JP3168077B2 - Method for producing ABS resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an ABS resin having excellent heat resistance, impact resistance, gloss, rigidity and the like.

[0002]

2. Description of the Related Art Conventionally, as an ABS resin production method, emulsion polymerization, bulk polymerization, bulk-suspension polymerization, solution polymerization and the like are known. The emulsion polymerization method in which a vinyl chloride monomer is added to carry out graft polymerization is advantageous in terms of glossiness, impact resistance and the like. However, recently, a so-called anionic polymerized rubber having a large degree of freedom in molecular structure is dissolved in a mixture of an aromatic vinyl monomer and a vinyl cyanide monomer, and bulk polymerization or bulk-suspension polymerization or solution polymerization is used. Trout AB
S has attracted attention because it has less impurities such as emulsifiers in the resin and is less likely to be discolored and discolored, and has no cost for treating wastewater containing soap and is advantageous in terms of cost.

[0003]

However, the ABS resin obtained by the bulk polymerization or the bulk-suspension polymerization has a poor balance of impact resistance, glossiness and rigidity, and furthermore has a high heat stability. Needed improvement.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art. By using a specific rubber in a specific method, the heat resistance is extremely excellent, and An object of the present invention is to provide a method for producing a mass ABS resin in which the balance among impact, gloss, and rigidity is greatly improved.

That is, according to the present invention, a mixture of an aromatic vinyl monomer and a vinyl cyanide monomer is hydrogenated with 5 to 85 mol% of the conjugated diene units of the conjugated diene rubber.
5% by weight styrene solution viscosity (SV) at 5 ° C. is 5 to 5
0 centipoise (cps), the ratio of the weight average molecular weight to the number average molecular weight measured by GPC is 1.2 to 4.0, and the Mooney viscosity ML1 + 4 (100 ° C.) is 20 to 150. The total amount of hydrogenated rubber and all monomers is 1
The polymer was dissolved at a concentration of 2 to 50% by weight as a polymer under stirring and polymerized under stirring in the presence of a radical initiator to give an average particle size of 0.1
This is a method of producing ABS resin by forming rubbery particles of about 0.9 μm and performing bulk polymerization or bulk-suspension polymerization or solution polymerization.

Hereinafter, the present invention will be described in detail. The partially hydrogenated rubber used in the present invention is obtained by partially hydrogenating a known conjugated diene-based rubber, and is represented by using, for example, the following monomer units.

[0007]

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[0008]

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However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen, a mer group, or an ethyl group; R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are hydrogen;
It is any of a methyl group, an ethyl group, a methoxy group, an ethoxy group, a trialkylsilyl group and a trialkoxysiloxy. The molar ratios of the monomer units represented by the general formulas i) to v) are represented by A, B, C, D and E (mol%), respectively.
The hydrogenation rate of the conjugated diene unit (C + D) /
(A + B + C + D) is 5 to 85 mol%. 5 mol%
If it is less than 8, the ABS deterioration resistance of the obtained ABS resin is inferior, and 8
If it exceeds 5 mol%, the grafting property is reduced and the impact resistance is poor. The hydrogenation rate of the conjugated diene unit is preferably 9 to 60 mol%, more preferably 15 to 45 mol%.

The molar ratio E of the styrene monomer is 0 to 34 mol%, and the molar ratio of the conjugated diene monomer (A + B + C + D)
Is preferably 100 to 66 mol%. If the molar ratio of the styrene-based monomer is too large, the impact resistance of the obtained ABS-based resin decreases. E is more preferably 26 mol% or less. Among them, the molar ratio A of unsaturated 1,4 bonds is preferably A / (A + B + C + D) of 10% or more,
For the molar ratio B of unsaturated 1,2 bonds, B / (A + B +
C + D) is preferably 20% or less. When the molar ratio A of the unsaturated 1,4 bond is too small, the impact resistance of the ABS resin obtained is poor, and when the molar ratio B of the unsaturated 1,2 bond is too large, the heat resistance of the ABS resin obtained becomes poor. Inferior.

The monomer units i) to v) may be random, block, or tapered. However, it must be in a rubber state at room temperature, and preferably has a glass transition temperature of -50 to -110 ° C.
Further, the temperature is more preferably -70 to -110 ° C for the impact resistance of the obtained ABS resin. The 5% by weight styrene solution viscosity (SV) at 25 ° C. of the partially hydrogenated rubber used in the present invention needs to be 5 to 50 centipoise (cps). If it is less than 5 cps, the resulting ABS resin has poor impact resistance, and if it exceeds 50 cps, the gloss and rigidity are poor. 5cps especially when glossiness is important
It is preferably at least 20 cps and less than 20 cps, especially when the impact resistance is emphasized.

