 0,7ϊ parts of sodium soap of disproportionated Kolopno -

nium was added to the system and the polymerization proceeded for a total of 48 hours continued, with a rubber latex (b) rr.with a Degree of conversion of 93.5% was obtained. The rubber latex thus obtained had an average one Particle diameter of 0.38 μ, a degree of swelling of 15 and a gel content of 76%. Then became A resin composition was produced as in Example 1, except that the rubber latex (b) was used.

Table 1

Comparative example 4

A resin composition was produced as in Example 2, except that the rubber latex (b) was used.

The resin compositions thus obtained according to Examples 1 to 8 and Comparative Examples 1 to 4 were on examined their physical properties, whereby the results shown in Table 1 were obtained.

example average Graft r metal mold 80 ° C Enamel Turbidity (% Notch impact ) Total light transmission Metal shape part exploitation Form printing index temperature
30 ° C toughness after the metal mold (%) through 70 kg / cm * Form printing Izod Form printing knife the 90.5 60 kg / cm * 70 kg / cm ² Temperature of Form printing Rubber- 91.8 6.5 5.5 30 ° C 70 kg / cm ² latex 90.3 2.5 2.3 90.2 (μ) (%) 91.5 (g / 10 min) 6.2 (kg cm / cm ² ) 5.1 Form printing 91.8 90.0 2.7 2.6 60 kg / cm ² 90.3 Comparative example 1 0.15 78 91.6 28 7.0 2.7 5.8 90.0 91.5 Comparative example 2 0.15 78 89.8 30th 3.3 2.7 3.0 91.5 90.5 example 1 0.20 72 90.8 35 8.2 5.7 7.0 90.1 91.5 Example 2 0.20 72 89.5 33 6.2 5.9 5.8 91.3 89.5 Example 3 0.28 72 90.2 38 9.2 8.5 9.0 90.1 90.5 Example 4 0.28 72 85.8 34 IU 8.8 93 91.4 89.8 Example 5 0.28 68 89.0 40 20.1 8.2 19.5 89.2 90.0 Example 6 0.28 107 31 19.5 8.7 18.5 90.0 86.5 Example 7 0.35 71 41 9.2 89.5 88.0 Example 8 0.35 71 38 8.9 89.7 Comparative example 3 0.38 70 48 9.2 85.3 Comparative example 4 0.38 70 42 9.4 88.2 Metal shape Table 1 (continued) Form printing example Total light transmission (%) 70 kg / cm Temperature dei Temperature of
80 ° C 5.8 Form printing Form printing 2.2 60 kg / cm ² 60 kg / cm ² 6.0 Comparative example 1 90.2 6.6 2.5 Comparative example 2 91.5 2.4 5.6 example 1 89.9 6.0 3.0 Example 2 91.5 2.5 6.2 Example 3 90.1 7.0 5.7 Example 4 91.4 3.2 8.5 Example 5 89.5 7.5 9.0 Example 6 90.5 6.5 18.5 Example 7 90.0 9.1 18.3 Example 8 89.9 12.3 Comparative example 3 85.2 22.1 Comparative example 4 89.0 193

Table 1 shows that with an average particle diameter of the styrene-butadiene rubber from 0.15 μ the resin is always transparent, regardless on the conditions of injection molding; however, it has a low impact resistance and its practical value is limited If the average particle diameter of the styrene-butadiene rubber is 038 μ, then has the hair has a low transparency and shows a mist-like haze. With an average On the other hand, the resin has a surface diameter of 0.20 to 035 μ for styrene-butadiene rubber Total light transmission greater than 89%, and a haze value less than 10%, and the

Transparency is not influenced by the molding conditions. Furthermore, the resin shows a notched Izod impact strength of more than 5 kg / cm ² .

Example 9

A graft copolymer latex was made by polymerizing the same acrylonitrile-styrene-methyl methacrylate monomer mixture as in Example 1, which was added continuously over a period of 90 minutes, in the presence of the rubber latex B prepared with the ratio between the rubber latex B and the monomer mixture 5: 3 fraud. It was made in the same manner as in Example 1

produced a resin composition, but using the graft copolymer latex produced as above became.

