JP3090519B2 - Modifier for thermoplastic synthetic polymer and polymer composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic synthetic polymer modifier and a polymer composition containing the same. Because thermoplastic synthetic polymers have excellent properties as materials,
Widely used in various industrial fields. However, thermoplastic synthetic polymers generally have large nonpolar properties, and thus have problems in antistatic properties and dyeability. The present invention relates to a modifier capable of imparting an excellent antistatic property and a dyeing property to a thermoplastic synthetic polymer, which has durability and does not reduce the physical properties of the thermoplastic synthetic polymer, and The present invention relates to a polymer composition containing

[0002]

2. Description of the Related Art Numerous attempts have been made to introduce an ionic group into a thermoplastic synthetic polymer as a means for imparting an antistatic property and a dyeing property to the thermoplastic synthetic polymer. Among these, as a means for introducing a sulfonic acid group into a thermoplastic synthetic polymer, an example in which a non-reactive compound having a sulfonic acid group is added (JP-A-62-28303)
5), there is an example in which a reactive compound having a sulfonic acid group is copolymerized (JP-A-62-299526). However, in the former example, since the non-reactive compound is easily removed by water or a solvent, there is a drawback that the durability of the effect is low, and in the latter example, the desired effect is not obtained. Since it is necessary to increase the copolymerization ratio of the reactive compound, there is a disadvantage that the physical properties of the thermoplastic synthetic polymer are reduced. Therefore, in order to improve such disadvantages, examples of adding a polyetherester or an aliphatic polyester having a sulfonic acid group introduced therein (US Pat. No. 4,600,123), and examples of introducing a reactive compound having a sulfonic acid group to a molecular terminal of a synthetic polymer (particularly, US Pat. (Japanese Unexamined Patent Publication No. 62-238883) has been proposed. However,
The former example has a drawback that the heat resistance is insufficient due to the presence of the aliphatic polyester portion and the polyether portion, and the latter example has a sufficient effect of modifying the concentration of the sulfonic acid group. Cannot be raised to the extent that
There is a disadvantage that a desired effect cannot be obtained.

[0003]

The problem to be solved by the present invention is that the conventional means cannot provide the desired antistatic properties or dyeing properties originally, or have low durability or have a thermoplastic synthetic property. This is to reduce the intrinsic physical properties of the polymer.

[0004]

Means for Solving the Problems Thus, the present inventors have
As a result of intensive studies from the above viewpoint, it has been found that it is correct and suitable to use a polyester obtained by copolymerizing 30 mol% or more of an isophthalic acid derivative having phosphonium sulfonate as a substituent as a dicarboxylic acid component.

That is, the present invention relates to an aromatic dicarboxylic acid unit containing 30 mol% or more of a phosphonium sulfoisophthalate unit represented by the following formula 1, and a diol unit derived from a dihydric alcohol represented by the following formula 2: A thermoplastic synthetic polymer modifier comprising a polyester comprising: a thermoplastic synthetic polymer having no sulfonic acid group in the molecule; and a thermoplastic synthetic polymer having no sulfonic acid group in the molecule. And a polymer composition containing the modifier for a thermoplastic synthetic polymer in an amount of 0.1 to 8% by weight as a sulfoisophthalate unit represented by the following formula (3).

[0006]

(Equation 1)

[0007]

(Equation 2)

[0008]

(Equation 3)

In the formulas (1) and (2), R ^{1 to} R ^{4 are the} same or different and are an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an aromatic hydrocarbon group, an aralkyl group, an alkylallyl group. 2 to 22 hydrocarbon groups

In the phosphonium sulfoisophthalate unit represented by the formula 1, the phosphonium constituting the cation portion includes 1) tetramethylphosphonium,
1 carbon atom such as tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium, trioctylmethylphosphonium, tributylethylphosphonium, trimethylbutylphosphonium, triethyloctylphosphonium, tributyloctylphosphonium, trimethyllaurylphosphonium, trimethylstearylphosphonium, etc.
A phosphonium having from 18 to 18 aliphatic hydrocarbon groups, 2)
Phosphonium having an aromatic hydrocarbon group such as tetraphenylphosphonium, triphenylmethylphosphonium and triphenylethylphosphonium; 3) an aralkyl group or an alkylallyl group such as triphenylbenzylphosphonium, tritolylbutylphosphonium and tributylbenzylphosphonium; And phosphonium having the same. Of these, tetrabutylphosphonium,
Tetraphenylphosphonium is preferred.

