JPH111522A - High rubber content graft copolymer and thermoplastic resin composition with excellent impact resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high rubber content graft copolymer having excellent impact strength, especially excellent surface impact strength. SOLUTION: Transmission electron microscope analysis-image analysis method (TEM
Method), the volume average particle diameter Mv of the rubber polymer is from 200 to
Within the range of 800 nm and the particle size distribution
The particle size at which the cumulative distribution from the smaller particle size side when plotted on the n-Rammler diagram is 15% is d
Assuming that the particle diameter at which 1,85% is obtained is d2, the formula: Sd =
(D2-d1) / 2, the ratio S of Sd and Mv defined by
Rubber polymer 30 to 9 having d / Mv of 0.25 to 0.8
In the presence of 0 parts by weight, at least one selected from the group consisting of a vinyl cyanide monomer, an aromatic vinyl monomer, and an acrylic acid or methacrylate monomer.
A high rubber content graft copolymer obtained by polymerizing 70 to 10 parts by weight of a kind monomer and 0 to 30 parts by weight of a monomer copolymerizable therewith.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a graft copolymer having a high rubber content and a thermoplastic resin composition using the same, which is excellent in impact resistance.

[0002]

2. Description of the Related Art As a rubber reinforced resin, ABS resin, A
ES resins are widely known and are used industrially in large quantities. As a method for producing an ABS resin, the following two methods are generally used. (A) A method obtained by polymerizing 75 to 95% by weight of a monomer composed of styrene and acrylonitrile in the presence of 5 to 25% by weight of a rubber polymer. (B) An ABS resin having a high rubber content obtained by polymerizing 20 to 60% by weight of a monomer composed of styrene and acrylonitrile in the presence of 40 to 80% by weight of a rubber polymer, was separately polymerized. Styrene-acrylonitrile copolymer (A
S resin) and the content of the rubber polymer in the compound is 5 to 5.
A method of obtaining an ABS resin by adjusting to 25% by weight. According to this method, various kinds of ABS resins having different qualities can be produced with high productivity by appropriately selecting the amount of the ABS resin having a high rubber content and appropriately selecting the type of the AS resin. The rubber polymer used for these rubber reinforced resins has an optimum particle size for developing impact resistance, and it is generally accepted that the value differs depending on the resin used as the matrix. . 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 sizes ranging from m) to several μm (thousands of nm) are used. Also, various types of rubbers are used.

[0003] In order to more efficiently develop the impact strength of ABS resin, a method using various rubber polymers has been proposed. Above all, there are many examples in which attention is paid to the rubber particle size distribution and improvement methods are proposed.
Combined use of medium particle size rubber and large particle size rubber of several microns disclosed in JP-A-232138, (2) JP-A-60-2
No. 3438, small particle size rubber, use of a graft polymer co-grafted to a medium particle size rubber mixture,
(3) disclosed in JP-A-62-199645;
There is a combination of a small particle size rubber and a medium particle size rubber having a low graft ratio. As a method for obtaining these rubbers, (4) a method using a plurality of types of acid latexes having different enlargement abilities is reported in JP-A-3-21650.

[0004]

However, for different thermoplastic resins, it is necessary to prepare a high rubber content graft copolymer in which the rubber polymer has a different particle size distribution, and one type of high rubber content is required. There is a problem that the impact strength of the graft copolymer is insufficient. Accordingly, the present invention provides a high rubber content graft copolymer which can obtain excellent impact strength even with different thermoplastic resins.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to achieve the above object, and as a result, have obtained a high rubber content which can obtain excellent impact strength even with different thermoplastic resins using only one kind of acid latex. The present inventors have found that a graft copolymer can be produced, and have reached the present invention.

