JP3499710B2 - Graft copolymer and rubber-modified thermoplastic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a rubber-modified thermoplastic resin composition which, when blended with a styrene resin and its alloy, is excellent in impact resistance, surface property of a molded article, and excellent in heat resistance, rigidity and processability. And a graft copolymer capable of providing

[0002]

BACKGROUND OF THE INVENTION Rubber-modified styrenic resins and alloys of rubber-modified styrenic resins are excellent in heat resistance, impact resistance, rigidity, surface properties and molding processability. It is widely used not only for automobiles but also for interior materials such as automobile pillars and instrument panels, housings for home electric appliances such as jar rice cookers and microwave ovens, and housings for OA equipment such as telephones, computer displays and facsimiles.

In the rubber-modified styrene resin, the control of the particle size distribution of the rubber and the uniform dispersion of the graft copolymer (copolymer in which the monomer is grafted on the rubber polymer) in the matrix are the mechanical properties and surface properties of the molded article. It is essential for the expression of various physical properties such as. Particularly, impact resistance and surface appearance are greatly affected by the graft copolymer.

Recently, in the case of rubber-modified styrene resin,
From the viewpoints of productivity, convenience of controlling various grades, impact resistance, surface property of molded products, etc., a method for producing a graft copolymer by using a rubber polymer produced by a coagulation and enlargement method has been proposed. . The cohesive enlargement method is a method of coagulating and enlarging small particle rubber into large particle rubber by using a coagulating and expanding agent such as hydrochloric acid, sulfuric acid, acetic acid, sodium carbonate, and acid group-containing (meth) acrylic polymer. Rubber having various particle size distributions can be produced from small particle rubber. However, it is not easy to control the particle size by a flocculant, and even if the desired particle size is obtained during expansion, the particle size may change during graft polymerization, or the latex viscosity may increase abnormally during expansion or graft polymerization, There were many cases where a large amount of agglomerates were generated and latex was coagulated. Especially when an acid group-containing (meth) acrylic polymer is used, the mechanical stability of the enlarged latex is improved, but the above-mentioned problems still remain.

Further, when a rubber-modified styrene-based resin and a rubber-modified styrene-based resin alloy are produced using the obtained graft copolymer, the characteristics of the molded product, particularly impact resistance and surface appearance are expected as expected. There was a problem not to do.

[0006]

Means for Solving the Problems The present inventors have found that when a cohesive thickener, especially an acid group-containing (meth) acrylic polymer is used, a (meth) acrylic water-soluble polymer is produced, Thought to affect the stability of the latex,
As a result of intensive studies from various fields, they have found that the above problems can be solved by using a special emulsifier, and have reached the present invention.

That is, the present invention provides (1) a diene rubber polymer and / or an acrylic rubber polymer (A) having a volume average particle diameter of 100 to 2000 nm, which is produced by a coagulation and hypertrophy method, and the following formula (1): To vinyl cyanide compound (x), alkyl methacrylate (y), aromatic vinyl compound (z), and alkyl acrylate copolymerizable therewith, maleimide compound, and (meth) acrylic acid And a graft ratio ((graft part (Ag) / rubber polymer (A) × 100) of 10 to 80, which is composed of a graft part (Ag) composed of at least one monomer (n) selected from the group consisting of % By weight,
Further, in all the emulsifiers, an emulsifier containing 5% by weight or more of an emulsifier having a molecular occupied area of 35 A ² or less is used in an amount of 0.05 to 7 parts by weight based on 100 parts by weight of the graft copolymer (I),
The present invention relates to a graft copolymer obtained by emulsion polymerization.

45 ≧ x + (y / 4) ≧ 5 (1) x + y + z + n = 100 (2) 45 ≧ x ≧ 0 (3) 90 ≧ y ≧ 0 (4) 95 ≧ z ≧ 10 (5) 30 ≧ n ≧ 0 (6) In formulas (1) to (6), x, y, z, and n represent weight% of each component.

The present invention further provides (2) a rubber polymer (A).
Is 5 to 50% by weight of at least one unsaturated acid (c) of acrylic acid, methacrylic acid, itaconic acid, and crotonic acid, and at least one (meth) alkyl having an alkyl group with 1 to 12 carbon atoms. Acrylate (d) 50 to 95% by weight, and monomers 0 to 4 copolymerizable with (c) and (d)
The graft copolymer according to the above item (1), which is a rubber polymer produced by a coagulation and enlargement method using an acid group-containing latex (S) prepared by polymerizing 0%.

The present invention further relates to (3) a rubber-modified thermoplastic resin composition comprising the graft copolymer (I) described in the above (1) or (2) and a styrene resin (II).

The present invention further provides (4) a rubber-modified thermoplastic resin comprising the graft copolymer (I) according to the above (1) or (2), a styrene resin (II) and a vinyl chloride resin (III). It relates to a resin composition.

The present invention further provides (5) a rubber-modified thermoplastic resin composition comprising the graft copolymer (I) according to the above (1) or (2), a styrene resin (II) and a polycarbonate resin (IV). Regarding things.

