JP6574092B2 - Masterbatch manufacturing method - Google Patents

Description

  The present invention relates to a method for producing a masterbatch in which a functional imparting agent 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 2009-102633 A JP 2006-96939 A

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

  As a result of intensive studies on the above problems, the present inventor completed the present invention by supplying a functionality-imparting agent with a side feeder.

That is, the present invention is as follows .
( A) A method for producing a masterbatch containing 47 parts by mass or less of (B) a functionality-imparting agent with respect to 100 parts by mass of a styrene-based thermoplastic resin,
Using an extruder, supplying the functionality-imparting agent (B) with a side feeder,
The extruder is a twin screw extruder, the L / D of the section to the first kneading part downstream from the side feeder is 0.6 to 2.0,
The kneading part has (1) on the most upstream side and (3) on the most downstream side, and between (1) and (3), at least one (5), (1) At least one or more from (4),
(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) Notched screw block (5) L / D = 0.3-3.0, R / D = 0.3-3.0, R / D = 0.3-3.0, R / D = 0. 3 to 1.5 progressive screw block (where L is the length of the kneading block and the progressive screw block (mm), D is the screw diameter (mm), B is the number of blades constituting the kneading block (sheets) ), Α is the twist angle (degrees) between two adjacent blades, and R is the lead length (mm) of the screw block It is.)
L / D of the kneading part is 7 to 14,
(B) The method for producing a masterbatch, wherein the function-imparting agent is a hindered amine light stabilizer and / or a benzotriazole ultraviolet absorber .

  According to the present invention, it has become possible to produce a master batch in which a functionality-imparting agent is blended at a high concentration, which has been difficult to produce until now.

It is a schematic diagram which shows the area from the side feeder and the first kneading | mixing part downstream from a side feeder prescribed | regulated by this invention, and a side feeder to a kneading part.

  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.

(B) Functionality-imparting agent used in the present invention is (A) one that melts prior to the styrene-based thermoplastic resin, and is a hindered amine-based light stabilizer, a benzotriazole-based UV absorber, and a benzophenone-based UV absorber. , Triazine UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, nickel complex UV absorbers, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, anionic antistatic agents , Cationic antistatic agents, nonionic antistatic agents, amphoteric antistatic agents, bromine-based flame retardants, phosphorus-based flame retardants, and the like. Of these, hindered amine light stabilizers and benzotriazole ultraviolet absorbers are preferred. (B) Functionality-imparting agents 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) And hindered amine compounds such as -1,2,3,4-butanetetracarboxylate. 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 functionality imparting agent is 47 mass parts or less with respect to 100 mass parts of (A) styrene-type thermoplastic resins. Preferably it is 40 mass parts or less. 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, a fatty acid lubricant as a lubricant, an aliphatic amide lubricant, a metal soap lubricant, a talc as a foam nucleating agent, a pigment as a colorant, a dye, 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

  A side feeder is used as the method for charging the (B) functionality-imparting agent of the present invention. When charged from the main hopper, the (B) functionality-imparting agent melts before the (A) styrenic thermoplastic resin and kneading is not sufficiently performed, and (A) the styrenic thermoplastic resin becomes unmelted, Vent up. The L / D of the section from the side feeder to the first kneading section downstream from the side feeder is preferably 0.6 to 2.0. More preferably, it is 0.8-1.8.

The screw design of the first kneading section downstream from the side feeder is not particularly limited, but a screw design that satisfies the following conditions is preferable.
The kneading part has (1) on the most upstream side and (3) on the most downstream side, and has at least one (5) and at least one from (1) to (4) between the kneading parts.
(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) Notched screw block (5) L / D = 0.3-3.0, R / D = 0.3-3.0, R / D = 0.3-3.0, R / D = 0. A progressive screw block that is 3 to 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) Notched screw block with L / D = 0.4-2.8, R / D = 0.4-1.4 (5) L / D = 0.4-2.8, R / D = 0. 4 to 1.4, progressive screw block where L is the length of the kneading block and the progressive screw block (mm), D is the screw diameter (mm), B is the number of blades constituting the kneading block (sheets) , Α represents a twist angle (degree) between two adjacent blades, and R represents a lead length (mm) of the screw block.
It is preferable that L / D of a kneading part is 7-14. More preferably, it is 8.5-12.

