JP3114949B2 - 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, examples of adding a non-reactive compound having a sulfonic acid group (JP-A-62-230835,
U.S. Pat. No. 3,665,054), an example of copolymerizing a reactive compound having a sulfonic acid group (JP-A-62-299526, U.S. Pat.
SP3950311). 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 a defect, an example of adding an aliphatic polyetherester into which a sulfonic acid group is introduced (US Pat. No. 4,0061,0061)
23), an example in which a polyamide having a sulfonic acid group introduced therein is added (US Pat. No. 4,035,346), and an example in which a reactive compound having a sulfonic acid group is introduced into a molecular terminal of a synthetic polymer (JP-A-62-238883) has been proposed. . However,
In the former case, the heat resistance is insufficient due to the presence of the aliphatic polyether moiety, and it is necessary to increase the amount of addition to obtain the desired effect. There is a disadvantage that the intrinsic physical properties of the polymer are reduced. The latter two examples have the disadvantage that the desired effect cannot be obtained because the concentration of the sulfonic acid group cannot be increased to the extent that the modifying effect can be sufficiently exhibited.

[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 modified polyamide obtained by copolymerizing 60% by mole or more of isophthalamide having phosphonium sulfonate as a substituent as an amide unit.

[0005] That is, the present invention relates to a method wherein 60
１００100 mol% is a phosphonium sulfoisophthalic amide unit represented by the following formula 1, and 40 to 0 mol% is a monoamino monocarboxylic amide unit represented by the following formula 2 and / or A thermoplastic synthetic polymer modifier characterized by being composed of a modified polyamide which is a dicarboxylic acid amide unit shown, and the thermoplastic synthetic polymer modifier and having no sulfonic acid group in the molecule A polymer composition comprising a thermoplastic synthetic polymer and containing the modifier for a thermoplastic synthetic polymer in an amount of 0.1 to 10% by weight as a phosphonium sulfoisophthalic amide unit represented by the following formula 1: Related to

[0006]

(Equation 1)

[0007]

(Equation 2)

[0008]

(Equation 3)

[In the formulas 1 to 3, R¹~ R^Four: Simultaneous or different fats having 1 to 18 carbon atoms
Aliphatic hydrocarbon group or aromatic hydrocarbon group R^Five: H or -N (CH_Three)_Two  A¹~ A^Three: The same or different divalent organic groups n: an integer of 4 to 10 at the same time]

The phosphonium sulfoisophthalic amide unit of the formula 1 is derived from phosphonium sulfoisophthalic acid and a diamine. In the phosphonium sulfoisophthalic acid amide unit, the phosphonium constituting the cation portion includes 1) tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium, trioctylmethylphosphonium, tributylethylphosphonium, trimethyl Phosphonium having an aliphatic hydrocarbon group having 1 to 18 carbon atoms, such as butylphosphonium, trimethyllaurylphosphonium, and trimethylstearylphosphonium; 2) aromatic hydrocarbons such as tetraphenylphosphonium, triphenylmethylphosphonium, and triphenylethylphosphonium And phosphonium having a group. Of these, tetrabutylphosphonium and tetraphenylphosphonium are advantageous.

In the phosphonium sulfoisophthalic acid amide unit represented by the formula 1, as the constituent diamine, there are aliphatic diamine, polyoxyalkylene ether diamine and aromatic diamine. Examples of such aliphatic diamines include tetramethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and the like.As the polyoxyalkylene ether diamine, polyoxyalkylene bis-
Aminopropyl ether and the like can be mentioned, and further, as the aromatic diamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane and the like can be mentioned.

The monoaminomonocarboxylic amide units of the formula 2 are derived from caprolactam or monoaminomonocarboxylic acid. As such caprolactam,
ε-caprolactam, enantholactam, α- (N,
N'-dimethylamino) -ε-caprolactam, ω-laurolactam and the like, and examples of monoaminomonocarboxylic acids include 6-aminocaproic acid, 9-nonanoic acid, 11-aminoundecanoic acid, and 17-aminohepta Decanoic acid and the like. Of these, ε-caprolactam and 6-aminocaproic acid are advantageous.

The dicarboxylic acid amide unit represented by the formula 3 is derived from an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid and a diamine. Such aliphatic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, suberic acid,
Azelaic acid, undecadioic acid, pimelic acid, dodecanedioic acid, eicosantioic acid, and the like, and aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and the like. The above-mentioned thing is mentioned. Among these dicarboxylic acid amide units, a hexamethylene adipamide unit and a hexamethylene sebacamide unit are advantageous.

In the modified polyamide used as the modifier for a thermoplastic synthetic polymer of the present invention, at least 60 mol% of all amide units are phosphonium sulfoisophthalic amide units represented by the formula 1, and 40 mol%. The following are monoamino monocarboxylic amide units represented by the formula 2 and / or dicarboxylic amide units represented by the formula 3. Preferably, 60 to 80 mol% of all amide units are phosphonium sulfoisophthalic amide units represented by the formula 1, and 40 to 20 mol% are monoamino monocarboxylic amide units represented by the formula 2. Things. When the amount of the phosphonium sulfoisophthalic acid amide unit represented by the formula 1 in the total amide unit is less than 60 mol%, it is necessary to increase the amount thereof to obtain a desired effect. Decreases physical properties.

