JPS60202150A - Antistatic polymer composition - Google Patents

Abstract

PURPOSE:The titled compsn. keeping excellent antistatic performance semipermanently and having an excellent antistatic property even after weight reduction working, which comprises a thermoplastic polymer, polyoxyalkylene glycol (deriv.) and specified vinyl polymer. CONSTITUTION:A vinyl polymer is obtd. by polymerizing (a) a vinyl monomer such as styrene, (b) at least 3mol% vinyl-base unsaturated sulfonic acid (or sulfonate) such as sodium p-styrenesulfonate and (c) at least 1mol% unsaturated aliph. carboxylic acid alkyl ester in which the alkyl group has 1-15 carbon atoms such as methyl (meth)acrylate. Then at least one thermoplastic polymer such as polyethylene terephthalate, 0.1-10wt%, based on the total of (a) and (b), polyoxyalkylene glycol (deriv.) of weight-average M.W.>=1,000 and the above vinyl polymer in such an amt. as to contain 0.5-18wt%, based on the total of (b) and (c), component (a) are compounded.

Description

Detailed Description of the Invention The present invention does not impair the excellent physical properties of the original thermoplastic polymer and has excellent antistatic properties, and has excellent antistatic properties even after weight reduction processing with an alkaline aqueous solution. The present invention relates to a composition.

In general, hydrophobic polymeric substances are easily charged due to friction, peeling, etc., and this charging causes various problems in molded products, and also has drawbacks such as shock due to discharge and dust accumulation during use. are doing. To eliminate these drawbacks, attach an antistatic agent to the surface of the molded product or mix it inside! Which method is proposed?

Among the above proposals, the method of blending an antistatic agent into a polymeric substance is known as a relatively durable method. For example, a method of blending a polyoxyalkylene glycol into a thermoplastic polymer such as polyethylene terephthalate has been disclosed. There is. however.

In order to obtain polyester molded products, such as fibers and films, having sufficient antistatic performance by employing the above method,
It is necessary to incorporate polyoxyalkylene glycol in an amount exceeding 10% by weight, which significantly reduces the formability of fibers or films, and the physical properties of the resulting fibers and films, especially the stability of dyed products against light, are extremely poor. It has disadvantages such as poor performance. A method to solve this problem is to use a polyester-insoluble material with an average molecular weight of 10,000 to 300.
00 polyethylene glycol, and further a gold sulfonate such as sodium dodecylbenzenesulfonate, etc.
Japanese Patent Publication No. 44-31828 No. 1 Japanese Patent Publication No. 46-4262 discloses a method of reducing the amount of polyoxyalkylene glycol by using a low molecular weight compound containing i in combination.
This is proposed in Publication No. 9, etc.

However, even with these methods, it is still not possible to achieve both excellent antistatic properties and the physical properties inherent in polyester; in order to obtain excellent antistatic properties, physical properties must be sacrificed; If given priority, the antistatic performance would not be satisfactory, and in particular, the antistatic performance would have the drawback of lacking durability. In order to solve the above-mentioned problems, the present inventors have developed a thermoplastic polymer composition consisting of a derivative thereof and a vinyl unsaturated sulfonic acid or a salt thereof. However, it has been found that the antistatic properties are lost when weight-reducing treatment using an alkaline aqueous solution, which is commonly applied to polyester fibers, etc.

The present inventors have conducted intensive research to improve the above-mentioned drawbacks, and as a result, have finally completed the present invention. That is, the present invention includes a thermoplastic polymer (A), at least one polyoxyalkylene glycol or its derivative (B) in an amount of 0.1 to 10% by weight based on the total composition, and a vinyl polymer (C). An antistatic polymer composition, wherein the vinyl polymer (C) is vinyl/
At least 3 moles of a monomer unit consisting of an L'-based unsaturated sulfonic acid or a salt thereof and at least 1 mole of an unsaturated aliphatic carboxylic acid alkyl ester whose alkyl group has 1 to 15 carbon atoms. This is an antistatic polymer composition characterized by:

The thermoplastic polymer used in the present invention is typically polyester. Polyester means a linear polymer polymerized from a dibasic acid and a dihydric alcohol or from an oxyhydric acid, or a copolymer thereof, such as a dicarboxylic acid whose main component is terephthalic acid or its lower alkyl Examples include polyesters obtained from esters and glycols. Polyamides are also suitable. Here, polyamide refers to a polymer of monoaminocarboxylic acid, a polymer obtained by polymerizing diamine and dicarboxylic acid, or a copolymer thereof. Others, polyethylene,
It can also be applied to olefin polymers such as polypropylene, and vinyl polymers such as polyvinyl chloride and polymethyl methacrylate. .