Example 10

A resin composition was produced as in Example 2, except that the graft copolymer latex produced according to Example 9 was used was used.

Example 11

A graft copolymer latex was polymerized by adding the same acrylonitrile-styrene-methyl methacrylate monomer mixture as in Example 1 was added continuously over a period of 5 hours to the rubber latex B; The relationship between the rubber latex B and the monomer mixture was 1: 3. It became a resin composition like after Example 1 prepared, but using the graft copolymer latex prepared as above became.

Example 12

A resin composition was produced in the same manner as in Example 2 except that of Example 11 produced graft copolymer latex is used became.

Comparative example 5

A graft copolymer latex was produced by polymerization, using the same acrylonitrile-styrene-methyl methacrylate monomer mixture as in example 1 continuously over a period of 15 Minutes to which rubber latex B was added. The ratio between rubber latex B and monomer mixture was 10: 1. A resin composition was produced in the same manner as in Example 1, however, the graft copolymer latex prepared as above was used.

Comparative example 6

A resin composition was prepared in the same manner as in Example 2 except that according to Comparative Example 5 produced graft miscible polymer latex was used.

Comparative example 7

A graft copolymer latex was produced by polymerization by adding the same acrylonitrile-styrene-methyl methacrylate monomer mixture as in Example 1 was added continuously to the rubber latex B over a period of 30 minutes. The ratio between rubber latex B and monomer mixture was 5: 1. there has been a Resin mass in the same way as according to the example! produced, however, as produced above Graft copolymer Latix was used.

Comparative example 8

A resin composition was produced as in Example 2, except that that in Comparative Example 7 produced graft mixture was used.

Comparative example 9

A graft copolymer latex was produced by polymerization using the same acrylonitrile-styrene-methyl methacrylate monomer mixture as in Example 1, added continuously to the rubber latex B over a period of one hour became. The ratio between rubber latex B and monomer mixture was 5: 2.

A resin composition was produced as in Example 1, except that the graft copolymer latex produced above was used was used.

Comparative example 10

A resin composition was produced as in Example 2, but with that in accordance with Comparative Example 9 produced graft copolymer latex was used.

The resin compositions according to Examples 9 to 12 and the Comparative Examples 5 to 10 were examined for their physical properties, with those in Table 2 The results given were obtained: this table also shows the physical properties of the Resin compositions given according to Examples 3 and 4.

25th

35

Table 2 example

Graft
prey

Notch total light transmission (%) impact strength temperature of the
after metal mold 30 ⁰ C Izod

(kg

Temperature of the metal mold 80 ° C turbidity (%)

Temperature of
Metal mold 30 ⁰ C

Temperature of the metal mold 8O ⁰ C

^ ü ?? τη? "?" ¹ ? I? ™ ^{aruc] i} Form printing Form printing Form printing Form- Form-

60kg / cm * 70kg / cm * 60kg / cm * 70kg / an '60kg / cm * 70kg / cm * printing pressure

^ 60 kg / 70 kg /

en * to *

Comparative 9 example 5 Comparison 9 example 6 Comparison 17th example 7 Comparison 17th example 8 Comparison 30th for example Comparison 30th example 10 Example 9 52

8.4

7.9

8.2

86.2 86.0 87.0 89.1 65.6 37.4 253 73 86.5 86.2 88.0 903 67.1 42.0 273 5.7 87.0 87.2 88.2 893 45.0 26.8 173 8.0 87.0 873 89.0 903 502 29.8 n / A 5.0 88.0 88.2 88.7 89.2 28.4 20.2 123 8.0 89.0 89.8 893 91.0 243 21.0 143 53 89.7 90.0 89.9 39.9 123 103 8.2 63