The present invention further provides (6) a rubber-modified thermoplastic resin composition comprising the graft copolymer (I) according to the above (1) or (2), a styrene resin (II) and a polyamide resin (V). Regarding things.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of the diene rubber polymer and the acrylic rubber polymer (A) used in the production of the graft copolymer of the present invention include polybutadiene rubber, styrene-butadiene rubber and acrylonitrile-butadiene. Rubber, butadiene- (meth) acrylic acid ester rubber, styrene-acrylonitrile-butadiene rubber, poly (meth) acrylic acid ester rubber, (meth) acrylic acid ester-styrene-acrylonitrile rubber, (meth) acrylic acid ester-styrene-acrylonitrile -Butadiene rubber and the like. These rubber polymers alone,
Alternatively, two or more kinds can be used in combination. The volume average particle size of the diene rubber polymer and the acrylic rubber polymer (A) is
From the viewpoint of impact strength and surface property, it is in the range of 100 to 2000 nm, preferably 150 to 1500 nm, and more preferably 180 to 1200 nm. If the volume average particle size exceeds the above range, the gloss of the surface of the molded article tends to decrease, and the impact strength tends not to be sufficiently exhibited, while if it is less than the above range, the impact strength tends to decrease.

The rubber polymer (A) includes rubber latex, acrylic acid, methacrylic acid, itaconic acid,
Unsaturated acid (c) 5 of at least one of crotonic acid
50% by weight, at least one (meth) alkyl acrylate (d) having 1 to 12 carbon atoms in the alkyl group (50)
95% by weight, and a rubber polymer produced by a coagulation and enlargement method using an acid group-containing latex (S) prepared by polymerizing 0 to 40% of a monomer copolymerizable with (c) and (d). Is preferable from the viewpoint of impact strength. In particular, the rubber polymer (A) contains 5 to 25% by weight of at least one unsaturated acid (c) of acrylic acid, methacrylic acid, itaconic acid and crotonic acid, and the alkyl group has 1 to 12 carbon atoms.
At least one alkyl acrylate (d) 5-3
0% by weight, 80 to 20% by weight of at least one alkyl methacrylate (e) having 1 to 12 carbon atoms in the alkyl group, (c), (d), an aromatic vinyl monomer copolymerizable with (e) Body and / or a monomer having two or more polymerizable functional groups in the molecule, and / or an acid group-containing latex (S) prepared by polymerizing 0 to 40% of a vinyl cyanide compound. The rubber polymer produced by the coagulation and enlargement method used is preferable from the viewpoint of impact strength. Examples of the alkyl acrylate include alkyl acrylates having an alkyl group having 1 to 12 carbon atoms such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, and dodecyl acrylate. Examples of the alkyl methacrylate include alkyl methacrylate having an alkyl group having 1 to 12 carbon atoms such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate and dodecyl methacrylate. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, p-hydroxystyrene, p-chloromethylstyrene and the like. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. The amount of the acid group-containing latex used is 0.1 to 15 parts by weight (solid content) with respect to 100 parts by weight (solid content) of rubber latex,
The range of preferably 0.3 to 10 parts by weight (solid content), particularly preferably 0.5 to 8 parts by weight (solid content) is impact strength,
It is preferable in terms of manufacturing stability.

The graft copolymer (I) of the present invention has a graft ratio ((graft part (Ag) / diene rubber polymer (A)) × 100) in terms of impact resistance, surface property and processability. It is in the range of 10 to 80% by weight, preferably 15 to 75
%, More preferably 20 to 60% by weight. If the graft ratio is less than the above range, the impact resistance tends to decrease, while if it exceeds the above range, the workability tends to decrease.

The graft part (Ag) in the graft copolymer (I) is a vinyl cyanide compound (x), an alkyl methacrylate (y), an aromatic vinyl compound having a composition represented by the following formulas (1) to (6). (Z), and an alkyl acrylate copolymerizable therewith, a maleimide compound,
It is composed of at least one monomer (n) selected from the group consisting of (meth) acrylic acid.

45 ≧ x + (y / 4) ≧ 5 (1) x + y + z + n = 100 (2) 45 ≧ x ≧ 0 (3) 90 ≧ y ≧ 0 (4) 95 ≧ z ≧ 10 (5) 30 ≧ n ≧ 0 (6) In the formulas (1) to (6), x, y, z, and n represent the weight% of each component (hereinafter the same).

Preferably, the graft portion (Ag) is a vinyl cyanide compound (x), an alkyl methacrylate (y), an aromatic vinyl compound (z), and a vinyl cyanide compound (y) having a composition represented by the following formulas (7) to (12): At least one monomer (n) selected from the group consisting of an alkyl acrylate copolymerizable with these, a maleimide compound, and (meth) acrylic acid.
Composed of.

40 ≧ x + (y / 4) ≧ 10 (7) x + y + z + n = 100 (8) 40 ≧ x ≧ 0 (9) 90 ≧ y ≧ 0 (10) 90 ≧ z ≧ 10 (11) 20 ≧ n ≧ 0 (12) Particularly preferably, the graft part (Ag) has the following (13)
To vinyl cyanide compound (x), alkyl methacrylate (y), aromatic vinyl compound (z), and alkyl acrylate copolymerizable therewith, maleimide compound, and methacrylic acid. It is composed of at least one monomer (n) selected from

35 ≧ x + (y / 4) ≧ 15 (13) x + y + z + n = 100 (14) 35 ≧ x ≧ 0 (15) 85 ≧ y ≧ 0 (16) 85 ≧ z ≧ 10 (17) 10 ≧ n ≧ 0 (18) If the vinyl cyanide compound (x) and the alkyl methacrylate (y) exceed the specified amount in the above formula, the processability decreases, and if the amount is less than the specified amount in the above formula, the impact resistance decreases. If the amount of the aromatic vinyl compound (z) exceeds the specified amount in the above formula, impact resistance will decrease, and if it falls below the specified amount in the above formula, workability will decrease. If the amount of the alkyl acrylate, maleimide compound, or (meth) acrylic acid exceeds the specified amounts in the above formula, the impact resistance will decrease.