The polyoxyalkylene glycol or its derivative (B) referred to in the present invention can be mixed into thermoplastic synthetic fibers to impart antistatic properties, for example, in Japanese Patent Publication No. 39-5214, Japanese Patent Publication No. 57-4724, etc. As seen in
This refers to all commonly known substances, and specific examples include polyethylene glycol, polypropylene glycol, random or block copolymers of ethylene oxide and propylene oxide, polytetramethylene glycol, and polytetramethylene glycol. Polyoxyalkylene compounds with hydroxyl groups at both ends, such as block copolymers obtained by adding ethylene oxide to neopentyl glycol, and compounds obtained by adding ethylene oxide to bisphenol glycol. Phenoxypolyethylene glycol, sodium sulfophenoxypolyethylene glycol/I/, difenoquine polyethylene glycol, compounds in which 2 moles of monophenoxy polyethylene glycol are bonded with 1 mole of tolylene diisocyanate, such as compounds with one or both ends Through an ether bond, one or both ends of a blocked polyoxyalkylene compound, polyethylene glycol laurate, polyethylene glycol phosphate, or a partially alkaline salt thereof, polyethylene glycol phosphonate, or a partially alkaline salt thereof Esterified polyether compounds, block copolymers of polyethylene glycol and polyethylene terephthalate, block copolymers of polytetramethylene glycol and polyethylene terephthalate or polybutylene terephthalate, polyethylene glycol and polyε-
Block copolymer with capramide polyethylene glycol/l/, one end or both ends cyanoethylated;
Examples of Riri include compounds obtained by adding ethylene oxide to polyethylene glycol-p11 or secondary alkylamine in which the cyano group is converted into an amino group.

It goes without saying that the polyether compound referred to in the present invention is not limited to the above specific examples, and may be a single compound or a mixture of two or more of these compounds.

In (B) above, one and both ends are -OH.

In the case of a group containing an active hydrogen represented by -COOH, -NH2, etc., the weight average molecular weight (hereinafter abbreviated as molecular weight) of its CB is preferably 5000 or more. Also, when one end is blocked by a group having active hydrogen and the other end is blocked by a group not having active hydrogen.

The molecular weight of (B) is preferably 4,000 or more.

In addition, when both ends are blocked with a group having no active hydrogen, the molecular weight of (B) is preferably 1000 or more.

The CB to be used in the present invention is as described above (
B), and furthermore, this additional content should be included (
B) Add antioxidants, ultraviolet absorbers, pigments, and organic or inorganic ionic compounds in advance.

Other additives may also be mixed.

It is appropriate that the polyoxyalkylene glyco/L't 7c derivative be present in the entire composition in an amount of 0.1 to 10% by weight.

If it is less than 0.1% by weight, excellent antistatic properties cannot be obtained, and if it exceeds 10% by weight, the physical properties of the resulting composition,
In particular, the stability of dyed products against light deteriorates, and the moldability and
This is not preferable because it also causes a decrease in spinning operability.

Next, in the present invention, the vinyl polymer (C) to be used in combination with polyoxyalkylene glycol has a monomer unit consisting of a vinyl unsaturated sulfonic acid or a salt thereof and an alkyl group having 1 to 1 carbon atoms in its constituent units. It must contain 15 unsaturated aliphatic carboxylic acid esters.

Monomers consisting of vinyl unsaturated sulfonic acids or salts thereof include 1, for example, styrene sulfonic acid.