Further, in the rubber of the present invention, graft reactivity and heat stability are conflicting performances, and unsaturated 1,4
The bonding unit A (mol%) and the unsaturated 1,2 bonding unit B (mol%) are preferably in the range of 5 ≦ 0.1A + B ≦ 20. If it is smaller than this range, the heat resistance is good, but the grafting property is poor. If it is larger than this range, the grafting property is good, but the heat stability is poor, which is not preferable. More preferably, in the rubber having a low SV as in the present invention and the rubber having a small number of double bonds, a condition for causing an appropriate graft reaction is required, and the SV (cps), the unsaturated 5 ≦ 0.1A + B ≦ 20 and −0.25SV + 11.25 ≦ 0.1A + B ≦ −0.2 between 1,4 bond units A (mol%) and unsaturated 1,2 bond units B (mol%)
It is preferably within the range of 5 SV + 27.5. Outside of these ranges, moderate graft reactivity will not be obtained,
If the grafting reactivity is too low or too high, sufficient impact resistance cannot be obtained, and a balance with other properties such as glossiness cannot be obtained.

The molecular weight distribution of the partially hydrogenated rubber used in the present invention must be such that the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn measured by GPC is from 1.2 to 4.0. is there. A obtained when the molecular weight distribution is too large
The particle size distribution of the rubber particles of the BS-based resin is widened, giant particles are easily generated, the impact resistance is reduced, and the balance between glossiness and impact resistance is also reduced. If the molecular weight distribution is too small, it becomes difficult to process or obtain the polymer as a rubber, and even if obtained, the impact resistance is poor. The molecular weight distribution is preferably such that Mw / Mn is 1.5
３3.5. The molecular weight distribution is measured by a gel permeation chromatograph (GPC) according to a conventional method.

The molecular weight distribution of the partially hydrogenated rubber measured by GPC may be one peak, two peaks or more. The Mooney viscosity ML1 + 4 (100 ° C.) of the partially hydrogenated rubber used in the present invention needs to be 20 to 150. If the Mooney viscosity is out of this range, it is difficult to process or obtain a rubber, and even if it is obtained, it is not a moderately branched partially hydrogenated rubber used in the present invention. It is not possible to obtain an ABS resin excellent in balance among impact resistance, glossiness and rigidity, which is the object of the present invention. The Mooney viscosity is preferably 20-100, more preferably 25-50.
It is.

The partially hydrogenated rubber used in the present invention can be obtained by partially hydrogenating a conjugated diene rubber obtained by a known method. The conjugated diene rubber obtained by a known method generally includes all rubbers used for producing impact-resistant styrene resins. For example, polybutadiene (low cis polybutadiene and high cis polybutadiene), styrene-butadiene copolymer (random and block SBR), polyisoprene, butadiene-isoprene copolymer, butadiene-isoprene-styrene copolymer, natural rubber, and the like. Among them, butadiene-based polymer rubbers containing butadiene as a monomer component in an amount of 50% by weight or more, such as polybutadiene and styrene-butadiene copolymer, are preferred examples.

The conjugated diene rubber before hydrogenation for obtaining the partially hydrogenated rubber used in the present invention is preferably
Those having a branch or a homopolymer block of a styrene monomer are preferred. The method for synthesizing these conjugated diene rubbers may be a continuous polymerization method or a batch polymerization method. The partially hydrogenated rubber used in the present invention can be obtained by partially hydrogenating the above conjugated diene rubber. As the hydrogenation method, any conventionally known method may be used. L. Ra
mp, et al, J.M. Amer. Chem. Soc. ,
83, 4672 (1961). Hydrogenation using the described triisobutylborane catalyst, Hung Yu
Chen, J.M. Polym. Sci. Polym. Le
ter Ed. , 15, 271 (1977), or hydrogenation using an organocobalt-organoaluminum catalyst or an organic nickel-organoaluminum catalyst described in JP-B-42-8704. Pd, Rh described in JP-A-58-17103.
And the like, using a heterogeneous catalyst carrying a metal such as hydrogen.

