JPH10226741A - High-rubber-content mabs resin composition and rubber-modified thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. excellent not only in impact strength and surface properties but also in stiffness, heat resistance, flowability, and heat stability by mixing a graft copolymer obtd. from a diene rubber and/or an acrylic rubber having a specified particle size and an alkyl methacrylate, etc., with a copolymer obtd. from a vinyl cyanide compd. and an arom. vinyl compd., etc. SOLUTION: 60-95 pts.wt. graft copolymer (A) comprising 90-50wt.% diene rubber and/or acrylic rubber having a vol. average particle size of 30-1,000nm and 10-50wt.% graft part comprising 30-98mol% alkyl methacrylate and 70-0mol% arom. vinyl compd. is mixed with 40-5 pts.wt. copolymer (B) comprising 25-60mol% vinyl cyande compd. and 75-40mol% arom. vinyl compd. Ingredient A has a graft ratio of 10-80wt.%. Ingredient B has an Mw of 5,000-90,000 and a ratio of Mw/Mn of 1.5-4.5. Both ingredients A and B are ones obtd. by emulsion polymn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a rubber-rich MAB.
More specifically, the present invention relates to an S resin composition and a rubber-modified thermoplastic resin composition containing the same. The present invention relates to a rubber-rich MABS resin composition capable of providing a rubber-modified thermoplastic resin composition having excellent heat resistance, rigidity, and processability, and a rubber-modified thermoplastic resin composition containing the same. Rubber-modified thermoplastic resin consisting of graft copolymer, styrene resin and vinyl chloride resin has heat resistance, impact resistance, rigidity,
Due to its excellent surface properties, it has recently been widely used for housings of OA equipment such as computer displays and facsimile machines.

[0002]

2. Description of the Related Art The housings of these OA equipments are formed by an injection molding method and tend to be thinner year by year. Therefore, materials excellent in impact resistance, surface properties and fluidity are required. I have. The above-mentioned materials are economical and diversified in grades, and in recent years, have been prepared by blending a vinyl chloride resin, a styrene resin powder, beads, pellets, etc. with a graft copolymer powder as a matrix. . The rubber-modified thermoplastic resin requires that the graft copolymer (copolymer obtained by grafting a monomer to the rubber polymer) be uniformly dispersed in the matrix in order to develop various physical properties such as mechanical properties and surface properties of the molded product. is there. In particular, the impact resistance and surface appearance are greatly affected by the graft copolymer.

[0003] In these materials, the molecular weight of a vinyl chloride resin or a styrene resin is set to be low in order to ensure fluidity during molding. Therefore, the rubber content of the graft copolymer is 40 to 80. %, The viscosity difference between the graft copolymer and the matrix is large, and the graft copolymer is difficult to disperse in the matrix. When a low-viscosity styrene resin is used in combination, the graft copolymer is more difficult to disperse. As described above, the graft copolymer having poor dispersion lowers the impact resistance of the material and lowers the surface properties of the molded article such as gloss. Further, in order to melt and mix and disperse, high temperature and high kneading are required, and properties such as impact resistance, surface properties, and thermal stability are reduced.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and in particular, has a rubber-modified thermoplastic resin composition having excellent impact resistance and surface properties, and also having excellent rigidity, heat resistance, fluidity and thermal stability. It provides things.

[0005]

The graft copolymer is a polymer obtained by grafting a monomer such as methyl methacrylate, styrene or acrylonitrile to a rubber polymer in order to impart compatibility with a vinyl chloride resin or a styrene resin. It is. The present inventors have conducted intensive studies on the graft copolymer and found that the properties of the rubber-modified thermoplastic resin composition formed by mixing the graft copolymer with a vinyl chloride-based resin and a styrene-based resin have been improved in the graft copolymer. The present inventors have found that the composition is significantly affected by the composition of a small amount of the co-present copolymer, and have reached the present invention.

That is, a first aspect of the present invention is that (A) 90 to 50 parts by weight of a diene rubber polymer and / or an acrylic rubber polymer (Ad) having a volume average particle diameter of 30 to 1000 nm and an alkyl methacrylate unit Graft copolymer consisting of 30 to 98 mol%, 70 to 0 mol% of an aromatic vinyl compound unit and 0 to 30 mol% of a monomer unit copolymerizable therewith, 10 to 50 parts by weight of a graft portion (Ag) 6
0 to 95 parts by weight, (B) 25 to 60 mol% of a vinyl cyanide compound unit, and 75 to 40 of an aromatic vinyl compound unit
Mol%, and 0 to 30 monomer units copolymerizable therewith.
(A) the graft ratio of the graft copolymer is 10 to 80% by weight, and the weight average molecular weight Mw of the copolymer (B) is 5,000 to 5,000. 90000 and ratio M with number average molecular weight Mn
A rubber characterized in that w / Mn is from 1.5 to 4.5, and wherein the (A) graft copolymer and (B) copolymer are obtained by polymerization by an emulsion polymerization method. High content M
The content is an ABS resin composition.

