JP2000202887A - Manufacture of thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially stably manufacture by adding a liquid-like additive from a supply port provided between a final vacuum vent and a die, eliminating leakage of the additive to the vacuum vent side by a screw element constitution, and providing a distributing mixing function. SOLUTION: An adding facility of a liquid-like additive is provided between a final vacuum vent and a die, and the additive is supplied from a feed nozzle provided at a barrel of an extruder. A screw constitution between the nozzle and the vent is a special constitution of a single or a combination of a short lead screw element and a seal ring or the like for inhibiting to leak the additive to the vent side. Further, the screw constitution between the nozzle and the vent is a special constitution or the like of a combination of a cutout screw element or a cutout screw element having a distributing mixing function and a kneading screw element.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to the production of a thermoplastic resin composition containing an additive which is liquid when added to a thermoplastic resin. More specifically, a thermoplastic resin composition in which a liquid additive including a volatile liquid additive is added to a thermoplastic resin by using a special distributive mixing / melting extruder so that the additive which is liquid at the time of addition can be added at a high level. The present invention relates to a method for manufacturing a product.

[0002]

2. Description of the Related Art Thermoplastic resins take advantage of their properties and include OA equipment such as word processors, personal computers, printers and copiers, home appliances such as TVs, VTRs and audios, electric and electronic parts, automobile parts, miscellaneous goods and the like. Used in a variety of fields.

[0003] In recent years, in this field, higher functionality has been developed, and at the same time, various polymer additives have been added to impart functionality to the thermoplastic resin. For example, it is common practice to add liquid paraffin (mineral oil) to improve processability, or to add and mix silicone oil or the like to impart releasability or slidability. Furthermore,
It is common practice to add an antistatic agent, a flame retardant, and the like to provide an antistatic function and flame retardancy. However, some of these polymer additives are liquid compounds and liquid and volatile compounds.

[0004] Conventionally, as a method for producing a thermoplastic resin composition comprising a thermoplastic resin and a liquid additive as described above, a thermoplastic resin (hereinafter, referred to as a base) having a pellet shape and / or a powder shape as a base is generally used. Resin) and liquid additives are solid-mixed in a tumbler mixer, Henschel mixer, super mixer, etc., temporarily stored in a hopper (storage tank), and melt-kneaded using a single-screw, twin-screw, special extruder, etc. Has been used. However, in these production methods, when the amount of the liquid additive to the base resin exceeds several parts by weight, it is difficult to uniformly mix the liquid additive with the base resin. Further, even if mixing is possible, there is a problem that the mixture hardens in a lump or the surface becomes sticky, so that a fixed amount feed to a weighing machine or an extruder in the front cannot be performed.

Further, even if the raw material can be fed to the extruder, there are problems such as poor plasticization of the resin due to insufficient shearing, fluctuations in extrusion due to poor distribution and mixing of liquid additives, and fluctuations in the composition.

[0006] When the volatile additive is kneaded into the base resin in a liquid state by the above-mentioned production method, the same behavior as described above is exhibited. Furthermore, even if feed could be made to the extruder,
There is a problem that a part / or most of the volatile additive is volatilized in the vacuum degassing step, and a satisfactory product cannot be obtained.

On the other hand, Japanese Patent Application Laid-Open No. 10-29238 discloses a special production condition (average degree of decompression at a vent opening of 1%) for producing a thermoplastic resin composition comprising a styrene resin and a liquid volatile additive. To 300 Torr and an average vent port temperature of 150 to 300 ° C.). Japanese Patent Application Laid-Open No. 8-92264 discloses a method for producing a flame-retardant resin composition by supplying a liquid phosphoric acid ester compound to a styrene resin in the middle (supplying the styrene resin at a downstream side of a styrene resin feed site).

However, even in these methods, there is a problem that stable production is difficult due to the amount of the liquid additive and the composition of the liquid additive, and the production efficiency is low. Further, there is a problem that the overall length (L / D) of the extruder becomes extremely long.

[0009]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention has been made in the production of a thermoplastic resin composition containing a liquid additive in a thermoplastic resin, which is free from the above-mentioned problems. It is an object of the present invention to stably produce a plastic resin composition industrially.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, added a liquid additive after the final vacuum vent and a screw between the final vacuum vent and the die. As an element configuration, liquid additives are prevented from leaking to the final vacuum vent side, and
The present invention has been achieved by manufacturing with an extruder in which screw elements are combined so as to have a distributive mixing function.