A particularly preferred method of hydrogenation in the practice of the present invention is disclosed in Japanese Patent Application Laid-Open No. Sho 52-4 using a catalyst which can selectively hydrogenate a 1,2-vinyl bond prior to a 1,4-bond.
No. 1890, or use of a catalyst which can be hydrogenated under mild conditions of low temperature and low pressure.
No. 133203 and JP-A-60-220147.

The method of hydrogenation may be a continuous method or a batch method. The partially hydrogenated rubber used in the present invention may be used by blending a non-hydrogenated diene rubber with the rubber obtained by the above method. However, even in that case, the hydrogenation rate, solution viscosity, molecular weight distribution, Mooney viscosity, etc. of the whole rubber must be within the scope of the present invention.

According to the present invention, the partially hydrogenated rubber is dissolved in a concentration of 2 to 50% by weight based on the total amount of the partially hydrogenated rubber and all monomers as 100, and the polymerization is carried out under stirring in the presence of a radical initiator. When the amount of rubber used is less than this range, the impact resistance aimed at by the present invention cannot be obtained.On the other hand, when the amount is more than this range, the viscosity of the rubber solution becomes too high and the particle size is controlled. It will be difficult. Also, during the polymerization, a part of the monomer or a part of the polymer or a part of the mixture of the monomer and the polymer may be added, or the rubber may be added by adding a part of the polymer after the polymerization. It is also possible to dilute the components. In that case, the rubber component in the ABS resin finally obtained is 2
Preferably, it is about 40% by weight. If the content of the rubber component is too small, the impact resistance is poor, and if the content of the rubber component is too large, the tensile strength, rigidity, and gloss are poor. Rubber content is 5
-30% by weight is more preferred.

The aromatic vinyl monomer used in the present invention includes, in addition to styrene and vinylnaphthalene, side-chain alkyl-substituted styrene such as α-methylstyrene and α-ethylstyrene, vinyltoluene such as paramethylstyrene and vinylethylbenzene. Nucleus-substituted styrenes such as vinylxylene, ortho- or para-t-butylstyrene, halogenated styrenes such as monochlorostyrene, dichlorostyrene, tribromostyrene, tetrabromostyrene, para-hydroxystyrene, ortho-methoxystyrene, etc. Are used as an example and used as one kind or a mixture of two or more kinds. Of these, styrene, α
-Methylstyrene and paramethylstyrene are preferred.
Also, acrylonitrile as a vinyl cyanide monomer,
Methacrylonitrile, and derivatives thereof,
It is used as one kind or a mixture of two or more kinds.

The ratio of the aromatic vinyl monomer to the vinyl cyanide monomer used in the present invention is 50 to 90 parts by weight to 50 parts by weight.
It is preferably from 10 to 10 parts by weight, more preferably from 60 to 85 parts by weight to 40 to 15 parts by weight. In the present invention, it is also possible to use other copolymerizable monomers as a mixed monomer of an aromatic vinyl monomer and a vinyl cyanide monomer. In this case, as other monomers, acrylic acid, methacrylic acid and esters thereof such as methyl, ethyl, propyl, butyl, vinyl acetate, maleic anhydride, N-
Methylmaleimide, N-phenylmaleimide and the like are used, and the amount of the other copolymerizable monomer used is 0 to 30% by weight based on the entire monomer.

As the radical initiator used in the present invention, all known radical initiators conventionally used in the production of styrenic resins can be used, such as peroxyketals, dialkyl peroxides, diacyl peroxides, Examples thereof include peroxydicarbonates, peroxyesters, ketone peroxides, and hydroperoxides, and are used alone or in combination of two or more. Specifically, benzoyl peroxide, t-butylperoxy neodecanoate, 1,1-bis (t-
Butylperoxy) cyclohexane, 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, di-t
-Butyl peroxide and the like are preferably used.

The average particle size of the rubber particles in the present invention must be 0.1 to 0.9 μm. Outside of this range, if too small, the gloss is good but the impact resistance is poor. If too large, the rigidity and impact resistance are poor. More preferably, it is 0.2 to 0.7 μm. The method for controlling the average particle size of the rubber particles is easily obtained by using appropriate stirring conditions at the time of phase inversion when rubber particles are formed when the partially hydrogenated rubber having a specific structure used in the present invention is used. Particularly, the solution viscosity of the partially hydrogenated rubber, the graft ratio at the time of phase inversion, the viscosity of the resin phase forming the matrix, the number of rotations for stirring, and the like are important. Regarding the graft ratio at the time of phase inversion, in addition to the rubber structure, the type and amount of the radical initiator, the influence of the polymerization temperature, etc., the viscosity of the resin phase forming the matrix, the type and amount of the radical initiator, It is affected by the polymerization temperature and the type and amount of the chain transfer agent. Regarding the rotation speed of the stirring, the factor of the device is large, but it is controlled by increasing the stirring rotation speed to reduce the rubber particle diameter and decreasing the stirring rotation speed to increase the rubber particle diameter. You.