Unsaturated hydrocarbons and their salts such as vinylbenzyl sulfonic acid, vinyl sulfonic acid, (meth)allylsulfonic acid; (meth)acrylic acid sulfobutyl ester, (meth)
Sulfoalkyl esters of acrylic acid or methacrylic acid, such as acrylic acid sulfobutyl ester and (meth)acrylic acid sulfopropyl ester, or salts thereof; 2-acrylamide-2-methylpropanesulfonic acid or salts thereof; 1. The present invention Among these, those containing an aromatic ring such as styrene sulfonic acid, vinylbenzyl sulfonic acid or salts thereof are preferred. Examples of metals that form salts with the vinyl unsaturated sulfonic acid include alkali metals such as sodium, potassium, and lithium, and alkaline earth metals such as magnesium and calcium. From acid.

The metal salts are preferred.

In addition, the unsaturated aliphatic carboxylic acid alkyl ester which is another essential constituent unit of the vinyl polymer (C) is as follows:
(Meth)acrylic ester, vinyl acetate ester/L/ where the alkyl group is methyl μ, ethyl, propyl, butyl, amichexyl, 2-ethylhexyl, decyl, undecyl, tridecyl, tetragucci p, bentade V/I/
, methylene malonic acid ester/1/ (diester/I/, including monoester).

Examples include esde itaconate/1'% fumaric ester, maleic ester, and the like. The number of carbon atoms in the alkyl group is 1
If it exceeds 5, disadvantages such as a marked decrease in the monopolymerization rate during polymerization occur, which is not preferable.

The vinyl polymer (C) is copolymerized with the above-mentioned vinyl unsaturated sulfonic acid or its salt monomer unit and unsaturated aliphatic carboxylic acid alkyl ester together with other polymerizable unsaturated vinyl monomer units. It is preferable that Other polymerizable unsaturated vinyl monomers include conjugated diene monomers such as butadiene and isoprene; styrene, α
- Aromatic vinyl monomers such as methylstyrene and chlorostyrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, acrylamide, methacrylamide or N-alkyl substituted products thereof: Examples include vinyl halides and vinylidene halides such as vinyl chloride, vinyl bromide, vinylidene chloride, and vinylidene bromide; vinyl esters such as vinyl acetate and vinyl propionate. Mixtures can be used.

In the present invention, the vinyl polymer (C) has a monomer unit consisting of a vinyl unsaturated sulfonic acid or a salt thereof in its constituent units of 3 or more moles, preferably 57 moles or more and 90 moles or less, and more preferably It is desirable that 21 to 90 molds be contained. The monomer unit is 3 mo/I
/%, the above-mentioned polyoxyethylene glyco-μ
Or, even if it is used in combination with its derivative (B), sufficient antistatic performance cannot be obtained. Moreover, if it exceeds 90 molti, the moldability of the resulting composition will deteriorate, which is not preferable.

Furthermore, the vinyl polymer (C) contains 1 molti or more, preferably 1 molti or more and 60 molti or less of an unsaturated aliphatic carboxylic acid alkyl ester in which the alkyl group has 1 to 15 carbon atoms, and further A desirable content is 1 moA/% or more and 50 moA/% or less.

If the unsaturated aliphatic carboxylic acid alkyl ester is less than 17%, the antistatic properties will be lost due to weight reduction treatment with an aqueous alkali solution, and if it exceeds 60%/l/%, the moldability of the composition will deteriorate, which is undesirable. O In addition, as a method for obtaining the vinyl polymer (C), a scouting method can also be adopted, for example, an emulsion polymerization method 1wA
Usual radical addition polymerization and ionic polymerization such as turbidity polymerization and solution polymerization can be used. In addition to these methods, it is of course possible to adopt a method of introducing the monomer units by sulfonating the vinyl polymer.

Vinyl polymer (C) having the above structure in the present invention
The monomer unit consisting of vinyl unsaturated sulfonic acid or its salt is 0.5 to 0.5 to the total amount of (B) and (C).
Preferably, the content is 18% by weight,
Particularly preferably, it is 0.5 to 15% by weight. When the monomer unit is less than 0.5% by weight, effective antistatic properties cannot be obtained unless a large amount of #J polyoxyalkylene glycol t is used.

This results in a decrease in operability or a significant deterioration in physical properties. In addition, if the monomer content exceeds 18% by weight, it is possible to greatly reduce the amount of polyoxyalkylene glycol used, but this is not preferable because the light resistance of the resulting composition decreases, and when molded into fibers. is 15 times f
If it exceeds .fi, it is not preferable because it will lead to a decrease in operability such as spinnability.

