JP3358878B2 - Rubber latex, graft copolymer and thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an enlarged rubber latex, a graft copolymer using the rubber latex, and a rubber-reinforced thermoplastic resin composition having excellent impact resistance.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins such as polyvinyl chloride, polystyrene, polymethyl methacrylate, styrene-acrylonitrile copolymer resin, α-methylstyrene-acrylonitrile copolymer resin, styrene-acrylonitrile-phenylmaleimide copolymer resin, polyester Resins, polycarbonate resins, thermoplastic resins such as polyamide resins, or polymer alloys of these resins, such as styrene-acrylonitrile copolymer resins and polycarbonate resin alloys and α-methylstyrene-
For an acrylonitrile copolymer resin and an alloy of vinyl chloride resin, etc., a graft polymer obtained by graft-polymerizing a monomer that imparts compatibility with these resins and the alloy to a rubber-like polymer is blended. Rubber reinforced resins with improved impact resistance are generally widely used.

[0003] The rubber-like polymer used in these rubber-reinforced resins has an optimum particle size for exhibiting impact resistance, and the value generally varies depending on the resin used as the matrix. It recognized. In other words, it is said that it is necessary to use a rubber having a larger particle diameter for a polymer having higher brittleness, and it is actually 0.15 μm (150 n
Rubbers having various average particle diameters ranging from m) to several μm (thousands of nm) are used.

[0004] A wide variety of rubbers are used, and the most widely used rubbers are those comprising a diene (co) polymer and an acrylate (co) polymer. . Diene rubbers and acrylate rubbers are usually produced by emulsion polymerization and can be obtained in latex form. However, the particle size of the rubber obtained by the emulsion polymerization is not more than 0.1 unless a special operation is performed.
It is 1 μm (100 nm) or less, and the particle size is too small for a graft copolymer for a rubber-reinforced resin. For this reason, various methods have been implemented or proposed in order to obtain rubber latex having a desired large particle diameter. One is a method for producing a rubber latex having a large particle diameter by a polymerization operation. The other is a method in which small particle rubber obtained by ordinary emulsion polymerization is coagulated and enlarged to have a large particle diameter.

In the former method, for example, polymerization is carried out under stirring conditions of high polymer concentration / high shear, and rubber particles are unitarily enlarged during polymerization to obtain large particles. The biggest disadvantage of this method is that the polymerization time is long and 0.3 μm (300 nm)
A polymerization time of 50 to 100 hours is required in order to obtain particles of a certain degree, the productivity is extremely low, and this is not an industrially advantageous method.

In the latter method, the stability of the latex is reduced by adding an inorganic salt or an acid to the rubber latex to perform coagulation and enlargement. In this method, the particle diameter obtained is 0.2 μm (200 nm). , And is not an appropriate particle size in many cases for rubber-reinforced resins.
In addition, when large particles are to be produced by this method, a large amount of coagulum is formed, and it is difficult to carry out the method industrially.

As an improvement of this method, Japanese Patent Laid-Open Publication No. 50-256
55. That is, this is a method in which an acid group-containing latex comprising a copolymer of an alkyl acrylate and an unsaturated acid is added to a rubber latex having a pH of 7 or more to enlarge particles. Certainly, this method does not produce a large amount of coagulum and can produce a rubber having a large particle diameter of 0.3 μm (300 nm) or more. However, since the enlargement speed is high, enlarged rubber particles can be obtained with good reproducibility in a small-scale experiment in which acid latex and rubber latex can be mixed in a short time. However, there is a drawback that a large enlargement occurs and often causes a variation in particle size.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems of the enlarging method using an acid group-containing latex. By changing to a methacrylic acid ester having a higher glass transition temperature than that of an acid ester, the rate of enlargement is reduced to some extent, and it has been found that it is possible to stably increase the size of an industrial apparatus that requires a longer mixing time than an experimental apparatus. Reached. That is, the present invention
Stable even in industrial equipment by coagulation and enlargement using an acid group-containing latex obtained by copolymerization of unsaturated acid monomers, methacrylate monomers and monomers copolymerizable with them. That a rubber latex with a large particle diameter can be obtained, and that a rubber-reinforced thermoplastic resin obtained by blending a graft copolymer prepared using the enlarged rubber with a thermoplastic resin has high impact resistance It is based on.

