JPS6020964A - Antistatic polymer composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having durable antistatic properties imparted thereto without detriment to inherent physical properties, by blending a given amount of a polyoxyalkylene glycol and a given amount of a specified vinyl polymer with a thermoplastic polymer. CONSTITUTION:A vinyl polymer composed of at least 0.1mol% of a monomer unit (a) consisting of an unsaturated vinyl compd. having a polyoxyalkylene chain (e.g. polyoxyalkylene glycol acrylate), at least 3mol% of an unsaturated vinylsulfonic acid (salt) (b) (e.g. styrenesulfonic acid) and 0-96.9mol% of other unsaturated vinyl compd. (c) (e.g. vinyl acetate), is used. A thermoplastic polymer (A) such as a polyester, 0.1-10wt% (based on the total amount of compsn.) polyoxyalkylene glycol (derivative) (B) and 0.5-18wt% (based on the combined amount of components B and C) said vinyl polymer (C) are blended together.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition that does not impair the excellent physical properties of the two original thermoplastic polymers and has excellent antistatic properties.

In general, hydrophobic polymeric substances are easily charged with electricity due to friction, peeling, etc., and this charging causes various problems in molded products, and also has disadvantages such as giving a shock due to discharge and causing dust to adhere during use. There is. To eliminate these drawbacks, antistatic agents are applied to the surface of the molded product. Alternatively, methods such as mixing it internally have been 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 a polyester molded product 1, such as fiber or film, having sufficient antistatic performance by employing the above method, it is necessary to blend polyoxyalkylene glycol in an amount exceeding 10% by weight. They have drawbacks such as a marked decrease in moldability, and an extremely poor physical property of the resulting fibers and films, especially the light stability of dyed products. To solve this problem, polyethylene glycol with an average molecular weight of ff1lo000 to 30,000, which is insoluble in polyester, is used, and a low-molecular compound containing a metal salt of ionanurphonic acid, such as dodecylbenzenesulfonic acid sorta, is used in combination. A method of reducing the amount of glycol blended is proposed in Japanese Patent Publication No. 44-31828, Japanese Patent Publication No. 46-42629, 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 priority is given, the antistatic performance will not be satisfactory, and in particular, the antistatic performance will only have poor durability.

In view of the above-mentioned circumstances, the present inventors conducted extensive research and study in order to obtain a composition with excellent antistatic performance without impairing the excellent physical properties of the original thermoplastic polymer. We have finally completed the present invention. That is, the present invention
A composition in which a thermoplastic polymer (A) is blended with at least one polyoxyalkylene glycol or its derivative CB) in an amount of 0.1 to 10% by weight based on the total composition, and a vinyl polymer (C). The vinyl polymer (C) contains at least 0.1 mole of the monomer unit (A) consisting of an unsaturated vinyl compound containing a polyoxyalkylene compound.

The constituent units are a monomer unit consisting of vinyl unsaturated sulfonic acid or its salt (b) 3 moles or more, and a monomer unit consisting of another unsaturated vinyl compound (c) 0 to 96.9 moles. , the amount of (b) in the vinyl polymer (C) is 0.5 to 0.5 to the total amount of (B) and (C).
This is an antistatic polymer composition characterized in that the amount of the antistatic polymer is 18% by weight.

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 oxycarboxylic acid, or a copolymer thereof, such as a dicarboxylic acid whose main component is terephthalic acid or its lower argyl ester. and glycol. 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 a thermoplastic polymer fffl to impart antistatic properties, for example, in Japanese Patent Publication No. 39-521.
4, Japanese Patent Publication No. 57-4724, etc., this term refers to all commonly known substances, and specific examples include polyethylene glycol and holypropylene glycol.

Random or block copolymers of ethylene oxide and propylene oxide, polytetramethylene glycol, block copolymers obtained by adding ethylene oxide to polytetramethylene glycol, neopentyl glycol, and ethylene oxide added to bisphenol glycol. Polyoxyalkylene compounds with hydroxyl groups at both ends, such as monophenoxypolyethylene glycol, nonylphenoxypolyethylene glycol, sodium sulfophenoxypolyethylene glycol, diphenoxypolyethylene glycol, 2 moles of monophenoquine polyethylene glycol and 1 mole of tolylene diisocyanate. Polyoxyalkylene compounds whose one or both ends are blocked via an ether bond, such as compounds bonded with polyoxyalkylene, polyethylene glycol phosphates, and ethylene glycol phosphates.

