JP2823488B2 - Resin composition for cleaning flame-retardant resins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition for cleaning plastic processing machines. More specifically, the present invention relates to a resin composition for cleaning a flame-retardant resin, which is suitable for cleaning the processing machine after processing the flame-retardant resin.

[0002]

2. Description of the Related Art In the process molding of a flame-retardant resin, foreign matter caused by burning of a preceding resin adhered to a screw or a cylinder at the time of changing a product type is mixed into a succeeding resin product to impair the appearance. Various measures have been taken to eliminate these effects. Especially when molding chlorine-based flame-retardant resin using chlorinated paraffin etc., when switching the subsequent resin to a light-colored resin type, complicated work such as disassembly cleaning of the molding machine and co-washing with cleaning resin and long time are required. Cleaning work with production stoppage.

In order to solve these problems, various resin compositions for cleaning a molding machine have been developed as a method for cleaning the inside of the molding machine. For example, JP-A-62-195045 discloses that
Alkylbenzenesulfonic acid sodium salt 2-30% by weight of thermoplastic resin, water-repellent compound (higher fatty acid metal salt,
Wax, liquid paraffin, synthetic wax, etc.)
A composition containing 0% by weight is disclosed in JP-A-63-66245.
No. 2 to 30% by weight of an alkylbenzenesulfonic acid sodium salt in a thermoplastic resin, and an average particle size of 0.005 to 20%.
A composition containing 0.05 to 5% by weight of a powdery inorganic compound (silicon dioxide, diatomaceous earth, etc.) of
No. 1,809,41 discloses a composition in which 1 to 20% by weight of a boric acid ester calcium salt of a higher fatty acid monoglyceride and 2 to 45% by weight of an inorganic filler are blended in a thermoplastic resin.
Japanese Patent Application No. 4-670100 discloses that a thermoplastic resin is composed of an inorganic compound (such as silicic anhydride) having a calcium salt of boric acid ester of higher fatty acid monoglyceride of 0.5 to 15% and an average particle size of 0.005 to 20 μm. JP-A-58-149998 discloses a composition containing 5% by weight of a nonionic surfactant having a decomposition initiation temperature of 200 ° C. or higher.
15% by weight, metal soap 5-30% by weight, inorganic filler 20
-70% by weight and olefin-based resin 20-70% by weight
The cleaning resin composition comprising:
No. 9 is composed of a thermoplastic resin, an inorganic filler and a lubricant, wherein the inorganic filler is about 30 to 70% by weight, and the lubricant is about 1 to 3%.
A resin composition for cleaning in a molding machine characterized by occupying 0% by weight is disclosed.

[0004] However, when these cleaning resin compositions are used for cleaning a molding machine processed with a flame-retardant resin,
Deposits due to burning of the preceding flame-retardant resin adhered to the screw or cylinder of the extruder or injection molding machine cannot be completely removed. For example, cleaning by disassembly by removing the screw takes time and people, and cleaning by replacing the preceding resin with the succeeding resin requires a large amount of the succeeding resin. The adhering matter often mixes with the subsequent resin and impairs the appearance of the product.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve these problems of the prior art. In the case of switching types in the molding of a flame-retardant resin, it is difficult to adhere to a screw or a cylinder of a molding machine. When using the following resin to wash the deposit of the preceding flame-retardant resin or the deposit showing the burning phenomenon, the amount of resin used is reduced, the cleaning time is shortened, and the subsequent products are not adversely affected. An object of the present invention is to provide a resin composition for cleaning a resin.

[0006]

Means for Solving the Problems As a result of repeated studies on the above-mentioned problems, the present inventors have found that natural zeolites and synthetic zeolites are mixed with a thermoplastic resin in the form of calcium borate salt of higher fatty acid monoglyceride.
The present inventors have found that a resin composition for cleaning a flame-retardant resin which has a hardness at the time of melting and has a large peeling effect and can solve the above-mentioned problems can be obtained.

That is, the resin composition for cleaning a flame-retardant resin of the present invention is a composition for cleaning a resin processing machine containing a thermoplastic resin as a main component, wherein the thermoplastic resin contains a calcium borate ester of a higher fatty acid monoglyceride in the thermoplastic resin. 0.5 to 15% by weight based on the composition and 0.1 to 15% by weight of the zeolite based on the composition.

Preferred thermoplastic resins include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene terpolymer (hereinafter referred to as AB).
S resin) and at least one resin selected from the group consisting of acrylonitrile-styrene resin (hereinafter, referred to as AS resin). The mixing ratio of the thermoplastic resin is preferably from 75 to 90% by weight based on the composition. Also,
The resin composition for cleaning a flame-retardant resin is preferably processed into pellets.