The average particle diameter of the rubbery particles was
Take an electron micrograph by ultra-thin section method of S-based resin,
The particle diameter of 200 to 500 rubbery particles in the photograph was measured and averaged. That is, average particle size =
ΣnD ⁴ / ΣnD ³ , where n is the number of rubber particles having a particle diameter D. As the bulk polymerization method in the present invention, the polymerization is continued after the rubber particles are formed, and finally a mixed monomer of an aromatic vinyl monomer and a vinyl cyanide monomer is obtained. Is to continue the polymerization operation until the desired reaction rate is reached. At that time, in the first half of the polymerization reaction, appropriate stirring for controlling the particle diameter of the rubbery particles described above is necessary, while in the second half of the polymerization reaction, the viscosity in the system is increased due to excessive viscosity. The agitation may destroy the produced rubbery particles and should be the minimum agitation required to remove the heat of the polymerization reaction.

In the bulk-suspension polymerization method of the present invention, the first half of the polymerization reaction in which rubbery particles are formed is carried out by bulk polymerization, and then the reaction mixture is mixed with a suspension stabilizer and / or a surfactant. It is dispersed under stirring in an aqueous medium, and the second half of the polymerization reaction is completed by suspension polymerization. Also, in bulk polymerization or bulk-suspension polymerization,
A method of lowering the viscosity of the polymerization system by adding a diluting solvent at the start of or during the polymerization, that is, solution polymerization is also possible. Examples of the diluting solvent include toluene, ethylbenzene, xylene and the like.

Further, preferably, after completion of the polymerization, in order to remove volatile components such as unreacted monomers and solvents and, if necessary, to promote crosslinking of the rubber portion, a known method such as heating After treatment by a method using a devolatilizing apparatus, a vent extruder or the like. In the method of the present invention, the ratio of the graft copolymer to the partially hydrogenated rubber at the time when the polymerization conversion of the mixed monomer of the aromatic vinyl monomer and the vinyl cyanide monomer is 30% is 20 to 60% by weight. It is preferable to control the grafting property so as to obtain, more preferably, 30 to 55% by weight. If the proportion of the graft copolymer is too small, it is difficult to control the particle diameter of the rubbery particles within the target, and even if the target particle diameter is obtained by controlling the rotation speed of the stirring, it is obtained. The ABS resin has poor impact resistance. On the other hand, if the proportion of the graft copolymer is too large, the rubbery particles become hard and the obtained ABS resin has poor impact resistance, and the flowability of the ABS resin is lowered, which is not preferable for processing.

In the method of the present invention, the gel content (content of the toluene-insoluble portion) of the ABS resin obtained is 5-7.
It is preferably in the range of 5% by weight, more preferably in the range of 10 to 50% by weight. If the gel content is too small, the impact resistance of the resin will be poor, and if it is too large, the flowability of the resin will be reduced, which is not preferable in processing. The swelling index (swelling index) of the gel in the ABS resin in toluene is preferably in the range of 7 to 15. If the swelling index is too small, the impact resistance is poor, and if it is too large, the impact resistance is reduced and the gloss is also deteriorated.

In the present invention, a known chain transfer agent is preferably used. Examples of the chain transfer agent include α-
Methylstyrene dimer, n-dodecyl mercaptan,
t-dodecyl mercaptan, 1-phenylbutene-2-
Mercaptans such as fluorene, dipentene, and chloroform; terpenes; and halogen compounds. Further, in the present invention, the molecular weight of the matrix resin portion of the obtained ABS resin is preferably 100,000 to 400,000 in terms of weight average molecular weight. Further, the amount of the styrene oligomer remaining in the resin is preferably 1% by weight or less, particularly preferably 0.5% by weight or less for applications requiring a high heat distortion temperature.