That is, the present invention relates to (A) thermoplastic resin 100
In the method for producing a thermoplastic resin composition containing 25 parts by weight or less (but not including 0 parts by weight) of an additive which is liquid at the time of addition of (B), the liquid of (B) Additives are added from a supply port provided between the final vacuum vent and the die, and a screw element between the final vacuum vent and the die is used to prevent liquid additives from leaking to the final vacuum vent side, and to distribute and mix. This is a method for producing a thermoplastic resin composition produced by an extruder in which screw elements are combined so as to have a function.

Further, the present invention preferably provides (a) at least a notched screw element or a screw element between a die and a supply port of a liquid additive.
The distributing and mixing zone consisting of a combination having a notched screw element and a kneading element, and the distributing and mixing zone after the addition of the liquid additive is manufactured by an extruder having a distributing and mixing function while having a very short configuration of L / D = 5 to 10 (B) The screw element configuration between the final vacuum vent and the liquid additive supply port should be at least 0.8
(D) combining with a short lead screw element of D or less and using an extruder having L / D = 2 to 3;
The extruder is a twin-screw extruder, (d) the thermoplastic resin of (A) is a styrene resin, (e) the liquid additive of (B) is silicone oil, liquid paraffin (mineral oil), It is desired that at least one additive selected from a kneading type antistatic agent and a flame retardant is used. These may be any preferable combinations, and it is not necessary to select all of them.

Hereinafter, the present invention will be described in detail. The present invention relates to a method for producing a thermoplastic resin composition comprising (A) a thermoplastic resin and the liquid additive (B), wherein the (A) comprises a main component of the thermoplastic resin composition for molding. None, plays a role in maintaining the strength of the molded product, and (B) is a component for imparting functionality to (A).

The thermoplastic resin (A) of the present invention includes:
Examples include homopolymers of styrene, copolymers of monomers copolymerizable with styrene, and rubber-reinforced styrene resins. For example, polystyrene, rubber reinforced polystyrene (HIPS), acrylonitrile-styrene copolymer resin (AS), acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-
Examples include acrylic rubber-styrene copolymer resin (AAS), acrylonitrile-ethylene propylene rubber-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, and styrene-butadiene copolymer resin. In addition, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polyamide, methyl methacrylate resin, polypropylene and the like can be mentioned. These thermoplastic resins can be used alone or in combination of two or more.

The liquid additive (B) of the present invention includes a lubricant, a sliding agent, an antistatic agent, a flame retardant, a plasticizer, a stabilizer, an ultraviolet absorber, an antioxidant, a foaming agent, a coloring agent and the like. Liquid compounds therein may be used, and these may be used alone or in combination of two or more. The liquid additive does not necessarily need to be in a liquid state at normal temperature, and may be a liquid additive that is in a liquid state when mixed with a molten resin by an extruder. The liquid state is not particularly limited as long as it can be appropriately supplied by selecting a metering pump according to the characteristics (viscosity and the like) of the liquid additive.

Among the above additives, examples of the lubricant include silicone oil and liquid paraffin (mineral oil). Silicone oil can also be used for a sliding agent. The silicone oil used is a silicone oil for modifying plastics, such as dimethyl silicone oil, methylphenyl silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, and mercapto-modified silicone oil. These can be used alone or in combination of two or more.

The liquid paraffin is a mixture of liquid saturated hydrocarbons and the like, so-called mineral oil.

Examples of the antistatic agent (B) of the present invention include an amide compound having a hydroxyethyl group and a polyhydric alcohol fatty acid ester of a kneading type antistatic agent, and these may be used alone or in combination of two or more. Can be used simultaneously.

Examples of the flame retardant (B) of the present invention include a halogen-containing aromatic flame retardant and a phosphate ester flame retardant, and these may be used alone or in combination of two or more.

Examples of the halogen-containing aromatic flame retardants include tetrabromobisphenol A and dibromobisphenol A. Examples of the phosphoric acid ester-based flame retardant include compounds obtained by modifying a phosphoric acid ester with various substituents, various condensed-type phosphoric acid ester compounds, and the like, and one or two or more of these are used simultaneously. I can do it.