That is, the present invention relates to a rubber polymer obtained by a transmission electron microscope analysis-image analysis method (TEM method).
When v is in the range of 200 to 800 nm and the particle size distribution is plotted on a Rosin-Rammler diagram, the particle size at which the cumulative distribution from the smaller particle size side becomes 15% is d1, 85%. When the particle diameter is d2, the ratio Sd / Mv of Sd and Mv defined by the following equation (1), Sd = (d2-d1) / 2 (1) is 0.25 to 0.25.
In the presence of 30 to 90 parts by weight of the rubber polymer (A) having a ratio of 0.8, a group consisting of a vinyl cyanide monomer, an aromatic vinyl monomer, and an acrylic acid or methacrylate monomer At least one selected monomer 70
And 10 to 10 parts by weight of a monomer copolymerizable therewith.
A high rubber content graft copolymer (D) obtained by polymerizing parts by weight (claim 1), and a rubber polymer (A) were produced by an enlargement method using an acid group-containing latex (C). 2. A high rubber content graft copolymer (D) according to claim 1, which is a rubber polymer (claim 2), a rubber polymer (A).
Is a rubber polymer produced by an enlargement method by dividing and adding an acid group-containing copolymer latex (C) to a rubber latex (B). Polymer (D): (Claim 3) wherein the acid group-containing latex (C) used in the enlargement method comprises (a) an unsaturated acid 1
To 30% by weight, (b) 99 to 40% by weight of an acrylate ester and / or a methacrylate ester, (c) a monomer having an ethylenically unsaturated bond copolymerizable with the above (a) and (b) 4. The high rubber content graft copolymer (D) according to claim 2 or 3, which is a copolymer comprising 0 to 30% by weight, and an acid group-containing latex (C) used in an enlargement method. ) Is (a) 1 to 30% by weight of an unsaturated acid, (b) 99 to 40% by weight of a methacrylate,
4. The high rubber content according to claim 2, wherein (c) a copolymer comprising 0 to 30% by weight of a monomer having an ethylenically unsaturated bond copolymerizable with (a) and (b). The graft copolymer (D) is composed of the high rubber content graft copolymer (D) according to any one of claims 1 to 5 and another thermoplastic resin composition. And a thermoplastic resin composition wherein the content of (D) in the composition is 5 to 50% by weight.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The rubber polymer (A) in the graft copolymer (D) of the present invention is obtained by a transmission electron microscope analysis-image analysis method (TEM
Method), the volume average particle diameter Mv of the rubber polymer is from 200 to
The range is 800 mm. If this Mv is too small, the effect of improving the impact resistance will be small. If the Mv is too large, the gloss of the molded product after mixing with the thermoplastic resin will be reduced, or the surface impact strength will be reduced. Preferably, the volume average particle diameter Mv is 20
Those having a thickness of 0 to 650 nm, more preferably 250 to 500 nm are used. Further, regarding the particle size distribution of the rubber polymer (A), the following formula (1) Sd = (d2-d1) / 2 (1) [However, d1: the particle size of volume frequency on the Rosin-Rammler diagram] 15% of cumulative distribution curve from small side
Particle diameter at the point where d2: Rosin-Rammler
The particle size at the point where the cumulative distribution curve from the side of the smaller particle size of the volume frequency becomes 85% on the diagram], and the ratio Sd / Mv of the numerical value Sd indicating the dispersibility and the volume average particle size Mv.
Is in the range of 0.25 to 0.80. If this value is too large, the dispersibility at the time of mixing with the thermoplastic resin decreases, and if it is too small, the versatility decreases. Preferably, Sd / Mv is 0.1.
The range is 30 to 0.70, more preferably 0.30 to 0.50.

Specific examples of the rubber polymer (A) include diene rubber polymers such as polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butadiene-acrylate rubber, hydrogenated styrene-butadiene rubber, and ethylene. Olefin rubber polymers such as propylene rubber and ethylene-propylene-diene rubber; acrylic rubber polymers such as polyacrylate rubber and ethylene-acrylate rubber; and these may be used alone or in combination of two or more. Preferably, diene rubber is used, and more preferably, polybutadiene is used.

The rubber polymer (A) may be prepared by any method as long as it satisfies the above-mentioned requirements, but those produced by an enlargement method using an acid group-containing latex (C) may be used. It is preferable from the viewpoint of impact strength. Particularly preferably, alkyl acrylate and / or alkyl methacrylate-acrylic acid system and / or
Alternatively, a rubber polymer produced by enlarging and using a methacrylic acid-based acid group-containing latex is preferable.