Polyether compounds esterified at one or both ends, such as certain partially alkaline salts, phosphonates of polyethylene glycol, or partially alkaline salts thereof, block copolymers of polyethylene glycol and polyethylene terephthalate, polytetramethylene glycol and polyethylene Block copolymers with terephthalate or polybutylene terephthalate, block copolymers with polyethylene glycol and poly6-capramide, polyethylene glycol with one or both ends cyanoethylated, or polyethylene glycol with the cyano group converted into an amino group, Examples include compounds obtained by adding ethylene oxide to a primary or secondary alkylamine. 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.

Moreover, in the above (B), both ends are -OH.

In the case of a group having active hydrogen such as -COOH, -Nl2, etc., the weight average molecular weight (hereinafter abbreviated as bimolecular weight) of (B) is preferably 6,000 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 4000 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.

CB to be used in the present invention is one or more solid C
B) is sufficient. Furthermore, this additional C to be contained
B) Add antioxidants, ultraviolet absorbers, pigments, and organic or inorganic ionic compounds in advance.

Other additives may also be mixed.

The amount of such polyoxyalkylene glycol or its derivative CB) is 0.1 to 10% by weight in the entire composition.
It is appropriate to have it exist within the range of .

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, a vinyl polymer (C
) must contain a monomer unit (b) consisting of a vinyl unsaturated sulfonic acid or its salt and a monomer unit (a) consisting of an unsaturated vinyl compound containing a polyoxyalkylene compound in its groove unit. It is considered as a constituent unit.

Monomers consisting of vinyl unsaturated sulfonic acids or salts thereof include unsaturated hydrocarbons and their salts such as styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, (meth)allylsulfonic acid, etc. ; Sulfoalkyl esters of acrylic acid or methacrylic acid, such as (meth)acrylic acid sulfobutyl ester, (meth)acrylic acid sulfobutyl ester, (meth)acrylic acid sulfopropyl ester, or salts thereof; 2-acrylamide-2-methylpropane sulfone Acids or salts thereof can be mentioned, and in the present invention, those having aromatic rings such as styrene sulfonic acid, vinylbenzyl sulfonic acid or salts thereof are preferable.In addition, as vinyl unsaturated sulfonates, Alkali metal salts and alkaline earth metal salts are preferred.

In addition, as the unsaturated vinyl compound (a) containing polyoxyalkylene studs, acrylic acid ester of polyoxyalkylene glycol or Metac! J/L' acid-E-
Examples include esters such as esters and itaconic acid esters, N-substituted products of acrylamide and methacrylamide, and polyoxyalkylene glycol 7-(meth)allyl ether. The average molecular weight of the polyoxyalkylene monomer unit is 200 or more, preferably 400 or more,
5000 or less. When the average molecular weight is less than 200,
When forming into fibers, it is unsuitable because it causes long-term spinning operability, especially an increase in nozzle back pressure during spinning.

On the other hand, when the average molecular weight exceeds 5000, the polymerization rate decreases during polymerization of the vinyl polymer (C).

This is not preferred because a vinyl polymer cannot be obtained efficiently. Examples of the polyoxyalkylene group include polyoxyethylene glycol, polyoxypropylene glycol, polytetrahydrofuran, and copolymers thereof, and those containing oxyethylene units are particularly preferred. Further, one terminal of these polyoxyalkylene groups may be a 10H group or may be bonded to other organic groups other than the polymerizable unsaturated group via an ether bond, an ester bond, or the like.

The vinyl polymer (C) is a monomer consisting of the above-mentioned vinyl unsaturated sulfonic acid or its salt and a monomer consisting of an unsaturated vinyl compound containing a polyoxyalkylene compound, as well as other polymerizable unsaturated vinyl monomers. The polymer (iii) may be copolymerized. Examples of other polymerizable unsaturated vinyl monomers include conjugated diene monomers such as butadiene and isoprene; aromatic vinyl monomers such as styrene, α-methylstyrene, and chlorostyrene; acrylonitrile and methacrylonitrile. Vinyl cyanide monomers such as acrylic acid,
Methacrylic acid or esters thereof; acrylamide, methacrylamide, or N-alkyl substituted products thereof; vinyl halides and vinylidene halides such as vinyl chloride, vinyl bromide, vinylidene chloride, and vinylidene bromide; vinyl acetate, propion Examples include vinyl esters such as vinyl acid, and these monomers can be used alone or as a mixture.

