JPH0725978B2 - High weather resistance thermoplastic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent impact resistance, heat resistance, moldability and appearance of a molded article, and particularly excellent weather resistance.

(Prior Art and Problems to be Solved by the Invention) Conventionally, as a weather-resistant thermoplastic resin, a method of incorporating a saturated rubber-like polymer having few double bonds in the main chain has been proposed. It is known to use acrylic rubber and ethylene propylene rubber as typical ones. Although these saturated rubbers are stable to ultraviolet rays, they have the drawback that the gloss of the appearance of the molded product deteriorates when exposed to sunlight (ultraviolet rays) for a long period of time. In particular, recently, molded articles that are used outdoors for a long period of time are required to have a gloss that does not deteriorate, and therefore thermoplastic resins produced by these methods cannot be said to have sufficient weather resistance.

An object of the present invention is to provide a high weather resistance thermoplastic resin composition in which such drawbacks are improved.

(Means for Solving the Problems) The present invention provides 0.1 to 20% by weight of a polyfunctional vinyl compound (I), 50 to 99.9% by weight of an acrylate ester (II) having an alkyl group having 1 to 13 carbon atoms, and these. 95 to 60 parts by weight of a polymerizable monomer mixture (a) obtained by blending 0 to 30% by weight of another vinyl compound (III) copolymerizable with the diene polymer (b) 5 to 40 parts by weight. Of 50 to 50 in the presence of parts
In the presence of 5 to 50 parts by weight of a graft polymer rubber [A] obtained by emulsion polymerization to 93% and then stopping the polymerization, 0 to 100% by weight of an aromatic vinyl compound (IV), a methacrylic acid ester (V ) 0-100% by weight and vinyl cyanide compound (VI) 0-40% by weight to obtain a polymerizable monomer mixture [B], which is a thermoplastic resin [C] obtained by polymerizing 95-50 parts by weight. 20 to 90 parts by weight, 20 to 100% by weight of a methacrylic acid ester (VII) having an alicyclic hydrocarbon group having 5 to 22 carbon atoms, and other vinyl compounds copolymerizable therewith (VI
II) 5 to 40 parts by weight of a thermoplastic resin [D] obtained by polymerizing 0 to 80% by weight, and 70 to 80% by weight of an aromatic vinyl compound (IX) and 20 to 30 parts by weight of a cyanide compound (X). % Of thermoplastic resin [E] obtained by polymerizing 100% by weight of the resin is added so that the total amount becomes 100 parts by weight, and a high weather resistance thermoplastic resin composition containing a resin mixture obtained by mixing Regarding things.

First, the graft polymer rubber [A] will be described.

Examples of the polyfunctional vinyl compound (I) include ethylene glycol dimethacrylate, diethylene glycol diacrylate, divinylbenzene, diallyl phthalate, dicyclopentadiene acrylate, dicyclopentadiene methacrylate, and other polyvalent vinyl compounds, triallyl cyanurate, triallyl isocyanate. Examples include polyvalent allyl compounds such as nurate and diallyl phthalate. Among them, from the viewpoint of impact resistance, triallyl isocyanurate, triallyl cyanurate, dicyclopentadiene acrylate, dicyclopentadiene methacrylate, etc.
Triacryl isocyanurate or triallyl cyanurate is particularly preferable. The polyfunctional vinyl compound (I) is
It is used within the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, in the polymerizable monomer mixture (a). If it is less than 0.1% by weight, the degree of crosslinking is insufficient and the impact resistance is poor, and if it exceeds 20% by weight, the degree of crosslinking is excessive and the impact resistance is lowered.

Examples of the alkyl acrylate (II) having an alkyl group having 1 to 13 carbon atoms include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2
-Ethylhexyl acrylate and the like, of which butyl acrylate is particularly preferable. The acrylic ester (II) is used in the polymerizable monomer mixture (a) in an amount of 50 to 99.9% by weight, preferably 60 to 99.5% by weight. If it is less than 50% by weight, the properties of the obtained graft polymer rubber [A] will be deteriorated, and if it exceeds 99.9% by weight, the impact resistance will be deteriorated.

Other vinyl compounds (III) copolymerizable with these include unsaturated fatty acid esters other than the component (II), aromatic vinyl compounds, vinyl cyanide compounds, and the like.