[0010] The rubber polymer (A) is more preferably
It is a rubber polymer produced by adding the acid group-containing latex (C) to the rubber latex (B) and enlarging it. Regarding the method of adding the acid group-containing latex (C) to the rubber latex (B), any method may be used as long as the particle size distribution of the rubber polymer (A) in the above range can be obtained. Those obtained by dividing and adding the contained latex (C) are preferable from the viewpoint of impact strength. Further, 100 parts by weight of rubber latex (B) (solid content)
(A) 1 to 30% by weight of an unsaturated acid monomer,
(B) 99 to 40% by weight of an acrylate monomer and / or a methacrylate monomer, (c) copolymerizable with the unsaturated acid monomer or the (meth) acrylate monomer 0.2 to 15 parts by weight (solid content) of an acid group-containing latex (C) prepared by polymerizing 0 to 30% by weight of a monomer having a highly ethylenically unsaturated bond is added to perform coagulation hypertrophy. The rubber polymer obtained by this is preferred.

[0011] The production of the rubber polymer (A) by the enlargement method is 4
This is achieved by dividingly adding the acid group-containing latex (C) to the rubber latex (B) having a small particle diameter such as 0 nm to 200 nm. Although the number of divisions is not specified,
When the number of divisions is large, the peak of the particle size distribution is too broad, so it is preferably 2 to 5 times, more preferably 2 to 5 times.
Three times, most preferably twice. The amount of each addition does not need to be equal. The ratio of the n-th additional amount to the (n-1) -th additional amount is preferably 1: 5 to 20: 1, more preferably 1: 2 to 10: 1, and still more preferably 1: 1 to 8:
It is one. There is no particular limitation on the time between additions, but in order to stably obtain an enlarged particle diameter, it is preferably 5 minutes or more, more preferably 10 minutes or more, still more preferably 20 minutes or more, and most preferably 30 minutes. That is all. Regarding the processing temperature for the enlargement, the acid group-containing latex (C) may be added to the rubber latex (B) at a temperature of 40 ° C. or less for the first division, and the temperature may be raised to 40 to 90 ° C. with stirring. Conversely, the rubber latex (B) can be supplied later to a container in which the acid group-containing latex (C) is previously charged. 40-90 ° C for the second and subsequent times
Add the acid group-containing latex (C) while stirring, or cool the rubber latex (B) to 40 ° C. or lower, add the acid group-containing latex (C), and stir at 40 to 90 ° C. It is sufficient to raise the temperature to. The charging method is not particularly limited, and may be added all at once or continuously.

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 (C). By adding an inorganic salt, the effect of enlargement can be improved, and an enlarged rubber having a large particle diameter 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. pH
The adjustment may be made by adding an appropriate amount of one or more of compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium hydrogen carbonate.

[0013] The concentration of the rubber latex (B) to be 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 latex (C) used for enlargement, there is a tendency for the enlarged particle size to decrease as the rubber concentration decreases. It is also possible to add an emulsifier during the enlargement treatment to change the surface coverage of the rubber polymer 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.

Examples of the unsaturated acid monomer (a) used in the acid group-containing latex (C) include acrylic acid, methacrylic acid, itaconic acid, itaconic acid monoester, maleic acid monoester and crotonic acid. These can be used alone or in combination of two or more. Preferably, it is acrylic acid, methacrylic acid, or a mixture thereof. As the (meth) acrylic acid ester (b), an ester of (meth) acrylic acid and an alcohol having a linear or side chain having 1 to 12 carbon atoms is used, and methyl acrylate, ethyl acrylate and propyl acrylate are used. Butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. These are used alone or in combination of two or more. Preferred are methacrylates. (A) above,
As the ethylenically unsaturated bond monomer (c) copolymerizable with the monomer (b), styrene, α-methylstyrene,
In molecules such as aromatic vinyl monomers such as p-methylstyrene, allyl methacrylate, polyethylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate
Monomers having two or more polymerizable functional groups are exemplified. One or a combination of two or more selected from these monomers is used.

The proportion of the unsaturated acid monomer (a) in the acid group-containing latex (C) is from 1 to 30% by weight. 1% by weight
If it is less than 30% by weight, there is practically 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, and industrial Not suitable for production.

The remaining monomer copolymerized with the unsaturated acid monomer (a) is basically (b) a (meth) acrylic acid ester monomer, and 99 to 70% by weight is used. Is done. However, it is possible to replace a part of the (meth) acrylate monomer with a monomer (c) having an ethylenically unsaturated bond copolymerizable therewith. The amount is from 0 to 30% by weight, in which case the monomer (b) is from 99 to 40% by weight. When the amount of the monomer (c) exceeds 30% by weight, the hypertrophic ability decreases. In the case of a monomer having two or more polymerizable functional groups in the molecule, 0 to 3
It should be used in the weight percent range, beyond which the hypertrophic capacity is greatly reduced.