In the present invention, the vinyl polymer (C) has a monomer unit (b) consisting of a vinyl unsaturated sulfonic acid or a salt thereof in its constituent units of 3 or more moles, preferably 5 or more moles, and less than 90 moles. , more preferably 21 moles or more and less than 90 moles. When the monomer unit is less than 3 moles, sufficient antistatic performance cannot be obtained even when used in combination with the above-mentioned polyoxyalkylene glycol or its derivative CB). Moreover, if it exceeds 90 moles, the IJJ threadability will deteriorate when forming into fibers, etc., which is not preferable.

Furthermore, the vinyl polymer (C) must contain at least 0.1 mol % of a monomer consisting of the unsaturated vinyl compound (A) containing polyoxyalkylene compound in its constituent units. By containing 0.1 mol or more of this monomer, an excellent improvement in antistatic effect can be seen compared to a polymer that does not contain this monomer, and long-term fiber formability, especially during spinning, can be seen. Improvements are also made in increasing nozzle back pressure.

Note that any number of methods can be employed to obtain the vinyl polymer (C), and examples thereof include ordinary radical addition polymerization such as emulsion polymerization, suspension polymerization, and solution polymerization, and ionic polymerization. . In addition to these methods, it is of course possible to adopt a method of introducing the monomer units by nulphonating the vinyl polymer.

Vinyl polymer (C) having the above structure in the present invention
(CB)
The content should be 8% by weight, preferably 0.5-15% by weight. If the monomer unit is less than 0.5% by weight, effective antistatic properties cannot be obtained unless a large amount of the polyoxyalkylene glycol is used, resulting in decreased operability or significant deterioration of physical properties. invite 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 weight -
Exceeding this is not preferable because it causes a decrease in spinnability and other operability.

In addition, in the total composition, the total amount of polyoxyalkylene glycol or its derivative (B) and the monomer unit containing a polyoxyalkylene chain (A) constituting the vinyl polymer (C) is 10% by weight. % or less. If it exceeds 10 weight ff1%, the stability of the dyed product against light will deteriorate, which is not preferable.

In the present invention, any method can be used to blend the polyoxyalkylene glycol or its derivative (B) and the vinyl polymer (C) into the thermoplastic polymer (A). For example, polyoxyalkylene glycol or its derivative i (B) and vinyl polymer (C) are thoroughly mixed using water or an organic solvent, the resulting mixture is added to a molten thermoplastic polymer, and the mixture is thoroughly stirred. Examples include methods to do so. Specifically describing such a mixing method, after the synthesis of the thermoplastic synthetic polymer (A) is completed, polyoxyalkylene glycol or its derivative (B) and vinyl polymer CC) are added to (A) in the molten bed. The mixing ratio of the antistatic components can be adjusted by adding the mixture and stirring, mixing the pellets of (A) and the mixture of CB) and (C) by stirring in an extruder or spinning machine, or by such a method. Examples include a method in which a large so-called master chip is made in advance and mixed with chips of the required amount (A) before molding.

Further, the composition of the present invention may contain other optional additives such as antioxidants, ultraviolet absorbers, flame retardants, pigments, etc., but this does not impede the effects of the present invention in any way.

As described above, the composition of the present invention having such a structure maintains extremely excellent antistatic performance semi-permanently, incomparably with conventional compositions, and also maintains excellent antistatic performance of the target thermoplastic polymer. without damaging physical properties.

In particular, the composition has good sunlight stability for dyed products, and the various problems caused by band tK, which have hitherto been a problem, can be solved all at once. Furthermore, the composition enables stable operation over a long period of time when molded into fibers, films, sheets, etc. according to conventional methods, and has extremely high industrial value.