ί Continuation Graft Notch Total light transmission (%) •the Temperatu the Turbidity (%) oe r Temperature of shape example UUS- impact 30 ° C Metal shape 80 ° C 30 C Metal mold 8OC pressure beutc toughness t temperatut temperature 70 kg / after Metal shape Form printing Form printing Formdruek Metal shape Form printing shape cm ² Izod 70 kg / cm ² 60 kg / cm ² 70 kg / cm- ¹ 70 kg / cm ^: pressure 4.5 Form printing Form printing 60 kg / 5.6 (%) (kg 60 kg / cm ² 60 kg / cm ² cm ² 3.0 cm / cm- ') 90.7 91.3 91.4 9.7 6.5 6.2 90.5 90.1 90.0 5.8 7.0 5.6 52 8.2 90.7 91.5 91.4 91.6 10.3 3.0 3.2 Example 10 72 - 90.1 90.3 90.2 90.4 7.0 6.0 6.2 Example 3 72 8.8 91.4 90.7 90.5 90.6 3.3 5.8 5.9 Example 4 210 - 90.3 20th 6.5 Example 18 Example 11 210 8.5 90.7 6.0 Example 12 example 13th

A resin composition was prepared in the same manner as in Example 9 except that the time for the Addition of the monomer mixture was 30 minutes.

Example 14

A resin composition was prepared in the same manner as in Example 4 except that the time for the The addition of the monomer mixture was 30 minutes.

Example 15

A resin composition was prepared as in the same manner as in Example 3 except that the time for the addition of the monomer mixture was one hour.

Example 16

A resin composition was prepared as in Example 4, except that the duration of the addition of the Monomer mixture was one hour.

Example 17

A resin composition was prepared as in Example 3, except that the duration of the addition of the Monomer mixture was 5 hours.

A resin compound was produced as in Example 4, but the time taken for the addition of the Monomer mixture was 5 hours.

Comparative Example 11

A resin composition was prepared as in Example 3, but with the monomer mixture added once to the reactor and the polymerization was carried out at 70 ° C. for three hours.

Comparative example 12

There was prepared a resin composition as in Example 4 except that the monomer mixture is added at once to the reactor and the polymerization was carried out for three hours at 7O ⁰ C.

The resin compositions produced according to Examples 13 to 18 and Comparative Examples 11 and 12 were examined for their physical properties, those shown in Table 3 Results were obtained. Table 3 also shows the physical properties of those according to Examples 3 and 4 resin compositions obtained.

Table 3

example Addition time Graft yield Notch impact Total permeability Form printing of the monomer toughness after (%) 75 kg / cm ² mixed Izod 87.5 88.0 (min) (0/0) (kg cm / cm ² ) 89.4 Temperature of the metal mold 30 ° C 89.5 Comparative Example 11 0 69 Form printing 89.9 Comparative example 12 0 69 8.0 65 kg / cm ² 90.0 Example 13 30th 51 - 86.0 90.5 Example 14 30th 70 7.9 87.2 91.5 Example 15 60 72 - 89.3 90.5 Example 16 60 72 8.2 89.0 91.5 Example 3 150 72 - 89.8 609 545/376 Example 4 150 72 8.8 90.0 Example 17 300 78 - 90.1 Example 18 300 78 8.9 91.4 90.0 91.5

17th 20th Form printing 39 022 Metal shape 18th Metal shape 75 kg / cm ² Form printing Form printing Table 3 (continued) 89.2 75 kg / cm ² 75 kg / cm ² example Total light transmission 89.3 Cloudy (%) 17.0 Temperature of
80 ° C 7.2 Temperature of the metal mold 90.1 Temperature of 17.0 Form printing 7.0 Form printing 90.3 Form printing 12.4 65 kg / cm ² 7.2 65 kg / cm ² 90.7 65 kg / cm ² 11.0 10.3 6.0 Comparative Example 11 88.2 90.8 22.0 7.5 10.2 6.1 Comparative example 12 88.8 90.0 24.0 9.3 8.5 5.5 Example 13 89.7 91.6 13.2 5.8 7.2 5.6 Example 14 89.2 90.6 12.5 3.0 7.3 3.0 Example 15 90.0 91.7 9.2 5.5 6.8 5.4 Example 16 90.3 10.5 3.0 7.0 3.0 Example 3 90.1 7.0 3.2 Example 4 91.4 3.3 5.8 Example 17 90.7 6.8 3 ,! Example 18 91.4 3.5

It can be seen from Table 3 that the transparency of the mass obtained fluctuates greatly depending on the molding conditions when the monomer mixture is set to e _; n times is admitted.