Examples of the vinyl cyanide compound in the graft portion (Ag) include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene and bromostyrene. , Vinylnaphthalene and the like. Examples of the alkyl methacrylate include alkyl methacrylate having an alkyl group having 1 to 18 carbon atoms such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate. Examples of the alkyl acrylate include alkyl acrylates having an alkyl group having 1 to 18 carbon atoms such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and stearyl acrylate, and maleimide compounds include maleimide, butyl maleimide, and phenyl. Examples thereof include maleimide and cyclohexylmaleimide, and examples of (meth) acrylic acid include methacrylic acid and acrylic acid. Each of these may be used alone or in combination of two or more.

From the industrial viewpoint, acrylonitrile is used as a vinyl cyanide compound, styrene is used as an aromatic vinyl compound, methyl methacrylate is used as an alkyl methacrylate, butyl acrylate is used as an alkyl acrylate, phenylmaleimide is used as a maleimide compound, and (meth) acrylic acid is used. Methacrylic acid is preferred as

As the emulsifier used in the graft polymer of the present invention, an emulsifier having a molecular occupied area of 35 Å or less is an essential component. As such an essential emulsifier, specifically,
Examples thereof include the dicarboxylic acid salt of the formula (1) and the disulfonic acid salt of the formula (2).

[0025]

[Chemical 1]

[0026]

[Chemical 2]

In the formula (1), R ¹ has 8 to 22 carbon atoms.
Represents an alkyl group or an alkenyl group. In Formula (2), R ² represents an alkyl group or an alkenyl group having 8 to 22 carbon atoms, and Ph represents a phenyl group. In formula (1) and formula (2), M represents Na or K.

Examples of the dicarboxylic acid salt represented by the above formula (1) include potassium octenyl succinate, potassium nonenyl succinate, potassium decenyl succinate, potassium dodecenyl succinate, potassium tetradecenyl succinate, potassium hexadecenyl succinate, and octade. Potassium cenylsuccinate, Potassium eicosenylsuccinate, Potassium doeicosenylsuccinate, Sodium dodecenylsuccinate, Sodium tetradecenylsuccinate, Sodium hexadecenylsuccinate, Sodium octadecenylsuccinate, Dodecyl Sodium succinate, sodium tetradecyl succinate, sodium hexadecyl succinate, sodium octadecyl succinate, potassium dodecyl succinate, potassium tetradecyl succinate, potassium hexadecyl succinate, Such as potassium Kutadeshirukohaku acid, and the like.

Examples of the disulfonate represented by the above formula (2) include sodium octyl diphenyl ether disulfonate, sodium nonyl diphenyl ether disulfonate, sodium decyl diphenyl ether disulfonate, sodium dodecyl diphenyl ether disulfonate, sodium tetradecyl diphenyl ether disulfonate, and hexadecyl. Sodium diphenyl ether disulfonate, Sodium octadecyl diphenyl ether disulfonate, Sodium eicosyl diphenyl ether disulfonate, Sodium doecosyl diphenyl ether disulfonate, Sodium dodecenyl diphenyl ether disulfonate, Sodium tetradecenyl diphenyl ether disulfonate, Hexadecenyl diphenyl ether di Sodium ruphonate, sodium octadecenyl diphenyl ether disulfonate, potassium dodecyl diphenyl ether disulfonate, potassium tetradecyl diphenyl ether disulfonate, potassium hexadecyl diphenyl ether disulfonate, potassium octadecyl diphenyl ether disulfonate, potassium dodecenyl diphenyl ether disulfonate, tetrade Examples thereof include potassium cenyldiphenyl ether disulfonate, potassium hexadecenyl diphenyl ether disulfonate, potassium octadecenyl diphenyl ether disulfonate, and the like.

These dicarboxylic acid salts and disulfonic acid salts can be used alone or in combination of two or more kinds.

The emulsifier (E) essential to the present invention has a molecular occupied area of 35Å ² or less from the viewpoint of particle size control and impact resistance.
Preferably 32 Å ² or less, more preferably 30 Å ² or less, and from the viewpoint of expressing the effect of the emulsifier (E),
The amount of the emulsifier is 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and the total amount of the emulsifier is 0.05 to 7 parts by weight based on 100 parts by weight of the graft copolymer (I). , Preferably 0.1 to 6 parts by weight, more preferably 0.15 to 5 parts by weight.
If the total amount of the emulsifier is less than the above range relative to 100 parts by weight of the graft copolymer (A), the improving effect of the present invention tends not to be exerted, while if it exceeds the above range, mechanical properties such as impact resistance are largely deteriorated. The molecular occupied area in the present invention means the area occupied by one molecule of the emulsifier molecule when the emulsifier is in a saturated adsorption state in polystyrene latex at a temperature of 25 ° C.

Known emulsifiers other than the emulsifier (E), emulsification aids, for example, metal rosin acid salts such as potassium rosinate and sodium rosinate, higher fatty acid metal salts such as sodium palmitate and sodium oleate, dodecylbenzene sulfone. Sodium sulfonate such as sodium acid salt, sodium palmityl sulfonate and sodium dioctyl sulfosuccinate can be used in combination within the above range.

An emulsion polymerization method is essential for obtaining the graft copolymer (I) of the present invention in which the rubber particle size and the graft ratio are controlled. It is difficult to maintain a high grafting efficiency and control the grafting ratio to a composition within the scope of the present invention by a polymerization method such as bulk, suspension and solution.