The polyester used as the thermoplastic synthetic polymer modifier of the present invention comprises an aromatic dicarboxylic acid unit and
And a diol unit derived from the dihydric alcohol represented by the formula (2). In the aromatic dicarboxylic acid unit, the phosphonium sulfoisophthalate unit represented by the formula 1 as described above is used in an amount of 30 mol% or more, preferably 50 mol% or more, more preferably 70 mol% in the whole aromatic dicarboxylic acid unit. % Or more. The proportion occupied by the phosphonium sulfoisophthalate unit represented by the formula 1 is 30 in the total aromatic dicarboxylic acid unit.
If the amount is less than mol%, it is necessary to add a large amount of a thermoplastic synthetic polymer modifier in order to impart antistatic properties and dyeing properties, thereby lowering the physical properties of the thermoplastic synthetic polymer.

The aromatic dicarboxylic acid unit other than the phosphonium sulfoisophthalate unit represented by the formula 1 includes:
There are aromatic dicarboxylic acid units derived from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. Of these, terephthalic acid units are preferred.

The dihydric alcohol represented by the formula 2 has a hydrocarbon group having 2 to 22 carbon atoms.
1) ethylene glycol, propylene glycol, 1,
Aliphatic glycols such as 4-butanediol, neopentyl glycol and 1,6 hexanediol; 2) alicyclic glycols such as cyclohexanediol and cyclohexane-1,4-dimethanol; 3) aromatics such as p-xylylene glycol Glycol. Among such diol units derived from a dihydric alcohol, an ethylene glycol unit is advantageous.

The polyester used as the modifier for the thermoplastic synthetic polymer of the present invention may be an aromatic dicarboxylic acid or an ester-forming derivative thereof, such as a methyl ester or a hydroxyethyl ester thereof, and the above-mentioned glycols. Can be obtained by a known esterification or transesterification reaction followed by a polycondensation reaction.

The polyester used as the modifier for the thermoplastic synthetic polymer of the present invention has a molecular weight of 3,000 to 30.
000 is preferable, and 5,000 to 20,000 is more preferable. If its molecular weight is less than 3000,
Such a polyester tends to move in a thermoplastic synthetic polymer, and thus has a tendency to be inferior in durability. Conversely, if the molecular weight exceeds 30,000, the production of such a polyester requires ordinary condensation polymerization. In addition, a special reaction such as solid phase polymerization is required, which is disadvantageous.

The polymer composition of the present invention comprises the above-described modifier for a thermoplastic synthetic polymer and a thermoplastic synthetic polymer having no sulfonic acid group in the molecule. It comprises a synthetic polymer modifier represented by the formula (3) in an amount of 0.1 to 8% by weight as a sulfoisophthalate unit. In this case, when the main purpose is to impart antistatic properties, it is preferable to contain the sulfoisophthalate unit represented by the formula (3) in an amount of 0.2 to 4% by weight. In the case of imparting dyeing properties to cationic dyes, for example, 1 to 5 as the sulfoisophthalate unit represented by the formula (3)
It is preferable that the content be contained so as to be in a percentage by weight. If the amount to be contained is less than 0.1% by weight as the sulfoisophthalate unit represented by the formula 3, the desired effect of improving antistatic properties and dyeing properties cannot be obtained, and if it exceeds 8% by weight. ,
The physical properties of the polymer composition are significantly reduced.

As the thermoplastic synthetic polymer to which the present invention is applied, 1) vinyl polymer type polymer such as polyethylene, polypropylene, polystyrene and polymethyl methacrylate; and 2) polycondensation type polymer such as polyester, polycarbonate and polyamide. Molecules. Among these, the present invention is effective for polycondensation type polymers having a high processing temperature such as polyester, polycarbonate and polyamide, and particularly for polyethylene terephthalate and polybutylene terephthalate.