Example 19

A resin composition was produced as in Example 4, except that in the production of the Terpolymer latex 0.2% (based on the weight of the monomer mixture) sodium dioctyl sulfosuccinate as Emulsifier were used.

Example 20

A resin composition was produced as in Example 4, except that in the production of the Terpolymer latex, the time for the addition of the monomer mixture reduced to 30 minutes became.

Example 21

A resin composition was produced as in Example 4, except that in the production of the Terpolymer latex 1% sodium laurate was used.

Comparative example 13

The polymerization was carried out in the same manner as in Example 4, except that the

To prepare the terpolymer latex the monomer mixture was added all at once; this froze entire system during the polymerization.

Comparative example 14

A resin composition was produced as in Example 4, except that in the production of the Terpolymer latex increased the emulsifier concentrates to 1.0% and the monomer mixture at once was admitted. The polymerization lasted five hours.

Comparative example 15

A resin composition was produced as in Example 4, except that in the production of the Terpolymer latex increased the emulsifier concentration to 2% and the monomer mixture at once was admitted.

The resin compositions produced according to Examples 19 to 21 and Comparative Examples 13 to 15 were examined for their physical properties, those shown in Table 4 Results were obtained; Table 4 also shows the physical properties of those according to Example 4 obtained resin composition indicated.

Table 4 Emulsifier Duration of Extent of Notch impact 8.5 Total light Turbidity (%) Hot example Addition of the Block formation toughness after 8.3 permeability Monomers in the Izod 8.8 (o / o) mixed Terpolymer
latex 8.2 (%, based (min) (%, based on (kg cm / cm ² ) (Temperature (Temperature on the mono the terpolymer) 8.4 the metal the Meiall- mixture of meres) 7.9 form 6O ⁰ C form 6O ⁰ C Form printing Form printing 75 kg / cm ² ) 75 kg / cm ² ) 0.2 160 0 91.8 3.0 Example 19 0.3 30th 0 90.7 8.4 Example 20 0.3 160 0 91.5 3.2 Example 4 1.0 160 0 90.0 6.3 Example 21 0.3 0 100 Comparative example 13 1.0 0 0.5 85.3 17.2 Comparative example 14 2.0 0 0.2 87.3 18.0 Vrreleiehsbcisoiel 15

IO

Table 4 shows that with continuous addition of the Monomer mixture the emulsifier concentration can be greatly reduced, whereby the transparency of the obtained resin becomes higher.

Comparative example 16

A resin composition was produced as in Example 3, except that no polyorganosiloxane was used was used.

Comparative example 17

A resin composition was produced as in Example 4, except that no polyorganosiloxane was used was used.

Example 22 ' ⁵

A resin composition was obtained as in Example 3, except that 0.05 part (0.01%) of pofydimethylsiloxane (20 centistokes) was used as the polyorganosiloxane.

Example 23

A resin composition was produced as in Example 4, except that 0.01% polydimethylsiloxane (20 Centistokes) were used as the polyorganosiloxane.

Example 24

A resin composition was produced as in Example 3, except that 1.0% polydiethylsiloxane (3 Centistokes) was used as the polyorganosiloxane.

Example 25

A resin composition was produced as in Example 4, except that 1.0% polydiethylsiloxane (3 Centistokes) was used as the polyorganosiloxane.

Example 26

A resin composition was produced as in Example 3, but with 1.0% polymethylphenylsiloxane (30 centistokes) were used as the polyorganosiloxane.

Example 27

A resin composition was produced as in Example 3, but with 3% polymethylphenylsiloxane (30 centistokes) were used as the polyorganosiloxane.

Example 28

A resin composition was produced as in Example 4, but with 3% polymethylphenylsiloxane (30 centistokes) were used as the polyorganosiloxane.

Comparative example 18

A resin composition was produced as in Example 3, but with 4% polydimethylsiloxane (20th Centistokes) were used as the polyorganosiloxane.