The acid group-containing latex (C) 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, 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 contains a total of 1 monomer
0.2 to 4 parts by weight is used per 100 parts by weight. The emulsifier may be charged all at once in the early stage of the polymerization, or a part of the emulsifier may be used at the beginning and the rest may be added intermittently or continuously during the polymerization. The particle size of the acid group-containing latex (C) can be adjusted by changing the method of adding the emulsifier.

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 latex (C),
The monomer mixture comprising the above (a), (b) and (c)
The whole amount may be charged all at once in the early stage of polymerization, or a part may be initially charged and the rest may be added intermittently or continuously during the polymerization, or the whole amount may be intermittently or continuously added during the polymerization. May be added. When the polymerization is carried out by adding a monomer mixture, the composition of the monomer mixture to be added does not always need to be the same.

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

The high rubber content graft copolymer (D) according to the present invention is prepared by mixing the above rubber polymer (A) with 30 to 90%.
Parts by weight, preferably from 50 to 80 parts by weight, more preferably from 50 to 70 parts by weight, from an aromatic vinyl monomer, a vinyl cyanide monomer, and an acrylic acid or methacrylic acid ester monomer. 70 to 10 parts by weight of at least one monomer selected from the group consisting of
To 20 parts by weight, more preferably 50 to 30 parts by weight, and 0 to 30 parts by weight, preferably 0 to 20 parts by weight of a monomer copolymerizable therewith.

As the aromatic vinyl monomer, styrene,
Examples thereof include methylstyrene, chlorostyrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, p-isopropylstyrene, chlorostyrene, bromostyrene, and vinylnaphthalene. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and examples of the acrylic acid or methacrylate monomer include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, and butyl acrylate. Are used alone or in combination, but styrene and acrylonitrile are preferred. Further, other monomers copolymerizable with the above monomers include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-phenylmaleimide, N- (p-methylphenyl) Examples include N-substituted maleimides such as maleimide, unsaturated acid monomers such as acrylic acid and methacrylic acid, and glycidyl methacrylate.

The high rubber content graft copolymer (D) has an intrinsic viscosity (dl / g, 30
C, N, N'-dimethylformamide solution)
1 is preferable, and more preferably 0.15 to 0.1.
7, more preferably 0.2 to 0.5.

The graft ratio of the high rubber content graft copolymer (D) [(weight of polymer grafted on rubber polymer / weight of rubber polymer) × 100] is preferably 10 to 10
0%, more preferably in the range of 30 to 80%.

If a composition having a graft ratio within the above range is obtained, the high rubber content graft copolymer (D) can be prepared by any polymerization method, initiator, chain transfer agent or surfactant. I don't care. For example, it may be produced by a known bulk polymerization method, solution polymerization method, bulk-suspension polymerization method, suspension polymerization method, emulsion polymerization method, emulsion-suspension polymerization method, emulsion-bulk polymerization method such as bulk polymerization method. However, the emulsion polymerization method is preferred because the volume ratio between the graft portion and the rubber polymer portion is easily controlled. In addition, a known initiator such as a thermal decomposition initiator such as potassium persulfate or a redox initiator such as Fe-reducing agent-organic peroxide may be used as the initiator when polymerizing the thermoplastic resin. . Known chain transfer agents such as t-dodecyl mercaptan, n-dodecyl mercaptan, α-methylstyrene dimer, terpinolene,
You may use it in the range which can control the volume ratio of the graft part and rubbery polymer part of the high rubber content graft copolymer (D).

The thermoplastic resin composition of the present invention comprises the high rubber content graft copolymer (D) as described above and another thermoplastic resin composition, and the content of (D) in the composition is as follows. 5 to 50% by weight. The thermoplastic resin composition varies depending on the production method. For example, these are latex, suspension, slurry, solution, powder, beads,
It can be manufactured by mixing in the form of pellets or the like, or a combination thereof.