That is, the first aspect of the present invention is as follows: (A) (a) 1 to 30% by weight of an unsaturated acid monomer (b) 99 to 70% by weight of a methacrylate monomer (c) The above (a) And (b) an acid group-containing copolymer latex prepared by copolymerizing 0 to 30% by weight of a monomer having an ethylenically unsaturated bond and copolymerizable with (B) 100 weight parts of a rubber latex having a pH of 7 or more. Part (solid content) is added to 0.1 to 10 parts by weight (solid content) to enlarge the average particle diameter to 200 nm or more.

In the second aspect of the present invention, (A) (a) 1 to 30% by weight of an unsaturated acid monomer, (b) 99 to 70% by weight of a methacrylic acid ester monomer (c) (B) 100 parts by weight of a rubber latex having a pH of 7 or more (B) prepared by copolymerizing 0 to 30% by weight of a monomer having an ethylenically unsaturated bond copolymerizable with b) (Solid content), 0.1 to 10 parts by weight (solid content), and the resulting enlarged rubber 1 having an average particle diameter of 200 nm or more.
0 to 90 parts by weight, at least one monomer selected from an aromatic vinyl monomer, a vinyl cyanide monomer and a methacrylic acid ester monomer, or these monomers and the monomer A graft copolymer obtained by graft-polymerizing 90 to 10 parts by weight of a mixture of a monomer having an α, β-unsaturated bond and a copolymerizable monomer.

A third aspect of the present invention is that (A) (a) 1 to 30% by weight of an unsaturated acid monomer, (b) 99 to 70% by weight of a methacrylate monomer (c) (B) 100 parts by weight of a rubber latex having a pH of 7 or more (B) prepared by copolymerizing 0 to 30% by weight of a monomer having an ethylenically unsaturated bond copolymerizable with b) (Solid content), 0.1 to 10 parts by weight (solid content), and the resulting enlarged rubber 1 having an average particle diameter of 200 nm or more.
0 to 90 parts by weight, at least one monomer selected from an aromatic vinyl monomer, a vinyl cyanide monomer and a methacrylic acid ester monomer, or these monomers and the monomer Rubber-reinforced thermoplastic resin composition comprising a graft copolymer obtained by graft-polymerizing 90 to 10 parts by weight of a mixture of a monomer having an α, β-unsaturated bond and a copolymerizable monomer, and a thermoplastic resin The thing is the content.

The unsaturated acid monomer (a) used in the acid group-containing copolymer latex (A) includes acrylic acid, methacrylic acid, itaconic acid, itaconic acid monoester, maleic acid monoester and crotonic acid. Examples include acrylic acid, methacrylic acid, and mixtures thereof. As the methacrylic acid ester (b), an ester of methacrylic acid and an alcohol having a linear or side chain having 1 to 12 carbon atoms is used, and methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid are used. 2-ethylhexyl and the like can be exemplified. These are used alone or in combination of two or more.

The monomers copolymerizable with the above (a) and (b) include aromatic vinyl monomers such as styrene, α-methylstyrene and p-methylstyrene, acrylonitrile and methacrylonitrile. Vinyl cyanide monomers, acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or allyl methacrylate, polyethylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate And a monomer having two or more polymerizable functional groups in the molecule, such as triallyl trimellitate. These can be used alone or in combination of two or more.

The proportion of the unsaturated acid monomer (a) in the acid group-containing copolymer is from 1 to 30% by weight. If it is less than 1%, there is substantially no hypertrophic ability, and if it exceeds 30% by weight, polymerization of the acid group-containing latex is not impossible, but the formation of coagulum and the thickening of the latex during the polymerization occur. Not suitable for industrial production.