As the initiator for polymerizing the graft copolymer (I), known initiators such as a thermal decomposition initiator such as potassium persulfate and a redox initiator such as Fe-based reducing agent / organic peroxide are used. it can. As a chain transfer agent, tert
-Dodecyl mercaptan, n-dodecyl mercaptan,
Known chain transfer agents such as α-methylstyrene dimer and terpinolene can be used within the range in which the graft ratio of the present invention can be controlled.

In the polymerization, the monomer mixture to be graft-polymerized is added all at once or continuously to the latex of the rubber polymer (A), and the polymerization is carried out under radical generation.

The polymer powder can be recovered from the latex of the graft polymer (I) by a usual method, for example, calcium chloride, magnesium chloride, magnesium sulfate, an alkaline earth metal salt such as magnesium chloride, sodium chloride,
It can be carried out by a method in which an alkali metal salt such as sodium sulfate, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid and the like and an organic acid are added to coagulate the latex, followed by heat treatment and dehydration drying.
Also, a spray drying method can be used. At that time, in order to control deterioration of the polymer powder, fluidity, storability and the like, or to exert its characteristics, desired stabilizers, lubricants and the like may be added. Examples of the stabilizer include known hindered phenol-based stabilizers, sulfur-based stabilizers, phosphorus-based stabilizers and the like which are usually used for rubber-modified styrene-based resins and vinyl chloride-based resins. Examples of the lubricant include higher fatty acid bisamide, higher fatty acid amide, ester of higher fatty acid and higher alcohol, ester of higher fatty acid and higher alcohol, higher fatty acid metal salt, higher fatty acid, higher alcohol, olefin wax and the like. These stabilizers and lubricants may be added as they are, but it is preferable to mix them with the latex of the graft copolymer in a finely dispersed form, for example, in an emulsified or slurry state, in order to exert the effect more effectively. .

The graft copolymer of the present invention is used by blending it with a styrene resin or its alloy.

Examples of the styrene resin (II) which can be mixed with the graft copolymer (I) include acrylonitrile-styrene copolymer, acrylonitrile-styrene-α-methylstyrene copolymer and acrylonitrile-α-methylstyrene copolymer. , Acrylonitrile-styrene-phenylmaleimide copolymer, acrylonitrile-styrene-α
-Methylstyrene-phenylmaleimide copolymer, acrylonitrile-styrene-α-methylstyrene-phenylmaleimide copolymer, styrene-phenylmaleimide copolymer, polystyrene, styrene-phenylmaleimide copolymer, styrene-maleic anhydride copolymerization Known styrene copolymers such as a combination and a styrene-methyl methacrylate copolymer can be used. Alloys that can be mixed with the graft copolymer (I) include polycarbonate resin (IV) /
Acrylonitrile-styrene copolymer alloy, polycarbonate resin (IV) / acrylonitrile-α-methylstyrene-styrene copolymer alloy, polyamide resin (V) / acrylonitrile-styrene copolymer alloy,
Polyamide resin (IV) / acrylonitrile-α-methylstyrene-styrene copolymer alloy, vinyl chloride resin (III) / acrylonitrile-styrene copolymer alloy, vinyl chloride resin (III) / acrylonitrile-α-
Examples thereof include alloys of styrene resins such as a methylstyrene-styrene copolymer alloy.

Examples of the vinyl chloride resin (III) include polyvinyl chloride or a copolymer of vinyl chloride and 20% by weight or less of an α-olefin monomer such as ethylene or vinyl acetate. Examples of the polycarbonate resin (IV) include aromatic polycarbonate and aromatic-aliphatic polycarbonate, but in terms of heat resistance and impact resistance,
A bisphenol A aromatic polycarbonate is preferred. As polyamide resin (V), nylon 6, nylon 66, nylon 610, nylon 11, nylon 1
2, nylon 9 and the like can be mentioned, but nylon 6, nylon 66 and nylon 12 are preferable from the viewpoint of impact resistance and heat resistance.

In the case of a composition comprising a graft copolymer (I) / styrene-based resin (II), from the viewpoint of impact resistance and processability, the blending ratio of each component to the total amount of both: graft copolymer (I) / styrene resin (II) is 5 to 85% by weight / 95 to 15% by weight, preferably 10 to 75% by weight
/ 90 to 25% by weight, particularly preferably 15 to 65% by weight
/ 85-35% by weight.

In the case of a composition comprising a graft copolymer (I) / styrene resin (II) / vinyl chloride resin (III) or polycarbonate resin (IV) or polyamide resin (V), impact resistance and processability From the viewpoint of, the blending ratio of each component to the total amount of these: graft copolymer (I)
/ Styrene-based resin (II) / Vinyl chloride resin (III) or polycarbonate resin (IV) or polyamide resin (V) is 5 to 30% by weight / 85 to 5% by weight / 10 to 9
0% by weight, preferably 5-25% by weight / 75-10% by weight / 20-85% by weight, particularly preferably 7-23% by weight
/ 63 to 13% by weight / 30 to 80% by weight.

[0042]

EXAMPLES The present invention will now be described in more detail by way of examples, but these are merely examples and the present invention is not limited to these. Unless otherwise specified, "part" means part by weight and "%" means% by weight.

The abbreviations of the substances and emulsifiers (E) used in the examples and comparative examples are as follows.