[0007] The second aspect of the present invention is the above-mentioned rubber-rich MABS.
Resin composition (I) 5 to 60 parts by weight, vinyl chloride resin (II) 20 to 80 parts by weight, and styrene resin (III) 20
A rubber-modified thermoplastic resin composition comprising up to 75 parts by weight (total 100 parts by weight of (I), (II) and (III)) is included.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Graft copolymer (A) of the present invention
Specific examples of the diene rubber polymer and the acrylic rubber polymer (Ad) include butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butadiene-butyl acrylate rubber, butyl acrylate rubber, butyl acrylate-styrene rubber, Examples thereof include butyl acrylate-2-ethylhexyl (meth) acrylate rubber, butyl acrylate-acrylonitrile rubber, and the like, and these may be used alone or in combination of two or more. The volume average particle diameter of the diene rubber polymer and the acrylic rubber polymer (Ad) is 30 to 1000 nm, preferably 40 to 900 nm, more preferably 50 to 800 nm from the viewpoint of impact resistance. If the particle size exceeds 1000 nm, the gloss is reduced and the impact resistance is not sufficiently exhibited. If it is less than 30 nm, the impact resistance is significantly reduced. The graft ratio (% by weight) of the graft copolymer (A) of the present invention is calculated by the following formula: graft part (Ag) / rubber polymer (Ad)) × 100, and is 10 to 80% by weight, preferably 15 to 80% by weight. 75
%, More preferably 20 to 60% by weight. If the graft ratio is less than 10% by weight, the impact resistance decreases, and if it exceeds 80% by weight, the processability decreases.

The graft portion (Ag) in the graft copolymer (A) has an alkyl methacrylate unit of 30 to 98.
Mol%, preferably 40 to 95 mol%, more preferably 50 to 90 mol%, 70 to 0 mol%, preferably 60 to 5 mol%, more preferably 50 to 50 mol% of the aromatic vinyl compound unit.
-10 mol% and a monomer unit copolymerizable therewith 0
It is a polymer having a composition of from 30 to 30 mol%, preferably from 0 to 20 mol%, more preferably from 0 to 10 mol%. These are 100 mol% in total. When the amount of the alkyl methacrylate unit is less than 30 mol%, the impact resistance decreases, and when the amount exceeds 98 mol%, the processability decreases. If the amount of the aromatic vinyl compound unit exceeds 70 mol%, the impact resistance will be reduced. On the other hand, when the amount of the copolymerizable monomer unit exceeds 30 mol%, the impact resistance is reduced.

The alkyl methacrylate unit in the graft portion (Ag) is a residue such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, glycidyl methacrylate, etc. From the viewpoint of properties, the alkyl methacrylate preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms in the alcohol residue portion. As the aromatic vinyl compound unit, styrene, α-
It is a residue of methylstyrene, p-methylstyrene, chlorostyrene, bromostyrene, vinylnaphthalene and the like, and styrene is particularly preferred from the viewpoint of polymerizability and economy.
As the copolymerizable monomer unit, acrylonitrile,
Vinyl cyanide residue such as methacrylonitrile, alkyl acrylate compound residue such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, glycidyl acrylate, maleimide, phenylmaleimide, etc. Maleimide compound residue, acrylic acid, methacrylic acid residue, diallyl phthalate, triallyl cyanurate, and the residue of a bifunctional monomer such as allyl methacrylate, etc., from the viewpoint of polymerizability, economical efficiency, butyl Acrylate and acrylonitrile residues are preferred. The alkyl methacrylate unit, aromatic vinyl unit and copolymerizable monomer unit may be used alone or in combination of two or more. The ratio between the rubber polymer (Ad) and the graft portion (Ag) in the graft copolymer (A) of the present invention is 90 to 50 parts by weight for the former and 10 to 50 parts by weight for the latter.
Parts by weight. If the amount of the rubber polymer (Ad) is less than 50 parts by weight, the impact resistance and the fluidity are reduced, while if it exceeds 90 parts by weight, the heat resistance is reduced.

The copolymer (B) of the present invention comprises 25 to 60 mol% of a vinyl cyanide unit and 75 to 40 of an aromatic vinyl unit.
Mol%, and 0 to 30 monomer units copolymerizable therewith.
Consists of mole%. From the viewpoints of impact resistance and surface properties, the content is preferably 30 to 55 mol% of a vinyl cyanide unit, 70 to 45 mol% of an aromatic vinyl unit, and 0 to 20 mol% of a monomer unit copolymerizable therewith. . More preferably, 33 to 52 mol% of a vinyl cyanide unit and 67 of an aromatic vinyl unit are used.
~ 48 mol% and monomer units copolymerizable therewith
10 mol%. If the amount of the vinyl cyanide unit is less than 25 mol%, the impact resistance is reduced, and if it exceeds 60 mol%, the processability is reduced. If the amount of the aromatic vinyl unit is less than 40 mol%, the processability is reduced, and if it exceeds 75 mol%, the impact resistance is reduced. When the amount of the copolymerizable monomer unit exceeds 30 mol%, the impact resistance decreases.