The liquid additive (B) of the present invention is used in an amount of 25 parts by weight or less (but not including 0 parts by weight) based on 100 parts by weight of the thermoplastic resin (A). If the amount exceeds 25 parts by weight, the liquid additive may be insufficiently distributed and mixed, and the liquid additive may seep out or blow out from the die hole. In addition, the additive attached to the die hole is decomposed and deteriorated by heating at the die site for a long period of time, which causes eye dust.

The amount of the silicone oil, liquid paraffin (mineral oil), and antistatic agent (B) to be added is 25 parts by weight or less based on 100 parts by weight of the thermoplastic resin (A) (however, 0 parts by weight Not included), preferably 3 to 15 parts by weight, more preferably 5 to 10 parts by weight. The amount of the flame retardant added in (B) is (A)
25 parts by weight or less (however, not including 0 parts by weight) with respect to 100 parts by weight of the thermoplastic resin, preferably 5 to 15 parts by weight.
Parts by weight, more preferably 10 to 15 parts by weight.

The extruder used in the present invention is an extruder provided with a device for adding a liquid additive between a final vacuum vent and a die, and it is not always necessary to provide one vacuum vent.
As the extruder, any known extruder can be used as long as the above (A) can obtain sufficient plasticization and melt kneading before the final vacuum vent. Preferably, it is a twin screw extruder, more preferably a co-directional twin screw extruder.

In the equipment for adding a liquid additive of (B), a liquid is supplied from a feed nozzle provided in a barrel of the extruder at a discharge pressure equal to or higher than the resin pressure in the extruder by a well-known pump for transporting liquid. The feed nozzle has a check valve function at a contact portion with the resin.

The screw structure between the feed nozzle for adding the liquid additive (hereinafter referred to as liquid addition) and the final vacuum vent in (B) has a special configuration in which the liquid additive does not leak to the final vacuum vent side. For example, a short lead screw element and a configuration in which a short lead screw element having at least 0.8 D or less is combined and L / D = 2 or more may be used alone or in combination.
It is preferred to have 3. However, it is desirable that the lead length be short unless venting up. The term “lead” as used herein refers to the distance the screw makes one turn and travels in the axial direction. Here, L indicates the screw length of the extruder, and D indicates the inner diameter of the cylinder.

It is important that the screw structure between the liquid feed nozzle and the die be a special screw structure having a distributing and mixing function. For example, in consideration of the torsion angle, thickness, and number of disks of the disk, a combination configuration of a right kneading disk, a left kneading disk, a neutral, a notched screw, and the like can be given.
Preferably, a configuration comprising at least a notched screw element or a combination having a notched screw element and a kneading screw element is exemplified.

It is preferable that the ratio (L / D) of the screw length (L) of the extruder to the cylinder inner diameter (D) between the liquid feed nozzle and the die is 5.0 to 10. Furthermore, 7.0-10 are desirable. L / D = 5
If it is smaller, the structure becomes too tight, and there is a risk of venting up due to excessive back pressure on the final vacuum vent side, and deterioration of the resin and additives due to excessive shearing. When L / D is more than 10, the residence time in the extruder becomes long, and there is a possibility that the resin and additives are decomposed and deteriorated.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
Further, the addition amount of each material shown in parts by weight indicates their supply ratio.

Examples 1 to 3 A thermoplastic resin composition consisting of HIPS / silicone oil = 75 to 95/25 to 5 was produced by the following method. Using a Kobe Steel H-KTX-30XHT coaxial twin-screw extruder having a vent connected to a vacuum device, HIPS was supplied from the main feed opening, and the liquid was heated to a liquid temperature of 80 ° C. from the liquid feed nozzle. Feed silicone oil, melt extrusion temperature (barrel temperature) 180-200 ° C
In this case, the discharge rate is 50 kg / h and the screw rotation speed is 420 rpm
m, and a good product was obtained. Also, no inflow of silicone oil into the vent pot was observed. Further, the Si content in the product is almost equal to the theoretical value. The results are shown in Table 1. Example 1 below
Co-extruded twin screw extruder HK used in Kobe Steel Co., Ltd.
TX-30XHT, L / D = 46.8, final vent ~
L / D between the dies = 11, L / D between the liquid additive supply port and the die = 9, and the screw configuration between the final vent and the liquid additive supply port is a short lead screw element = 0.8 D The screw configuration between the supply port of the liquid additive and the die is notched screw element = 0.8D, kneading screw element = 1.0D, full flight screw element = 0.8D Were used in combination of four.