BA: butyl acrylate BMA: butyl methacrylate St: styrene MAA: methacrylic acid MMA: methyl methacrylate tDM: tert-dodecyl mercaptan CHP: cumene hydroperoxide AN: acrylonitrile PMI: N-phenylmaleimide αMSt: α-methylstyrene DAP : Diallyl phthalate emulsifier (E-1): a mixture of a compound in which R ^{2 of the} formula (1) is an octadecenyl group and M is potassium and a compound in which R ^{2 of the} formula (I) is a hexadecenyl group and M is potassium. , Molecular occupied area = 23Å ² emulsifier (E-2): R ^{2 of the} formula (1) is a dodecenyl group,
Compound in which M is sodium, molecular occupied area = 29Å ² emulsifier (E-3): R ^{2 in the} formula (2) is a dodecyl group, and M
Is a sodium, a molecular occupied area = 28Å ² emulsifier (E-4): sodium rosinate, a molecular occupied area = 43Å ² emulsifier (E-5): sodium dioctylsulfosuccinate, a molecular occupied area = 78Å ² , and an emulsifier Occupied Area of Graft Copolymer (I)
Graft ratio, volume average particle diameter of rubber polymer, reduced viscosity,
The polymerization conversion rate was determined as follows.

[Molecular occupation area of emulsifier] The molecular occupation area of sodium lauryl sulfate is 43Å based on the literature (Miura et al., Journal of Industrial Chemistry, 412, 64, 1961).
² , the adsorption amount of various emulsifiers was calculated by the soap titration method at 25 ° C. using polystyrene latex, and the molecular occupied area was calculated.

[Graft ratio] The graft ratio was obtained by dissolving the powder of the graft copolymer (I) in methyl ethyl ketone and centrifuging to obtain the soluble and insoluble contents of methyl ethyl ketone. Further, methanol was added to the methyl ethyl ketone-soluble matter to cause precipitation, and the precipitate was taken out. The graft ratio was calculated from the ratio of the insoluble matter of this precipitate and methyl ethyl ketone and the polymerization conversion ratio.

[Volume Average Particle Diameter of Rubber Polymer] The rubber polymer latex was measured with a Microtrac UPA particle size distribution meter manufactured by Nikkiso Co., Ltd.

[Reduced viscosity] The styrene resin (II) was dissolved in a dimethylformamide solution at a concentration of 0.3 g / dl, and the solution viscosity was measured at 30 ° C. with an Ostwald viscometer and calculated.

[Polymerization conversion rate] The polymerization conversion rate was determined by gas chromatography analysis.

[Examples and Comparative Examples] 1. Production of rubber polymer (A) (1) Production of rubber polymers (A-1) and (A-2) In the first step, the rubber polymers (A-1) and (A-2) are enlarged. The unexpanded rubber polymer required for this was produced.

The following materials were charged in a 100 L polymerization machine.

Pure water 220 parts Potassium persulfate 0.2 parts tDM 0.2 parts After removing air in the polymerization machine with 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 rate was 96%. The average particle size of the unexpanded rubber polymer was 85 nm.

As a second step, an acid group-containing latex (S) necessary for enlarging the unexpanded rubber polymer into rubber polymers (A-1) and (A-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 The contents of the reactor were heated to 70 ° C. under a nitrogen stream while stirring. After reaching 70 ° C, BMA 25 parts, BA5
Part, tDM 0.1 part, and CHP 0.15 part were added dropwise over 2 hours, and then BMA 50 parts and BA4
Parts, 16 parts of MAA, 0.5 parts of tDM, and 0.15 parts of CHP were added dropwise over 4 hours, and after completion of the addition, stirring was continued at 70 ° C. for 1 hour to complete polymerization to obtain an acid group-containing latex (S). The polymerization conversion rate was 99%.

In the third step, the unenlarged rubber polymer and the acid group-containing latex (S) produced above were used to produce enlarged rubber polymers (A-1) and (A-2).

Acid group-containing latex (S) 3 prepared above in 100 parts (solid content) of unexpanded rubber polymer latex
After adding a part (solid content) at 60 ° C., stirring was continued for 1 hour for enlargement to produce a rubber polymer (A-1). The average particle size of the rubber polymer (A-1) was 320 nm. To 100 parts (solid content) of the latex of unexpanded rubber polymer, 6 parts of 2 parts (solid content) of the acid group-containing latex (S) previously produced were added.
After the addition at 0 ° C., stirring was continued for 1 hour to be enlarged, and a rubber polymer (A-2) was produced. Rubber polymer (A-2)
Had an average particle diameter of 580 nm.

(2) Production of rubber polymer (A-3) The monomer was polymerized into 70 parts of butadiene and 30 parts of styrene in the same manner as in the above-mentioned unexpanded rubber polymer. The polymerization was completed in 20 hours, the conversion rate was 97% and the average particle size was 9%.
It was 0 nm. The obtained unenlarged rubber polymer was used to enlarge 3.5 parts of the previously-prepared acid group-containing latex (S) in the same manner as the rubber polymer (A-1). The average particle size of the obtained rubber polymer (A-3) was 250 nm.

(3) Production of rubber polymer (A-4) In the same manner as in the case of the unexpanded rubber polymer, 70 parts of butadiene and 30 parts of butyl acrylate were polymerized as a monomer. The polymerization was completed in 22 hours, the conversion rate was 96%, and the average particle size was 80 nm. The obtained unenlarged rubber polymer was used to enlarge 3.5 parts of the previously-prepared acid group-containing latex (S) in the same manner as the rubber polymer (A-1). The average particle size of the obtained rubber polymer (A-4) is 280.
was nm.