In the present invention, a necessary amount of a known stabilizer such as an antioxidant or an ultraviolet ray inhibitor is preferably added.
As the antioxidant, for example, octadecyl-3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,2 ′ -Methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), 2,4-
Bis [(octylthio) methyl] -o-cresol, triethylene glycol-bis [3- (3-t-butyl-
5-methyl-4-hydroxyphenyl) propionate], tris (dinonylphenyl) phosphite, dilaurylthiodipropionate, and the like, and the amount thereof is preferably 0.01 to 5 parts per 100 parts by weight of the resin. Parts by weight, more preferably 0.1 to 2 parts by weight.

As the ultraviolet stabilizer, for example, 2- (5
Triazoles such as -methyl-2-hydroxyphenyl) benzotriazole and 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, and bis (2,2,6,6-tetramethyl-4) -Piperidyl)
Hindered amines such as sebacate, and pt
-Butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone and the like. Particularly preferred are triazole-based and hindered amine-based single or combined systems. The amount of the ultraviolet stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, per 100 parts by weight of the resin.

Further, the ABS resin obtained in the present invention can be blended with a flame retardant and a flame retardant auxiliary as needed to give a flame retardant formulation. There are various types of flame retardants, but all known flame retardants are included, and halogen-based flame retardants, phosphorus-based flame retardants, and the like are effective. For example, decabromodiphenyl oxide, tetrabromobisphenol A, oligomers of tetrabromobisphenol A, tris- (2,3-dibromopropyl-1) isocyanurate, ammonium phosphate, red phosphorus, tricresyl phosphate and the like can be mentioned. . Examples of the flame retardant aid include antimony trioxide, antimony pentoxide, sodium antimonate, antimony trichloride, antimony pentachloride, zinc borate, barium metaborate, and zirconium oxide. The flame retardant is preferably 5 to 100 parts by weight of the resin.
40 parts by weight, and the flame retardant aid is preferably resin 100
It is used in an amount of 2 to 20 parts by weight per part by weight.

Further, if necessary, various additives usually used, for example, an internal lubricant such as polydimethylsiloxane and liquid paraffin, a lubricant, a releasing agent, an antistatic agent, a coloring agent, various fillers and the like are compounded. It is possible to Various other resins can be added to the ABS resin obtained in the present invention. Other resins include GP-polystyrene, high impact polystyrene, AS resin, and other ABS
Resin, AES resin, styrene-methacrylate resin,
MBS resin, styrene-maleic anhydride copolymer resin,
Styrene-butadiene block copolymer resin, methacrylic resin, polyphenylene ether resin, polycarbonate resin, nylon resin, polyester resin such as PBT, polyvinyl chloride resin and the like are used. By adding these resins, heat resistance, rigidity, impact resistance and the like are imparted, and the resin is blended according to its use.

The ABS resin obtained in the present invention is molded and used by a conventionally known method and used. Its applications are electrical appliances, OA equipment cabinets, housings, etc.
There are a wide variety of interior and exterior parts for automobiles, parts for homes and furniture, and many others.

[0034]

EXAMPLES Some examples will be shown below to show specific embodiments of the present invention, which are intended to more specifically explain the gist of the present invention and are not intended to limit the present invention. is not.

[0035]

Example 1 A polymerization vessel having an inner volume of 10 liters and equipped with a stirring blade and a jacket was charged from the bottom with a concentration of 15% by weight of 1,3.
N-butadiene in n-hexane was fed continuously at a rate of 300 ml / min, simultaneously with 0,18 parts by weight of n-butyllithium and also with 0.13 parts by weight of tetramethylethylenediamine per 100 parts by weight of monomer.
The polymerization was carried out by mixing and stirring at a rotation speed of 150 rpm and a polymerization temperature of 90 ° C., and the overflowing living polymer solution was introduced into a Noritake static mixer (18 elements). In front of the static mixer, 0, 9 equivalents of silicon tetrachloride n relative to the feed lithium
A coupling reaction was carried out by adding a hexane solution, and further introduced into a hydrogenation reactor having an internal volume of 4 liters. A hydrogenation catalyst was added in front of the hydrogenation reactor, and partial hydrogenation was continuously performed under high-speed stirring by controlling the hydrogen feed amount at a hydrogenation temperature of 100 ° C. so as to obtain a predetermined hydrogenation rate. As a hydrogenation catalyst, an equimolar amount of n was added to a di-p-tolylbis (1-cyclopentadienyl) titanium / cyclohexane solution.
Butyllithium was added and mixed at 20 ° C., and after 3 minutes, an equimolar amount of methanol was added, and 30 ppm of titanium per polymer was added. Water and a stabilizer were added to the polymer solution discharged from the hydrogenation reactor, and the mixture was introduced into hot water under high-speed stirring to distill off the solvent, followed by heating and drying to obtain a partially hydrogenated rubber.