The HIPS used here was HI-U2U manufactured by Denki Kagaku Kogyo Co., Ltd., and the silicone oil used was KF96H (kinematic viscosity 30,000 centistokes / 25 ° C.) manufactured by Shin-Etsu Chemical Co., Ltd.

Comparative Example 1 The same thermoplastic resin composition as in Example 1 was produced by the following method. After dry blending HIPS and silicone oil at a mixing ratio of 95/5, a co-axial twin screw extruder H-KTX-30 manufactured by Kobe Steel having a vent connected to a vacuum device.
XHT (L / D = 46.8, L between last vent and die)
/ D = 11), the mixture was put into the hopper of the main feed supply port, and fed from the quantitative feeder to the main feed opening. When melt kneading was performed at a melt extrusion temperature (barrel temperature) of 180 to 200 ° C. in the same manner as in Example 1, the mixture was blocked in the hopper and in the main feed supply port, making it difficult to perform quantitative feeding. In addition, the mixture was always manually broken to block the mixture and the mixture was fed to the main feed supply port. However, a phenomenon of poor plasticization of the resin due to poor shear occurred and extrusion was not possible. The results are shown in Table 1.

Examples 4-6 HIPS / liquid paraffin (mineral oil) = 75-
A thermoplastic resin composition consisting of 95/25 to 5 was produced by the following method. Using a Kobe Steel H-KTX-30XHT coaxial twin-screw extruder having a vent connected to a vacuum device, HIPS is supplied from the main feed opening, and liquid paraffin (normal temperature) is fed from a liquid feed nozzle. , Melt extrusion temperature (barrel temperature) 180-200 ° C
The discharge rate is 50 kg / h and the screw rotation speed is 350 rpm
m, and a good product was obtained. Also, no inflow of liquid paraffin into the vent pot was observed. The results are shown in Table 2.

The HIPS used here was HI-U2U manufactured by Denki Kagaku Kogyo Co., Ltd., and the liquid paraffin (mineral oil) was White Lec 3 manufactured by Mobile Oil Co., Ltd.
35 (kinematic viscosity 70 centistokes / 40 ° C.) was used.

Comparative Example 2 The same thermoplastic resin composition as in Example 4 was produced by the following method. HIPS and liquid paraffin (mineral oil)
Was dry-blended at a mixing ratio of 95/5, and a co-axial twin screw extruder H-KTX-30XHT manufactured by Kobe Steel Co., Ltd. having a vent connected to a vacuum device (L / D = 46.8, between the final vent and the die) Of L / D = 11), the mixture was put into the hopper of the main feed supply port, and fed from the fixed amount feeder to the main feed opening. When melt-kneading was performed at a melt extrusion temperature (barrel temperature) of 180 to 200 ° C. as in Example 4, the mixture was blocked in the hopper and the main feed supply port as in the case of silicone oil, making it difficult to feed quantitatively. Met. In addition, when the mixture was always manually blocked to break the blocking and sent to the main feed supply port, the HIPS slipped and could not be extruded because it did not bite into the screw. The results are shown in Table 2.

Examples 7 to 9 HIPS / kneading type antistatic agent = 75 to 95/25 to
5 was produced by the following method. HIP was performed using a co-axial twin screw extruder H-KTX-30XHT manufactured by Kobe Steel Co., Ltd. having a vent connected to a vacuum device.
S is supplied from the main feed opening, and a kneading type antistatic agent (normal temperature) is fed from the liquid feed nozzle, and the melt extrusion temperature (barrel temperature) is 180 to 200 ° C.
Discharge rate 50kg / h, extruder screw rotation speed 350r
A good product was obtained by melt extrusion at pm. Further, no inflow of the antistatic agent into the vent pot was observed. The results are shown in Table 3.

The HIPS used here was HI-U2U manufactured by Denki Kagaku Kogyo Co., Ltd., and the mixed antistatic agent was an electrostripper EA (Kinematic viscosity 9) manufactured by Kao Corporation.
0 centistokes / 25 ° C.).