The remaining monomer to be copolymerized with the unsaturated acid monomer (a) is basically a methacrylate monomer (b), and 99 to 70% by weight is used. However, it is possible to replace a part of the methacrylate monomer with the monomer (c) having an ethylenically unsaturated bond copolymerizable with these (a) and (b). The amount is from 0 to 30% by weight, and if it exceeds 30% by weight, in the case of an aromatic vinyl monomer, the hypertrophic ability decreases and the unagglomerated particles increase. In the case of an acrylate monomer, the enlargement speed is increased, and it is difficult to control the particle size. In addition, in the case of a monomer having two or more polymerizable functional groups in the molecule, it should be used in the range of 0 to 3% by weight. It will drop significantly.

As the rubber latex (B) having a pH of 7 or more, a diene rubber or an acrylate rubber containing 50% by weight or more of a diene can be used. Examples of the diene rubber include polybutadiene and acrylonitrile-butadiene copolymer. Examples thereof include a copolymer, a styrene-butadiene copolymer, and a butyl acrylate-butadiene copolymer, and these may be used alone or in combination of two or more.

The acid group-containing copolymer latex (A) is produced by emulsion polymerization. As the emulsifier used for the polymerization, a sulfonic acid-based or sulfate-based emulsifier is mainly used, and examples thereof include sodium alkylbenzenesulfonate, sodium paraffinsulfonate, sodium dialkylsulfosuccinate, and sodium alkylsulfate. It is also possible to use a carboxylic acid-based emulsifier as a supplement. Such emulsifiers include higher fatty acid alkali metal salts such as sodium oleate, sodium palmitate,
There are potassium stearate, alkali metal salts of rosin acid and alkali metal salts of alkenyl succinic acid. These may be used alone or in combination of two or more. The emulsifier is used in an amount of 0.2 to 4 parts by weight based on 100 parts by weight of the monomer. The emulsifier may be charged all at once in the early stage of polymerization,
Some may be used initially and the rest added intermittently or continuously during the polymerization. By changing the method of adding the emulsifier, the particle size of the acid group-containing latex can be adjusted.

As the polymerization initiator, either a thermal decomposition type initiator or a redox type initiator can be used. Specific examples of the former include potassium persulfate and ammonium persulfate, and the latter include systems such as cumene hydroperoxide-sodium formaldehyde sulfoxylate-iron salt. These may be used alone or in combination of two or more. The polymerization initiator may be charged in its entirety at the beginning of the polymerization, or may be partially used at the beginning and the rest may be added intermittently or continuously during the polymerization. To adjust the molecular weight, chain transfer agents such as t-dodecyl mercaptan, n-dodecyl mercaptan, terpinolene can also be used.

In the polymerization of the acid group-containing copolymer latex (A), the monomer mixture may be charged in its entirety at the beginning of the polymerization, or may be partially charged at the beginning and the remainder may be intermittently charged during the polymerization. , Or the whole amount may be added intermittently or continuously during the polymerization. When the polymerization is carried out by adding a monomer, the composition of the monomer to be added does not always need to be the same. In the initial stage of polymerization, after a part of the monomers other than the unsaturated acid monomer among the monomers subjected to the polymerization are added and polymerized, then the remaining monomer containing the unsaturated acid monomer is added. The polymerization can also be terminated by adding additional bodies.

The average particle size of the acid group-containing copolymer latex (A) is from 30 to 500 which can be generally produced by emulsion polymerization.
It may be in the range of nm. Preferably, the average particle diameter of the acid group-containing copolymer latex (A) is such that the enlarged particle diameter is 20.
50-300n to stably enlarge to 0nm or more
m. The average particle diameter after the enlargement is preferably 200 nm or more from the viewpoint of the impact resistance of the thermoplastic resin.
Before latex rubber latex is produced by emulsion polymerization,
It is necessary that the pH is 7 or more. At a pH below 7, no hypertrophy occurs. The average particle diameter of the rubber latex before the enlargement is usually less than 200 nm, preferably 150 nm or less.

