JP2016030812A - Method for producing master batch and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a method for producing a master batch obtained by blending a light-resistant stabilizer with a thermoplastic resin in a high concentration; and a molded article thereof.SOLUTION: There are provided: a method for producing a thermoplastic resin composition, which is a method for producing a master batch containing 12 to 47 pts.mass of (B) a light-resistant stabilizer based on 100 pts.mass of (A) a styrene-based thermoplastic resin using an extruder, where the cylinder temperature of a first conveying part of the extruder is lower than the melting point of (B) the light-resistant stabilizer; and a molded article molded using the master batch produced by the production method.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing a masterbatch in which a light-resistant stabilizer is blended in a high concentration with a thermoplastic resin, and a molded product thereof.

Conventionally, a masterbatch method has been used as a method for imparting various functions to a thermoplastic resin. These techniques include the following.

JP 2012-072335 A JP 2009-102633 A

This invention makes it a subject to provide the manufacturing method of a masterbatch which mix | blended the light-resistant stabilizer with the high concentration with the thermoplastic resin, and its molded article.

  As a result of intensive studies on the above-mentioned problems, the present inventor has completed the present invention by defining the cylinder temperature of the first conveying section of the extruder.

That is, the present invention is as follows.
1. (A) A master batch production method containing 12 to 47 parts by mass of (B) a light-resistant stabilizer with respect to 100 parts by mass of a styrene-based thermoplastic resin. A method for producing a thermoplastic resin composition, wherein the temperature is equal to or lower than the melting point of the (B) light-resistant stabilizer.
2. The extruder is a twin screw extruder, and the first kneading section has at least one kneading block (1) to (3) below and (4) a forward feed screw block, and the most upstream side of the kneading section. (1), (3) on the most downstream side, and L / D of the kneading part is 8-15, The manufacturing method of said 1 characterized by the above-mentioned.
(1) Kneading block with L / D = 0.4 to 1.5, B = 3 to 10 and α = 20 to 80 degrees (2) L / D = 0.4 to 1.5, B = Kneading block with 3-10 sheets, α = 90 degrees (3) Kneading block with L / D = 0.4-1.5, B = 3-10 sheets, α = 100-170 degrees (4) L / D = 0.3-3.0, R / D = 0.3-1.5 forward screw block (where L is the length of the kneading block and the forward screw block (mm), D is the screw The diameter (mm), B represents the number of blades constituting the kneading block (sheets), α represents the twist angle (degrees) between two adjacent blades, and R represents the lead length (mm) of the screw block. )
3. (A) The manufacturing method of said 1 or 2 whose styrene-type thermoplastic resin is a polystyrene resin.
4). The molded product shape | molded using the masterbatch manufactured with the manufacturing method in any one of said 1-3.

  According to the present invention, it has become possible to produce a master batch containing a light-resistant stabilizer at a high concentration, which has been difficult to produce until now.

It is a schematic diagram which shows the 1st conveyance part prescribed | regulated by this invention.

  Examples of the (A) styrenic thermoplastic resin used in the present invention include polystyrene resin (GP-PS resin), impact-resistant polystyrene resin (HI-PS resin), acrylonitrile butadiene styrene resin (ABS resin), and acrylonitrile styrene. Resin (AS resin), polymethacryl styrene resin (MS resin), etc. are mentioned. Among these, polystyrene resin is preferable.

Examples of the (B) light-resistant stabilizer used in the present invention include hindered amine light stabilizers, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, and nickel complex salts. System ultraviolet absorbers and the like. Of these, hindered amine light stabilizers and benzotriazole ultraviolet absorbers are preferred. (B) The light-resistant stabilizer can be used alone or in combination of two or more. When using together, it can mix in arbitrary ratios.

  Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 2 , 2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane Tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6, 6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) ) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl- 4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2, 6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Piperidylamino) hex 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6 , 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2,6 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] hindered amine compounds such as aminoundecanoic the like. Among them, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate is preferable.

Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl)- 5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2 , 2′-methylenebis [6- (2H-benzotriazol-2-yl) -4-tert-octylphenol, 6- (2-benzotriazolyl) -4-tert-octyl-6′-tert-butyl-4 '-Methyl-2,2'-methylenebisphenol] and the like. Among them, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole is preferable.

  (B) The compounding quantity of a light-resistant stabilizer is 12-47 mass parts with respect to 100 mass parts of (A) styrene-type thermoplastic resins. Preferably it is 18-40 mass parts. When it exceeds 47 parts by mass, the melt viscosity of the strand is lowered and pelletization is difficult.