Comparative Example 3 The same thermoplastic resin composition as in Example 8 was produced by the following method. 90 HIPS and electro stripper EA
After dry blending at a mixing ratio of / 10, a coaxial twin-screw extruder H- manufactured by Kobe Steel Co., Ltd. having a vent connected to a vacuum device.
KTX-30XHT (L / D = 46.8, final vent ~
Using L / D between dies = 11), the mixture was charged into the hopper of the main feed supply port, and fed from the quantitative feeder to the main feed opening. When melt-kneading was performed at a melt extrusion temperature (barrel temperature) of 180 to 200 ° C. in the same manner as in Example 8, the mixture was blocked in the hopper and the main feed supply port as in the case of silicone oil, making it difficult to feed quantitatively. Met. In addition, although the blocking of the mixture was broken manually and sent to the main feed supply port, the HIPS slipped like the liquid paraffin (mineral oil) and could not be extruded because it did not bite into the screw. The results are shown in Table 3.

Examples 10 to 15 A thermoplastic resin composition comprising HIPS / phosphate ester = 75 to 95/25 to 5 was produced by the following method. HIPS was supplied from the main feed opening using a co-directional twin screw extruder H-KTX-30XHT manufactured by Kobe Steel having a vent connected to a vacuum device, and the liquid was heated to a liquid temperature of 80 ° C from a liquid feed nozzle. The phosphate ester is fed, and at a melt extrusion temperature (barrel temperature) of 170 to 210 ° C,
Discharge rate 50kg / h, extruder screw rotation speed 350r
A good product was obtained by melt extrusion at pm. Also, no phosphate ester flowed into the vent pot. Furthermore, the phosphorus (P) content in the product is almost equal to the theoretical value. The results are shown in Tables 4 and 5.

The HIPS used here was HI-U2U manufactured by Denki Kagaku Kogyo Co., Ltd., and the phosphate ester was Example 10
In No. 12 to 12, an aromatic condensed phosphoric acid ester (hereinafter abbreviated as CR733S) manufactured by Daihachi Chemical Industry Co., Ltd.
In Examples 13 to 15, triphenyl phosphate (hereinafter abbreviated as TPP) manufactured by Daihachi Chemical Co., Ltd. was used.

Comparative Example 4 The same thermoplastic resin composition as in Example 11 was produced by the following method. After HIPS and CR733S are dry-blended at a mixing ratio of 90/10, a co-axial twin-screw extruder H-KTX-30 manufactured by Kobe Steel having a vent connected to a vacuum device.
XHT (L / D = 46.8, L between last vent and die)
/ D = 11), the mixture was put into the hopper of the main feed supply port, and fed from the quantitative feeder to the main feed opening. When melt kneading was performed at a melt extrusion temperature (barrel temperature) of 170 to 210 ° C. in the same manner as in Example 11, similar to the silicone oil, the inside of the hopper was melted.
In addition, the mixture was blocked at the main feed supply port, and it was difficult to feed quantitatively. In addition, the mixture was always manually broken to block the mixture and sent to the main feed supply port.
In the same manner as in the above, the HIPS slipped and did not bite into the screw so that extrusion was not possible. The results are shown in Table 4.

Comparative Example 5 The same thermoplastic resin composition as in Example 14 was produced by the following method. After dry blending HIPS and TPP in a 90/10 blend ratio, a co-axial twin screw extruder H-KTX-30XHT manufactured by Kobe Steel having a vent connected to a vacuum device.
(L / D = 46.8, L / D between final vent and die)
Using 11), the mixture was put into the hopper of the main feed supply port, and fed from the quantitative feeder to the main feed opening. When the melt kneading was attempted at a melt extrusion temperature (barrel temperature) of 170 to 210 ° C. as in Example 14, the mixture was blocked in the hopper and at the main feed supply port as in Comparative Example 4, and the quantitative feed was reduced. It was difficult. In addition, the mixture was always manually broken to block the mixture, and the mixture was fed to the main feed supply port. However, extrusion could not be performed due to the occurrence of strand bumps and vent up due to poor shearing. The results are shown in Table 5.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

Examples 16 to 18 Thermoplastic resin compositions comprising ABS / silicone oil = 75 to 95/25 to 5 were produced by the following method. Using a Kobe Steel H-KTX-30XHT coaxial twin-screw extruder having a vent connected to a vacuum device, ABS was supplied from the main feed opening, and the liquid was heated to 80 ° C. from a liquid feed nozzle. Feed silicone oil, melt extrusion temperature (barrel temperature) 200 ~ 210 ℃,
Melt extrusion was performed at a discharge rate of 50 kg / h and a screw rotation speed of 450 rpm to obtain a good product. Also, no inflow of silicone oil into the vent pot was observed.
Further, the Si content in the product is almost equal to the theoretical value.
The results are shown in Table 6.