The molecular weight of the copolymer (B) is important in terms of impact resistance and surface appearance. The molecular weight of the copolymer (B) is 500 in terms of weight average molecular weight Mw (in terms of polystyrene).
0 to 90000, from the viewpoint of impact resistance and surface appearance, preferably 10,000 to 80000, more preferably 150
00 to 70000. Weight average molecular weight Mw of 500
If it is less than 0, the impact resistance decreases, and if it exceeds 90000, the impact resistance and the surface appearance deteriorate. That is, conventionally, AB
The molecular weight of the acrylonitrile-styrene copolymer generally used as the S resin and the AS resin is 100,000 to 400,000 in terms of the weight average molecular weight Mw. The copolymer (B) having this molecular weight has impact resistance and surface appearance. Is significantly reduced.

The ratio Mw / Mn of the number average molecular weight Mn to the weight average molecular weight Mw of the copolymer (B) is 1.5 to 4.5, preferably 1.8 to 4.2, and more preferably 2. 0
４4.0. If Mw / Mn is less than 1.5, the workability is reduced, and if it exceeds 4.5, the impact resistance is reduced.

Examples of the vinyl cyanide compound of the copolymer (B) include acrylonitrile and methacrylonitrile.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, p-isopropylstyrene, chlorostyrene, bromostyrene, and vinylnaphthalene. These may be used alone or in combination of two or more. From an industrial viewpoint, acrylonitrile is particularly preferred as the vinyl cyanide compound, and styrene is particularly preferred as the aromatic vinyl compound. Examples of the copolymerizable monomer include (meth) acrylic acid and its (meth) acrylate-based monomers such as methyl, ethyl, propyl, butyl, 2-hydroxyethyl, 2-ethylhexyl, and glycidyl, maleimide, Maleimide monomers such as N-methylmaleimide N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (p-methylphenyl) maleimide and the like, and these may be used alone or Used in combination of more than one species.

The rubber-rich MABS resin composition of the present invention comprises 60 to 95 parts by weight of the graft copolymer (A) and 40 to 5 parts by weight of the copolymer (B). From the viewpoint of impact resistance and surface appearance, preferably, the graft copolymer (A)
65 to 90 parts by weight, 35 to 10 parts by weight of copolymer (B),
More preferably, the amount is 68 to 88 parts by weight of the graft copolymer (A) and 32 to 12 parts by weight of the copolymer (B). (A),
(B) The total amount is 100 parts by weight. Copolymer (B)
However, if it is less than 5 parts by weight, the surface appearance deteriorates, and if it exceeds 40 parts by weight, the impact resistance decreases.

In order to obtain the rubber-rich MABS resin composition of the present invention, the graft copolymer (A) and copolymer (B) must be produced by an emulsion polymerization method. In the bulk polymerization method, the suspension polymerization method, the solution polymerization method, and the like, particularly in the case of a rubber-rich resin, the graft ratio of the graft copolymer (A) and the control of the molecular weight of the copolymer (B) are within the scope of the present invention. Is difficult to obtain.

Graft copolymer (A), copolymer (B)
Known initiators such as a thermal decomposition initiator such as potassium persulfate and a redox initiator such as an Fe-reducing agent-organic peroxide can be used as an initiator for polymerizing the compound. As the chain transfer agent, known chain transfer agents such as t-dodecyl mercaptan, n-dodecyl mercaptan, α-methylstyrene dimer, terpinolene and the like can be used as long as the graft ratio of the present invention can be controlled. Examples of emulsifiers include potassium rosinate, metal rosinate such as sodium rosinate, higher fatty acid metal salts such as sodium palmitate and sodium oleate, sodium dodecylbenzenesulfonate, sodium palmitylsulfonate, sodium dioctyl sulfosuccinate, and the like. Known emulsifiers such as sodium sulfonate can be used. The polymerization may be carried out by adding a monomer mixture to be graft-polymerized or copolymerized at once or continuously and polymerizing under radical generation.

In order to accurately control the graft ratio of the graft polymer (A) and the molecular weight of the copolymer (B) within the scope of the present invention, the graft polymer (A) and the copolymer (B) must be used. After individual polymerization, a method of latex blending is preferred. By controlling polymerization conditions such as an initiator, a chain transfer agent, an emulsifier, a polymerization temperature, a water amount, and a monomer addition method, the graft polymer (A) and the copolymer (B) can be formed at once during the graft polymerization.