In the present invention, any method can be adopted to blend the polyoxyalkylene glycol or its derivative (B) and the vinyl polymer (C) into the thermoplastic polymer (A). Glyco-l
Examples include a method of sufficiently mixing v or its derivative (B) and a vinyl polymer (C) using water or an organic solvent, adding the resulting mixture to a molten thermoplastic polymer, and then stirring and mixing thoroughly. . The following is a concrete description of such a mixing method.

After the synthesis of the thermoplastic synthetic polymer (A), the molten (
A method in which a mixture of polyoxyalkylene glycol or its derivative (B) and vinyl polymer (C) is added to A) and mixed with stirring, and the pellet of (A) and the mixture of (B) and (C) are extruded into an extrusion molding machine. A so-called master chip with a high mixing ratio of one component with antistatic properties is prepared by stirring or mixing in a spinning machine, or by such a method, and this is mixed with chip 5 consisting of the required amount (A) before molding. In the present invention, for example, when formed into fibers, (B) is blended into (A) in a sushi-like manner, and in the (B) , and therefore, in the mixing vessel, (B) and (C)
It is preferable to mix in advance the material (C) which has a shape in which these are dispersed.

The composition of the present invention may also contain any other additives.

For example, the inclusion of antioxidants, ultraviolet absorbers, flame retardants, pigments, etc. does not impair the effects of the present invention.

As described above, the composition of the present invention having such a structure can be formed into fibers, films, sorting, etc. according to conventional methods, and maintains extremely excellent antistatic performance incomparable to conventional compositions. However, even if the composition is subjected to a weight reduction process using an aqueous alkaline solution or the like, its antistatic properties are not impaired at all, and the composition can be applied to an extremely wide range of uses.

Note that in the present invention, excellent antistatic properties cannot be obtained even if only the polyoxyalkylene polymer (C) is blended into the thermoplastic polymer, and polyoxyalkylene glycol or its derivative (
Excellent antistatic properties can only be obtained by using B) in combination.

It is not clear why the inclusion of an unsaturated aliphatic acid alkyl ester in the vinyl polymer (C) imparts durability against weight reduction processing using an antistatic alkaline aqueous solution.

Because the ester group is introduced into the vinyl polymer (C), the compatibility with polyalkylene glycol is improved, and furthermore, the ester group and the varnish-IL/exchange reaction occur during high-temperature melting. Even if there is a sulfonic acid or a salt thereof that easily takes up an alkaline aqueous solution, it will not be easily eluted, so it is thought that the extremely excellent effects described above are exhibited.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is of course not limited to the following Examples.

It should be noted that all percentages and parts shown in the examples are based on weight unless otherwise specified.

In addition, the measurement of the cow shelf life and light resistance in the following examples was performed by the following method.

(1) Half-life: The filaments obtained by melt-spinning are made into a melis knitted fabric.

After scouring and air-drying the silk cloth in a conventional manner, it was heated at 160°C for 1
preset for 30 minutes, apply a voltage of 10 KV for 30 seconds using a static honest meter (manufactured by Otsuki Shokai),
The half-life was measured at 20° C. and 50% relative humidity. The durability of the antistatic property was determined by washing the above knitted fabric in a household washing machine at 40°C for 20 minutes with a 0.5f/I aqueous solution of a neutral activator, and then washing it in hot water at 40°C for 5 minutes. After washing with overflow water for 20 minutes, it was dehydrated and dried at 60° C. for 30 minutes. Evaluation was made by measuring the half-life of the sample after repeating this operation.

The knitted fabric after being subjected to the weight loss treatment using an alkaline aqueous solution was also subjected to the above-mentioned washing treatment, and then its half-life was measured by the above-mentioned method.

(2) Light resistance: Resolin Blue FBL (manufactured by Bayer AG, dispersible dye) silk fabric obtained in the same manner as above and dyed with a dye solution of 1 towf at 130°C for 1 hour in a conventional manner and washed by reduction. The dyed knitted fabric was irradiated for 40 hours using a fade meter, and the degree of discoloration was evaluated by grading it on a blue scale.