The ABS used here was GR2000 manufactured by Denki Kagaku Kogyo Co., Ltd., and the silicone oil used was KF96H (kinematic viscosity 30,000 centistokes / 25 ° C.) manufactured by Shin-Etsu Chemical Co., Ltd.

Comparative Example 6 The same thermoplastic resin composition as in Example 16 was produced by the following method. After dry blending ABS and silicone oil at a mixing ratio of 95/5, a co-axial twin-screw extruder H-KTX-30 manufactured by Kobe Steel having a vent connected to a vacuum device.
XHT (L / D = 46.8, L between last vent and die)
/ D = 11), the mixture was put into the hopper of the main feed supply port, and fed from the quantitative feeder to the main feed opening. When melt-kneading was performed at a melt extrusion temperature (barrel temperature) of 200 to 210 ° C. in the same manner as in Example 16, the mixture was blocked in the hopper and in the main feed supply port, making it difficult to feed quantitatively. In addition, when the mixture was constantly broken by hand and sent to the main feed supply port, the ABS slipped and could not be extruded because it did not bite into the screw. The results are shown in Table 6.

Examples 19-21 ABS / liquid paraffin (mineral oil) = 75-9
A thermoplastic resin composition consisting of 5/25 to 5 was produced by the following method. Using a Kobe Steel H-KTX-30XHT coaxial twin-screw extruder having a vent connected to a vacuum device, ABS was supplied from the main feed opening, and liquid paraffin (normal temperature) was fed from a liquid feed nozzle. , Melt extrusion temperature (barrel temperature) 200-210 ° C
With a discharge rate of 50 kg / h and a screw rotation speed of 400 rpm
m, and a good product was obtained. Also, no inflow of liquid paraffin into the vent pot was observed. The results are shown in Table 7.

The ABS used here was GR2000 manufactured by Denki Kagaku Kogyo KK, and the liquid paraffin (mineral oil) was White Wrec 33 manufactured by Mobil Sekiyu KK
5 (kinematic viscosity 70 centistokes / 40 ° C.).

Comparative Example 7 The same thermoplastic resin composition as in Example 19 was produced by the following method. ABS and liquid paraffin (mineral oil)
Was dry-blended at a mixing ratio of 95/5, and a co-axial twin screw extruder H-KTX-30XHT manufactured by Kobe Steel Co., Ltd. having a vent connected to a vacuum device (L / D = 46.8, between the final vent and the die) Of L / D = 11), the mixture was put into the hopper of the main feed supply port, and fed from the fixed amount feeder to the main feed opening. When melt kneading was performed at a melt extrusion temperature (barrel temperature) of 200 to 210 ° C. in the same manner as in Example 19, the mixture was blocked in the hopper and in the main feed supply port as in the case of silicone oil, making it difficult to feed quantitatively. Met. In addition, when the blocking of the mixture was broken manually and sent to the main feed supply port at all times, the ABS slipped as in Comparative Example 6 and could not be extruded because it did not bite into the screw. The results are shown in Table 7.

Examples 22 to 24 ABS / kneading type antistatic agent = 75 to 95/25 to 5
Was produced by the following method.
Using a Kobe Steel H-KTX-30XHT coaxial twin-screw extruder having a vent connected to a vacuum device, HIPS is supplied from the main feed opening, and a kneading type antistatic agent (normal temperature) is supplied from a liquid feed nozzle. )
Melt extrusion temperature (barrel temperature) 200 to 210 ° C, discharge rate 50 kg / h, extruder screw rotation speed 400 rpm
And a good product was obtained. Further, no inflow of the antistatic agent into the vent pot was observed. The results are shown in Table 8.