The method for recovering the polymer powder of the rubber-rich ABS resin composition of the present invention from the latex composed of the graft polymer (A) and the copolymer (B) includes a general method,
For example, calcium chloride, magnesium chloride, alkaline earth metal salts such as magnesium sulfate, sodium chloride, alkali metal salts such as sodium sulfate, hydrochloric acid,
After adding an inorganic acid such as sulfuric acid, phosphoric acid, and acetic acid and an organic acid to coagulate the latex, heat treatment and dehydration drying can be performed. Also, a spray drying method can be used. As a method of recovering the polymer powder, a method of adding an inorganic acid or an organic acid to coagulate the latex, followed by heat treatment and dehydration drying is particularly preferable in terms of impact resistance and surface properties.

When coagulating, heat-treating and dehydrating and drying the latex, control of deterioration, flowability, storage stability, etc. of the polymer powder,
In order to exhibit the properties of the rubber-modified thermoplastic resin composition, desired stabilizers, lubricants and the like can be added.
As the stabilizer, a rubber-modified vinyl chloride-based resin, a known tin-based stabilizer usually used for rubber-modified styrene-based resin,
Inorganic stabilizers, epoxy stabilizers, hindered phenol stabilizers, sulfur stabilizers, phosphorus stabilizers and the like.
Examples of the lubricant include higher fatty acid bisamides, higher fatty acid amides, esters of higher fatty acids and higher alcohols, esters of higher fatty acids and polyhydric alcohols, metal salts of higher fatty acids, higher fatty acids, higher alcohols, and olefin waxes. These may be used alone or in combination of two or more. These stabilizers and lubricants may be added as they are. Hindered phenol-based stabilizers, sulfur-based stabilizers, phosphorus-based stabilizers, and the like, preferably, the stabilizer is used in a finely dispersed form, for example, an emulsified or slurry state ABS-rich ABS resin in order to exhibit its effect more. It is preferred to mix it with a latex or slurry of the composition.

The vinyl chloride resin (II) of the present invention includes a vinyl chloride homopolymer, a copolymer of vinyl chloride and a monoolefin monomer such as ethylene, vinyl acetate, methyl methacrylate and butyl acrylate of not more than 20% by weight. Polymers, and post-chlorinated vinyl chloride. These can be used alone or in combination of two or more, and those having different degrees of polymerization can be used in combination of two or more. MABS Resin Composition High in Rubber of the Present Invention (I)
As the vinyl chloride resin (II) which particularly exhibits an effect, the viscosity average degree of polymerization is preferably from 300 to 800, more preferably from 350 to 750, still more preferably from 400 to 7
00.

The styrenic resin (III) of the present invention includes:
Acrylonitrile-styrene copolymer, acrylonitrile-styrene-α-methylstyrene copolymer, acrylonitrile-α-methylstyrene copolymer, acrylonitrile-styrene-phenylmaleimide copolymer, acrylonitrile-styrene-α-methylstyrene-phenylmaleimide Copolymer, styrene-phenylmaleimide copolymer, polystyrene, styrene-phenylmaleimide copolymer, styrene-maleic anhydride copolymer, styrene-methyl methacrylate copolymer, styrene-phenylmaleimide-methyl methacrylate copolymer, Known styrene copolymers such as a styrene-phenylmaleimide-α-methylstyrene-methyl methacrylate copolymer are exemplified. These may be used alone or in combination of two or more. As the styrene-based resin (II) in which the rubber-rich MABS resin composition (I) of the present invention particularly exhibits an effect, the reduced viscosity is preferably 0.15 to 0.45 dl /.
g, more preferably 0.20 to 0.42 dl / g, and still more preferably 0.25 to 0.40 dl / g.

The rubber-modified thermoplastic resin of the present invention contains 5 to 60 parts by weight, preferably 7 to 50 parts by weight, more preferably 8 to 40 parts by weight of the rubber-rich MABS resin composition (I).
20 to 80 parts by weight, preferably 25 to 75 parts by weight, more preferably 30 to 70 parts by weight of the vinyl chloride resin (II),
Styrene resin (III) 20 to 75 parts by weight, preferably 25
To 68 parts by weight, more preferably 30 to 62 parts by weight [total 100 parts by weight of (I) + (II) + (III)]. Outside the above range, the balance of surface properties, impact resistance, workability, and the like is reduced.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but these are merely examples, and the present invention is not limited thereto. Unless otherwise specified, "parts" indicates parts by weight and "%" indicates% by weight. Also,
In the following description, abbreviations represent the following substances, respectively. BA: butyl acrylate BMA: butyl methacrylate St: styrene MAA: methacrylic acid tDM: t-dodecyl mercaptan CHP: cumene hydroperoxide DAP: diallyl phthalate MMA: methyl methacrylate AN: acrylonitrile PMI: N-phenylmaleimide VC: vinyl chloride αMSt: α-methylstyrene