Polyoxyalkylene glycol or its derivative CB
) and the vinyl polymer (C), it is not clear why it is possible to exhibit such excellent antistatic properties and durability, and also to enable stable operability over a long period of time during molding. 1 The vinyl polymer used in the present invention is a polymeric substance, unlike the conventionally used low-molecular-weight surfactant-like sulfonate-containing substances, and this polymeric substance has polyoxygen as a side chain. Since it has alkylene glycol, it is uniformly dispersed in polyoxyalkylene glycol or its derivative (B).

In addition, agglomeration is less likely to occur, and the flow of charge in the polyoxyalkylene glycol becomes smoother, resulting in extremely excellent antistatic properties and durability, as well as operational stability during molding. .

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 half-life % light resistance of the following examples was performed by the following method.

(1) Half-life: After melt spinning, the filaments obtained in Knee 2 are knitted into Melyanu 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 Statec Honest Meter (manufactured by Shishido Shokai),
The half-life was measured at 20° C. and 50% relative humidity. The durability of the anti-banding property was determined by washing the above-mentioned silk cloth 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 and surrounding it with T-20, it was dehydrated and dried at 60°C for 30 minutes.This operation was repeated and the half-life of the sample was measured and evaluated.The half-life measured by the above method was 100 If it is less than 2 seconds, it is considered to have antistatic properties.

(2> Light resistance: The refined silk cloth obtained in the same manner as above was dyed with a 1% owf dyeing solution of Resolin Blue FBL (Bayer GmbH 1 official dye) at 130'C for 11 hours.

A dyed knitted fabric dyed by a conventional method and subjected to reduction washing was irradiated with a fade meter for 40 hours, and the degree of discoloration was evaluated by grading it on a blue scale.

Example 1 21.3 parts of 7fV (denoted as St), 50 parts of sodium p-styrene sulfonate (denoted as SpSS), and methoxypolyethylene glycol (45 mol) (methacrylate) (
28.7 parts of PEG(45)MA) were polymerized in an aqueous system using a redox catalyst (potassium persulfate-acidic sodium sulfite) to obtain a vinyl polymer (I). The obtained polymer emulsion liquid was neutralized, and then the average molecular weight was 2.
0000 polyoxine ethylene glycol (1) was dissolved and mixed, and water was removed at 80°C under reduced pressure to obtain (1) / (1
) = 1/9 was obtained ((5 parts of 5pSS is contained in the resin).

On the other hand, polyethylene terephthalate was polymerized by a conventional method, and after the polymerization was completed, 4.0% of the obtained resinous material (1) was added, stirred and mixed to obtain a composition, and then discharged from a polymerization can by a conventional method. and cut it to obtain chips (5pSS in the composition).
Unit is 0.200%, PEG (45) MA small unit 0.1
(contains 15%).

After drying the obtained composition according to a conventional method, a test spinning machine equipped with a filter on the spinneret was used, and a spinneret having 24 spinning holes with a hole diameter Q of 3 sm was used to obtain a discharge rate of 20 f/2.
The fibers were spun at a spinning temperature of 280° C. and a winding speed of 1300 m/min. The increase in nozzle back pressure after 5 days was 1.5 kf/-, indicating good spinnability. Thereafter, the filament was drawn, knitted, and its half-life and light resistance were measured. The half-life is 5.5 seconds after one wash and 5.8 seconds after 20 washes.

The light resistance was good at grade 4 to 5, and it had excellent durable antistatic properties and light resistance.

Comparative Example 1゜A knitted fabric made of filaments obtained by adding 4 g of only (1) used in Example 1 to polyethylene terephthalate after completing one polymerization in the same manner as in Example 1 has a half-life of one washing. is 180 seconds or more.

The light resistance was grade 4.

The half-life of knitted fabric using filament obtained by adding 12% of (I) was 8.0 seconds after 20 washes.
The light resistance was extremely low at grade 2.

Comparative Example 2゜In the same manner as in Example 1, 3.6% of (H) and 0.4% of (I) sodium salt of linide benzenesulfonic acid were added to polyethylene terephthalate after completion of polymerization. , obtained filament.

The half-life of the stockinette knitted fabric using this filament was 35 seconds after one wash, but it was 180 seconds or more after 20 washes, and was not durable. In addition, the light resistance was 4th to 5th grade.