The enlargement treatment is performed by adding 0.1 to 10 parts by weight (solid content) of the acid group-containing copolymer latex (A) to 100 parts by weight (solid content) of the rubber latex (B) and mixing. Achieved. The amount of the acid group-containing latex added is 0.
When the amount is less than 1 part by weight, coagulation enlargement does not substantially occur. If the amount exceeds 10 parts by weight, the diameter of the enlarged particles becomes smaller, and undesired phenomena such as a reduction in impact resistance also occur in physical properties.

The type of the acid group-containing latex used for the enlargement is not limited to one type. By using two or more types of acid group-containing latexes having different hypertrophic abilities, it is also possible to obtain an enlarged rubber having a double peak distribution or a wide particle size distribution. The processing temperature for the enlargement is preferably from 20 to 80 ° C, more preferably from 40 to 70 ° C. The acid group-containing latex may be added after the temperature of the rubber latex reaches the enlargement treatment temperature, or may be added to the rubber latex at a temperature of 40 ° C. or less, preferably 35 ° C. or less, and stirred for 40 to 90 ° C.
The temperature can be raised to ° C. to perform the enlargement treatment. Conversely,
The rubber latex can be supplied later to a container in which the acid group-containing latex has been charged in advance.

At the time of the enlargement treatment, 0.01 to 5 parts by weight of an inorganic salt can be used in addition to the acid group-containing latex. By adding an inorganic salt, the effect of enlargement can be improved, and an enlarged rubber having a large particle size can be obtained. As the inorganic salt, an alkali metal salt such as sodium chloride or sodium sulfate or an oxyacid salt such as potassium alum is used, and these are used alone or in combination of two or more. The pH at the time of the enlargement treatment may be on the alkaline side (that is, pH 7 or more), but it is preferable to adjust the pH to 9 or more because the enlargement speed is improved. The pH may be adjusted by adding an appropriate amount of one or more of compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium hydrogen carbonate.

[0024] The concentration of the latex subjected to the enlargement treatment is also an important factor. It is possible to control the enlarged particle diameter by adjusting the rubber concentration. Although the final particle size distribution varies depending on the composition of the acid group-containing copolymer latex used for the enlargement, the tendency for the enlarged particle size to decrease as the rubber concentration decreases is recognized. It is also possible to add an emulsifier during the enlargement treatment to change the emulsifier coverage on the surface of the rubber latex particles, thereby changing the particle diameter after the enlargement. That is, by increasing the emulsifier coverage on the surface by adding an emulsifier, the enlarged particle diameter can be reduced as compared with the case where no emulsifier is added.

The production of the graft copolymer using the enlarged rubber obtained by the above treatment can be carried out by a usual emulsion polymerization method. That is, in the presence of 10 to 90 parts by weight of the enlarged rubber latex, 90 to 10 parts by weight of a monomer or a monomer mixture to be graft-polymerized are added all at once or continuously, and the radical polymerization initiator is used for graft polymerization. I just need. At the time of graft polymerization, an emulsifier may be newly added. The polymerization initiator may be of a thermal decomposition type or a redox type. The monomer or monomer mixture used is determined in consideration of the compatibility with the thermoplastic resin when the graft polymer is blended with the thermoplastic resin to produce a rubber-reinforced resin. Specifically, at least one monomer selected from an aromatic vinyl monomer, a vinyl cyanide monomer, and a methacrylic acid ester monomer, or a copolymer of these monomers with the monomer Mixtures with possible α, β-unsaturated monomers. Examples of the copolymerizable monomer having an α, β-unsaturated bond include acrylic ester, methacrylic acid, acrylic acid and the like. Preferably, 10 to 90% by weight of an aromatic vinyl monomer, 90 to 10% by weight of a vinyl cyanide monomer and / or a methacrylate monomer, and an α, β-unsaturated bond copolymerizable therewith. It is a mixture of the monomers having 0 to 20% by weight.

The polymer powder can be recovered from the graft copolymer latex after polymerization by a conventional method, for example, adding a salt of an alkaline earth metal such as calcium chloride, magnesium chloride or magnesium sulfate, sodium chloride or sodium sulfate to the latex. Alkali metal salts such as hydrochloric acid,
A method of coagulating the latex by adding an inorganic acid such as sulfuric acid, phosphoric acid, and acetic acid and an organic acid, followed by dehydration and drying is used. Also, a spray drying method can be used.