The calcium salt of a boric acid ester of a higher fatty acid monoglyceride used in the composition of the present invention is a calcium salt of a boric acid ester derived from a higher fatty acid monoglyceride having an alkyl group having 11 to 17 carbon atoms. Is 0.5 to 15 with respect to the composition.
% By weight, preferably 1 to 10% by weight. If the content is less than 0.5%, the effect of washing the preceding flame-retardant resin is small, and if it exceeds 15% by weight, the lubricity with the screw is increased and granulation becomes difficult. The calcium salt of borate ester of higher fatty acid monoglyceride is obtained by reacting higher fatty acid monoglyceride and boric acid at a molar ratio of, for example, 1: 0.2 to 1, at a reaction temperature of 95 to 200 ° C., and then obtaining the obtained reaction product. It can be obtained by neutralizing with calcium hydroxide. Examples of the higher fatty acid monoglyceride include stearic acid monoglyceride, lauric acid monoglyceride, myristic acid monoglyceride, palmitic acid monoglyceride, and behenic acid monoglyceride. Is mentioned. A specific example is "GX-8076" under the trade name of Daiichi Kogyo Seiyaku Co., Ltd.
There may be mentioned boric acid ester calcium salts of higher fatty acid monoglycerides which are more commercially available.

The zeolite used in the composition of the present invention is a so-called aluminum hydrated silicate mineral (ie, a crystalline alumino, a hydrated alkali metal salt or an alkaline earth metal salt of silicate, and Na, K,
Ca or the like is used and belongs to nature, but synthetic zeolite is used. ), And those having an effective diameter of 0.11 mm or less are preferable. When the effective diameter exceeds 0.1 mm,
The quality of molded products may be impaired. As a specific example, zeolite commercially available from Union Showa Co., Ltd. under the trade name "Molecular Sieve 13X" can be mentioned.

The resin composition for cleaning a flame-retardant resin of the present invention may contain metal soaps such as calcium stearate, magnesium stearate and zinc stearate, and waxes such as carbanner wax and polyethylene wax, if necessary. Can be added.

The composition of the present invention is prepared by mixing predetermined amounts of a thermoplastic resin, a calcium borate ester of a higher fatty acid monoglyceride, and a hydrous silicate mineral (zeolite) of aluminum having a specific particle size by using a stirring and mixing device. And a melt-kneading temperature of 170 to 300 ° C.
And extruded into a pellet. As the stirring and mixing device, a normal stirring and mixing device such as a Henschel mixer, a super mixer, a tumbler mixer, and a ribbon blender may be used. As the extruder, a single-screw extruder, a twin-screw extruder, a co-kneader, or the like can be used. Pelletization may be performed by cutting the extruded strand in water, fog or air.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these.

[0015]

【Example】

Example 1 High-density polyethylene [melt index (JISK6
760: 190 ° C.) 0.325 g of a homopolymer of 0.3 g / 10 min], and boric acid calcium salt [GX-80
76 ", manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 0.250 kg of zeolite having an average particle size of 10 μm or less [“ 13X ”, manufactured by Union Showa Co., Ltd.], and 0.075 kg of calcium stearate. The mixture was stirred with a 20-liter high-speed mixer for 2 minutes at a rotation speed of 500 rpm, and the mixture was fed to a twin-screw extruder having a screw L / D of 30 and a cylinder diameter of 30 mm, and a cylinder temperature of 190 ° C and a die temperature of The strand was extruded at 200 ° C., cooled in a water bath, and cut with a pelletizer to obtain a milky white granular resin composition for cleaning a flame-retardant resin. The following cleaning tests were performed: a 32 ton injection molding machine (15 g per shot,
1 kg of a flame-retardant ABS resin (“Sebian V (trademark) SER90”, black, Daicel Chemical Industries, Ltd.) was molded in a hopper at 20 ° C. at a temperature of 230 ° C. and allowed to stay for 1 hour. Next, the resin composition was burned using a resin composition for cleaning a flame-retardant resin, and washed until the foreign matter was removed. After washing, the composition was removed with high density polyethylene. The amount of the composition required for washing was 0.695 kg, and the amount of high-density polyethylene used was 0.240 kg. No burns or foreign substances were found in the high-density polyethylene molded thereafter.

Comparative Example 1 Using a Henschel mixer and an extruder according to Example 1, 4.050 kg of high-density polyethylene, 0.750 kg of a calcium borate ester salt of higher fatty acid monoglyceride as a raw material, and 0.05% of calcium stearate were used.
0 kg, 0.050 kg of stearic acid, 0.1 kg of silica.
100 kg were mixed and extruded. Using this composition, a cleaning test was performed under the same conditions as in Example 1. The amount of the composition used was 1.610 kg, and the amount of high-density polyethylene required for replacement was 1.055 kg. Burning and foreign matter were slightly observed in the high-density polyethylene molded thereafter.

