JPH0781010B2 - Method for producing solid chlorinated polyolefin - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a solid product of chlorinated polyolefin, and more specifically, to the surface of pellets or strands of a chlorinated ethylene copolymer resin or an adhesive resin composition containing at least 1% thereof. The present invention relates to a method for producing a resin solid having excellent blocking resistance by coating with a polyalkyl glycol and powder.

Solids of chlorinated ethylene copolymer resin are resins that can be safely transported mainly in the state of solvent-free raw materials for paints, inks, and adhesives, and can reduce the deterioration of workability due to blocking during use. The industrial utility value is extremely high in that it is able to supply.

[0003]

2. Description of the Related Art As a method for obtaining a solid product of chlorinated polyolefin, there are a drum drying method, a solvent replacement method, a method using an extruder with a vent, and the like. However, there is a problem in that the solid matter is likely to be blocked during storage and transportation of the solidified product, which significantly impairs workability during use.

As a method for solving this problem, a method of coating the surface of resin pellets with an anti-adhesion powder (Japanese Patent Laid-Open No. Hei 10 (1999) -242242)
No. 01-288408) and a method of mixing a low molecular weight crystalline polyolefin into a resin (Japanese Patent Publication No. 51-44974), but the former method does not sufficiently adhere the anti-adhesion powder to the resin pellets. In some cases, it may not be possible to exhibit sufficient blocking resistance by peeling during transportation, and in the latter method, the physical properties of the original resin deteriorate due to the low molecular weight crystalline polyolefin mixed in the resin, especially in the solvent. Problems may occur in solubility, compatibility with other resins, adhesiveness to a coated object when used as a paint or ink.

[0005]

In the present invention, while solving the above problems, it is possible to obtain solid pellets or strands of chlorinated polyolefin excellent in blocking resistance without impairing the original physical properties of chlorinated polyolefin. With the goal.

[0006]

According to the present invention, pellets or strands of a chlorinated ethylene copolymer resin or an adhesive resin composition containing at least 1% of the chlorinated ethylene copolymer resin are powder-averaged to a powder having an average particle diameter of 0.005 to 10 μm. Immerse in polyalkyl glycol having a molecular weight of 100 to 4000 or dispersed in an aqueous solution thereof and then dry it to attach polyalkyl glycol and powder to the surface of resin pellets or strands in an amount of 0.01 to 1% by weight relative to the resin. The method solves the above problems.

Here, the chlorinated ethylene copolymer resin means
Ethylene-vinyl ester copolymer, ethylene-α, β
It shows chlorinated compounds such as unsaturated carboxylic acid copolymers and ethylene-α-olefin copolymers, and has a chlorine content of 5 to 60.
% Of all chlorinated ethylene copolymer resins that exhibit tackiness at room temperature to 50 ° C.

Further, as an adhesive resin composition containing at least 1% of this, a chlorinated resin such as chlorinated polypropylene, chlorinated polybutadiene, chlorinated polymethylpentene, chlorinated polyethylene, etc. is added to the above chlorinated polyethylene copolymer resin. Mixed with general-purpose resins such as polyurethane, polyester, poly (meth) acrylate, melamine resin, polyamide, and maleinized polyolefin, and mixed with a mixture of two or more resins selected from these. It also includes things.

Pellets and strands show the shape of solidified resin, pellets are spherical with a diameter in the range of 1 to 10 mm, and strands are cylindrical with a circular cross section with a diameter of 1 to 10 mm and their length. Is usually 1 to 30 mm, but when used in the method of the present invention, it may have a linearly continuous shape for continuous treatment.

When solidifying these resins, the method is not particularly limited, but a method using an extruder is preferable, and particularly for pelletizing, a resin equipped with an underwater cutter at the resin outlet of the extruder is used for continuous solidification. What can be processed is desirable.

The types of powder for preventing adhesion include clays such as kaolinite and pyrophyllite, inorganic systems such as talc, silica, mica, magnesium carbonate and calcium carbonate, polyethylene wax, ethylene vinyl acetate copolymer. Organic powders such as saponified products and low molecular weight polypropylene are used, and among them, inorganic silica or talc is preferably used. The particle size of these powders is 0.005
The range is preferably from 10 to 10 μm, more preferably from 0.01 to 5 μm. If it is smaller than this range, the blocking resistance is difficult to be exhibited due to the aggregation of the powder particles, and if it is larger than this range, the adhesion to the resin is poor and the powder tends to peel off during transportation, which is not preferable.