By blending the graft copolymer recovered as a powder with another thermoplastic resin, a rubber-reinforced thermoplastic resin composition can be produced. Instead of recovering the graft copolymer alone, after blending the latex of the graft copolymer with the latex of the thermoplastic resin produced by emulsion polymerization, recover it as a powder by the coagulation dehydration method or spray drying method described above. Thus, a rubber-reinforced thermoplastic resin composition can be obtained. Further, by blending the rubber-reinforced thermoplastic resin obtained by this method with another thermoplastic resin, a rubber-reinforced resin of a polymer alloy of a thermoplastic resin can be obtained.

Specific examples of the thermoplastic resin include styrene-acrylonitrile copolymer resin, α-methylstyrene-styrene-acrylonitrile copolymer resin, styrene-acrylonitrile-N-substituted maleimide copolymer resin,
Styrene-acrylonitrile copolymer resin and polyvinyl chloride alloy, α-methylstyrene-styrene-acrylonitrile copolymer resin and polyvinyl chloride alloy, styrene-acrylonitrile copolymer resin and polycarbonate resin alloy, α-methylstyrene-styrene- Acrylonitrile copolymer resin Polycarbonate resin alloy, styrene-acrylonitrile copolymer resin and polyester resin alloy, α-methylstyrene-styrene-acrylonitrile copolymer resin and polyester resin alloy, styrene-acrylonitrile-methacrylic acid copolymer resin and polyamide resin Alloys of α-methylstyrene-styrene-acrylonitrile-methacrylic acid copolymer resin and polyamide resin. As for the proportion of the compound,
It is preferable to mix the rubber so that the ratio of the rubber in the manufactured compound is 5 to 35%. If the proportion of rubber is less than 5% by weight, the effect of improving the impact resistance is insufficient, and 35% by weight.
When the ratio exceeds the above range, the effect of improving the impact resistance is smaller than that of the ratio lower than that, and disadvantages such as a decrease in heat resistance and processability tend to occur due to an increase in the rubber component.

The resin blend is prepared by a general method, for example, using a blender such as a Henschel mixer or a ribbon blender, a powder comprising a graft copolymer or a blend of a graft copolymer and a thermoplastic resin, and a powder of another thermoplastic resin. After blending pellets, flakes, etc., it can be carried out by melt-kneading using a kneader or an extruder. After blending them with a blender or the like, they may be melt-kneaded with an extruder or the like. At this time, desired stabilizers, lubricants, pigments, fillers, and the like can be added.

As the stabilizer, hindered phenol-based stabilizers, phosphorus-based stabilizers, and sulfur-based stabilizers are suitable, and these may be used alone or in combination of two or more. Examples of hindered phenol-based stabilizers include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl-butane, n-octadecyl-3- (3 ′,
5′-di-tert-butyl-4-hydroxyphenyl) propionate), tetrakis [methylene-3
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-
4-hydroxyphenylpropionate], pentaerythritol-tetrakis [3- (3,5-di-tert)
-Butyl-4-hydroxyphenyl) propionate]), 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis (4-methyl-6
tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol),
Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate) and the like are exemplified.

Examples of the sulfur-based stabilizer include 3,3′-thiodipropionic acid, dialkyl-3,3′-thiodipropionate, pentaerythrityl-tetrakis (3-alkylthiopropionate), and tetrakis [methylene −
3- (alkylthio) propionate] methane, bis [2-methyl-4- (3-alkyl-thiopropionyloxy) -5-tert-butylphenyl] sulfide and the like.

Examples of the phosphorus-based stabilizer include stearylphenyl phosphite, tris (mono, di, nonylphenyl) phosphite, distearylpentaerythritol diphosphite, and tris (2,4-di-tert-butylphenyl) phosphite. Fight, di (2,4-di-tert)
-Butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4-diphenylenephosphonite, bis (2
6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. These stabilizers can be used alone or in combination of two or more.