Comparative example 19

A resin composition was produced as in Example 4, but with 4% polydimethylsiloxane (20 Centistokes) were used as the polyorganosiloxane.

The resin compositions according to Examples 22 to 28 and Comparative Examples 16 to 19 were on their physical properties study, whereby the results shown in Table 5 were obtained; in Table 5 also shows the physical properties of the resin composition according to Example 3.

Table 5 Polyorgano Amount of Notch impact Total light Turbidity (%) example siloxane Polyorgano- toughness after
I ι η H permeability (%) SIIUXdMS
(%) ι L υ u
(kg cm / cm ² ) Temperature of temperature Metal mold 6O ⁰ C the metal mold
6O ⁰ C _ 0 2.7 90.2 5.2 Comparative example 16 - 0 2.7 91.5 2.8 Comparative example 17 A. 0.01 5.2 90.2 5.2 Example 22 A. 0.01 5.5 91.5 2.8 Example 23 A. 0.15 8.7 90.1 6.0 Example 3 B. 1.0 8.2 90.0 8.2 Example 24 B. 1.0 8.3 90.0 4.5 Example 25 C. 1.0 5.7 90.3 6.2 Example 26 C. 3.0 6.8 89.3 10.3 Example 27 C. 3.0 6.0 89.5 9.8 Example 28 A. 4.0 9.2 88.0 72.0 Comparative example 18 A. 4.0 9.2 85.2 72.0 Comparative example 19

A: polydimethylsiloxane (20 centistokes).

B: Polydiethylsiloxane (3 centistokes).

C: polymethylphenylsiloxane (30 centistokes).

Table 5 shows that even with the addition of an extremely small amount of polydimethylsiloxane the mass obtained has a greatly improved impact strength and its transparency is only slightly reduced other polyorganosiloxanes which improve polydiethylsiloxane, polymethylphenylsiloxane or the like are effective the impact strength of the resin composition obtained. However, the polyorganosiloxanes are in large If quantities are added, the resin compositions obtained become cloudy and have a lower transparency.

Comparative Examples 20 to 27

Example 3 was repeated with the difference that the substances given in Table 6 instead of the

Polydimethylsiloxane were added. Resin compositions were those given in Table 6 maintain physical properties, d. H. with inferior impact strength.

Table 6 example

additive

lot

Notched impact strength
lzod

transparency

Comparative example 16 without 0 2.7 satisfactory Comparative example 20 liquid paraffin 03 2.7 satisfactory Comparative Example 21 liquid paraffin 2.0 2.6 cloudy Comparative Example 22 Barium stearate 0.5 2.8 cloudy Comparative Example 23 Barium stearate 2.0 2.8 opaque Comparative Example 24 Polyethylene glycol (cp = 1000) 0.5 2.7 satisfactory Comparative Example 25 Polyethylene glycol (cp = 1000) 2.0 2.7 somewhat cloudy Comparative Example 26 Stearic acid 2.0 2.6 satisfactory Comparative Example 27 Stearic acid 4.0 2.3 satisfactory

Example 29
Manufacture of rubber latex D

The polymerization was carried out in exactly the same manner as in the preparation of the rubber latex B in Gear set. After a polymerization time of 20 hours, the polymerization was terminated, wherein a rubber latex D with an average

Particle diameter of 0.27 μ, a degree of swelling of 00 and a gel content of 0 was obtained.

Using this rubber latex D, a resin composition was obtained in the same manner as in Example 5 manufactured.

example

Using the rubber latex D, a resin composition was obtained in the same manner as in Example 4 manufactured.