(4) Production of rubber polymer (A-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 230 parts Sodium palmitate 1 part Sodium formaldehyde sulfoxylate 0.3 parts EDTA 0.01 parts Ferrous sulfate 0.0025 parts While stirring the contents of the reactor up to 60 ° C. under a nitrogen stream. The temperature was raised. After reaching 60 ° C., BA 100 parts, DAP2.
A mixture of 5 parts and 0.3 part of CHP was continuously added dropwise over 5 hours. At 1 hour and 3 hours after the dropping, 1 part and 0.5 part of sodium palmitate were added, respectively. 6 after the dropping
Stirring was continued for 1 hour at 0 ° C. to obtain an unexpanded rubber polymer. The polymerization conversion rate was 98%, and the average particle size was 105 nm.
2.5 parts of the acid group-containing latex (S) produced above was used to obtain the rubber polymer (A-1).
Enlarged in the same manner as. Obtained rubber polymer (A
The average particle size of -4) was 420 nm.

2. Production of Graft Copolymer (I) (1) Production of Graft Copolymer (I-1) In a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet, and a thermometer, the following substances were added. Was charged.

Pure water 108 parts Rubber polymer (A-1) (solid content) 60 parts Emulsifier (E-1) 1 part Sodium formaldehyde sulfoxylate 0.3 parts EDTA 0.01 parts Ferrous sulfate 0.0025 The reactor was stirred and the temperature was raised to 60 ° C. under a nitrogen stream. After reaching 60 ° C, 10 parts AN, 30 parts St, CHP
0.4 part of the mixture was added dropwise continuously over 5 hours. After the dropwise addition was completed, stirring was continued at 60 ° C. for 2 hours to complete the polymerization and obtain a graft polymer (I-1). The polymerization conversion rate is 98%,
The graft ratio was 48%. Latex viscosity is 34c
The ps and the amount of agglomerates were 0.03%.

(2) Production of Graft Copolymer (I-2) In the same manner as in the graft copolymer (I-1), 0.3 part of the emulsifier (E-2) was used, and the rubber polymer ( A-2) 7
0 parts (solid content) to 20 parts MMA, 8 parts St, 2 parts BA,
A graft copolymer (I-2) was produced by polymerizing a mixture of 0.3 parts of CHP. The polymerization conversion rate was 98% and the graft rate was 28%. Latex viscosity is 63 cps,
The amount of agglomerates was 0.02%.

(3) Production of Graft Copolymer (I-3) In the same manner as in the graft copolymer (I-1), 3.1 parts of the emulsifier (E-1) was used and the rubber polymer ( A-3) 5
Polymerize St 43 parts, AN 12 parts to 5 parts (solid content),
Graft copolymer (I-3) was produced. The polymerization conversion rate was 99% and the graft rate was 58%. The latex viscosity was 46 cps and the agglomerate amount was 0.08%.

(4) Production of Graft Copolymer (I-4) In the same manner as in the graft copolymer (I-1), 1.5 parts of the emulsifier (E-1) was used, and the rubber polymer ( A-4) 6
A graft copolymer (I-4) was produced by polymerizing 0 part (solid content) of 11 parts of AN, 26 parts of St, and 3 parts of BA. The polymerization conversion rate was 98% and the graft rate was 48%. The latex viscosity was 35 cps and the agglomerate amount was 0.05%.

(5) Production of Graft Copolymer (I-5) In the same manner as in graft copolymer (I-1), 0.6 part of emulsifier (E-3) was used, and rubber polymer ( A-5) 6
5 parts (solid content) of 25 parts of MMA, 5 parts of St, and 5 parts of BA were polymerized to produce a graft copolymer (I-5). The polymerization conversion rate was 99% and the graft rate was 40%. The latex viscosity was 43 cps and the agglomerate amount was 0.07%.

(6) Preparation of Graft Copolymer (I-6) In the same manner as in graft copolymer (I-1), 1 part of emulsifier (E-4) was used to prepare graft copolymer (I-6). -6)
Was manufactured. Polymerization conversion rate is 98%, graft rate is 44
%Met. The latex viscosity was 220 cps and the agglomerate amount was 0.43%.

(7) Preparation of graft copolymer (I-7) In the same manner as in graft copolymer (I-2), 0.3 part of emulsifier (E-5) was used to prepare graft copolymer (I-5). (I-
7) was produced. The polymerization conversion rate was 96% and the graft rate was 26%. The latex viscosity was 260 cps and the agglomerate amount was 0.42%.

(8) Preparation of Graft Copolymer (I-8) In the same manner as in graft copolymer (I-3), 3.1 parts of emulsifier (E-4) was used to prepare graft copolymer (I-4). (I-
8) was produced. The polymerization conversion rate was 98% and the graft rate was 57%. The latex viscosity was 330 cps and the agglomerate amount was 0.55%.

(9) Preparation of Graft Copolymer (I-9) In the same manner as in graft copolymer (I-4), 1.5 parts of emulsifier (E-4) was used to prepare graft copolymer (I-4). (I-
9) was produced. The polymerization conversion rate was 97% and the graft rate was 49%. The latex viscosity was 240 cps and the agglomerate amount was 0.35%.

(10) Preparation of graft copolymer (I-10) In the same manner as in graft copolymer (I-5), 0.6 part of emulsifier (E-4) was used to prepare graft copolymer (I-5). (I-
10) was produced. The polymerization conversion rate was 98% and the graft rate was 41%. The latex viscosity was 310 cps and the amount of coagulum was 0.47%.