  Other additives can be added as long as the object of the present invention is not impaired. For example, brominated flame retardants such as flame retardants, phosphorus flame retardants, etc., antioxidants such as phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants, fatty acid lubricants as lubricants, aliphatic amide lubricants Metal soap-type lubricants, foam nucleating agent talc, colorant pigments, dyes, antistatic nonionic surfactants, cationic surfactants, and the like.

  A known mixing technique can be applied to the pre-blending method of the present invention. For example, a mixing apparatus such as a mixer-type mixer, a V-type blender, and a tumbler-type mixer can be used.

The extruder of the present invention is not particularly limited, and a known mixing technique can be applied. Suitable melt kneading apparatuses include a single screw extruder, a special single screw extruder, a twin screw extruder, and the like. Preferably, it is a twin screw extruder

  The cylinder temperature of the 1st conveyance part of the extruder of this invention is below the melting point of (B) light-resistant stabilizer. More preferably, the temperature is 10 ° C. or more lower than the melting point. When the cylinder temperature of the first transport unit is higher than the melting point, (B) the light-resistant stabilizer melts before (A) the styrenic thermoplastic resin and kneading is not sufficiently performed, and (A) the styrenic thermoplastic resin is It becomes unmelted and vents up.

Although there is no restriction | limiting in particular in the screw design of a 1st kneading part, The screw design which satisfy | fills the following conditions is preferable.
It has at least one kneading block (1) to (3) and (4) a forward feed screw block, and has (1) on the most upstream side of the kneading section and (3) on the most downstream side.
(1) Kneading block with L / D = 0.4 to 1.5, B = 3 to 10 and α = 20 to 80 degrees (2) L / D = 0.4 to 1.5, B = Kneading block with 3-10 sheets, α = 90 degrees (3) Kneading block with L / D = 0.4-1.5, B = 3-10 sheets, α = 100-170 degrees (4) Progressive screw block with L / D = 0.3-3.0 and R / D = 0.3-1.5 Preferably,
(1) Kneading block with L / D = 0.7 to 1.4, B = 6 to 8 and α = 20 to 70 degrees (2) L / D = 0.7 to 1.4, B = Kneading block with 6-8 sheets, α = 90 degrees (3) Kneading block with L / D = 0.7-1.4, B = 6-8 sheets, α = 130-160 degrees (4) L / D = 0.4 to 2.8, R / D = 0.4 to 1.4 forward screw block where L is the length of the kneading block and the forward screw block (mm), D is the screw diameter (Mm), B represents the number of blades constituting the kneading block (sheets), α represents the twist angle (degrees) between two adjacent blades, and R represents the lead length (mm) of the screw block.
The L / D of the kneading part is 8-15. Preferably it is 10-14.

As an example of arrangement, (1) (2) (1) (4) (1) (1) (2) (2) (2) (2) (2) (1) (3) from the upstream side
(1) (1) (2) (2) (1) (4) (1) (2) (2) (1) (2) (1) (3)
(1) (2) (1) (4) (1) (2) (2) (1) (4) (1) (2) (2) (3)
Etc.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

(A) As the styrenic thermoplastic resin, a styrene polymer having a reduced viscosity of 1.03 dl / g was used. The reduced viscosity said here was measured with the following method.

[Measurement of reduced viscosity (ηsp / C)]
A mixed solvent of 17.5 ml of methyl ethyl ketone and 17.5 ml of acetone is added to 1 g of a thermoplastic resin and dissolved by shaking at a temperature of 25 ° C. for 2 hours. The methanol component is added to precipitate the resin component, and the insoluble component is filtered and dried. The resin component obtained by the same operation was dissolved in toluene to prepare a sample solution having a polymer concentration of 0.4% (mass / volume). The sample solution and pure toluene were measured at a constant temperature of 30 ° C. using a Ubbelohde viscometer, and the number of seconds during which the solution flowed was measured.
ηsp / C = (t1 / t0-1) / C
t0: Pure toluene flow down seconds
t1: Sample solution flow down seconds
C: Polymer concentration

(B) The following were used as a light-resistant stabilizer.
(B-1) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, trade name “JF-90” (manufactured by Johoku Chemical Industry Co., Ltd., melting point 85 ° C.).
(B-2) 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, trade name “TINUVIN P” (manufactured by BASF, melting point 128 to 132 ° C.)

[Possibility of pelletization]
Whether or not pelletization was possible was evaluated as “◯” when the strand coming out from the strand outlet 5 of the die part 4 was water-cooled and then guided to a pelletizer, where continuous pelletization was possible, and “x” when impossible.