Tabel 7th Plug Enamel Notch Total opacity shape (%) shape Cloudiness shape Temperature of shape example the end index impact pressure pressure pressure Metal mold 80 ^r C pressure prey tenacious 75 kg / Temperature of 75 kg / 75 kg / 75 kg / speed Temperature of cm ² Metal mold 8O ⁰ C cm ² ςιτι ² shape cm ² after Metal mold 3O ⁰ C 88.5 88.9 8.0 pressure 6.5 (%) lzod 90.0 shape 90.0 Temperature of 6.0 65 kg / 5.8 shape pressure Metal mold 30 C cm ² pressure 65 kg / 7.1 65 kg / cra ^! shape 6.5 75 37 9.0 cm ² 88.8 pressure example 29 75 35 8.5 88.6 90.0 65 kg / example 30th 89.5 cm ² 8.3 6.3

Examples 31 to

Resin compositions were prepared in the same manner as in Example 3, except that the amounts of Graft copolymer latex and the terpolymer latex to the rubber concentrations given in Table 8 were discontinued.

Examples 35 bis

Resin compositions were prepared in the same manner as in Example 4, except that the amounts of The graft copolymer latex and the terpolymer latex were adjusted so that the values listed in Table 8 indicated rubber concentrations were obtained

The resin compositions according to Examples 31 to 38 were examined for their physical properties, the results shown in Table 8 were obtained; in table 8 are also the physical Properties of the resin compositions according to Examples 3 and 4 are given.

Table 8 Styrene 20 39 022 Concentralization (kg ■ cm / cni ^J ) Enamel f 24 Cloudiness 23 example Butadiene (O / o) 5.2 ' index Rubber- 5 8.5 Total light Notch impact 10 27 permeability toughness 20th 45 (g / 10 min) (0/0) after 1 ζ ο d 30th 51 47 5.2 Example 31 40 5.3 38 (0/0) 5.6 Example 3 5 8.8 19th 91.0 8.9 Example 32 10 29 10 90.0 10.2 Example 33 20th 44 5.3 88.5 11.4 Example 34 30th 53 45 88.2 2.8 Example 35 40 34 88.0 3.2 Example 4 17th 91.8 6.3 Example 36 9 91.5 9.4 Example 37 5 89.5 10.7 Example 38 88.3 88.2

4i

Table 8 shows that the resin compositions have high impact resistance when the rubber concentration is more than 5%. The resin compositions have a lower one as the rubber concentration increases Melt index and a somewhat lower transparency, but are still up to a rubber concentration of 40% practically usable.

Example 39

The graft copolymer latex produced according to Example 3 was coagulated into a powder in a 10% aqueous sulfuric acid solution. 100 parts of this

Table 9

Powders were made using a Henschel mixer 400 parts of a bead polymer mixed by suspension polymerization of a monomer mixture of 12% acrylonitrile, 40% styrene and 48% methyl methacrylate in the presence of 0.1% of one Partial saponification product of polymethyl methacrylate and 0.8% lauroyl peroxide was obtained, as well with 1.5 parts of 2,6-di-tert-butyl-4-methylphenol and 0.75 parts of polydimethylsiloxane (10 centistokes). The received The mixture was formed into pills by means of an extruder, which were then molded into a resin mass became. The physical properties of the resin composition thus obtained are shown in Table 9.

Enamel notch total light ductility (%)
index impact

tough- temperature of metal- temperature of metal-

form 30-C form 80 ° C

after

17 ο d form printing form printing form printing form printing

65 kg / cm ² 75 kg / cm ² 65 kg / cm ² 75 kg / cm ²

Turbidity (%)

Metal mold temperature 30 "C

Temperature of the metal mold 8O ⁰ C

Form printing
65 kg / cm ²

Form printing
75 kg / cm ²

Form printing
65 kg / cm ²

Molding pressure 75 kg / cm ²

7.8

885

88.6

88.2

88.4 9.3

9.1

9.0

8.9

Examples 40 and 41 and
Comparative Examples 28 and 29

Graft copolymer latexes were prepared in the same way as in Example 1, except that the rubber latex B was graft mixed with the monomer mixtures shown in Table 10. Further terpolymer latexes were obtained in the same way as in Example 1, except that the monomer mixtures given in Table 10 were used.

Table 10

Resin compositions were prepared in the same manner as in Example 1, except that those thus obtained Graft copolymer latexes and terpolymer latexes were used.