The modified polyamide used as a modifier for a thermoplastic synthetic polymer of the present invention comprises a dicarboxylic acid or an ester-forming derivative thereof, such as a methyl ester or an ethyl ester thereof, which constitutes each unit. , A known amidation reaction of diamine with caprolactam or monoaminomonocarboxylic acid, and a subsequent polycondensation reaction.

The modified polyamide used as a modifier for a thermoplastic synthetic polymer of the present invention has a molecular weight of 2,000 to 1,
5000 is preferable, and 3000-10000 is more preferable. If the molecular weight is less than 2,000, the modified polyamide tends to move in the thermoplastic synthetic polymer, so that the durability tends to be poor. Conversely, if the molecular weight exceeds 15,000, the modified polyamide tends to move. In order to produce a high quality polyamide, a special reaction such as solid phase polymerization is required in addition to ordinary polycondensation, 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. The synthetic polymer modifier is 0.1 to 10 as a phosphonium sulfoisophthalic acid amide unit represented by the formula 1.
% By weight. In this case, if the main purpose is to impart antistatic properties, the formula 1
It is preferable that the content is 0.2 to 6% by weight as a phosphonium sulfoisophthalic amide unit represented by the following formula. It is preferable to include the phosphonium sulfoisophthalamide unit represented by 1 in an amount of 1 to 8% by weight. When the content is less than 0.1% by weight as a phosphonium sulfoisophthalic acid amide unit represented by the formula 1, the desired effect of improving the antistatic property and the dyeing property cannot be obtained. If the amount exceeds the above range, the physical properties of the polymer composition are significantly reduced.

Examples of the thermoplastic synthetic polymer to which the present invention is applied include 1) polycondensation polymers such as polyamide and polyester, and 2) vinyl polymerization polymers such as polyvinyl chloride, polystyrene and polyacrylonitrile. Among these, the present invention relates to aliphatic polyamides,
It is effective for polycondensation type polymers having a high processing temperature such as aromatic polyamides and polyesters, especially for polyhexamethylene adipamide and polycapramide.

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.

[0020]

【Example】

Test Category 1 (Production of Modified Polyamide Used as Modifier for Thermoplastic Synthetic Polymer) Example 1 (Production of Modified Polyamide A) Tetrabutylphosphonium obtained according to the method described in JP-A-2-188592 -5-sulfoisophthalic acid 90
7.2 g, 232 g of hexamethylenediamine, 29.2 g of adipic acid, 200 g of water, and 200 g of methanol were charged into an autoclave, and charged in a nitrogen gas stream over 3 hours.
The temperature was raised to 50 ° C. to distill water and methanol. Then, gradually increase the pressure to 1 mm while increasing the temperature to 240 ° C over 4 hours.
The pressure was reduced to Hg, and the mixture was further reacted at 265 ° C. for 2 hours to obtain modified polyamide A. The modified polyamide A had a pale yellow transparent solid appearance, a carboxyl value of 15.7, an amine value of 16.3, and an average molecular weight of 3500 (calculated from the carboxyl value and the amine value; the same applies hereinafter).

Example 2 (Production of Modified Polyamide B) 638.4 g of dimethyl tetrabutylphosphonium-5-sulfoisophthalate and 185.6 hexamethylenediamine obtained according to the method described in JP-A-2-188592.
g, 200 g of water and 200 g of methanol were charged into an autoclave and heated for 2 hours while passing nitrogen gas. Next, 80.8 g of sebacic acid and 45.2 g of ε-caprolactam.
After the addition of water, the temperature was gradually raised to 150 ° C. to distill water and methanol. The temperature was raised to 265 ° C. over 4 hours, the pressure was set to 1 mmHg, and the polycondensation was performed for 1 hour to obtain a modified polyamide B. This modified polyamide B had a pale yellow solid appearance, a carboxyl value of 7.3, an amine value of 7.8, and an average molecular weight of 7,400.

Examples 3 to 11 (Modified polyamides CK)
Production of modified polyamide C in the same manner as in Example 1 or 2
~ K was obtained.

Comparative Example 1 (Production of Modified Polyamide R-1) Na-5-sulfoisophthalic acid 160.8 g, hexamethylenediamine 232 g, terephthalic acid 232.5 g,
200 g of water and 200 g of methanol were charged into an autoclave, and the temperature was raised to 150 ° C. over 3.5 hours in a nitrogen gas stream to distill water and methanol. Then, the pressure was gradually reduced to 1 mmHg while increasing the temperature to 240 ° C. over 4 hours, and the reaction was further performed at 265 ° C. The viscosity increased significantly with the progress of the reaction, and the stirring became impossible. Therefore, the reaction was interrupted, and the modified polyamide R-1 as the content was taken out. This modified polyamide R-1 had a pale yellow solid appearance, a carboxyl value of 12.2, an amine value of 12.6, and an average molecular weight of 4,500.

