JPS5851965B2 - Antistatic acrylonitrile polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antistatic acrylonitrile polymer marine composition having excellent antistatic performance and excellent moldability, particularly fiber moldability.

Conventionally, various antistatic polymer compositions containing conductive substances such as carbon black have been known in the fields of paints, adhesives, rubbers, films, fibers, and the like.

Attempts to make antistatic substances antistatic or conductive by incorporating carbon black into them are common, partly because carbon black is inexpensive.

However, carbon black is very bulky fine particles and is prone to secondary agglomeration, so it is very difficult to uniformly disperse carbon black.

Moreover, in order to obtain the desired antistatic properties or conductivity, it is necessary to mix a large amount of carbon black.
It is very difficult to obtain a stable carbon black-containing resin composition with excellent film formation and coating properties.

For example, when spinning a resin composition containing carbon black, if the dispersion state of carbon black is poor, the furnace pressure will increase significantly over time, making stable spinning impossible, resulting in spinnerets clogging, yarn breakage, and stretching. It had the fatal drawback of not being able to avoid problems such as sexual misconduct.

As a method to avoid such troubles, for example, as shown in JP-A-52-103525, a block polyether ester grafted with acrylonitrile is used as an antistatic polymer, and carbon black is added to this. A technique has been proposed in which the graft polymer is dispersed and oriented in a fiber-forming acrylonitrile polymer, but this graft polymer has a strong affinity with the acrylonitrile polymer and the shape of the sea-island structure is insufficient. It was not possible to sufficiently improve the spinning stability and reeling properties, and the results were not satisfactory in terms of fiber properties and electrical conductivity.

The present inventors have arrived at the present invention as a result of further studies on such prior art.

That is, the present invention provides an antistatic acrylonitrile polymer composition in which a carbon black-containing antistatic polymer is dispersed and oriented in an acrylonitrile polymer, and a block polyether polyester copolymer as the antistatic polymer. The present invention relates to an antistatic acrylonitrile polymer composition comprising a modified block polyether polyester obtained by graft polymerizing acrylonitrile and at least one vinyl monomer more hydrophobic than acrylonitrile.

Hydrophobicity here means that the solubility in water at 20° C. is lower than that of AN.

The object of the present invention is to prepare an antistatic polymer composition, particularly in fibers, comprising an antistatic polymer containing an AN polymer and carbon black. The antistatic polymer in which the antistatic polymer in which carbon black is dispersed and the AN-based polymer coexist stably by providing appropriate miscibility between the carbon black and the antistatic polymer and stronger affinity between the carbon black and the antistatic polymer. The object of the present invention is to provide a spinning dope with improved properties.

The AN-based polymer used in the present invention is at least 80
There is no particular limitation as long as it is a fiber-forming polyacrylonitrile or AN-based copolymer containing molar AN, and any known AN-based polymer can be used.

The term "AN polymer" as used herein refers to AN polymers and copolymers thereof. Examples of AN polymers include, for example, acrylic acid, methacrylic acid, itaconic acid, and lower alkyl esters thereof. ,styrene,
Examples include those containing styrene derivatives, allylsulfonic acid, meta-allylsulfonic acid, styrenesulfonic acid or metal salts thereof, methacrylatelyl, acrylamide, methacrylamide, vinyl acetate, vinylidene chloride, and the like.

These AN-based polymers may be used alone or in combination of two or more.

Examples of the carbon black used in the present invention include channel black, furnace black, and acetylene black, but furnace black is preferred from the viewpoint of dispersibility.

Of course, Kowa et al.'s carbon black may be pretreated with a solvent, a surfactant, or other means without any problem.

Next, in the present invention, in a mixed polymer solution consisting of the AN polymer and an antistatic polymer, carbon black is uniformly and stably dispersed in the antistatic polymer, and even after it is molded. , excellent antistatic properties were obtained by suppressing the elution of carbon black in the AN polymer.

The above antistatic polymer is a modified block polyether polyester obtained by graft polymerizing AN and at least one vinyl monomer more hydrophobic than AN to a block polyether polyester copolymer composed of polyalkylene glycol and polyester. It is.

Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polyoxyethylene oxypropylene glycol, etc. having an average molecular weight of at least about i, ooo.

Polyesters include aliphatic polyesters such as polyethylene adipate, polyethylene sebacate, polyethylene azelate, polybutylene azelate, polyethylene terephthalate, polybutylene terephthalate,
Aromatic polyesters such as polyethylene isophthalate can be exemplified.

Further, as the vinyl monomer more hydrophobic than AN, at least one monomer selected from styrene, methyl acrylate, methyl methacrylate, and octyl acrylate is used.

The ratio of polyether in such an antistatic polymer, that is, a block polyether ester copolymer, is from 60 to
The preferred range is 95% by weight and 5% to 40% polyester.

If the polyether ratio is less than 60% by weight, it becomes poorly soluble in solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, etc., and spinnability is significantly reduced when mixed with AN polymer. It is undesirable because it dissolves easily.

Next, the ratio of the vinyl monomer, ie, AN and the vinyl monomer more hydrophobic than AN, to the block polyether ester copolymer is preferably in the range of 5 to 60% by weight.

The relationship between AN and other vinyl monomers is that the hydrophobic vinyl monomer is 5% of the total vinyl monomers charged in the copolymer.
-80 weight φ, preferably 20-60 weight rice cake.

If it is less than 5%, the antistatic properties will not be improved sufficiently, and if it exceeds 80%, problems such as easy fibrillation will occur when the antistatic polymer composition is made into fibers.

The above-mentioned carbon black is uniformly dispersed in such an antistatic polymer, and the blending ratio of carbon black contained in this antistatic polymer is 1% to the polymer.
Amounts ranging from 0 to 200 weight units, preferably from about 15 to 100 weight units, or from about 0.5 to 30 weight units, preferably from 2 to 1 weight units per weight of molded articles obtained from the polymer compositions of the present invention.
A range of 5 yen is good.

That is, if the blending ratio of carbon black is less than the above-mentioned range, the antistatic properties will not be sufficient, while if it exceeds this range, the dispersibility of carbon black will be poor, the carbon black will tend to aggregate, and spinning will become difficult, which is not preferable.

The carbon black-containing antistatic polymer thus obtained and the AN-based polymer are mixed and combined, and in this case, the mixing ratio of the AN-based polymer and the antistatic polymer is the antistatic amount per mixed weight of both. The amount of the polymer is preferably in the range of 2 to 60 parts by weight, preferably 5 to 45 parts by weight.

If it is less than about 2 slopes, the antistatic property will not be fully demonstrated.
In addition, if the weight exceeds 60 weight, problems will occur in the mechanical properties and formability of the molded product, especially the fibers. For example, fibers may adhere during the fiber manufacturing process, and the spinning condition will deteriorate, resulting in no practical use of fibers. I can't.

A molded article obtained by spinning such a mixed polymer composition, for example, has a clearer boundary between the antistatic polymer and the AN polymer, and has significantly improved antistatic properties.

As a result, in order to obtain a predetermined antistatic property, it is possible to reduce the mixing ratio of the antistatic polymer, resulting in improved spinnability, stretchability, and yarn quality as derivative effects.

The method for producing the above-mentioned composition of the present invention will be exemplified.

In the present invention, the AN polymer and the antistatic polymer are dissolved in a solvent, but if the two polymers are produced by a solution polymerization method, the trouble of redissolving them can be eliminated.

Such a solvent may be a common solvent for the AN-based polymer and the antistatic polymer, and is not particularly limited, but includes, for example, dimethylformamide (D), dimethylacetamide (DMA), and dimethylsulfoxide (DMSO).
Or a mixed solvent thereof is preferably used.

The polymer concentration in a composition containing an AN polymer or an antistatic polymer is usually 10 to 30 weight φ.

Further, the method for preparing the polymer composition of the present invention is not particularly limited, but for example, preparing an AN-based polymer solution,
Separately, an antistatic polymer solution is prepared using the same solvent as the AN polymer solution.

Carbon black is added little by little while stirring the antistatic polymer solution, and is further stirred and mixed to uniformly and finely disperse it.