The analytical values of the obtained rubber are shown in Table 1. Analysis of the microstructure is by NMR. Next, an ABS resin using a partially hydrogenated rubber is produced. Using a polymerization tank having an internal volume of 10 liters equipped with a stirring blade and a jacket, 16 parts by weight of the rubber, 63 parts by weight of styrene, 21 parts by weight of acrylonitrile, 20 parts by weight of toluene, and triethylene glycol-bis [3- (3- t-butyl-5-methyl-4-
[Hydroxyphenyl) propionate] 0.05 parts by weight, 0.05 parts by weight of benzoyl peroxide, and 0.10 parts by weight of α-methylstyrene dimer were initiated at 90 ° C. while stirring at 50 rpm in a nitrogen atmosphere.
After 4 hours, 2 hours at 110 ° C, 2 hours at 135 ° C, 1 hour
The polymerization was continued by sequentially raising the temperature to 50 ° C. × 2 hours and 170 ° C. × 2 hours, and finally devolatilized by heating at 250 ° C. for 45 minutes to obtain ABS resin pellets through an extruder. 30% conversion of styrene copolymer by sampling on the way
The ratio of the graft copolymer to the rubber was determined. The measurement of the ratio of graft copolymer to rubber is
The sampled polymer solution was vacuum-dried, and the solid content was measured. The polymer solution was dissolved in a mixed solvent of MEK / methanol 90/10 and centrifuged to obtain an insoluble solid (rubber + graft polymer). It was calculated by determining the polystyrene content by UV. Further, a test piece was prepared by injection molding using the obtained ABS resin, and the physical properties were evaluated.

Table 2 shows the analytical values and physical property evaluation results of the ABS resin obtained. The gloss was evaluated for gloss at an angle of 20 °, the impact resistance was the Izod impact value at room temperature, the heat resistance was the retention rate of the Izod impact value after heat deterioration at 310 ° C. for 10 minutes using a heating press, and the discoloration resistance was Sunshine wafer. Discoloration after 63 hours at 63 ° C. of the zeometer was expressed as 優, 良, and 劣.

[0038]

Example 2 Using a polymerization tank having an inner volume of 30 liters and equipped with a stirring blade and a jacket, 0, 100 parts by weight of monomer
13 parts by weight of nbutyl lithium and 250 p per monomer
pm of 1,2-butadiene at a concentration of 15% by weight of 1,
An n-hexane solution of 3-butadiene was charged, and batch polymerization was performed at a peaking temperature of 90 ° C under stirring to obtain a living polymer solution. Further, 0 to 6 equivalents of silicon tetrachloride n-hexane solution was added to the feed lithium to carry out a coupling reaction. Then, the same hydrogenation catalyst as in Example 1 was added at 75 ° C., and hydrogen was blown from the bottom to give a predetermined amount. Partially hydrogenated to a degree of hydrogenation, and then added water and a stabilizer to the polymer solution, introduced into hot water under high-speed stirring to distill off the solvent, and dried by heating to obtain a partially hydrogenated rubber. .

Table 1 shows the analysis values of the obtained rubber. AB was prepared in the same manner as in Example 1 except that 12 parts by weight of the rubber, 66 parts by weight of styrene, and 22 parts by weight of acrylonitrile were used.
An S-based resin was obtained. Further, a test piece was prepared by injection molding using the obtained ABS resin, and the physical properties were evaluated. Table 2 shows the analysis values and the physical property evaluation results of the obtained ABS resin.

[0040]

Example 3 Two polymerization tanks each having a 10-liter internal volume and equipped with a stirring blade and a jacket were connected to each other, and a concentration of 1 containing 2800 ppm of tetrahydrofuran was measured from the bottom of the first one.
A 5% by weight solution of 1,3-butadiene in n-hexane was continuously fed at a rate of 200 ml / min, simultaneously with 0,15 parts by weight of n-butyllithium per 100 parts by weight of 1,3-butadiene. Polymerization was carried out by mixing and stirring at a rotation speed of 150 rpm and a polymerization temperature of 90 ° C., and the overflowed living polymer solution was introduced into the second bottom. From the bottom of the second unit, 48 parts by weight of styrene was added in an amount of 20% by weight based on 100 parts by weight of the first unit of butadiene.
Was added as a n-hexane solution, and the mixture was stirred at a polymerization temperature of 90 ° C. to carry out polymerization to obtain a living block polymer solution. Further, the mixture was deactivated by mixing with an equivalent amount of methanol using a static mixer, and then partially hydrogenated in the same manner as in Example 1 to obtain a partially hydrogenated rubber.