Other thermoplastic resins to be mixed with the high rubber content graft copolymer (D) include, for example, ABS resins, AES resins and AA having a rubber polymer content of less than 30% by weight.
S resin or AS resin, styrene resin such as HI polystyrene or polystyrene; olefin resin such as polyethylene or polypropylene; polyamide resin such as polyamide 6, polyamide 66, polyamide 46, or polyamide 12; polybutylene terephthalate, polyethylene Polyester resins such as terephthalate or polyarylate; polyphenylene ether resins such as polycarbonate resin, polyphenylene ether, or polyphenylene ether / styrene resin, or polyacetal, vinyl chloride resin, polysulfone, polyphenylene sulfide, polyether sulfone, ethylene-acetic acid There are vinyl copolymers, and these can be used alone or in combination of two or more.

Preferred other thermoplastic resins include the following (I) and (II) alone or (I) and (II):
In combination. (I) Obtained by polymerizing at least two monomers selected from the group consisting of an aromatic compound, a vinyl cyanide compound, a (meth) acrylate ester, and a maleimide monomer in the presence of a rubber polymer. And the rubber polymer content is 50% by weight
Less than the graft copolymer. In addition, the rubber polymer here,
Examples of the monomer include those described above. The inherent clay (dl /
g, 30 ° C., N, N′-dimethylformamide solution) is preferably in the range of 0.2 to 1, more preferably 0.3 to 0.6. (II) aromatic vinyl compounds, vinyl cyanide compounds,
(Meth) acrylic acid ester, obtained by polymerizing at least two kinds of monomers selected from the group of maleimide monomers, and having an intrinsic viscosity (dl / g, 30 ° C., N, N′-dimethylformamide) Solution) is preferably 0.25-1.
5, more preferably 0.5 to 1.2, even more preferably 0.5 to 0.8.

The above copolymer (I) includes, for example, A
Examples include BS resin, AES resin, AAS resin, MBS resin and the like, and among them, ABS resin and AES resin are preferable.

The above copolymer (II) includes the following copolymers. (A) A copolymer of an aromatic vinyl compound and a vinyl cyanide compound. The preferred composition ratio is 50 to 99% by weight of the former aromatic vinyl compound monomer and 1 to 50% by weight of the latter vinyl cyanide compound monomer. (B) A copolymer of an aromatic vinyl compound and a (meth) acrylate. (C) A copolymer comprising an aromatic vinyl compound, a maleimide-based monomer and, if necessary, a vinyl cyanide compound and / or a (meth) acrylate. In addition, a post-imide type copolymer obtained by imidizing an obtained copolymer using an unsaturated acid anhydride monomer instead of the maleimide-based monomer is also included herein. The above aromatic vinyl compound, vinyl cyanide compound,
(Meth) acrylic acid ester and maleimide monomer are the same as those described above.

The physical properties of the thermoplastic resin composition of the present invention comprising the high rubber content graft copolymer (D) and another thermoplastic resin are as follows. As well as the mixing ratio thereof. Therefore, the mixing ratio may be selected according to the desired physical properties, but in order to suitably achieve the object of the present invention, the content of (D) in the composition after mixing is 5 to 50% by weight, Rubber polymer (A) in composition
Is mixed to be 2 to 35% by weight. When the ratio of the rubber polymer (A) is 2% by weight or less, sufficient impact strength cannot be obtained. On the other hand, if it exceeds 35% by weight, the molded product becomes soft, which is not preferable.

Mixing of the high rubber content graft copolymer (D) with another thermoplastic resin may be performed by a method known per se. For example, the high-rubber content graft copolymer (D) and the latex obtained by emulsion polymerization of each of the other thermoplastic resin compositions may be mixed, salt-broken, solidified and dried, and then used. When recovering the polymer powder of the intended thermoplastic resin from the graft copolymer latex after polymerization, a usual method, for example, calcium chloride, magnesium chloride, salts of alkaline earth metals such as magnesium sulfate, sodium chloride, The latex can be coagulated by adding an alkali metal salt such as sodium sulfate, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, and acetic acid, and an organic acid, followed by dehydration and drying. Also, a spray drying method can be used. Further, the powder or pellets of the high rubber content graft copolymer (D) and the other thermoplastic resin composition may be kneaded. For example, it is manufactured by kneading a high rubber content graft copolymer (D), a thermoplastic resin, and, if necessary, various additives using an extruder, a roll, a Banbury mixer, a kneader, or the like. A preferable method is a method using an extruder, and examples of the extruder include a single screw extruder and a twin screw extruder.