The ABS used here was GR2000 manufactured by Denki Kagaku Kogyo Co., Ltd., and the kneading type antistatic agent was Electrostripper EA (Kinematic viscosity 90 manufactured by Kao Corporation).
(Centistokes / 25 ° C.).

Comparative Example 8 The same thermoplastic resin composition as in Example 23 was produced by the following method. ABS and Electrostripper EA 90
After dry blending at a mixing ratio of / 10, a coaxial twin-screw extruder H- manufactured by Kobe Steel Co., Ltd. having a vent connected to a vacuum device.
KTX-30XHT (L / D = 46.8, final vent ~
Using L / D between dies = 11), the mixture was charged into the hopper of the main feed supply port, and fed from the quantitative feeder to the main feed opening. When melt kneading was performed at a melt extrusion temperature (barrel temperature) of 200 to 210 ° C. in the same manner as in Example 23, the mixture was blocked in the hopper and the main feed supply port as in the case of silicone oil, making it difficult to feed quantitatively. Met. Also,
The blocking of the mixture was always broken manually and the mixture was sent to the main feed supply port. However, as in Comparative Examples 6 and 7, the ABS slipped and did not bite into the screw, preventing extrusion. The results are shown in Table 8.

Examples 25-30 A thermoplastic resin composition comprising ABS / phosphate ester = 75-95 / 25-5 was produced by the following method. HIPS was supplied from the main feed opening using a co-directional twin screw extruder H-KTX-30XHT manufactured by Kobe Steel having a vent connected to a vacuum device, and the liquid was heated to a liquid temperature of 80 ° C from a liquid feed nozzle. Feed phosphate ester,
Melt extrusion temperature (barrel temperature) 200 to 210 ° C, discharge rate 50 kg / h, extruder screw rotation speed 400 rpm
And a good product was obtained. Also, no phosphate ester flowed into the vent pot. Furthermore, the phosphorus (P) content in the product is almost equal to the theoretical value. The results are shown in Tables 9 and 10.

The ABS used here was GR2000 manufactured by Denki Kagaku Kogyo Co., Ltd.
In No. 27, an aromatic condensed phosphate ester manufactured by Daihachi Chemical Industry Co., Ltd. (hereinafter abbreviated as CR733S), and in Examples 28 to 30, triphenyl phosphate manufactured by Daihachi Chemical Co., Ltd. (hereinafter, referred to as TPP) Abbreviated).

Comparative Example 9 The same thermoplastic resin composition as in Example 26 was produced by the following method. After dry blending ABS and CR733S at a compounding ratio of 90/10, a co-axial twin screw extruder H-KTX-30X manufactured by Kobe Steel having a vent connected to a vacuum device.
HT (L / D = 46.8, L / D between final vent and die)
Using D = 11), the mixture was charged into the hopper of the main feed supply port, and fed from the quantitative feeder to the main feed opening. When melt kneading was performed at a melt extrusion temperature (barrel temperature) of 200 to 210 ° C. in the same manner as in Example 26,
In addition, the mixture was blocked at the main feed supply port, and it was difficult to feed quantitatively. In addition, even though the blocking was broken manually and sent to the main feed supply port, strand bumps and vent up occurred due to poor shearing, and ABS slipped and extruded without biting into the screw as in Comparative Examples 6, 7, and 8. Could not be done. The results are shown in Table 9.

Comparative Example 10 The same thermoplastic resin composition as in Example 29 was produced by the following method. After dry blending ABS and TPP in a 90/10 blend ratio, a co-axial twin screw extruder H-KTX-30XHT manufactured by Kobe Steel having a vent connected to a vacuum device.
(L / D = 46.8, L / D between antistatic agent addition port and die)
D = 9), the mixture was put into a hopper of a main feed supply port, and fed from a quantitative feeder to a main feed opening. When melt-kneading was performed at a melt extrusion temperature (barrel temperature) of 200 to 210 ° C. in the same manner as in Example 29, the mixture was blocked in the hopper and in the main feed supply port as in the case of silicone oil, making quantitative feed difficult. Met. In addition, the mixture was always manually broken to block the mixture and sent to the main feed supply port. However, as in Comparative Example 9, strand bumps and vent-up due to poor shearing and ABS slipped and could not be extruded because the ABS slipped into the screw. . The results are shown in Table 10.