For preparing the polymer composition of the present invention, a known kneading process can be applied. Such kneading processes include mills, calenders, kneaders, extruders and the like. The kneading temperature is equal to or higher than the melting point of the thermoplastic synthetic polymer, generally from 160 to 300 ° C. The polymer composition of the present invention can be processed into a polymer molded product using various molding methods. At the time of processing, any additive such as an antioxidant, an ultraviolet absorber, a flame retardant, a lubricating agent, and inorganic fine particles can be used together for various purposes as long as the effects of the present invention are not impaired.

[0019]

【Example】

Test Category 1 (Production of an ethylene glycol solution of phosphonium sulfoisophthalate, etc.) Production of an ethylene glycol solution (DC-1) of tetrabutylphosphonium-5-sulfoisophthalic acid-bis- (2-hydroxyethyl) ester 504, tetrabutylphosphonium-5-sulfoisophthalic acid obtained according to the method described in
Parts (1 mol, parts are parts by weight, hereinafter the same) and 500 parts of ethylene glycol were charged into a reaction vessel, and heated and stirred at 180 ° C. for 8 hours while distilling off water produced under a nitrogen stream.
Then, the mixture was concentrated at the same temperature under reduced pressure of an aspirator to obtain a solution of tetrabutylphosphonium-5-sulfoisophthalic acid-bis- (2-hydroxyethyl) ester in ethylene glycol (DC-1). This DC-1 had an acid value of 2.7 and a saponification value of 154.

In the same manner, tetraphenylphosphonium-5-sulfoisophthalic acid-bis- (2-hydroxyethyl) ester in ethylene glycol solution (DC-
2), an ethylene glycol solution of triethylbenzylphosphonium-5-sulfoisophthalic acid-bis- (2-hydroxyethyl) ester (DC-3), tributyloctylphosphonium-5-sulfoisophthalic acid-bis-
An ethylene glycol solution (DC-4) of (2-hydroxyethyl) ester was obtained. DC-2 has an acid value of 2.1 and a saponification value of 134, and DC-3 has an acid value of 3.2 and a saponification value of 170.
C-4 had an acid value of 3.0 and a saponification value of 137. Also US
According to the method described in P40335346, tetrabutylphosphonium-5-sulfoisophthalate-dimethyl (D
C-5) was obtained. This DC-5 has an acid value of 0.5 and a saponification value of 2
It was 10.

Preparation of an ethylene glycol solution (DC-10) of tetrabutylphosphonium-m-sulfobenzoic acid- (2-hydroxyethyl) ester Tetrabutylphosphonium-m-sulfobenzo obtained according to the method described in US Pat. No. 4,035,346. 460 parts of acid (1
Mol) and ethylene glycol (600 parts) were charged into a reaction vessel, and the resulting water was distilled off under a nitrogen stream.
For 8 hours. Then, at the same temperature, the mixture was concentrated under reduced pressure of an aspirator, and tetrabutylphosphonium-m-
An ethylene glycol solution of sulfobenzoic acid- (2-hydroxyethyl) ester (DC-10) was obtained. This D
C-10 had an acid value of 2.3 and a saponification value of 61.

Test Category 2 (Production of Polyester Used as Modifier for Thermoplastic Synthetic Polymer) Example 1 {Production of Polyester (A)} 715 parts of DC-1 obtained in Test Category 1 0.5 part of butyl titanate and 1.0 part of tetrabutylphosphonium hydroxide were charged into a reaction vessel, and the mixture was heated to 200 ° C. under aspirator vacuum and stirred.
Next, the mixture was heated and stirred up to 240 ° C. while increasing the degree of vacuum. Further, a polymerization reaction was carried out at the same temperature under a vacuum of 1 mmHg or less for 2 hours to obtain a polyester (A). This A had a pale yellow transparent solid appearance, an acid value of 4.3, a hydroxyl value of 6.6, and an average molecular weight of 10,300 (calculated from the acid value and the hydroxyl value, the same applies hereinafter).