[Extruder]
The extruder used for the Example and the comparative example used the twin-screw extruder (Toshiba Corp. make, TEM26SS: 14 barrel).
The kneading block and the progressive screw block used in the first kneading part are shown below. Moreover, all are 2 type.
B: L / D = 1.03, B = 7, α = 45 degrees C: L / D = 1.03, B = 5, α = 45 degrees F: L / D = 1.03, B = 7 sheets, α = 90 degrees G: L / D = 1.03, B = 5 sheets, α = 90 degrees I: L / D = 0.76, B = 5 sheets, α = 135 degrees L: L / D = 1.03, R / D = 1.03
The screw designs used in the examples and comparative examples of the first kneading part are shown below.
U: BFBLCCGGGFCI L / D = 13.1
V: BFBLCGFGCI L / D = 10.9

[Example 1]
(A) 100 parts by mass and (B-1) 15 parts by mass are supplied by separate quantitative feeders, the cylinder temperature is 70 ° C. for the first conveying unit, and 220 ° C. after the first kneading unit, for a total supply of 30 kg / Hour, screw rotation number 300 rpm, extrusion was performed at the first kneading part screw design U. The pelletization at that time was “◯”.

[Example 2]
(A) 100 mass parts and (B-1) 45 mass parts were extruded on the same conditions as Example 1. FIG.
The pelletization at that time was “◯”.

[Example 3]
It changed into the 1st kneading part screw design V, and the extrusion was performed on the same conditions as Example 2 others. The pelletization at that time was “◯”.

[Example 4]
Extrusion was performed under the same conditions as in Example 1 except that (A) 100 parts by mass and (B-2) 45 parts by mass were changed to 110 ° C. in the cylinder temperature of the first conveying unit. The pelletization at that time was “◯”.

[Example 5]
(A) 100 parts by mass, (B-1) 20 parts by mass, and (B-2) 20 parts by mass were extruded under the same conditions as in Example 1. The pelletization at that time was “◯”.

[Comparative Example 1]
(A) 100 mass parts and (B-1) 50 mass parts were extruded on the same conditions as Example 1. FIG.
At that time, the pelletization was “x” because the melt viscosity of the strand was low and the take-up was difficult.

[Comparative Example 2]
Extrusion was performed under the same conditions as in Example 1 except that (A) 100 parts by mass and (B-1) 30 parts by mass were changed to the cylinder temperature of the first conveying unit at 100 ° C. At that time, the pelletization was “x” because the unmelted material (A) was vented up from the vacuum vent 3.

[Comparative Example 3]
Extrusion was performed under the same conditions as in Example 1 except that (A) 100 parts by mass and (B-2) 30 parts by mass were changed to the cylinder temperature of the first conveying unit at 150 ° C. At that time, the pelletization was “x” because the unmelted material (A) was vented up from the vacuum vent 3.

With the production method satisfying the provisions of the present invention, it is possible to produce a masterbatch containing a high concentration of a light-resistant stabilizer that could not be produced until now, and to improve handling at the molding site. .

  1: Extruder, 2: Raw material inlet, 3: Vacuum vent, 4: Die part, 5: Strand outlet, 6: First transport part, 7: First kneading part

Claims (4)

  (A) A master batch production method containing 12 to 47 parts by mass of (B) a light-resistant stabilizer with respect to 100 parts by mass of a styrene-based thermoplastic resin. A method for producing a thermoplastic resin composition, wherein the temperature is equal to or lower than the melting point of the (B) light-resistant stabilizer. The extruder is a twin screw extruder, and the first kneading section has at least one kneading block (1) to (3) below and (4) a forward feed screw block, and the most upstream side of the kneading section. The manufacturing method according to claim 1, wherein (1) and (3) are provided on the most downstream side, and the L / D of the kneading part is 8 to 15.
(1) Kneading block with L / D = 0.4 to 1.5, B = 3 to 10 and α = 20 to 80 degrees (2) L / D = 0.4 to 1.5, B = Kneading block with 3-10 sheets, α = 90 degrees (3) Kneading block with L / D = 0.4-1.5, B = 3-10 sheets, α = 100-170 degrees (4) L / D = 0.3-3.0, R / D = 0.3-1.5 forward screw block (where L is the length of the kneading block and the forward screw block (mm), D is the screw The diameter (mm), B represents the number of blades constituting the kneading block (sheets), α represents the twist angle (degrees) between two adjacent blades, and R represents the lead length (mm) of the screw block. )   (A) The production method according to claim 1 or 2, wherein the styrenic thermoplastic resin is a polystyrene resin. The molded product shape | molded using the masterbatch manufactured with the manufacturing method of any one of Claims 1-3.

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