Examples 1 to 5 and Comparative Examples 1 to 5 Production of rubber polymer (Ad) (1) Production of rubber polymer part (Ad-1), (Ad-2) As the first step, the rubber polymer (Ad-1), (Ad-
An unexpanded rubber polymer required for enlarging in 2) was produced. The following substances were charged into a 100 L polymerization machine. Pure water 230 parts Potassium persulfate 0.2 parts tDM 0.2 parts After the air in the polymerization machine was removed by a vacuum pump, the following substances were charged. Sodium oleate 0.5 part Sodium rosinate 2 parts Butadiene 100 parts The temperature of the system was raised to 60 ° C to initiate polymerization. The polymerization was completed in 25 hours, and the conversion was 96%. The volume average particle size of the unexpanded rubber polymer was 85 nm.

As a second step, an acid group-containing latex (C) necessary for enlarging the unexpanded rubber polymer into the rubber polymers (Ad-1) and (Ad-2) was produced as follows. . The following substances were charged into a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet, and a thermometer. Pure water 200 parts Dioctyl sodium sulfosuccinate 0.7 parts Sodium formaldehyde sulfoxylate 0.5 parts While stirring the reactor, the temperature was raised to 70 ° C. under a nitrogen stream. After reaching 70 ° C., 25 parts of BMA, 5 parts of BA, tDM
After a monomer mixture of 0.1 part and 0.15 part of CHP was added dropwise over 2 hours, 50 parts of BMA, 4 parts of BA, and 16 parts of MAA were added.
, 0.5 parts of tDM and 0.15 parts of CHP were added dropwise over 4 hours. After completion of the addition, stirring was continued at 70 ° C for 1 hour to terminate the polymerization, thereby obtaining an acid group-containing latex (C). The polymerization conversion was 99%.

In the third step, rubber polymers (Ad-1) and (Ad-2) were produced by using the previously produced unexpanded rubber polymer and the acid group-containing latex (C). After adding 3 parts (solid content) of the acid group-containing latex (C) prepared above at 60 ° C. to 100 parts (solid content) of the unexpanded rubber polymer latex, stirring was continued for 1 hour to enlarge the rubber. Production of the coalescence (Ad-1) was performed. Rubber polymer (Ad-1)
Had a particle size of 320 nm. Further, 2.3 parts (solid content) of the acid group-containing latex (C) prepared above was added to 100 parts (solid content) of the unexpanded rubber polymer latex at 60 ° C., and stirring was continued for 1 hour to enlarge. And a rubber polymer (Ad
-2) was performed. The particle size of the rubber polymer (Ad-2) was 480 nm.

(2) Production of rubber polymer (Ad-3) In the same manner as in the above-mentioned unexpanded rubber polymer, a monomer was polymerized as 70 parts of butadiene and 30 parts of styrene. The polymerization was completed in 20 hours and the conversion was 97%. The particle size of the rubber polymer (Ad-3) was 90 nm.

(3) Production of rubber polymer (Ad-4) A monomer was polymerized in the same manner as in the above-mentioned unexpanded rubber polymer into 70 parts of butadiene and 30 parts of butyl acrylate. The polymerization was completed in 22 hours and the conversion was 96%. The particle size of the rubber polymer was 80 nm. Acid group-containing latex (C) 3.5 prepared from the obtained rubber polymer.
And then enlarged by the same method as that for the rubber polymer (Ad-1). The particle size of the obtained rubber polymer (Ad-4) is 28.
It was 0 nm.

(4) Production of Rubber Polymer (Ad-5) The following substances were charged into a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet, and a thermometer. Pure water 280 parts Sodium palmitate 0.05 part Sodium formaldehyde sulfoxylate 0.3 part EDTA 0.01 part Ferrous sulfate 0.0025 part The temperature was raised to 60 ° C under a nitrogen stream while stirring the reactor. . After reaching 60 ° C., 7 parts of BA, 0.05 parts of DAP, CH
After charging 0.04 parts of P at a time and polymerizing for 1 hour,
A mixture of 93 parts of BA, 2.3 parts of DAP and 0.2 parts of CHP was continuously dropped over 5 hours. At 1 hour and 3 hours after dropping, 0.5 parts and 1.2 parts of sodium palmitate were added. After completion of the dropping, stirring was continued at 60 ° C. for 1 hour to obtain a rubber polymer (Ad-5). The polymerization conversion was 98%, and the particle size of the rubber polymer (Ad-5) was 210 nm.