The resin compositions thus produced were on their

physical properties examined, the in

Results given in Table 10 were obtained in

Table 10 also shows the physical properties of the resin composition according to Example 3.

example Monomer mixture

Acrylic styrene methyl nitrile meth-

acrylate

Notched Izod impact strength Schmeteindex

Total-

Light transmission

nonchalance)

Turbidity ") discoloration

Comparative example O 45 55 3.8 20th 90.5 33 not discolored £ 09545/376 28 Betspid 40 2 44 54 6.0 23 91.1 3.6 not discolored Example 3 12th 40 48 83 34 91.4 33 not discolored Example 41 20th 38 42 93 30th 903 4.2 easy discolored Comparative example 30th 34 36 9.2 25th 89.6 5.0 strong 29 discolored *) The PnAe was at a MetaBform temperature from WTC and one Font of 75 kg / cm ' manufactured

Example 42 Manufacture of rubber latex F

The polymerization was initiated in the same manner as for the rubber latex B, whereby but a mixture of 40 parts of styrene and 60 parts of butadiene instead of the monomer mixture from 25 Parts of styrene and 75 parts of butadiene was used. After 35 hours a rubber latex F became with obtained a degree of conversion of 95.5%. The rubber latex F thus obtained had an average one Particle diameter of 0.28 μ, a degree of swelling of 16 and a gel content of 85%. the Particle diameter distribution of the latex F ranged from 0.1 to 1.5 μ.

A graft copolymer latex was prepared in the same manner as in Example 1, wherein However, the rubber latex F was used, on which a monomer mixture of 20% acrylonitrile, 60% Styrene and 20% methyl methacrylate was grafted on.

Furthermore, a terpolymer latex was prepared in the same manner as in Example 1, wherein however, a monomer mixture of 80 parts of acrylonitrile, 240 parts of styrene and 80 parts of methyl methacrylate was used and the amount of t-dodecyl mercaptan was adjusted to 1.0 part.

A resin composition was prepared in the same manner as in Example 1 except that thus prepared Graft copolymer latex and terpolymer latex were used.

Comparative example 30

A graft copolymer latex was prepared in the same manner as in Example 1, wherein "However, the rubber latex F was used on the a monomer mixture of 20% acrylonitrile, 70% styrene and 10% methyl methacrylate was grafted on.

Furthermore, a terpolymer latex was prepared in the same manner as in Example 1, wherein however, a monomer mixture of 80 parts of acrylonitrile, 280 parts of styrene and 40 parts of methyl methacrylate and t-dodecyl mercaptan were used in an amount of 1.0 part.

A resin composition was produced as in Example 1, but using the graft copolymer latex produced above and polymer latex were used.

The resin compositions according to Example 42 and Comparative Example 30 were tested for their physical properties

examined. where the in Tabel Results were obtained. Enamel Notch 11 specified Turbidity *) Table 11 index impact example tenacious speed Total- after light- lzod by- 35 8.3 casual- 10.3 42 7.5 ability *) 35 Example 42 Comparison 86.5 example 30 58

*) The sample was produced at a metal mold temperature of 80 ° C and with a mold pressure of 75 kg / cm ² .

Claims (1)

Patent claims: 1. Thermoplastic molding compound based on a polymer mixture of a butadiene rubber and a polymer mixture of styrene, Methyl methacrylate and acrylonitrile, at least a portion of the total of these three Monomers in the presence of butadiene rubber with an average particle diameter sers of about 0.3μΐη was polymerized, characterized by: (1) 97 to 99.99% by weight of a polymer mixture 15th (A) 10 parts by weight of a butadiene rubber made of polybutadiene or a styrene-butadiene rubber with at least 60% by weight of butadiene in an average particle diameter (based on the weight) of 0.20 to 0.35 μm, a particle diameter distribution in the range from 0.05 to 1.5 μm and a degree of swelling of at least 10 and (B) 15 to 190 parts by weight of a terpolymer, by polymerizing a monomer mixture of 30 to 65 wt .-% Styrene, 15 to 68 wt .-% methyl methacrylate and 2 to 20 wt .-% acrylonitrile obtained was, wherein at least 5 parts of the monomer mixture were polymerized in the presence of component (A), by adding them continuously or batchwise to component (A), and