Examples 2-7. Comparative Examples 3 to 5 Polyester filaments were obtained in the same manner as in Example 1, except that the vinyl polymer (1) used in Example 1 had the composition shown in Table 1. The first step was to increase the nozzle back pressure by spinning for 5 days, and to improve the antistatic property (half-life) of the filament.
Also listed in the table.

As is clear from Table 1, 5pSS in vinyl polymers
Antistatic properties cannot be obtained unless PE is 3 molti or more; on the other hand, PE
It can be seen that if G(45)MA is not 0.1 mol or more, the increase in nozzle back pressure for 5 days will exceed 30 ky/cTA, making long-term spinning difficult.

Examples 8 to 12, Comparative Examples 6 and 7 Vinyl polymer CI) used in Example 1
Polyester filaments were obtained in the same manner as in Example 1, except that a methacrylate monomer having a methoxypolyethylene glycol having the molecular weight shown in Table 2 was used instead of G(45)MA. The polymerization rate of the vinyl polymer, the increase in nozzle back pressure, and the antistatic properties of the filament are shown in Table 2. As is clear from Table 2, it is made of an unsaturated vinyl compound containing polyalkylene studs. It can be seen that the molecular weight of the polyalkylene monomer unit is preferably 200 to 5,000.

Examples 13-19. Comparative Example 8.9 The vinyl polymer used in Example 1 (S instead of In)
t 33.1 parts, 5pSS 50 parts, methoxypolyethylene glycol (22 mol) methacrylate (PEG (2
2) Using the vinyl polymer obtained from 16.9 parts of MA), the same procedure as Example 1 was used except that the amounts of 5pSS and PEG (22) MA in the composition were changed to the amounts shown in Table 3. A stockinette knitted fabric of polyester filament was obtained. Table 3 shows the pressure increase during spinning, the half-life of the knitted fabric after 20 washes, and the light resistance of the dyed fabric.

Table 3 As is clear from Table 3, in order to obtain excellent antistatic performance without impairing the light resistance of polyester, the amount of monomer consisting of vinyl unsaturated sulfonic acid or its salt is 0.5 ~1
8%, the total amount of unsaturated vinyl compounds containing polyoxyalkylene compounds and polyoxyalkylene compounds is 10%.
In addition, in order to obtain a filament with excellent antistatic properties and good operability, the content of vinyl unsaturated sulfonic acid or its salt must be 0.5 to 18%, as shown in the increase in nozzle back pressure. Furthermore, considering that yarn breakage sometimes occurred at 18% or more, 0.5 to 18% is appropriate.

Example 20 KSpSS85 instead of polymer (I) used in Example 1
A polyester filament was produced in the same manner as in Example 1, except that a vinyl polymer containing 5 parts of PEG (45) and 5 parts of MA was used. The increase in nozzle back pressure is 5 ky/
crA, and the antistatic property of the obtained filament (
half-life) is 5.6 seconds after 20 washes, and light resistance is 4.
It had an extremely excellent durable antistatic property of grade 5 to 5.

Example 21 A polyester filament was produced in the same manner as in Example 1, except that sodium salt of 2-acrylamide-2-methylpropanesulfonic acid was used instead of the polymer in Example 1. The half-life of the filament obtained is 5.5 seconds;
The light resistance was grade 4 to 5. Example 22 Nylon 6 chips and the VjjQii-like material obtained in Example 1 (
Nylon 6 / (1) / (1) = 97
/0.3/2.7, and then supplied to an extruder for melt extrusion spinning. The half-life of the obtained filament was 4.5 seconds, and the light resistance was grade 4. however.

Light resistance was evaluated by dyeing with Solway Blue B (manufactured by ICI, an acid dye).

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Claims] (1) Thermoplastic polymer (A) is blended with 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). The vinyl polymer (C) contains 0.1 mol or more of a monomer unit (A) consisting of an unsaturated vinyl compound containing a polyoxyalkylene compound, a vinyl unsaturated sulfonic acid or its A monomer unit consisting of a salt (b) 3 or more moles and a monomer unit consisting of another unsaturated vinyl compound (c) 0 to 96.9 moles as a constituent unit, and in the vinyl polymer (C). 0.0 for the total amount of (Ron is the CB) and (C).
An antistatic polymer composition characterized in that it is blended in an amount of 5 to 18% by weight.