2. Production of graft copolymer (A) (1) Production of graft copolymer (A-1) The following substances were placed in a reactor equipped with a stirrer, reflux condenser, nitrogen inlet, monomer inlet, and thermometer. Was charged. Pure water 280 parts Rubber polymer (Ad-1) (solid content) 65 parts Sodium formaldehyde sulfoxylate 0.3 parts EDTA 0.01 parts Ferrous sulfate 0.0025 parts Under a nitrogen stream while stirring the reactor. The temperature was raised to 60 ° C. After reaching 60 ° C., 25 parts of MMA, 10 parts of St, CHP
0.4 part of the mixture was added dropwise continuously over 5 hours. After completion of the dropwise addition, stirring was continued at 60 ° C. for 2 hours to terminate the polymerization, thereby obtaining a graft polymer (A-1). As shown in Table 1, the polymerization conversion was 98% and the graft ratio was 48%.

(2) Preparation of Graft Copolymer (A-2) In the same manner as for the graft copolymer (A-1), 70 parts of the rubber polymer (Ad-2) was added to 25 parts of MMA, 15 parts of St,
A5 parts and CHP0.3 parts were polymerized to obtain a graft copolymer (A-2). As shown in Table 1, the polymerization conversion was 9
At 9%, the graft ratio was 35%.

(3) Production of Graft Copolymer (A-3) In the same manner as for the graft copolymer (A-1), 55 parts of the rubber polymer (Ad-3) was added to 24 parts of MMA, 20 parts of St,
N1 parts were polymerized to produce a graft copolymer (A-3). As shown in Table 1, the polymerization conversion was 99% and the graft ratio was 58%.

(4) Production of Graft Copolymer (A-4) In the same manner as for the graft copolymer (A-1), 75 parts of the rubber polymer (Ad-4) were added to 22 parts of MMA, 1 part of St, and BA
Two parts were polymerized to produce a graft copolymer (A-4). As shown in Table 1, the polymerization conversion was 98% and the graft ratio was 25%.

(5) Production of Graft Copolymer (A-5) In the same manner as for the graft copolymer (A-1), 25 parts of MMA, 10 parts of St,
The polymer was polymerized in 0.3 part of HP, and the graft copolymer (A-
5) was produced. As shown in Table 1, the polymerization conversion rate was 98%.
And the graft ratio was 40%.

[0036]

[Table 1]

3. Production of copolymer (B) (1) Production of copolymer (B-1) The following substances were charged into a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet, and a thermometer. It is. Pure water 250 parts Sodium palmitate 2.0 parts Sodium formaldehyde sulfoxylate 0.5 parts EDTA 0.01 parts Ferrous sulfate 0.0025 parts The temperature was raised to 65 ° C under a nitrogen stream while stirring the reactor. . After reaching 65 ° C., 26 parts of AN, 74 parts of St, tDM
A mixture of 1.1 parts and 0.2 parts of CHP was dropped continuously over 7 hours. After completion of the dropwise addition, stirring was continued at 65 ° C. for 1 hour to complete the polymerization. As shown in Table 2, the polymerization conversion was 98%,
Mw was 48000 and Mw / Mn was 2.2.

(2) Production of copolymer (B-2) In the same manner as for copolymer (B-1), 23 parts of AN, St
A copolymer (B-2) was produced as 74 parts, 2 parts of MMA, 1 part of PMI, and 0.7 part of tDM. As shown in Table 2,
The polymerization conversion was 99%, Mw was 65,000, and Mw / Mn was 2.3.

(3) Preparation of copolymer (B-3) In the same manner as for copolymer (B-1), 30 parts of AN, St
A copolymer (B-3) was produced with 65 parts, 5 parts of BA, and 2.3 parts of tDM. As shown in Table 2, the polymerization conversion was 98%, Mw was 25,000, and Mw / Mn was 2.5.

(4) Production of Copolymer (B-4) In the same manner as for Copolymer (B-1), 25 parts of AN, St
75 parts and tDM of 0.25 parts, the copolymer (B-
4) was manufactured. As shown in Table 2, the polymerization conversion rate was 99%.
%, Mw was 140000, and Mw / Mn was 2.8.

[0041]

[Table 2]

4. Production of vinyl chloride resin (II) (1) Production of vinyl chloride resin (II-1) 130 parts of pure water, partially saponified polyvinyl alcohol 0.08
, 0.06 part of 2-mercaptoethanol, 0.04 part of 2-ethylhexyl peroxycarbonate and 100 parts of a vinyl chloride monomer, and the mixture was heated to 60 ° C. with stirring to initiate polymerization. The pressure inside the polymerization reactor is 7 kg / cm ² G
When the pressure was lowered to, unreacted monomers were recovered to obtain a slurry of a polyvinyl chloride polymer. The slurry was dehydrated and dried to obtain a vinyl chloride resin (II-1). As shown in Table 3, the viscosity average polymerization degree of the obtained resin was 450. (2) Production of vinyl chloride resin (II-2) In the same manner as in (II-1) above, 0.02 parts of 2-mercaptoethanol was used, polymerized at 58 ° C., and vinyl chloride resin (II- 2) was obtained. As shown in Table 3, the viscosity average polymerization degree of the obtained resin was 540. (3) Production of vinyl chloride resin (II-3) In the same manner as in the above (II-1), polymerization was carried out without using 2-mercaptoethanol, and vinyl chloride resin (II-3) was obtained.
I got As shown in Table 3, the viscosity average polymerization degree of the obtained resin was 620.