[0060]

[Table 6]

[0061]

[Table 7]

[0062]

[Table 8]

[0063]

[Table 9]

[0064]

[Table 10]

The method of analyzing the above liquid additive will be described below. (1) Content of silicon (Si): For quantification of KF96H in a product, a flat plate having a thickness of 3 mm was prepared from the product by a compression molding method, and a fluorescent X-ray analyzer (SXF-1 manufactured by Shimadzu Corporation) was used.
100), the fluorescent X-ray intensity of Si Kα radiation was determined. On the other hand, a calibration curve for the X-ray intensity and the Si content of a sample with a known Si content was separately prepared, and the Si content of the unknown sample was determined.

(2) Phosphorus (P) content: To determine the amount of phosphoric acid ester in a product, a flat plate having a thickness of 3 mm was prepared from the product by a compression molding method, and a fluorescent X-ray analyzer (SXF manufactured by Shimadzu Corporation) was used. -1100) was used to determine the fluorescent X-ray intensity of P Kα radiation. On the other hand, a calibration curve for the X-ray intensity and the P content of a sample with a known P content was separately prepared, and the P content of an unknown sample was determined.

[0067]

According to the present invention, when a thermoplastic resin composition containing an additive which is liquid at the time of addition to a thermoplastic resin is produced, the amount of the liquid additive to be added and the liquid More stable production is obtained regardless of the composition of the additive, and the production efficiency is good, poor plasticization of the resin, and extrusion fluctuation due to poor distribution and mixing of the liquid additive,
This is a method for producing a thermoplastic resin composition that enables a melt-extrusion method capable of uniformly mixing with high addition without problems such as fluctuation of the composition. Therefore, the thermoplastic resin composition obtained by the production method of the present invention is
It is useful in the field of advanced functions for A equipment and the like, and its industrial utility value is extremely large.

Continued on the front page F term (reference) 4F070 AA15 AA18 AA32 AA47 AA50 AA52 AA54 AB09 AC33 AC43 AC47 AC55 AC92 AC94 AE05 AE07 AE09 FA17 FB06 FC06 4F207 AA13 AB05 AB09 AB16 AH33 AH81 KA01 KA06 KA17 KF01 KA17 KF01 KA17 BB121 BC031 BC041 BC051 BC061 BG061 BN061 BN071 BN101 BN121 BN151 CF061 CF071 CG001 CH071 CL001 CP032 CP052 CP062 CP092 CP102 CP182 EH046 EJ057 EP006 EW047 FB107 FD106 FD137 GQ00

Claims (6)

[Claims] (1) 100 parts by weight of a thermoplastic resin (A)
(B) In a method for producing a thermoplastic resin composition containing 25 parts by weight or less (but not including 0 parts by weight) of an additive which is liquid at the time of addition, the liquid additive of (B) is subjected to a final vacuum. It is added from the supply port provided between the vent and the die, and further, as a screw element configuration between the final vacuum vent and the die, so that the liquid additive does not leak to the final vacuum vent side, and has a distribution mixing function. A method for producing a thermoplastic resin composition, wherein the method is produced by an extruder combining screw elements. 2. A screw element between a die and a supply port of a liquid additive, which comprises at least a notched screw element or a combination having a notched screw element and a kneading element, and is distributed after addition of the liquid additive. L / D = 5 in the mixing zone
The method for producing a thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is produced by an extruder having a dispersing and mixing function in a configuration of (10) to (10). Here, L indicates the screw length of the extruder, and D indicates the inner diameter of the cylinder. 3. The screw element configuration between the final vacuum vent and the liquid additive supply port is at least 0.8 D
Combining the following short lead screw elements, L
3. The method for producing a thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is produced by an extruder having / D = 2 to 3. Here, L indicates the screw length of the extruder, and D indicates the inner diameter of the cylinder. 4. The method for producing a thermoplastic resin composition according to claim 1, wherein the extruder is a twin-screw extruder. 5. The method for producing a thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is a styrene resin. 6. The liquid additive (B) is a silicone oil,
The method for producing a thermoplastic resin composition according to any one of claims 1 to 5, wherein the additive is at least one additive selected from liquid paraffin (mineral oil), a kneading type antistatic agent, and a flame retardant. .