Unsaturated fatty acid esters include cyclohexyl acrylate, methyl cyclohexyl acrylate, bornyl acrylate, isobornyl acrylate, adamantyl acrylate, and other cycloalkyl acrylates, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid 2 -Methyl methacrylate alkyl esters such as ethylhexyl, cyclohexyl methacrylate, methyl cyclohexyl methacrylate, bornyl methacrylate, isobornyl methacrylate, methacrylic acid cycloalkyl esters such as adamantyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, etc. Methacrylic acid aromatic ester, fluoromethyl methacrylate, fluoroethyl methacrylate, chloroethyl methacrylate Is methacrylic acid alkyl halide esters such as methacrylic acid bromoethyl.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, α-ethylstyrene, α-fluorostyrene,
Examples include α-chlorostyrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene and butylstyrene.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

The other vinyl compound (III) is used in the polymerizable monomer mixture (a) in an amount of 0 to 30% by weight. If it exceeds 30% by weight, the properties of the resulting graft polymer rubber [A] deteriorate.

Examples of the diene polymer (b) which becomes the graft main chain when obtaining the graft polymer rubber [A] include polybutadiene,
A butadiene-styrene copolymer, a butadiene-styrene-acrylonitrile copolymer, an acrylonitrile-butadiene copolymer, etc. can be used.

The diene polymer (b) is a polymerizable monomer mixture (a) 95
It is used in an amount of 5 to 40 parts by weight, preferably 15 to 30 parts by weight, based on 60 to 60 parts by weight. If the diene polymer (a) is less than 5 parts by weight, the impact resistance will decrease, and if it exceeds 40 parts by weight, the weather resistance will decrease. The diene polymer (b) is preferably used in the form of latex dispersed in an aqueous medium.

The emulsion polymerization method in which the above components are blended and emulsion-polymerized to obtain the graft polymer [A] can be carried out by a method generally known to those skilled in the art. In this emulsion polymerization, it is essential to stop the polymerization at a polymerization rate of 50 to 93%, preferably 60 to 90%, without performing the polymerization to 100%, in order to obtain high impact resistance. If the polymerization rate is less than 50%, the heat resistance will decrease. Further, if the polymerization rate exceeds 93%, the effect of improving impact resistance cannot be obtained.

In the present invention, the polymerization rate is determined by adding a polymerization inhibitor to the sampled polymerization reaction solution (latex in emulsion polymerization), removing the volatile components using an infrared moisture meter, and then measuring the weight of the nonvolatile components. ， Determined from this value and the stocking rate. The unit of the polymerization rate is%, which means% by weight.

In the presence of 5 to 50 parts by weight of the resulting graft polymer rubber [A], 0 to 100% by weight of an aromatic vinyl compound (IV), 0 to 100% by weight of a methacrylic acid ester (V) and a vinyl cyanide compound (VI ) 95 to 50 parts by weight of a polymerizable monomer mixture [B] obtained by blending 0 to 40% by weight is emulsion polymerized to obtain a thermoplastic resin [C]. When the ratio of the graft polymer rubber [A] and the polymerizable monomer mixture [B] is outside this range,
Weather resistance decreases.

Examples of the aromatic vinyl compound (IV) include α-substituted styrenes such as α-methylstyrene and α-ethylstyrene, substituted styrenes such as chlorostyrene, vinyltoluene and t-butylstyrene, styrene and the like.

As the methacrylic acid ester (V), methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. can be used.

Further, examples of the vinyl cyanide compound (VI) include acrylonitrile and methacrylonitrile. If the amount of the vinyl cyanide compound (VI) is too large, the moldability will be deteriorated, so use it in a range not exceeding 40% by weight.

The thermoplastic resin [C] is a graft polymer rubber [A] 5 to
95 to 50 parts by weight of a polymerizable monomer mixture [B] obtained by blending the above monomers in the presence of 50 parts by weight of latex, preferably 100 parts by weight of the total of [A] and [B]. It can be obtained by, for example, stirring and mixing at room temperature, dropping a mixed solution in an emulsified state, and emulsion polymerizing.