[0043]

[Table 3]

5. Production of styrene resin (III) (1) Production of styrene resin (III-1) The following substances were charged into a reactor equipped with a stirrer, reflux condenser, nitrogen inlet, monomer inlet, and thermometer. It is. Pure water 250 parts Sodium palmitate 1.5 parts Sodium formaldehyde sulfoxylate 0.5 parts EDTA 0.01 parts Ferrous sulfate 0.0025 parts The reactor was heated to 65 ° C under a nitrogen stream while stirring. . After reaching 65 ° C., 25 parts of AN, 75 parts of St, tDM
A mixture of 0.8 part and 0.2 part of CHP was dropped continuously over 6 hours. After completion of the dropwise addition, stirring was continued at 65 ° C. for 1 hour to complete the polymerization. As shown in Table 4, the polymerization conversion was 99%,
The reduced viscosity was 0.37 dl / g.

(2) Production of styrene resin (III-2) In the same manner as for copolymer (III-1), 27 parts of AN, St
11 parts, αMSt 62 parts, tDM 1.2 parts, CHP0.
Polymerized as 3 parts. As shown in Table 4, the polymerization conversion was 98% and the reduced viscosity was 0.28 dl / g.

(3) Production of styrene resin (III-3) In the same manner as for the copolymer (III-1), sodium palmitate was changed to 1.5 parts of sodium dioctylsulfosuccinate, 10 parts of AN, 40 parts of St, αMSt10 parts, PM
I15 parts, MMA 25 parts, tDM 1.0 part, CHP0.
Polymerized as 2 parts. As shown in Table 4, the polymerization conversion was 99% and the reduced viscosity was 0.33 dl / g. 2 parts of calcium chloride was added to the latex of the styrene resins (III-1) to (III-3) for coagulation. The coagulated slurry is subjected to heat treatment, dehydration drying and styrenic resin (III-1) to (III-
The powder of 3) was obtained.

[0047]

[Table 4]

6 Production of rubber-rich MABS resin composition and rubber-modified thermoplastic resin composition Graft copolymers (A-1) to (A)
-5) latex and 3. (B)
After mixing the latexes of -1) to (B-4) at the ratio shown in Table 5 (solid content ratio), 1 part of a hindered phenol-based stabilizer was added in the form of an emulsified aqueous dispersion, and the mixture was sufficiently stirred and mixed. The mixture was coagulated by adding 0.5 part of hydrochloric acid. The coagulated slurry was neutralized with sodium hydroxide, heat-treated, dehydrated and dried. As shown in Tables 5 and 6, the rubber-rich MABS resin powder (I
-1) to (I-11) were obtained.

[0049]

[Table 5]

[0050]

[Table 6]

Next, the obtained rubber-rich ABS resin powders (I-1) to (I-11) and 4. 5. The vinyl chloride resins (II-1) to (II-3) produced in the above item 5. The powders of the styrenic resins (III-1) to (III-3) produced in the above were used together with 2 parts of stearyl stearate and 2 parts of dibutyl tin maleate (based on 100 parts of the resin) at a ratio shown in Table 7 using a 20 L blender manufactured by Tabata Co., Ltd. Blend uniformly. Further, the mixture was melt-kneaded at a temperature of 180 ° C. with a 40 mm single screw extruder manufactured by Tabata Co., Ltd. to produce pellets of the rubber-modified thermoplastic resin composition.

[0052]

[Table 7]

From the results shown in Table 7, the rubber-modified thermoplastic resin composition using the rubber-rich MABS resin composition of the present invention represented by Examples 1 to 5 has particularly excellent impact resistance and surface properties. It is clear that the rigidity, heat resistance, fluidity, and thermal stability are also good.