When kneading various components using the above-described kneading method, all components may be kneaded at once.
Some components may be kneaded first, and the remaining components may be added or kneaded collectively or separately. Various additives can be added to the high rubber content graft copolymer (D) as needed. Also, when kneading is required,
The kneading can be performed by the method described above. Examples of various additives include known colorants, pigments, lubricants, weathering agents, antistatic agents, antioxidants, flame retardants, heat aging inhibitors, plasticizers, antibacterial and antifungal agents, and the like. Thermoplastic resin composition of the present invention, injection molding, sheet extrusion, vacuum molding,
Various molded products can be molded by profile extrusion, injection press, foam molding, blow molding, or hollow molding.

The thermoplastic resin composition of the present invention may be prepared by combining one or more antioxidants, heat stabilizers, UV absorbers, pigments, antistatic agents, lubricants and the like, if necessary, with one another. Can be used as appropriate. In particular, phenolic, sulfur-based antioxidants, phosphite-based, hindered amine-based stabilizers, benzophenone-based, benzotriazole-based ultraviolet absorbers used in styrene-based resins, and organopolysiloxanes, aliphatic hydrocarbons, Esters of higher fatty acids and higher alcohols, amides or bisamides of higher fatty acids and modified products thereof, oligoamides, internal and external lubricants such as metal salts of higher fatty acids, etc. Can be used for

Examples of the phenol-based stabilizer include 1,1,
3-tris [2-methyl-4-hydroxy-5-t-butylphenyl-butane, n-octadecyl-3-
(3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate], tetrakis [methylene-3
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] methane, triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-t-butyl- 4-
Hydroxyphenyl) propionate]), 2,6-di-t-butyl-4-methylphenol, 2,2′-methylenebis (4-methyl-6-t-butylphenol),
2,2'-methylenebis (4-ethyl-6-tert-butylphenol), tris- (3,5-di-tert-butyl-4)
-Hydroxybenzyl) -isocyanurate) and the like.

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-t-butylphenyl] sulfide and the like.

Examples of the phosphite-based stabilizer include stearylphenyl phosphite, tris (mono, di, nonylphenyl) phosphite, distearylpentaerythritol diphosphite, and tris (2,4-di-t-butylphenyl). Phosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) 4,4-
Diphenylenephosphonite, bis (2,6-di-t-
Butyl-4-methylphenyl) pentaerythritol diphosphite.

Hindered amine stabilizers include dimethyl-1- (2-hydroxyethyl) -4-succinate.
Hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-
Diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-
Tetramethyl-4-piperidyl) imino]], 2-
(3,5-di-t-butyl-4-hydroxybenzyl)
Bis-n-butylmalonate (1,2,2,6,6-
Pentamethyl-4-piperidyl) and the like. These stabilizers can be used alone or in combination of two or more.

Benzophenone-based and benzotriazole-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 2- (5-methyl). -2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-
Examples thereof include 2-hydroxyphenyl) -5-chlorobenzotriazole and 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole.

In the lubricant, examples of the organopolysiloxane include polydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane.
Examples of the aliphatic hydrocarbon include synthetic paraffin, polyethylene wax, and polypropylene wax. Examples of esters of higher fatty acids and higher alcohols include esters of montanic acid, stearyl stearate, behenyl behenate and the like. Amides of higher fatty acids, bisamides and modified products thereof are synthesized by a dehydration reaction from higher fatty acids such as stearic acid amide, ethylenebisstearic acid amide, stearic acid, dicarboxylic acids such as succinic acid, and diamines such as ethylenediamine. Compounds having a melting point higher than that of the bisamide can be exemplified. Examples of metal salts of higher fatty acids 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 in combination of two or more.

The thermoplastic resin composition of the present invention may contain a halogen-based or phosphite-based flame retardant, an antimony compound such as antimony trioxide, a silicone compound such as polydimethylsiloxane,
An aluminum compound such as alumina may be used in combination.

Further, in order to improve mechanical properties such as elastic modulus and heat resistance, reinforcing fibers such as glass fiber and carbon fiber, and fillers such as mica, talc, clay and glass beads can be used. .