As the lubricant, organopolysiloxane,
Examples thereof include aliphatic hydrocarbons, esters of higher fatty acids and higher alcohols, amides or bisamides of higher fatty acids and modified products thereof, and metal salts of higher fatty acids. Examples of the organopolysiloxane include polydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane. Examples of the aliphatic hydrocarbon include synthetic paraffin, polyethylene wax, polypropylene wax and the like. Examples of esters of higher fatty acids and higher alcohols include esters of montanic acid, stearyl stearate, and behenerbehenate. Amides of higher fatty acids, bisamides and modified products thereof include stearic acid amide, ethylene bisstearic acid amide,
A compound having a higher melting point than a bisamide synthesized by a dehydration reaction from a higher fatty acid such as stearic acid, a dicarboxylic acid such as succinic acid, and a diamine such as ethylenediamine can be exemplified. As metal salts of higher fatty acids,
Examples thereof include calcium, magnesium, aluminum, and cadmium salts of higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid. These lubricants can be used alone or as a mixture of two or more.

[0034]

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 noted,
"Parts" represents parts by weight, and "%" represents% by weight.

In the following description, abbreviations represent the following substances, respectively. MMA: methyl methacrylate BA: butyl acrylate MAA: methacrylic acid tDM: tertiary decyl mercaptan CHP: cumene hydroperoxide BMA: butyl methacrylate PBd: polybutadiene PBA: polybutyl acrylate AN: acrylonitrile α-t-S-α Methylstyrene PMI: Phenylmaleimide PVC: Polyvinyl chloride Ny-6: Naliron 6 PC: Polycarbonate PBT: Polybutylene terephthalate AO-20: Trade name (Hindered phenol type stabilizer manufactured by Asahi Denka) EBS: Ethylene bisstearyl amide HDT: Heat deformation temperature TS: Tensile strength EL: Elongation IZOD: Izod impact strength

Examples and Comparative Examples (A) Production of Acid Group-Containing Copolymer Latex The following substances were charged into a reactor equipped with a stirrer, reflux condenser, nitrogen inlet, monomer inlet, and thermometer. . Pure water 200 parts Dioctyl sodium sulfosuccinate 0.2 parts Sodium formaldehyde sulfoxylate 0.4 parts Sodium ethylenediamine tetraacetate 0.01 parts Ferrous sulfate 0.025 parts Up to 65 ° C under a nitrogen stream while stirring the reactor. The temperature rose. After reaching 65 ° C., the monomers (I) and (II) in Table 1 were continuously added dropwise over 6 hours. The addition speed was 16.7 parts / hour of monomer at a constant velocity. Also, sodium dioctyl sulfosuccinate was added to the solution for 0.4 hour at the first hour of polymerization.
And 0.4 hours later at the third hour. After dropping, 65 ° C
For 1 hour to complete the polymerization.

[0037]

[Table 1]

(B) Production of polybutadiene rubber The following substances were charged into a 100-liter polymerization machine. Pure water 200 parts Potassium persulfate 0.2 parts Tertiary decyl mercaptan 0.2 parts After reducing the pressure inside the polymerization machine, the following substances were charged. Sodium oleate 1 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 12 hours, and the conversion was 96%. The obtained rubber latex had an average particle diameter of 70 nm and a pH of 8.6.

(C) Production of polybutyl acrylate rubber 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 Sodium palmitate 2 parts Sodium formaldehyde sulfoxylate 0.4 parts Sodium ethylenediamine tetraacetate 0.01 parts Ferrous sulfate 0.0025 parts Heat the reactor to 65 ° C under a nitrogen stream while stirring the reactor. Was. After reaching 65 ° C., the following mixture was continuously dropped in 6 hours. After completion of the dropwise addition, stirring was continued at 65 ° C. for 1 hour to complete the polymerization. The polymerization conversion was 97%. The particle size of the polybutyl acrylate latex after polymerization is 80 nm,
pH was 8.2. Butyl acrylate 100 Triallyl cyanurate 2 Cumene hydroperoxide 0.1