Evaluation of physical properties and characteristics was performed by the following methods. [Graft ratio] The graft ratio is determined by the graft copolymer (A
The powder of p) was dissolved in methyl ethyl ketone and centrifuged to obtain a methyl ethyl ketone soluble component and an insoluble component of the thermoplastic resin composition. Methanol was added to the methyl ethyl ketone-soluble matter to cause precipitation, and the precipitate was taken out. The graft ratio was determined from the ratio of the precipitate to the methyl ethyl ketone insoluble component and the polymerization conversion ratio. [Volume average particle diameter of rubber polymer] The rubber polymer latex was measured by a Nicomp particle size analyzer manufactured by Pacific Science Corporation. [Weight average molecular weight Mw, and ratio Mw /
Measurement of Mn] The copolymer (B) was subjected to GPC analysis, and the ratio Mw / Mn to the weight average molecular weight Mw and the number average molecular weight Mn was measured.
Was calculated using polystyrene as a standard. [Reduced viscosity] 0.3 g / dl in dimethylformamide solution
After dissolving the styrenic resin (III) to a concentration of 3, the solution viscosity was measured at 30 ° C. using an Ostwald viscometer and calculated. [Viscosity average polymerization degree] The viscosity average molecular weight of the vinyl chloride resin (II) was measured based on JIS K6721. [Polymerization conversion rate] The polymerization conversion rate was calculated by gas chromatography analysis.

[Properties of Rubber-Modified Thermoplastic Resin Composition] Impact resistance was evaluated by IZOD impact strength. The IZOD impact strength was evaluated at 23 ° C. according to the method of ASTM D-256 standard (１ ／ inch thickness) (unit: kgcm / cm).
Tensile strength (unit: kg / cm ² ), tensile elongation (unit%)
Was evaluated at 23 ° C. using a No. 1 dumbbell according to the method of ASTM D638 standard. Flexural strength (unit: kg / c
m ² ) and flexural modulus (unit: kg / cm ² ) are ASTM D
Evaluation was performed at 23 ° C. according to the method of 790 standard. Heat resistance (HD
T) was evaluated at the heat deformation temperature of 18.6 kg / cm ² load according to ASTM D648 (unit: ° C.).

The surface appearance was visually determined using a No. 1 dumbbell by a 5-point evaluation method according to the following criteria. 5 points: glossy, the surface is smooth, and no fish eyes or bumps are recognized. 4 points: glossy, the surface is smooth, and some fish eyes are observed, but no bumps are observed. 3 points: glossy, surface is smooth, fish eyes are observed, but no bumps are observed. 2 points: Slightly glossy, slightly rough on the surface, and slightly uneven. 1 point: Low gloss, rough surface, and considerable bumps.

The test pieces used for the above-mentioned IZOD impact strength, tensile strength, tensile elongation, flexural strength, flexural modulus, heat resistance and surface properties were FAS100B manufactured by FANUC CORPORATION.
Using an injection molding machine, molding was carried out at a cylinder temperature of 180 ° C., which was provided for evaluation. Fluidity is FANUC F
Using AS100B injection molding machine, cylinder temperature 19
Flow length (unit: mm) of the resin in a spiral mold having a thickness of 3 mm at 0 ° C. and an injection pressure of 1350 kg / cm ² .
Was evaluated. In each case, the larger the value, the better.

[0058]

As described above, the rubber-rich MA of the present invention is used.
The BS resin composition provides a rubber-modified thermoplastic resin composition having excellent heat resistance, rigidity, and processability, as well as excellent impact resistance and molding surface properties.

Claims (3)

[Claims] (A) a volume average particle size of 30 to 1000 nm
90 to 50 parts by weight of a diene rubber polymer and / or an acrylic rubber polymer (Ad), an alkyl methacrylate unit of 30 to 98 mol%, and an aromatic vinyl compound unit of
0 mol% and monomer units 0 to 30 copolymerizable therewith.
(B) 60-95 parts by weight of a graft copolymer comprising 10-50 parts by weight of a graft part (Ag) consisting of mol%
Copolymer 40 consisting of 25 to 60 mol% of a vinyl cyanide compound unit, 75 to 40 mol% of an aromatic vinyl compound unit, and 0 to 30 mol% of a monomer unit copolymerizable therewith.
And the graft ratio of the (A) graft copolymer is 10 to 80 parts by weight.
And the weight average molecular weight Mw of the copolymer (B) is 5,000 to 5,000.
The ratio Mw / Mn of 90000 and the number average molecular weight Mn is 1.5 to 4.5, and the (A) graft copolymer and (B) copolymer are obtained by polymerization by an emulsion polymerization method. A highly rubber-containing MABS resin composition, characterized in that: 2. A rubber-rich MABS resin composition (I) according to claim 1, 5 to 60 parts by weight, a vinyl chloride resin (II).
20 to 80 parts by weight and styrene resin (III) 20 to 75
Parts by weight [total 100 parts by weight of (I), (II) and (III)]
A rubber-modified thermoplastic resin composition comprising: 3. The rubber modified product according to claim 2, wherein the viscosity average polymerization degree of the vinyl chloride resin (II) is 300 to 800, and the reduced viscosity of the styrene resin (III) is 0.15 to 0.45 dl / g. Thermoplastic resin composition.