[0043]

EXAMPLES Hereinafter, the present invention will be described with reference to specific examples, but these examples do not limit the present invention. In the following description, "parts" indicates parts by weight and "%" indicates% by weight. In the following description, abbreviations represent the following substances, respectively. BMA: butyl methacrylate, BA: butyl acrylate, St: styrene, AN: acrylonitrile, MAA: methacrylic acid, tDM: tertiary dodecyl mercaptan, CHP: cumene hydroperoxide, EDTA: disodium ethylenediaminetetraacetate,

Prior to the description of the examples, composition analysis,
The method for evaluating the characteristics of the resin composition is described below. [Measurement of Reduced Viscosity] Pellets of the resin composition were dissolved in methyl ethyl ketone and centrifuged to obtain a methyl ethyl ketone soluble portion of the resin composition. Take out this soluble matter,
The reduced viscosity at 30 ° C. was measured as a 0.3 g / dl N, N-dimethylformamide solution. [Volume average particle diameter (Mv) of rubber polymer, volume ratio S
d] The volume average particle diameter Mv of the rubber polymer (A) and the rubber latex (B) in the resin composition was measured by the method described on the board. Dissolve the resin composition pellets in acetone,
Soluble components other than the graft copolymer were removed by centrifugation to obtain a graft copolymer portion. The graft copolymer was dispersed in acetone, a small amount of this dispersion was added to an epoxy resin, and the mixture was thoroughly mixed and dispersed. Thereafter, the epoxy resin in which the graft copolymer was dispersed was cured by heating to obtain a measurement sample. The sample is stained with a known method (osminium tetroxide, and the cut piece is observed with a microtome under a transmission electron microscope: the rubber polymer part is black and the graft part is white)
So, I took a photo. The images of the 20,000 × and 100,000 × observations were subjected to image analysis as follows using LUZEX IID manufactured by NIRECO Corporation. From the image analysis of the entire rubber polymer, the average particle size Mv was determined. In addition, d2 and d1 were obtained from the plot on the Rosin-Rammler particle size diagram for the cumulative distribution at that time, and Sd was obtained by the following equation (1). Sd = (d2 / d1) / 2 (1) [Composition of graft portion] Regarding the composition of the graft portion of the high rubber content graft copolymer (D), the methyl ethyl ketone insoluble content of pellets of the resin composition was determined by IR. An analysis was performed to determine the composition. [Conversion rate during polymerization] The conversion rate during polymerization was calculated from the solid content concentration. [Characteristics of resin composition] Impact resistance was 100 mm x 150
The 2 mm thick flat plate test piece was evaluated at a falling weight strength of 23 ° C. The evaluation value was represented by a half breaking height × a falling weight load = half breaking energy (kgfm). IZOD impact strength is AS
A notched 1/4 "thick test specimen was evaluated at 23 ° C. based on the TM D-256 standard. In each case, the larger the numerical value, the better.

(1) Production of Rubber Latex (B) The following substances were charged into a 100 L polymerization machine. Pure water 280 parts Potassium persulfate 0.2 parts tDM 0.2 parts Next, after the air in the polymerization machine was removed with a vacuum pump, 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, the conversion was 96%, and the volume average particle diameter (Mv) was 74 [nm].

(2) Production of Latex Containing Acid Group (C) 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 formaldehyde sulfoxylate 0.3 parts Sodium dioctyl sulfosuccinate 0.6 parts (C-1) 0.4 parts (C-2) 0.5 parts (C-3) 0.1 parts (C -4) The temperature of the reactor was increased to 70 ° C under a nitrogen stream while stirring. After reaching 70 ° C., the monomers shown in Table 1 were continuously and uniformly dropped over 5 hours. After completion of the dropwise addition, stirring was continued at 70 ° C. for 1 hour to terminate the polymerization, thereby obtaining four types of acid group-containing latexes (C-1 to C-4).

[0047]

[Table 1]

(3) Production of rubber polymer (A) The rubber latex (B) obtained in (1) above was mixed with the acid group-containing latex (C) obtained in (2) at 60 ° C.
Then, 3 parts were added to 100 parts of the rubber latex (B) while stirring and divided as shown in Table 2 to increase the particle diameter, and 10 kinds of rubber polymers (A) shown in Table 2 were added. -1
To A-10).