Table 1 shows the analytical values of the obtained rubber. Using the above rubber, an ABS resin was obtained in the same manner as in Example 2. Further, a test piece was prepared by injection molding using the obtained ABS resin, and the physical properties were evaluated. Table 2 shows the analysis values and the physical property evaluation results of the obtained ABS resin.

[0042]

Example 4 A partially hydrogenated rubber block was obtained in the same manner as in Example 3 except that the amount of tetrahydrofuran, the amount of n-butyllithium and the amount of styrene for the second group were changed. Table 1 shows the analysis values of the obtained rubber. 20 parts by weight of the above rubber, styrene 6
0 parts by weight, 20 parts by weight of acrylonitrile, 30 parts of toluene
An ABS resin was obtained in the same manner as in Example 1 except that parts by weight were used. Further, a test piece was prepared by injection molding using the obtained ABS resin, and the physical properties were evaluated.

Table 2 shows the analytical values and the results of evaluation of physical properties of the obtained ABS resin.

[0044]

Example 5 A living block polymer solution was obtained in the same manner as in Example 3 except that the amount of tetrahydrofuran, the amount of n-butyllithium, and the amount of styrene for the second group were changed. Further, a coupling reaction was carried out in a static mixer using silicon tetrachloride in the same manner as in Example 1, and then continuous partial hydrogenation was performed to obtain a partially hydrogenated rubber.

Table 1 shows the analytical values of the obtained rubber. An ABS resin was obtained in the same manner as in Example 1 using the above rubber. Further, a test piece was prepared by injection molding using the obtained ABS resin, and the physical properties were evaluated. Table 2 shows the analysis values and the physical property evaluation results of the obtained ABS resin.

[0046]

Comparative Example 1 The same operation as in Example 1 was carried out except that the hydrogenation reaction of the polybutadiene rubber was not carried out. Table 1 shows the analysis values of the obtained rubber, and Table 2 shows the analysis values and physical property evaluation results of the obtained ABS resin.

[0047]

Comparative Example 2 The same operation as in Example 1 was carried out except that the degree of hydrogenation of the polybutadiene rubber was 95%. Table 1 shows the analysis values of the obtained rubber, and Table 2 shows the analysis values and physical property evaluation results of the obtained ABS resin.

[0048]

Comparative Example 3 An experiment was carried out in the same manner as in Example 1 except that the amount of n-butyllithium, the amount of tetramethylethylenediamine, and the degree of hydrogenation were changed. Table 1 shows the analysis values of the obtained rubber.
Table 2 shows the analysis values and physical property evaluation results of the obtained ABS resin.
Shown in

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

As described above, according to the present invention, the heat resistance stability, which is a drawback of the conventional ABS resin, is extremely excellent, and the shock resistance,
Excellent A that solves balance of glossiness and rigidity at once
It provides a method for producing a BS resin, and is a method that can be easily implemented at low cost without greatly changing the conventional production process for an ABS resin.
Very useful.

Claims (1)

(57) [Claims] 1. A mixture of an aromatic vinyl monomer and a vinyl cyanide monomer is hydrogenated with 5 to 85 mol% of conjugated diene units of a conjugated diene rubber, and 5% by weight of styrene at 25 ° C. Solution viscosity (SV) is 5 to 50 centipoise (cps), ratio of weight average molecular weight to number average molecular weight measured by GPC is 1.2 to 4.0, Mooney viscosity ML1
+4 (100 ° C.) is 20 to 150, and the total amount of the partially hydrogenated rubber and all monomers is 100.
Dissolved at a concentration of about 50% by weight, and polymerized under stirring in the presence of a radical initiator to give an average particle diameter of 0.1 to 0.9 μm.
A method for producing an ABS resin, comprising forming rubbery particles of the above and subjecting the resultant to bulk polymerization or bulk-suspension polymerization or solution polymerization to produce an ABS resin.