Next, the thermoplastic resin [D] will be described. As the raw material of the component [D], a methacrylic acid ester (VI) having an alicyclic hydrocarbon group having 5 to 22 carbon atoms is used. The methacrylic acid ester (VII) particularly has 8 to 22 carbon atoms.
Those having an alicyclic hydrocarbon group of are preferable. Examples thereof are norbornyl methyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] deca-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6 ] deca-9-yl methacrylate, tricyclomethacrylate. [5.2.1.0 ^2,6 ] deca-3-methyl, tricyclomethacrylate [5.2.1.0 ^2,6 ] deca-4-
Examples include methyl. In addition, it is not preferable to use the above-mentioned acrylate ester having a hydrocarbon group instead of the component (VII) because the heat resistance is lowered.

Other copolymerizable vinyl compounds (VIII) copolymerized with the (VII) component include unsaturated fatty acid esters other than the (VII) component, aromatic vinyl compounds,
Examples thereof include vinyl cyanide compounds. Examples of unsaturated fatty acid esters include alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl cyclohexyl acrylate, bornyl acrylate, isobornyl acrylate, acrylic acid. Acrylic acid cycloalkyl esters such as adamantyl, methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate, methacrylic acid aromatics such as phenyl methacrylate, benzyl methacrylate and naphthyl methacrylate. Alkyl halides such as esters, fluoromethyl methacrylate, fluoroethyl methacrylate, chloroethyl methacrylate, bromoethyl methacrylate, etc. There is an ester and the like.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, α-ethylstyrene, α-fluorostyrene,
Examples include α-chlorostyrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene and butylstyrene.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

The thermoplastic resin [D] is produced by polymerizing 20 to 100% by weight of the methacrylic acid ester (VII) and 0 to 80% by weight of another vinyl compound (VIII) copolymerizable therewith. If the methacrylic acid ester (VII) is less than 20% by weight, the weather resistance is poor. The polymerization method is preferably emulsion polymerization or suspension polymerization, and can be carried out by a conventional method using a polymerization initiator or the like.

Next, the thermoplastic resin [E] will be described. Examples of the aromatic vinyl compound (IX) as a raw material of the component [E] include the aromatic vinyl compound (I) described in the description of the component [C].
V) and the same cyan compound (IX) as the vinyl cyanide compound (VI).

In the production of the thermoplastic resin [E], 70 to 80% by weight of the aromatic vinyl compound (IX) and 30 to 20% by weight of the vinyl cyanide compound (X) are mixed and polymerized. If the amount of vinyl cyanide compound exceeds 30% by weight, the moldability is deteriorated, and if it is less than 20% by weight, impact resistance etc. is deteriorated.

As a method for polymerizing the component [E], a suspension polymerization method and an emulsion polymerization method are preferable, and the polymerization can be carried out by a conventional method using a polymerization initiator.

The high weather resistance thermoplastic resin composition of the present invention comprises 20 to 90 parts by weight of the thermoplastic resin [C], 5 to 40 parts by weight of the thermoplastic resin [D], and the thermoplastic resin [E].
5 to 40 parts by weight are added so that the total amount is 100 parts by weight, and the mixture is mixed to obtain a resin mixture. If the amount of the component [C] is less than 20 parts by weight, the mechanical strength of the thermoplastic resin composition of the present invention will decrease, and if it exceeds 90 parts by weight, the weather resistance will decrease. If the amount of the component (D) is less than 5 parts by weight, the weather resistance, especially the gloss of the appearance of the molded product after long-term outdoor exposure, will decrease, and if it exceeds 40 parts by weight, the impact resistance will decrease. From the viewpoint of weather resistance, the component [D] is particularly preferably 20 to 40 parts by weight. Further, if the amount of the component [E] is less than 5 parts by weight, the fluidity will be poor, and if it exceeds 40 parts by weight, the mechanical properties, particularly the impact resistance will be deteriorated.

The high weather resistance thermoplastic resin composition according to the present invention comprises other resins, colorants, phenol-based antioxidants,
Add various additives such as lubricants and UV absorbers,
The mixture is mixed with a mixer or the like, and preferably melt-kneaded with an extrusion kneader maintained at a temperature of 240 to 260 ° C. to form a pellet. This pellet is, for example, as a thermoplastic molding material,
Used for various molded products.