Example 2 Polypropylene [Melt flow rate (JIS K675)
8: 230 ° C.) 1.0 g / 10 min homopolymer]
4.400 kg of boric acid ester calcium salt [“GX-807”
6 ", manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 0.025 kg of zeolite having an average particle diameter of 10 μm or less [“ 13X ”manufactured by Union Showa Co., Ltd.], 0.050 kg of calcium stearate, stearic acid Of 0.025 kg in a high-speed mixer with an internal volume of 20 liters at a rotational speed of 500 r
Stir at pm for 2 minutes to mix. This mixture was prepared in Example 1
Same as above, cylinder temperature 190 ℃, die temperature 200 ℃
To obtain a granular resin composition for washing a flame-retardant resin. Then, a flammable polypropylene [“Chisso Polypro 2654”) was added to the hopper of a 32 ton injection molding machine.
1 kg at a temperature of 200 ° C.
It was molded and held for one hour. Next, the resin composition was burned using a resin composition for cleaning a flame-retardant resin, and washed until the foreign matter was removed. After washing, the composition was removed with polypropylene. The amount of the cleaning resin composition required for cleaning was 0.815 kg, and the amount of polypropylene was 0.305 kg. No burns or foreign substances were found in the high-density polypropylene molded thereafter.

Comparative Example 2 Using a Henschel mixer and an extruder according to Example 1, 3.890 kg of polypropylene and 0.1% of calcium borate ester of higher fatty acid monoglyceride as a raw material were used.
400 kg, 0.050 kg of zinc stearate, 0.060 kg of stearic acid, 0.60 of calcium carbonate
0 kg were mixed and extruded. Using this composition, a cleaning test was performed under the same conditions as in Example 2. The amount of the composition used is 1.570 kg, the amount of polypropylene required for replacement is:
It was 0.890 kg. Burning and foreign matter were slightly observed in the polypropylene molded thereafter.

Example 3 Polystyrene [Melt Flow Index (JISK6)
871: 200 ° C.) 1.7 g / 10 min homopolymer], 4.150 kg, calcium borate ester salt [“GX-80
76 ", manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 0.150 kg of zeolite having an average particle size of 10 μm or less [“ 13X ”manufactured by Union Showa Co., Ltd.], and 0.100 kg of magnesium stearate. The mixture was stirred with a 20-liter high-speed mixer at 500 rpm for 2 minutes, and then mixed with flammable polystyrene ["DIX-SK", Mitsubishi Monsanto Kasei Co., Ltd.] in a hopper of a 32-ton injection molding machine. Was molded at a temperature of 200 ° C. and kept for 1 hour, then burned using a resin composition for cleaning a flame-retardant resin, and washed until foreign matters were removed. The amount of the cleaning resin composition required for cleaning was 0.805 kg, and the amount of polystyrene used was 0.300 kg. Burnt, foreign matter was observed.

Comparative Example 3 Using a Henschel mixer and an extruder according to Example 1, 4.425 kg of polystyrene and 0.1% of calcium borate ester of higher fatty acid monoglyceride as a raw material were used.
500kg, 0.075k of magnesium stearate
g were mixed and extruded. Example 3 using this composition
A cleaning test was performed under the same conditions as those described above. The amount of the cleaning resin composition used was 1.600 kg, and the amount of polystyrene required for replacement was 0.985 kg. Then, in the molded polystyrene, slightly burned and foreign substances were observed.

Example 4 Granulation and an experiment were conducted under the same conditions as in Example 1, and an ABS resin was used as a resin for subsequent substitution.

Example 5 Granulation and an experiment were conducted under the same conditions as in Example 3, and an ABS resin was used as a resin for subsequent substitution.

Example 6 Granulation and an experiment were performed under the same conditions as in Example 2.

The above results are summarized in Table 1. In Table 1, PP is polypropylene, PS is polystyrene, PE
Represents polyethylene. Time required for cleaning test (mi
n) indicates the total use time of the cleaning resin composition and the use time of the replacement subsequent resin.

[0025]

[Table 1]

[0026]

From the comparison between the examples and the comparative examples, the amount of the flame-retardant resin cleaning composition used in cleaning a molding machine using the flame-retardant resin cleaning resin composition of the present invention is as follows. About one-half that of the conventional cleaning resin composition, the amount of the replacement resin used for cleaning is one-third or less as compared with the conventional one, and the time required for cleaning is about one-third as compared with the conventional one. It can be seen that the number can be reduced to 3. As described above, since the washing of the molding machine using the flame-retardant resin composition of the present invention does not require the use of a large amount of subsequent resin, the amount of waste is reduced, which can contribute to solving environmental problems.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 25/04 C08L 25/04 55/02 55/02 101/00 101/00 C11D 1/68 C11D 1/68 3/37 3 / 37 (58) Field surveyed (Int.Cl. ⁶ , DB name) C08K 3/00-5/59 C08L 1/00-101/14 C11D 1/00-3/60 B29C 33/00-33/76

Claims (3)

(57) [Claims] 1. A composition for cleaning a resin processing machine comprising a thermoplastic resin as a main component, wherein the thermoplastic resin contains 0.5 to 15% by weight of a calcium borate ester of a higher fatty acid monoglyceride based on the composition and zeolite. Is contained in an amount of 0.1 to 15% by weight based on the composition. 2. The thermoplastic resin is selected from the group consisting of low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene terpolymer, and acrylonitrile-styrene copolymer. The resin composition for cleaning a flame-retardant resin according to claim 1, which is at least one kind of resin. 3. The resin composition for cleaning a flame-retardant resin according to claim 1, which is processed into pellets.