Examples 2-7 Polyester (B)
Production of (G)｝ Polyester (B) ~
(G) was obtained.

Example 8 {Production of Polyester (H)} 426 parts of DC-5 obtained in Test Category 1, 39 parts of dimethyl terephthalate, 360 parts of 1,4-butanediol,
As a catalyst, 1.0 part of tetrabutyl titanate and 1.0 part of tetrabutyl phosphonium hydroxide were charged into a reaction vessel, and transesterification was performed at 180 ° C. under normal pressure. Next, the mixture was heated and stirred to 200 ° C. under reduced pressure of the aspirator, and then heated to 240 ° C. while increasing the degree of reduced pressure. Further, a polymerization reaction was carried out at the same temperature under a vacuum of 1 mmHg or less for 2 hours to obtain a polyester (H). This H
Had a pale yellow transparent solid appearance, an acid value of 8.5, a hydroxyl value of 6.5, and an average molecular weight of 7,500. Table 1 summarizes the contents of the polyesters (A) to (H) obtained in Examples 1 to 8.

Comparative Example 1 {Production of Polyester (R-1)} 267 parts of an ethylene glycol solution of Na-5-sulfoisophthalic acid-bis- (2-hydroxyethyl) ester (saponification value 126), terephthalic acid-bis 254 parts of-(2-hydroxyethyl ester), 0.5 part of tetrabutyl titanate and 1.0 part of tetrabutyl phosphonium hydroxide as a catalyst were charged into a reaction vessel, and the reaction was carried out in the same manner as in Example 1. . The viscosity increased significantly with the progress of the reaction, and stirring became impossible, so the reaction was interrupted and the content of the polyester (R-
1) was taken out. This R-1 has a white solid appearance,
The acid value was 8.2, the hydroxyl value was 41.8, and the average molecular weight was 2,200.

Comparative Examples 2-4 Polyester (R-2)
Production of (R-4)} Polyester (R-2) in the same manner as in Example 1.
To (R-4). Table 1 summarizes the contents of the polyesters (R-1) to (R-4) obtained in Comparative Examples 1 to 4.

[0027]

[Table 1]

In Table 1, DC-1 to DC-5, DC-10: obtained in test section 1 DC-6: terephthalic acid-bis- (2-hydroxyethyl) ester DC-7: isophthalic acid-bis -(2-hydroxyethyl) ester DC-8: dimethyl terephthalate DC-9: Na-5-sulfoisophthalic acid-bis- (2
-Hydroxyethyl) ester in ethylene glycol solution DC-11: adipic acid-bis- (2-hydroxyethyl) ester HD: 1,6-hexanediol BG: 1,4-butanediol Polymer composition: aromatic constituting polyester IPS-1: Tetrabutylphosphonium-5-sulfoisophthalic acid IPS-2: Tetrabutylphosphonium-5-sulfoisophthalic acid IPS-3: Triethylbenzyl Phosphonium-5-sulfoisophthalic acid IPS-4: Tributyloctylphosphonium-5-sulfoisophthalic acid IPS-5: Na-5-sulfoisophthalic acid TPA: Terephthalic acid IPA: Isophthalic acid AA: Adipic acid EG: D Tylene glycol BS: tetrabutylphosphonium-m-sulfobenzoic acid MW: molecular weight

Test Category 3 (Preparation of Polymer Composition and Evaluation Thereof) The thermoplastic synthetic polymer and the polyester obtained in Test Category 2 were kneaded with a blending amount shown in Table 3 using a twin screw extruder.
Pelletized. After drying the pellets with hot air, test pieces were prepared using an injection molding machine (manufactured by Nissei Plastics Industries, Ltd.).
The tensile strength and surface resistance of this test piece were measured. The results are shown in Table 2. The tensile strength is ASTM-D
638. The surface resistance of the test piece was 20
After leaving overnight in a constant temperature and humidity room at 65 ° C. × 65% RH, measurement was performed using a super insulation resistance meter (SM-5E, manufactured by Toa Denpa Kogyo KK). After washing for 20 minutes and leaving overnight in a thermo-hygrostat at 20 ° C. × 65% RH, measurement was performed in the same manner.