Table 1 collectively shows the charged amounts of the respective materials in the production of the graft copolymer (I) and the characteristic values of the obtained graft copolymer (I).

3. Manufacture of styrene resin (II) (1) Manufacture of styrene resin (II-1) Charge the following substances to a reactor equipped with a stirrer, reflux condenser, nitrogen inlet, monomer inlet and thermometer. It is.

Pure water 250 parts Sodium palmitate 2.5 parts Sodium formaldehyde sulfoxylate 0.5 parts EDTA 0.01 parts Ferrous sulphate 0.0025 parts While stirring the reactor contents 65 under nitrogen flow. The temperature was raised to ° C. After reaching 65 ° C, AN26 part, St74
Part, 0.4 parts of tDM, and 0.2 parts of CHP were continuously added dropwise over 6 hours. After completion of the dropping, stirring was continued at 65 ° C. for 1 hour to complete the polymerization. The polymerization conversion rate was 99% and the reduced viscosity was 0.65.

(2) Production of Styrenic Resin (II-2) AN27 was prepared in the same manner as the styrene resin (II-1).
Part, St9 part, αMSt64 part, tDM0.35 part, C
Polymerized as 0.4 parts HP. The polymerization conversion rate was 98%, and the reduced viscosity was 0.61.

(3) Production of Styrenic Resin (II-3) In the same manner as in the styrenic resin (II-1), sodium palmitate was changed to 2.5 parts of sodium dioctylsulfosuccinate, 23 parts of AN, 42 parts of St, αMSt10
Part, PMI 15 part, MMA 10 part, tDM 0.35 part,
Polymerized as 0.2 parts CHP. Polymerization conversion rate is 99%,
The reduced viscosity was 0.63.

(4) Production of styrene resin (II-4) AN25 was prepared in the same manner as styrene resin (II-1).
Parts, St 75 parts, tDM 0.9 parts, and CHP 0.2 parts. Polymerization conversion rate is 99%, reduced viscosity is 0.39
Met.

Table 2 shows the amount of each material used in the production of the styrene resin (II) and the obtained styrene resin (I
The characteristic values of I) are shown together.

4. Production of rubber-modified thermoplastic resin composition (Examples 1 to 5, Comparative Examples 1 to 5) The latex of the graft copolymer (I) and the styrene resin (II) in the ratio (solid content ratio) shown in Table 3. After mixing, 1 part of a hindered phenolic stabilizer (100 parts of resin) was added in the state of an emulsion-dispersed aqueous solution, and after sufficiently stirring and mixing, 2 parts of calcium chloride (100 parts of resin) was added and solidified. . The solidified slurry was heat-treated and dehydrated and dried to obtain a powder in which the graft copolymer (I) and the styrene resin (II) were mixed.

A powder prepared by mixing the graft copolymer (I) and the styrene resin (II) together with 1 part of ethylenebisstearylamide (100 parts of resin), 20 L manufactured by Tabata Co., Ltd.
Blended evenly with a blender. Furthermore, it was melt-kneaded at a temperature of 200 ° C. to 260 ° C. with a 40 mm ml axial extruder manufactured by Tabata Co., Ltd. to produce pellets of the rubber-modified thermoplastic resin composition.

(Examples 6 and 7, Comparative Examples 6 and 7) A powder obtained by mixing the graft copolymer (I) and the styrene resin (II) and a commercially available polyvinyl chloride resin (polymerization degree 600) (II).
The powder of I) in the ratio of Table 4 is stearyl stearate 2
Part, 2 parts of dibutyl tin malate (above, to resin 100
Part) and blended uniformly with a 20 L blender manufactured by Tabata Co., Ltd. Furthermore, it was melt-kneaded at a temperature of 160 to 180 ° C. with a 40 mm ml axial extruder manufactured by Tabata Co., Ltd. to produce pellets of the rubber-modified thermoplastic resin composition.

(Examples 8 and 9, Comparative Examples 8 and 9) Powder obtained by mixing the graft copolymer (I) and the styrene resin (II) and a commercially available polycarbonate resin (viscosity average molecular weight 25
000) (IV) powder was uniformly blended with 1 part of stearyl stearate (100 parts of resin) in a ratio of Table 4 using a 20 L blender manufactured by Tabata Co., Ltd. Furthermore, Inc.
It was melt-kneaded at a temperature of 230 to 270 ° C. with a Tabata 40 mm screw shaft extruder to produce pellets of the rubber-modified thermoplastic resin composition.

(Examples 10 and 11, Comparative Examples 10 and 11)
Powder obtained by mixing the graft copolymer (I) and the styrene resin (II) and a commercially available polyamide resin (6,6 nylon,
A powder having a viscosity average molecular weight of 30,000) (V) at a ratio shown in Table 4 was used in an amount of 1 part of ethylenebisstearylamide and 3 parts of Reedda GP-100 (acid-modified acrylic-polymethylmethacrylate) manufactured by Toa Gosei Chemical Industry Co., Ltd. Resin 100
Part) and blended uniformly with a 20 L blender manufactured by Tabata Co., Ltd. Furthermore, it was melt-kneaded at a temperature of 240 to 260 ° C. with a 40 mm ml axial extruder manufactured by Tabata Co., Ltd. to produce pellets of the rubber-modified thermoplastic resin composition.

Various properties of the obtained rubber-modified thermoplastic resin composition were measured. The results are shown in Tables 3 and 4.