[0049]

[Table 2]

(4) Production of Graft Copolymer (D) 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 Rubber polymer (A) (solid content) Predetermined amount shown in Table 3 Sodium formaldehyde sulfoxylate 0.3 parts EDTA 0.01 parts Ferrous sulfate 0.0025 parts Nitrogen stream while stirring the reactor The temperature was raised to 60 ° C. below. After reaching 60 ° C., the monomer mixture in Table 3 was continuously added dropwise over 4 hours. After completion of the dropwise addition, stirring was continued at 60 ° C. for 1 hour to terminate the polymerization.

[0051]

[Table 3]

0.5 parts of a phenolic stabilizer was added to the produced latex, and 2 parts of calcium chloride was added to coagulate. The solidified slurry was dehydrated and dried to obtain 13 kinds of resin powders (D-1 to D-13).

(5) Copolymer (II) The following three copolymers were used. II-I: AN 25%, St 75% copolymer, reduced viscosity 0.74 II-2: AN 29%, St 71% copolymer, reduced viscosity 0.82 II-3: AN 31%, St 69% copolymer, reduced Viscosity: 0.67 (6) Production of thermoplastic resin composition After mixing the graft copolymer (D) produced in (4) above and the copolymer (II) in (5) in the ratio shown in Table 4 Then, 1 part of ethylenebisstearylamide was blended and uniformly blended with a 20-liter blender manufactured by Tabata Co., Ltd.
Further, a single screw extruder of 40 m / m manufactured by Tabata Co., Ltd.
Examples 1 to 11 were melt-kneaded at a temperature of 40 to 270 ° C.
And pellets of the thermoplastic resin compositions of Comparative Examples 1 to 4 were produced.

[0054]

[Table 4]

From the results shown in Table 4, it is clear that the thermoplastic resin compositions of the present invention represented by Examples 1 to 11 have excellent impact strength, particularly excellent surface impact strength.

[0056]

As described above, the thermoplastic resin composition obtained from the high rubber content graft polymer of the present invention has excellent impact strength, particularly excellent surface impact strength.

Claims (6)

[Claims] 1. Transmission electron microscope analysis-image analysis method (TEM
Method), the volume average particle diameter Mv of the rubber polymer is from 200 to
Within the range of 800 nm and the particle size distribution
The particle size at which the cumulative distribution from the smaller particle size side when plotted on the n-Rammler diagram is 15% is d
Assuming that the particle diameter at which 1,85% becomes d2 is d2, the ratio Sd / Mv of Sd to Mv defined by the following equation (1), Sd = (d2-d1) / 2 (1) is 0. 25-
In the presence of 30 to 90 parts by weight of the rubber polymer (A) having a ratio of 0.8, a group consisting of a vinyl cyanide monomer, an aromatic vinyl monomer, and an acrylic acid or methacrylate monomer At least one selected monomer 70
And 10 to 10 parts by weight of a monomer copolymerizable therewith.
High rubber content graft copolymer (D) obtained by polymerizing parts by weight. 2. The high rubber content graft copolymer (D) according to claim 1, wherein the rubber polymer (A) is a rubber polymer produced by an enlargement method using an acid group-containing latex (C). 3. The rubber polymer (A) is characterized in that it is a rubber polymer produced by an enlargement method by dividing and adding an acid group-containing copolymer latex (C) to a rubber latex (B). The high rubber content graft copolymer (D) according to claim 1. 4. An acid group-containing latex (C) used in the enlargement method comprises (a) 1 to 30% by weight of an unsaturated acid, (b) 99 to 40% by weight of an acrylate and / or methacrylate, The high rubber content graft according to claim 2 or 3, wherein c) is a copolymer comprising 0 to 30% by weight of a monomer having an ethylenically unsaturated bond copolymerizable with (a) and (b). Copolymer (D). 5. An acid group-containing latex (C) used in the enlargement method comprises (a) 1 to 30% by weight of an unsaturated acid, (b) 99 to 40% by weight of a methacrylic acid ester, and (c) the (a). The high rubber content graft copolymer (D) according to claim 2 or 3, which is a copolymer comprising 0 to 30% by weight of a monomer having an ethylenic unsaturated bond copolymerizable with (b). . 6. The high-rubber content graft copolymer (D) according to claim 1 and another thermoplastic resin composition, and the content of (D) in the composition. Is 5-5
0% by weight of a thermoplastic resin composition.