Example 1 40 parts of styrene (denoted as St), 50 parts of sodium p-styrene sulfonate (denoted as SPSS), and 10 parts of methyl methacrylate (denoted as MMA) were combined with a redox catalyst (ammonium persulfate-acidic sodium sulfite). was used to polymerize in an aqueous system to obtain vinyl polymer (I) (polymerization rate 92
%). The obtained polymer emulsion solution was neutralized, and then polyoxyethylene glycol having an average molecular weight of 20,000 was added.
l/(II) was dissolved and mixed, and water was removed at 80°C under reduced pressure to obtain a resinous material (ffi) consisting of (2)/(II) = 2/s (5 pss units in (■) is 10
part included).

On the other hand, polyethylene terephthalate was polymerized by a conventional method, and after the polymerization was completed, 3% of the obtained resinous material (m) was added,
After stirring and mixing to obtain a composition, the mixture was discharged from a polymerization can by a conventional method and cut to obtain chips.

This composition was spun and drawn by a conventional method to obtain filaments. This filament was knitted and its half-life and light resistance were measured. The half-life was 6.7 seconds after one wash and 7.5 seconds after 20 washes, and the light resistance was grade 4 to 5, indicating excellent durable antistatic properties and light resistance. Next, the above-mentioned knitted fabric before washing was subjected to weight loss processing in a 202/l sodium hydroxide aqueous solution at a bath ratio of 1:100 at 97°C for 50 minutes to obtain a silk fabric with a weight loss rate of 20%. The half-life of this silk cloth after one washing was 9.8 seconds, and even after 20 washings, it was 10.5 seconds, indicating excellent durable antistatic properties.

Comparative Example 1: Half reduction after one washing of a knitted silk fabric obtained in the same manner as in Example 1 except that the vinyl polymer CI) used in Example 1 was polymerized from 50 parts of 5t and 50 parts of 5PSS. The period was 7.3 seconds, the half-life after 20 washes was 8.0 seconds, and the light resistance was grade 4-5. Next, alkali weight loss processing was performed in the same manner as in Example 1 to obtain a silk fabric with a weight loss rate of 19%. The half-life of this silk fabric after one wash was 180 seconds or more, and its antistatic properties were completely lost.

Examples 2-6. Comparison 1 Examples 2 to 3 The composition ratio of the vinyl polymer (I) used in Example 1 was set as shown in Table 1, and the amount of 5 pss in the resinous material (I [) was 1
The resinous material (I[) was mixed with polyethylene terephthalate 1/- so that the amount of polyoxyethylene glycol (II) was 2.5% based on the total composition.
) A polyester filament was obtained in the same manner as in Example 1, except that the polyester filament was blended with the polyester filament. Spinnability at that time, antistatic property (half-life) and hydration of the obtained filament The half-life after 20% weight loss is shown in Table 1 in the same manner as in Example 1 using an IJium aqueous solution. vinegar.

Table 1 As is clear from Table 1, 1 mol/L or more of MMA is required to maintain sufficient antistatic properties even after alkali reduction, and 60 mol/L of MMA is required to obtain filaments with good spinning operation. It can be seen that a value of /% or less is desirable.

Examples 7 to 10, Comparative Example 4 Vinyl was prepared in the same manner as in Example 1 except that methacrylic acid alkyl ester) V shown in Table 2 was used instead of MMA in the vinyl polymer (I) of Example 1. A system polymer was obtained. Table 2 shows the polymerization rate at that time and the half-life of the filament after the alkali weight loss (20 inches) when these vinyl polymers were used.

Table 2 As is clear from Table 2, when the number of carbon atoms in the alkyl group of the unsaturated carboxylic acid alkyl ester exceeds 15, the polymerization rate decreases significantly, which is not preferred.

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Claims] (1) Thermoplastic polymer (A) contains at least one polyoxyalkivin glycol or its derivative (B) in an amount of 0.1 to 10% by weight based on the total composition and a vinyl polymer (C). An antistatic polymer composition, wherein the vinyl polymer (C) contains at least 3 mo/L'% of a monomer unit consisting of a vinyl unsaturated sulfonic acid or a salt thereof and an alkyl group. At least one unsaturated aliphatic carboxylic acid alkyl ester having 1 to 15 carbon atoms
An antistatic polymer composition characterized in that it has a mole percent bond of metal. (2) The antistatic polymer composition according to claim (1), wherein the thermoplastic polymer is polyester.