(Examples) Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. Hereinafter, "parts" and "%" mean "parts by weight" and "% by weight", respectively.

Production Example 1-1 Production of graft polymer rubber [A] [Blending composition] (1) Polybutadiene latex 300 parts (solid content) (Sumitomo Nogataku SN-800) (2) Butyl acrylate 700 parts (3) Triallyl isocyanurate 14 parts (4) Potassium persulfate 0.5 part (5) Deionized water 300 parts (6) Emulsifier; KS soap (fat 8 parts potassium acidate) (Kao Soken Co., Ltd. trade name) (7) ) Sodium sulfite 0.09 parts (8) Deionized water 2000 parts [Polymerization operation] Charge component (1) and components (6), (7), and (8) dissolved uniformly in a reaction vessel, mix and stir, and then uniformly The dissolved components (2) and (3) are added. After substituting with nitrogen, components (4) and (5) were added and the temperature was raised to 60 to 65 ° C.
After polymerizing for about 3 hours, it was cooled to terminate the polymerization.
The polymerization rate at this time was 71%.

1-2 Emulsion polymerization of thermoplastic resin [C] (graft copolymer) [blending composition] [Polymerization operation] Component (1) is placed in a reaction vessel and uniformly dissolved. The component (2) uniformly dissolved is added to this, and the mixture is stirred. After nitrogen substitution, the component (3) is added and the temperature is raised to 65 ° C. and kept for about 1 hour to bring the polymerization rate to 70%. After that, about 2 parts of a mixed solution of the components (4), (5), and (6) that were uniformly dissolved were prepared.
It is dropped into the reaction vessel over a period of time and polymerized at 65 ° C. 65
After about 5 hours at 0 ° C, the component (7) is added when the polymerization rate reaches 80 to 85%, the polymerization temperature is raised to 80 ° C and the polymerization is completed for about 2 hours to complete the polymerization. The polymerization rate at this time was 98%. The latex-like reaction solution obtained here was salted out in hot water in which potassium iovan was dissolved, dehydrated and dried to obtain a resin powder (thermoplastic resin [C]).

1-3 Production of thermoplastic resin [D] (methacrylic acid ester copolymer) [Blending composition] Component (1) 300 parts of tricyclomethacrylate [5.2.1.0 ^2,6 ] deca-8-yl Component (2) Methacryl Methyl acid 700 parts Component (3) Lauroyl peroxide 4 parts Component (4) n-octyl mercaptan 1 part Component (5) Basic calcium phosphate 10% 42 parts Aqueous solution component (6) Dodecylbenzenesulfonic acid 0.002 part Sodium component (7) ) Sodium sulfate 0.5 parts Component (8) Deionized water 1200 parts [Polymerization operation] Put components (5) and (6), (7) and (8) in a 4 liter separable flask equipped with a stirrer and a condenser and stir and mix. To obtain a suspension medium. To this was added the components (1) and (2) in which the components (3) and (4) were dissolved, stirred and polymerized under nitrogen atmosphere at 60 ° C for 3 hours and then at 98 ° C for 4 hours. The coalesced particles were washed with water, dehydrated and dried to obtain polymer particles.

1-4 Production of thermoplastic resin [E] (aromatic copolymer) [blending composition] [Polymerization operation] The component (2) is placed in a reaction vessel and stirred. Add the homogeneously dissolved component (1) to this, 65 ℃, 10 hours, then 105
Polymerization was completed at 2 ° C. for 2 hours. The polymerization rate at this time is
It was 98%. The obtained polymer particles were washed with water, dehydrated and dried to obtain polymer particles.

Example 1 A thermoplastic resin in which 500 parts of the copolymer obtained in 1-2 of the above Production Example, 300 parts of the copolymer obtained in 1-3 and 200 parts of the copolymer obtained in 1-4 were mixed. 3 parts of carbon and stabilizer (0.2 parts of phenolic antioxidant Irvanox 1076 (manufactured by Ciba Geigy) and 4.8 parts of calcium stearate) in the mixture.
Cylinder temperature of 24 is obtained by mixing 5 parts with a 30 mmφ extruder.
The mixture was extruded at 0 ° C to form a pellet. A predetermined test piece was prepared using an injection molding machine by using this pellet, and the weather resistance accelerated test by a Sunshear in weather meter and the mechanical property were evaluated using this test piece. The results are shown in Table 1.