[Characteristics of Rubber-Modified Thermoplastic Resin Composition] Impact resistance was evaluated by IZOD impact strength. IZOD impact strength (unit: kgcm / cm) is ASTM D256
It was measured at 23 ° C. by the standard (1/4 inch thickness) method.

The tensile strength (unit: kg / cm ² ) and the tensile elongation (unit:%) were measured at 23 ° C. using a No. 1 dumbbell according to the method of ASTM D638 standard.

The bending strength (unit: kg / cm ² ) and the bending elastic modulus (unit: kg / cm ² ) were measured at 23 ° C. by the method of ASTM D790 standard.

Heat resistance (HDT, unit: ° C) is ASTM
The heat distortion temperature under a load of 18.6 kg / cm ² defined by the D648 standard was evaluated. (Unit: ° C.) The surface appearance was visually evaluated by using a No. 1 dumbbell and the following 5-point evaluation method. 5 points: glossy, smooth surface, fish eye,
There is no problem. 4 points: glossy, smooth surface, some fish eyes, but no spots. 3 points: Glossy, smooth surface with fish eyes, but no spots. 2 points: There is a little gloss, and there is a little grain on the surface.
There are some spots. 1 point: There is little gloss, the surface is rough, and there are a lot of spots.

The test pieces used for the above-mentioned IZOD impact strength, tensile strength, tensile elongation, bending strength, bending elastic modulus, heat resistance and surface property were molded using a FANUC FAS100B injection molding machine and evaluated. I went to The cylinder temperature was set to 180 ° C. for those containing a vinyl chloride resin and 240 to 270 ° C. for others.

The fluidity is FAS10 manufactured by FANUC CORPORATION.
Using a 0B injection molding machine, those containing vinyl chloride resin have a cylinder temperature of 190 ° C., others have a cylinder temperature of 250 ° C., injection pressure of 1350 kg / cm ² ,
The flow length (unit: mm) of the resin in the spiral mold having a thickness of 3 mm was evaluated.

The larger the numerical value is, the better the characteristics are.

From the results shown in Tables 3 and 4, the rubber-modified thermoplastic resin compositions using the graft copolymers of the present invention represented by Examples 1 to 11 are particularly excellent in impact resistance and surface property, It is clear that the rigidity, heat resistance, fluidity and thermal stability are also good.

[0094]

[Table 1]

[0095]

[Table 2]

[0096]

[Table 3]

[0097]

[Table 4]

[0098]

EFFECT OF THE INVENTION Grafts obtained by grafting the graft component by the emulsion polymerization method using a specific emulsifier on the rubber polymer (A) having a specific volume average particle size produced by the coagulation and enlargement method of the present invention. When the copolymer is blended with a styrene resin or its alloy, it has excellent impact resistance and surface property of the molded product,
Moreover, a rubber-modified thermoplastic resin composition having excellent heat resistance, rigidity and processability can be obtained.

Continuation of front page (51) Int.Cl. ⁷ identification code FI C08L 77/00 C08L 77/00 (56) Reference JP-A-5-78431 (JP, A) JP-A-3-66741 (JP, A) JP-A-5-345812 (JP, A) JP-A-8-12704 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 279/00

Claims (6)

(57) [Claims] 1. A diene rubber polymer and / or an acrylic rubber polymer (A) having a volume average particle size of 100 to 2000 nm, which is produced by a coagulation and enlargement method, and is represented by the following formulas (1) to (6). At least selected from the group consisting of a vinyl cyanide compound (x), an alkyl methacrylate (y), an aromatic vinyl compound (z), and an alkyl acrylate copolymerizable therewith, a maleimide compound, and (meth) acrylic acid having a composition It is composed of a graft part (Ag) composed of one kind of monomer (n) and has a graft ratio ((graft part (Ag) / rubber polymer (A) × 100).
Is 10 to 80% by weight, and an emulsifier containing 5% by weight or more of an emulsifier having a molecular occupied area of 35 A ² or less based on 100 parts by weight of the graft copolymer (I) in all the emulsifiers.
Graft copolymer obtained by emulsion polymerization using 05 to 7 parts by weight. 45 ≧ x + (y / 4) ≧ 5 (1) x + y + z + n = 100 (2) 45 ≧ x ≧ 0 (3) 90 ≧ y ≧ 0 (4) 95 ≧ z ≧ 10 (5) 30 ≧ n ≧ 0 (6 ) In the formulas (1) to (6), x, y, z and n represent the weight% of each component. 2. The rubber polymer (A) comprises 5 to 50% by weight of at least one unsaturated acid (c) selected from acrylic acid, methacrylic acid, itaconic acid and crotonic acid, and the alkyl group has 1 carbon atom. To 12 to 50% by weight of at least one (meth) alkyl acrylate (d), and (c),
The graft copolymer according to claim 1, which is a rubber polymer produced by a coagulation and enlargement method using an acid group-containing latex (S) prepared by polymerizing 0 to 40% of a monomer copolymerizable with (d). Polymer. 3. A rubber-modified thermoplastic resin composition comprising the graft copolymer (I) according to claim 1 or 2 and a styrene resin (II). 4. A rubber-modified thermoplastic resin composition comprising the graft copolymer (I) according to claim 1 or 2, a styrene resin (II) and a vinyl chloride resin (III). 5. A rubber-modified thermoplastic resin composition comprising the graft copolymer (I) according to claim 1 or 2, a styrene resin (II) and a polycarbonate resin (IV). 6. A rubber-modified thermoplastic resin composition comprising the graft copolymer (I) according to claim 1 or 2, a styrene resin (II) and a polyamide resin (V).