(D) Enlargement treatment The polybutadiene rubber obtained in the above (B) and the above (C)
The polybutyl acrylate rubber obtained in the above was enlarged as follows. That is, as shown in Table 2, the rubber latexes (B) and (C) were mixed with the acid group-containing copolymer latexes (A-1) to (A-2) and (a-1) obtained in (A) for 25 times. After addition of a predetermined amount at ° C, the mixture was heated with stirring and heated to 60 ° C over 40 minutes, and stirring was continued at that temperature for another 30 minutes to complete the hypertrophy.

[0041]

[Table 2]

(E) Production of Graft Copolymer 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 Enlarged rubber (solid content) Predetermined amount shown in Table 1 Sodium dodecylbenzenesulfonate 2 parts Sodium formaldehyde sulfoxylate 0.2 parts Sodium ethylenediaminetetraacetate 0.01 parts Ferrous sulfate 0.0025 parts Reaction The vessel was heated to 60 ° C. under a nitrogen stream while stirring. After reaching 60 ° C., the mixture of Table 3 was dropped continuously over 4 hours. After completion of the dropwise addition, stirring was continued at 60 ° C. for 1 hour to complete the polymerization (E-1 to E-4). Also, as a comparison,
Non-blowing small particle polybutadiene rubber latex (d
-1) was subjected to the same graft copolymerization (e).
-1).

[0043]

[Table 3]

(F) Production of thermoplastic resin latex The substances shown in Table 4 and monomer (I) 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 Sodium dioctyl sulfosuccinate 1.0 part Sodium formaldehyde sulfoxylate 0.4 parts Sodium ethylenediamine tetraacetate 0.01 parts Ferrous sulfate 0.0025 parts While stirring the reactor, up to 65 ° C under a nitrogen stream. The temperature was raised. After reaching 65 ° C., the monomer (II) in Table 4 was continuously
Dropped in time. Also, 0.5 part of sodium dioctylsulfosuccinate was added at the first hour of polymerization and 0.5 part at the third hour.
Part added. After dropping, stirring was continued at 65 ° C. for 1 hour,
The polymerization was completed (F-1 to F-3). The same polymerization was carried out by changing the emulsifier to sodium palmitate instead of sodium dioctylsulfosuccinate (F-
4).

[0045]

[Table 4]

(G) Production of rubber-reinforced thermoplastic resin composition Graft copolymer latex produced in (E) and (F)
After mixing the thermoplastic resin latex prepared in the above at the ratio shown in Table 5, 0.5 part of a phenolic stabilizer was added, and 2 parts of calcium chloride was added to coagulate. The coagulated slurry was dehydrated and dried to obtain a rubber-reinforced thermoplastic resin powder (G-1).
~ G-5, g-1).

[0047]

[Table 5]

Next, the compounding agents shown in Table 6 or other thermoplastic resins are blended into the obtained thermoplastic resin powder, and the mixture is melt-kneaded in an extruder to produce thermoplastic resin pellets, and has a heat distortion temperature (HDT), Tensile strength (TS), elongation (E
L), Izod impact strength (IZOD), falling weight impact strength, and various physical properties of fluidity were evaluated. Table 7 shows the results of the physical property evaluation. Table 7 shows that the rubber-reinforced thermoplastic resin compositions (H-1 to H-7) of the present invention are particularly excellent in impact resistance, and have a good balance of heat resistance and workability.

[0049]

[Table 6]

[0050]

[Table 7]

[0051]

EFFECT OF THE INVENTION The enlarged rubber latex of the present invention,
A graft copolymer using the rubber latex and a rubber-reinforced thermoplastic resin composition obtained by blending the graft copolymer have particularly excellent impact resistance, and also have excellent heat resistance and processability.