[0030]

[Table 2]

In Table 2, PET: polyethylene terephthalate (tensile strength = 55)
0 kg / cm ² ) PBT: polybutylene terephthalate (tensile strength = 55
0 kg / cm ² ) PC: polycarbonate (tensile strength = 580 kg / cm ² ) PS: polystyrene (tensile strength = 380 kg / cm ² ) PMMA: polymethyl methacrylate (tensile strength = 60)
0 kg / cm ² ) SIP unit: ratio of sulfoisophthalate unit in polymer composition Tensile strength ratio: tensile strength ratio to blank

Test Category 4 (Preparation of polymer composition, spin drawing and evaluation thereof) Polyethylene terephthalate as a thermoplastic synthetic polymer and the polyester obtained in Test Category 2 were biaxially mixed at the blending amounts shown in Table 3. Using an extruder, the mixture was melt-mixed at 290 ° C. and pelletized. The pellets were dried at 130 ° C. for 5 hours and then heated at 295 ° C. using a spinning machine (SM-907, manufactured by Teijin Engineering Limited) using a spinneret having 24 circular spinning holes having a hole diameter of 0.25 mm. Melt spinning,
The sheet was picked up at a picking speed of 2500 m / min. Then, it was drawn by a conventional method to obtain a polyester yarn of 75 denier and 24 filaments. The polyester yarn was treated with a 0.5% aqueous solution of sodium hydroxide at 90 ° C. for 30 minutes to perform an alkali weight reduction treatment. The rate of decrease in yarn strength and the rate of weight loss after the alkali weight reduction treatment were measured, and these were used as indices of alkali hydrolysis resistance. Further, the polyester yarn obtained above was treated with a cationic dye (Cathion CD-FRLH / Cathion Blue CD-FBLH = 1 /
1. Hodogaya Chemical Co., Ltd.) is dyed at 120 ° C. for 60 minutes in a dyeing bath containing 2% OWF (containing 3 parts / liter of Na ₂ SO _{4 and} 0.3 parts / liter of CH ₃ COOH as auxiliaries) and dyeing. Yarn was obtained. The dyeability of the dyed yarn was visually observed and evaluated according to the following criteria. The dyed yarn is further washed with a 0.1% aqueous solution of Zab (trade name) in a household washing machine at 40 ° C. for 10 minutes, and then thoroughly washed with running water, and the washing resistance is visually checked with the item before washing. Comparative observation was made. The results are shown in Table 3.

Criteria for dyeing ability ：: Vivid dark blue X: Dark dark blue Criteria for washing resistance ：: No discoloration Δ: Slight discoloration X: Discoloration

[0034]

[Table 3]

In Table 3, PET and SIP units: the same as in Table 2 PET yarn strength: 4.8 g / d (d is denier)

[0036]

As is apparent from the above description, the present invention as described above provides a thermoplastic synthetic polymer having excellent durability, which does not deteriorate the physical properties of the thermoplastic synthetic polymer. There is an effect that antistatic properties and dyeing properties can be imparted.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. An aromatic dicarboxylic acid unit containing not less than 30 mol% of a phosphonium sulfoisophthalate unit represented by the following formula 1, and a diol unit derived from a dihydric alcohol represented by the following formula 2: A modifier for a thermoplastic synthetic polymer, comprising a polyester to be formed. (Equation 1) (Equation 2) [In the formulas 1 and 2, R ^{1 to} R ⁴ : an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an aromatic hydrocarbon group, an aralkyl group, an alkylallyl group, which are the same or different at the same time. Hydrocarbon group 2. The thermoplastic synthetic polymer modifier according to claim 1, comprising a thermoplastic synthetic polymer having no sulfonic acid group in the molecule. Is 0.1 to 8% by weight as a sulfoisophthalate unit represented by the following formula 3: (Equation 3)