As an example of the arrangement, from the upstream side, (1) (2) (1) (3) (5) (1) (1) (2) (2) (1) (2) (1) (2) (3 ),
(1) (2) (3) (5) (4) (4) (4) (4) (1) (2) (1) (2) (3),
(1) (1) (2) (2) (5) (4) (4) (4) (1) (1) (2) (2) (3),
(1) (2) (1) (3) (5) (4) (4) (4) (1) (5) (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 the functionality-imparting agent.
(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 6 of the die portion 5 was water-cooled and then led 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, notched screw block and progressive screw block used in the kneading section are shown below. Moreover, all are 2 type.
B: L / D = 1.04, B = 5 sheets, α = 45 degrees C: L / D = 0.77, B = 5 sheets, α = 45 degrees F: L / D = 1.04, B = 7 sheets, α = 90 degrees G: L / D = 0.77, B = 5 sheets, α = 90 degrees I: L / D = 0.77, B = 5 sheets, α = 135 degrees K: L / D = 0.77, R / D = 1.03, notch M: L / D = 0.77, R / D = 1.03
The screw designs used in the examples and comparative examples of the first kneading section downstream from the side feeder are shown below.
U: BFCIMCCGGCGGF L / D = 11.58
The L / D of the section from the side feeder to the kneading part is 1.63.
V: BFMKKKBBF L / D = 9.04
The L / D of the section from the side feeder to the kneading part is 0.83.

[Example 1]
(A) 100 parts by mass is supplied from the main hopper with a quantitative feeder, (B-1) 15 parts by mass is supplied with a side feeder, the cylinder temperature is 200 ° C., the total supply amount is 30 kg / hour, and the screw rotation speed The kneading part was extruded with a screw design U at 300 rpm. 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]
(A) 100 mass parts and (B-2) 45 mass parts were extruded on the same conditions as Example 1. FIG. 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]
(A) 100 parts by mass and (B-1) 30 parts by mass were mixed using a tumbler, then fed from the main hopper with a quantitative feeder, and the others were extruded under the same conditions as in Example 1. The pelletization at that time was “x” because the unmelted material (A) was vented up from the vent 1.

[Comparative Example 3]
(A) 100 parts by mass and (B-2) 30 parts by mass were mixed using a tumbler, then fed from the main hopper with a quantitative feeder, and the others were extruded under the same conditions as in Example 1. The pelletization at that time was “x” because the unmelted material (A) was vented up from the vent 1.

The production method that satisfies the provisions of the present invention can produce a masterbatch containing a high-concentration functional imparting agent that could not be produced until now, and can improve handling at the molding site. it can.

1: Extruder, 2: Main hopper, 3: Vent 1, 4: Vent 2, 5: Die section, 6: Strand outlet, 7: Side feeder, 8: Section from side feeder to kneading section, 9: Side feeder The first kneading section downstream

Claims (1)

(A) A method for producing a masterbatch containing 47 parts by mass or less of (B) a functionality-imparting agent with respect to 100 parts by mass of a styrene-based thermoplastic resin,
Using an extruder, supplying the functionality-imparting agent (B) with a side feeder,
The extruder is a twin screw extruder, the L / D of the section to the first kneading part downstream from the side feeder is 0.6 to 2.0,
The kneading part has (1) on the most upstream side and (3) on the most downstream side, and between (1) and (3), at least one (5), (1) At least one or more from (4),
(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) Notched screw block (5) L / D = 0.3-3.0, R / D = 0.3-3.0, R / D = 0.3-3.0, R / D = 0. 3 to 1.5 progressive screw block (where L is the length of the kneading block and the progressive screw block (mm), D is the screw diameter (mm), B is the number of blades constituting the kneading block (sheets) ), Α is the twist angle (degrees) between two adjacent blades, and R is the lead length (mm) of the screw block It is.)
L / D of the kneading part is 7 to 14,
(B) The method for producing a masterbatch, wherein the function-imparting agent is a hindered amine light stabilizer and / or a benzotriazole ultraviolet absorber.

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