Continuation of the front page (72) Inventor Hiroki Yoshino 8-7, Babadori, Tarumizu-ku, Kobe-shi, Hyogo (56) References JP-A-60-118834 (JP, A) JP-A-59-108056 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08C 1/065 C08F 279/02 C08L 9/10

Claims (9)

(57) [Claims] (A) (a) an unsaturated acid monomer
30% by weight (b) 99-70% by weight of methacrylic acid ester monomer (c) 0-30% by weight of a monomer having an ethylenically unsaturated bond copolymerizable with the above (a) and (b) (B) 100 parts by weight (solid content) of a rubber latex having a pH of 7 or more and 0.1 to 10 parts by weight (solid content) of an acid group-containing copolymer latex prepared by polymerization. Rubber latex characterized by being enlarged to 200 nm or more. 2. (A) (a) unsaturated acid monomers 1 to 3
0% by weight (b) Methacrylic acid ester monomer 99 to 70
(C) an acid group-containing copolymer latex prepared by copolymerizing 0 to 30% by weight of a monomer having an ethylenically unsaturated bond copolymerizable with the above (a) and (b),
(B) An enlarged rubber 1 having an average particle diameter of 200 nm or more obtained by adding 0.1 to 10 parts by weight (solid content) to 100 parts by weight (solid content) of a rubber latex having a pH of 7 or more.
0 to 90 parts by weight, at least one monomer selected from an aromatic vinyl monomer, a vinyl cyanide monomer and a methacrylic acid ester monomer, or these monomers and the monomer A graft copolymer obtained by graft-polymerizing 90 to 10 parts by weight of a mixture of a monomer and a monomer having an α, β-unsaturated bond copolymerizable therewith. (A) (a) an unsaturated acid monomer
30% by weight (b) Methacrylic acid ester monomer 99-70
(C) an acid group-containing copolymer latex prepared by copolymerizing 0 to 30% by weight of a monomer having an ethylenically unsaturated bond copolymerizable with the above (a) and (b), B) An enlarged rubber 1 having an average particle diameter of 200 nm or more obtained by adding 0.1 to 10 parts by weight (solid content) to 100 parts by weight (solid content) of a rubber latex having a pH of 7 or more.
0 to 90 parts by weight, at least one monomer selected from an aromatic vinyl monomer, a vinyl cyanide monomer and a methacrylic acid ester monomer, or these monomers and the monomer Rubber-reinforced thermoplastic resin composition comprising a graft copolymer obtained by graft-polymerizing 90 to 10 parts by weight of a mixture of a monomer having an α, β-unsaturated bond and a copolymerizable monomer, and a thermoplastic resin object. 4. The rubber-reinforced thermoplastic according to claim 3, wherein the thermoplastic resin is a copolymer resin comprising an aromatic vinyl monomer, a vinyl cyanide monomer and another monomer copolymerizable therewith. Resin composition. 5. A thermoplastic resin comprising an aromatic vinyl monomer, a vinyl cyanide monomer, an N-substituted maleimide monomer and another monomer copolymerizable therewith. 4. The rubber-reinforced thermoplastic resin composition according to 3. 6. A polymer alloy comprising a copolymer resin comprising an aromatic vinyl monomer, a vinyl cyanide monomer and another monomer copolymerizable therewith, and a polyvinyl chloride resin. The rubber-reinforced thermoplastic resin composition according to claim 3. 7. The thermoplastic resin is a polymer alloy of a copolymer resin comprising an aromatic vinyl monomer, a vinyl cyanide monomer and another monomer copolymerizable therewith, and a polycarbonate resin. Item 4. A rubber-reinforced thermoplastic resin composition according to item 3. 8. The thermoplastic resin is a polymer alloy of a polyester resin and a copolymer resin comprising an aromatic vinyl monomer, a vinyl cyanide monomer and another monomer copolymerizable therewith. Item 4. A rubber-reinforced thermoplastic resin composition according to item 3. 9. A polyamide resin, wherein the thermoplastic resin comprises an aromatic vinyl monomer, a vinyl cyanide monomer, an unsaturated acid monomer and another monomer copolymerizable therewith, and a polyamide resin. The rubber-reinforced thermoplastic resin composition according to claim 3, which is a polymer alloy of the following.