In the present invention, the polyalkyl glycol is a particularly important element, and its type includes polyethylene glycol, polypropylene glycol, polybutylene glycol, and copolymer resins of these. Of these, polypropylene glycol is most preferably used. The number average molecular weight of these polyalkyl glycols is preferably in the range of 100 to 4000, preferably 5
00 to 3000 is preferable. If the molecular weight is less than this range,
Swelling of the solidified resin surface makes blocking easier,
If it is larger than this range, the tackiness of the polyalkyl glycol is increased, which makes it easier for the solidified resins to aggregate,
Also, the viscosity of the mixture with the powder and its water suspension increases,
It is not preferable because uniform treatment cannot be performed.

As a method for adhering the mixture of the powder and the polyalkyl glycol to the surface of the solidified resin, a method of immersing the resin solidified product in the mixture or an aqueous dispersion thereof is used. As a simple method, the mixture or the aqueous solution thereof is used. It is also possible to use a method in which the dispersion is sprinkled directly on the resin solid.
However, this method is not very preferable because it is difficult to uniformly treat the resin surface. The amount of powder and polyalkyl glycol attached to the solidified resin is
The range of 0.01 to 1% is preferable, and if it is less than this range, the blocking resistance cannot be sufficiently exhibited, and if it is more than this range, the physical properties inherent to the resin are deteriorated, which is not preferable.

The weight ratio of the powder to the polyalkyl glycol is preferably in the range of 1: 1 to 20: 1. When the amount of the polyalkyl glycol is more than that, the surface of the solidified resin becomes tacky and the blocking resistance is reduced. On the contrary, if the amount is small, the adhesion of the powder to the surface of the solidified resin is poor and the powder easily peels off, and the blocking resistance is easily impaired.

A mixture of these powders and polyalkyl glycol within the above range may be directly attached to the surface of the solidified resin, but these are dissolved and dispersed in 2 to 20 times its weight of water to form a slurry form. You can use it. By using powder and polyalkyl glycol in the form of a water slurry, even if surface treatment is performed by dipping the solidified resin into the slurry, a sufficiently uniform treatment can be performed, and a solidified product that is continuous in operation. Can be manufactured.

These methods for producing a solidified resin are effective in producing a solid chlorinated ethylene-vinyl acetate copolymer resin in a chlorinated ethylene copolymer resin. Here, the chlorinated ethylene-vinyl acetate copolymer resin refers to a product obtained by chlorinating an ethylene-vinyl acetate copolymer resin having a vinyl acetate content of 10 to 80% in a chlorine content range of 5 to 60%. It is something to say. Chlorinated ethylene-vinyl acetate copolymer resin is widely used as a raw material resin for paints, inks and adhesives, and is particularly useful as a resin for special gravure ink, which is a printing ink for plastic films. Chemical resins have many industrial advantages such as solvent reduction problems, light weight transportation, and workability improvement due to blocking resistance, so their utility value is extremely high.

[0017]

According to the present invention, when solidifying a chlorinated ethylene copolymer resin, the surface of the solidified resin is coated with a water dispersion slurry obtained from powder having a predetermined particle size and polyalkyl glycol having a predetermined molecular weight or an aqueous solution thereof. By doing so, it is intended to prevent aggregation (blocking) between the solidified resins.

Conventionally, when the adhesive resin is molded into pellets or strands by an extruder, it has been necessary to quickly cool the resin in order to prevent the resins from sticking to each other. If sufficiently cooled here, blocking due to solidification can be prevented, but blocking phenomenon due to temperature rise and moisture absorption during subsequent storage and transportation cannot be prevented. Therefore, a blocking resistant agent using powder has been used for the adhesive resin, but the powder cannot be effectively adhered to the pellet surface because the resin is cooled during pelletization. However, there was a problem that the powder came off during subsequent storage and transportation. When the powder is used as a water-dispersed slurry, the dispersion stability of the powder itself in water is important for uniform adhesion to the surface of the solidified resin and affects the blocking resistance.