Example 2 An example except that 500 parts of the copolymer obtained in Production Example 1-2, 400 parts of the copolymer obtained in 1-3 and 100 parts of the copolymer obtained in 1-4 were mixed. A test piece was prepared and evaluated in the same manner as in 1.

Example 3 Example except that 500 parts of the copolymer obtained in Production Example 1-2, 200 parts of the copolymer obtained in 1-3 and 300 parts of the copolymer obtained in 1-4 were mixed. A test piece was prepared and evaluated in the same manner as in 1.

Comparative Example 1 Except that 500 parts of the copolymer obtained in Production Example 1-2, 45 parts of the copolymer obtained in 1-3 and 455 parts of the copolymer obtained in 1-4 were mixed. Test pieces were prepared and evaluated in the same manner as in Example 1.

Example 4 A thermoplastic resin [D] monomer was prepared by adding 900 parts of tricyclo [5.2.1.0 ^2,6 ] deca-8-yl methacrylate and n-acrylic acid.
Test pieces were prepared and evaluated in the same manner as in Example 1 except that 100 parts of butyl was used and the thermoplastic resin [D] polymerized in the same manner as in Production Example 1-3 was used. The results are shown in Table 1.
Shown in.

Comparative Example 2 A thermoplastic resin prepared by mixing 500 parts of the copolymer obtained in Production Example 1-2 and 500 parts of the copolymer obtained in 1-4 was prepared in the same manner as in Example 1 to prepare a test piece and evaluated. did.

(Effects of the Invention) The high weather resistance thermoplastic resin composition of the present invention is excellent in weather resistance, particularly in the gloss retention rate of the appearance of molded articles, and is most suitable for various outdoor applications such as housings.

Claims (3)

[Claims] 1. A polyfunctional vinyl compound (I) in an amount of 0.1 to 20% by weight, an acrylate ester (II) having an alkyl group of 1 to 13 carbon atoms in an amount of 50 to 99.9% by weight, and other vinyl copolymerizable therewith. In the presence of 5 to 40 parts by weight of a diene-based polymer (b), 95 to 60 parts by weight of a polymerizable monomer mixture (a) obtained by compounding 0 to 30% by weight of a compound (III) are added. 50 ~
In the presence of 5 to 50 parts by weight of a graft polymer rubber [A] obtained by emulsion polymerization to 93% and then stopping the polymerization, 0 to 100% by weight of an aromatic vinyl compound (IV), a methacrylic acid ester (V ) 0-100% by weight and vinyl cyanide compound (VI) 0-40% by weight to obtain a polymerizable monomer mixture [B], which is a thermoplastic resin [C] obtained by polymerizing 95-50 parts by weight. 20 to 90 parts by weight, 20 to 100% by weight of a methacrylic acid ester (VII) having an alicyclic hydrocarbon group having 5 to 22 carbon atoms, and other vinyl compounds copolymerizable therewith (VI
II) 5 to 40 parts by weight of a thermoplastic resin [D] obtained by polymerizing 0 to 80% by weight, and 70 to 80% by weight of an aromatic vinyl compound (IX) and 20 to 30 parts by weight of a cyanide compound (X). % Of thermoplastic resin [E] obtained by polymerizing 100% by weight of the resin is added so that the total amount becomes 100 parts by weight, and a high weather resistance thermoplastic resin composition containing a resin mixture obtained by mixing object. 2. The highly weather-resistant thermoplastic resin composition according to claim 1, wherein the polyfunctional vinyl compound (I) is triallyl isocyanurate and / or triallyl cyanurate. 3. A methacrylic acid ester (VII) having an alicyclic hydrocarbon group having 5 to 22 carbon atoms is norbornyl methacrylate, norbornyl methyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decadecane. 8-yl, tricyclomethacrylate [5.2.1.0 ^2,6 ] deca-9-yl, tricyclomethacrylate [5.2.1.0 ^2,6 ] deca-3-methyl, tricyclomethacrylate [5.2.1.0 ^2,6 ] deca The high weather resistance thermoplastic resin composition according to claim 1 or 2, which is selected from -4-methyl.