The obtained carbon black-containing antistatic polymer solution is added to the AN-based polymer solution and mixed with stirring to prepare a polymer composition having a desired composition.

The molded product, especially the fiber, of the carbon black-containing polymer composition obtained in this way is formed in such a way that the antistatic polymer containing carbon black is formed as a more distinct independent phase in the AN polymer, and the fiber is further formed by stretching. It has a structure that is oriented and dispersed in the axial direction, and exhibits significantly superior antistatic properties compared to molded products using antistatic polymers that are simply graft polymerized with AN.

On the other hand, in molded products, especially fibers, there is almost no adhesion between single filaments, and the performance of the fibers is significantly improved.

The present invention will be specifically explained below using Examples.

However, the electrical resistivity was measured as follows.

20.000 denier, 10 cr IL sample at 40% R
H.

Both ends were held with clamps in an atmosphere of 20° C., a voltage of 100 μm was applied, the electrical resistance R was measured, and it was determined by calculation.

Percentages in the examples refer to weight.

Example 1 Adipic acid and ethylene glycol were charged into a batch-type esterification apparatus, and the esterification reaction was carried out while distilling off water.
A polyethylene adipate prepolymer is obtained.

This polyethylene adipate and polyethylene glycol (molecular weight 2,000) were charged into a batch polycondensation apparatus together with tetraisopropyl titanate to obtain a block polyether ester consisting of polyethylene adipate and polyethylene glycol.

This block polyether ester is polyethylene adipate/polyethylene glycol (25/75) wt.
It was the composition ratio of guilt.

100 parts of this block polyetherester was added to DMS0
Dissolved in 870 parts, using ammonium persulfate as a catalyst, 30 parts of AN, 18 parts of AN/12 parts of methyl methacrylate,
18 parts AN/12 parts styrene, 18 parts AN/12 parts octyl acrylate 18 parts N/12 parts methyl acrylate
Each of the parts was graft-polymerized to obtain a polymer solution.

Furnace black=ll for each of these polymer solutions
=40 (manufactured by Mitsubishi Kasei Co., Ltd., average particle size 20 mμ) was added and thoroughly stirred using a homomixer.

The amount of furnace black added at this time was 28 yen to the polymer obtained by grafting each component onto the block polyether ester.

The mixed solution in which this carbon black was finely dispersed was mixed with AN/
Methyl acrylate/sodium methallylsulfonate (94,
015,770,3) D of AN polymer consisting of mole φ
Mixed spinning with MSO solution.

The content of carbon black in the fiber is 7φ.

When the specific resistance of the obtained fibers was examined, the results are shown in Table 1.

Example 2 The block polyether ester obtained in Example 1 was graft-polymerized by the method of Example 1 while changing the ratio of AN/methyl methacrylate.

The charging composition was 30 parts by weight of vinyl monomer per block polyether ester.

AN/N/methyl methacrylate combination is l 0010.80
/20.60/40.40/60.20/80 (weight ratio), Furnace black #40 was added to each obtained polymer solution so that the diameter of the modified block polyether ester was 28φ, and a homomixer was added. Stirred by.

This carbon black-containing polymer solution is mixed with the AN-based copolymer solution and the carbon black in the fiber is 7%, and A
7 for N/methyl acrylate (40/60),
The mixture was mixed to give a ratio of 6, 5, and 4, and spun according to a conventional method.

The electrical resistivity of the obtained fibers is shown in Table 2.

The conductivity is significantly improved by introducing methyl methacrylate as a grafting component.

However, if the copolymerization rate of methyl methacrylate is too high, the fibers tend to fibrillate, and a level of 80 φ copolymerization rate of methyl methacrylate is problematic.

Claims (1)

[Claims] 1. In an antistatic acrylonitrile polymer composition in which a carbon black-containing antistatic polymer is dispersed and oriented in an acrylonitrile polymer, acrylonitrile is added to a block polyether polyester copolymer as the antistatic polymer. An antistatic acrylonitrile polymer composition comprising a modified block polyether polyester obtained by graft polymerization of and at least one monomer selected from styrene, methyl acrylate, methyl methacrylate, and octyl acrylate.