In the present invention, by using a polyalkyl glycol together with the powder, the water-dispersed slurry of the powder is uniformly stabilized by the surface-active effect of the polyalkyl glycol, and the powder is evenly distributed on the surface of the solidified resin. It is considered to have the effect of promoting adhesion. Also, the number average molecular weight of 100 to 40
The polyalkyl glycol of 00 does not have adhesiveness more than necessary and does not dissolve the chlorinated ethylene copolymer resin, so that it has an anti-blocking effect by itself. It is considered that the combined use of the two makes it possible to exert anti-blocking performance that is unexpected when used alone as a result of the synergistic effect of the two.

[0020]

EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited to the examples.

(Example-1) A chlorinated ethylene-vinyl acetate copolymer resin (a resin having a molecular weight of 200,000 obtained by chlorinating EVA having a vinyl acetate content of 14% to a chlorine content of 32%) was extruded from an extruder and then put in water. It was cut with an underwater cut pelletizer and pelletized. Next, 100 parts of amorphous silica powder (average particle size 2 μm) and polypropylene glycol (hereinafter P
Abbreviated as PG. 50 parts of a number average molecular weight of 1000) was dissolved and dispersed in 1500 parts of water and introduced into a slurry which was stirred at a high speed. After surface treatment, excess slurry was removed and dried.
The amount of the powder and PPG attached to the pellet was 0.08%.

Example 2 A chlorinated ethylene-vinyl acetate copolymer resin (a resin having a molecular weight of 200,000 obtained by chlorinating EVA having a vinyl acetate content of 28% to a chlorine content of 32%) was extruded from an extruder and then put in water. It was cut with an underwater cut pelletizer and pelletized. Next, 100 parts of amorphous silica powder (average particle size 2 μm) and 50 parts of polypropylene glycol (number average molecular weight 1000) are dissolved and dispersed in 1500 parts of water and introduced into a slurry which is stirred at a high speed, and subjected to a surface treatment. After that, excess slurry was removed and dried. The amount of the powder and PPG attached to the pellet was 0.06%.

(Example-3) A chlorinated ethylene-vinyl acetate copolymer resin (a resin having a molecular weight of 200,000 obtained by chlorinating EVA having a vinyl acetate content of 28% to a chlorine content of 32%) was extruded from an extruder and then put in water. It was cut with an underwater cut pelletizer and pelletized. Next, 100 parts of amorphous silica powder (average particle size 2 μm) and 80 parts of polypropylene glycol (number average molecular weight 3000) are dissolved and dispersed in 2000 parts of water and introduced into a slurry which is stirred at a high speed, and subjected to a surface treatment. After that, excess slurry was removed and dried. The amount of the powder and PPG attached to the pellet was 0.10%.

(Example-4) A chlorinated ethylene-vinyl acetate copolymer resin (a resin having a molecular weight of 200,000 obtained by chlorinating EVA having a vinyl acetate content of 28% to a chlorine content of 32%) was extruded from an extruder, 100 parts of regular silica powder (average particle size 2 μm) and 100 parts of polypropylene glycol (number average molecular weight 2000)
After being surface-treated while being linearly drawn into a slurry that is dissolved and dispersed in 2000 parts of water and stirred at high speed, while cooling,
Excess slurry was removed, and the mixture was cut into strands with a pelletizer and dried. The amount of the powder and PPG attached to the pellet was 0.11%.

(Example-5) A chlorinated ethylene-vinyl acetate copolymer resin (a resin having a molecular weight of 200,000 obtained by chlorinating EVA having a vinyl acetate content of 28% to a chlorine content of 32%) was extruded from an extruder and then air-cooled. Immediately after cutting into strands with a pelletizer, amorphous silica powder (average particle size 2 μm) 100
Parts and polypropylene glycol (number average molecular weight 2000) 1
00 parts was dissolved and dispersed in 2000 parts of water and put into a slurry which was stirred at a high speed to perform a surface treatment, and then an excess slurry was removed and dried. The amount of the powder and PPG attached to the pellet was 0.09%.

(Example-6) A chlorinated ethylene-vinyl acetate copolymer resin (a resin having a molecular weight of 200,000 obtained by chlorinating EVA having a vinyl acetate content of 28% to a chlorine content of 32%) was extruded from an extruder and then air-cooled. Immediately after cutting into strands with a pelletizer, amorphous silica powder (average particle size 2 μm) 100
Parts and polypropylene glycol (number average molecular weight 1000) 1
After applying a surface treatment by sprinkling a slurry in which 00 parts were mixed, excess slurry was removed and dried. The amount of the powder and PPG attached to the pellet was 0.50%.

(Comparative Example-1) A chlorinated ethylene-vinyl acetate copolymer resin (a resin having a molecular weight of 200,000 obtained by chlorinating EVA having a vinyl acetate content of 28% to a chlorine content of 32%) was extruded from an extruder and then put in water. It was cut with an underwater cut pelletizer and pelletized. Next, 100 parts of amorphous silica powder (average particle size 2 μm) was dissolved and dispersed in 1000 parts of water and introduced into a slurry which was stirred at a high speed. After surface treatment, excess slurry was removed and dried. The amount of powder adhering to the pellets was 0.1%.

(Comparative Example 2) A chlorinated ethylene-vinyl acetate copolymer resin (a resin having a molecular weight of 200,000 obtained by chlorinating EVA having a vinyl acetate content of 28% to a chlorine content of 32%) was extruded from an extruder and then put in water. It was cut with an underwater cut pelletizer into pellets and dried as it was.

Evaluation Method of Blocking Resistance A cylindrical container having an inner diameter of 40 cm and a height of 70 cm was charged with the surface-treated solidified resin, and a disc having a diameter of 39 cm (1 k
g), put a load of 3 kg on it, and leave it in the atmosphere of the specified temperature. After 24 hours, the load is removed and the cylindrical container is turned upside down to measure the time until all the solidified resin flows out of the container. The test is run at several temperatures and ranked as in Table 1 below by the highest temperature at which all of the solidified resin is discharged within 1 minute.

[0030]

[Table 1]

Table 2 summarizes the anti-blocking effect of the examples and comparative examples.

[0032]

[Table 2]

[0033]

As shown in the above examples, the effects of the present invention are clear, and are summarized as follows.

(1) When solidifying a chlorinated ethylene copolymer resin, it was possible to obtain a solidified product having sufficient blocking resistance in any shape of pellets and strands.

(2) By using the powder and polyalkyl glycol in combination as an anti-blocking agent, the dispersion of the powder is maintained uniformly, especially when treated with an aqueous dispersion slurry, and the resin solidified product has a uniform blocking resistance. Was able to be granted.

(3) The polyalkyl glycol assists the adhesion of the powder to the solidified resin, and the blocking resistance can be stabilized.

(4) Since it is possible to solidify the chlorinated ethylene copolymer, solvent problems in the fields of paints, inks and adhesives using this resin, and safety in transportation, etc. The problem can be reduced.

Claims (5)

[Claims] 1. Pellets or strands of a chlorinated ethylene copolymer resin or an adhesive resin composition containing at least 1% thereof, and a powder having an average particle size of 0.005 to 10 μm and a polyalkyl glycol having a number average molecular weight of 100 to 4000. A chlorinated polyolefin solid product obtained by immersing the product in a resin or in an aqueous solution dispersed therein and then drying it to deposit 0.01 to 1% by weight of polyalkyl glycol and powder on the resin pellet or strand surface with respect to the resin. Manufacturing method. 2. A chlorinated ethylene copolymer resin obtained by chlorinating an ethylene-vinyl acetate copolymer having a vinyl acetate content of 10 to 80% to a chlorine content of 5 to 60%.
The method for producing a chlorinated polyolefin solid according to claim 1, which is a vinyl acetate copolymer resin. 3. A resin pellet or a strand surface is treated with a dispersion of powder in polyalkyl glycol in a weight ratio of 1: 1 to 20: 1. Chlorinated polyolefin solid product manufacturing method. 4. The surface of resin pellets or strands is treated with a slurry in which powder is dispersed in polyalkyl glycol and dissolved and dispersed in 2 to 20 times its weight of water. Manufacturing method of polyolefin solids. 5. The method for producing a solid chlorinated polyolefin according to any one of claims 1 to 4, wherein the powder is silica or talc.