Comparative Examples 2 to 4 (Modified polyamide R-2 to
Production of R-4) In the same manner as in Example 1, the modified polyamides R-2 to R-2 were prepared.
R-4 was obtained.

The modified polyamides A obtained in Examples 1 to 11
K and the modified polyamides R-1 to R- obtained in Comparative Examples 1 to 4.
Table 1 summarizes the raw material composition and physical properties of No. 4.

[0026]

[Table 1]

In Table 1, composition: expressed as dicarboxylic acid, diamine, caprolactam or monoaminomonocarboxylic acid which is a constituent material of each unit * 1: dicarboxylic acid * 2: diamine * 3: caprolactam or monoaminomonocarboxylic acid Carboxyl number: 1/100% of modified polyamide dissolved in benzyl alcohol and cresol red as indicator
Amine value measured by 100N KOH-benzyl alcohol titration: Dissolve the modified polyamide in m-cresol;
Average MW: Average molecular weight IPS-1: Tetrabutylphosphonium-5-sulfoisophthalic acid IPS-2: Tributyloctylphosphonium-5-sulfo measured by 1/100 N p-toluenesulfonic acid titration using thymol blue as an indicator Isophthalic acid IPS-3: Tetraphenylphosphonium-5-sulfoisophthalic acid IPS-4: Triethylbenzylphosphonium-5-sulfoisophthalic acid IPSM-1: Dimethyl tetrabutylphosphonium-5-sulfoisophthalate IPS-Na: Na-5 Sulfoisophthalic acid BS-1: Tetrabutylphosphonium-m-sulfobenzoic acid IPA: Isophthalic acid TPA: Terephthalic acid AA: Adipic acid SA: Sebacic acid HMDA: Hexamethylenediamine DDM: Diaminodiph Nirumetan PGDA: Polyethylene glycol (molecular weight 1100)
Diamine CAPR: ε-caprolactam LAUR: ω-laurolactam

Test Category 2 (Preparation of Polymer Composition and Evaluation Thereof) The thermoplastic synthetic polymer and the modified polyamide obtained in Test Category 1 were kneaded by a twin screw extruder at the compounding amounts shown in Table 2. And 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-
It was measured based on D638. The surface resistance of the test piece was 2
After leaving overnight in a constant temperature and humidity room of 0 ° C. × 65% RH, the measurement was performed using a super insulation resistance meter (SM-5E, manufactured by Toa Denpa Kogyo KK). Further, the test piece was washed with city water under running tap water for 5 minutes, and water adhering to the surface was removed with filter paper.
The measurement was carried out in the same manner after leaving overnight in a constant temperature and humidity room of% RH.

[0029]

[Table 2]

In Table 2, NY-6: polycapramide (tensile strength = 2000 kg / c)
m ² ) NY-66: polyhexamethylene adipamide (tensile strength = 1200 kg / cm ² ) PET: polyethylene terephthalate (tensile strength = 55)
0 kg / cm ² ) PS: polystyrene (tensile strength = 520 kg / cm ² ) SIP unit: ratio of phosphonium sulfoisophthalic amide unit in the polymer composition Tensile strength ratio: tensile strength ratio to blank

Test Category 3 (Preparation of polymer composition, spinning drawing and evaluation thereof) Nylon 66 as a thermoplastic synthetic polymer and Test Category 1
Was melt-mixed at 274 ° C. using a twin-screw extruder at the compounding amounts shown in Table 3, and pelletized. The pellets were dried at 120 ° C. for 20 hours, and then heated at 285 ° 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. It was melt-spun and pulled at a drawing speed of 2500 m / min. And stretch in the usual way,
A nylon 66 yarn of 75 denier 24 filaments was obtained. This filament was removed by scabbing, using a basic dye diacryl Supra red 3BL (trade name, manufactured by Mitsubishi Kasei Co., Ltd.), a dyeing concentration of 3% owf, a dyeing bath PH of 4.0,
Dyeing was performed for 2 hours while boiling at a bath ratio of 1:50. After dyeing, soaped for 20 minutes, washed with water and dried to obtain a dyed yarn. The dyeability of the dyed yarn was visually observed and evaluated according to the following criteria. Further, the dyed yarn is washed with a 0.1% aqueous solution of Zab (trade name, manufactured by Kao Corporation) in a home washing machine at 40 ° C. for 10 minutes, and then thoroughly washed with running water to obtain a washing resistance before washing. And observed visually. The results are shown in Table 3.

Criteria for Dyeability The degree of dyeability was divided into five grades of 1st to 5th grades, and 1 → 5th grade was evaluated as light color → dark color.

[0033]

[Table 3]

In Table 3, NY-66, SIP unit: Same as in Table 2 NY-66 yarn strength: 5.2 g / d (d is denier)

[0035]

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 69/42 C08L 101/00

Claims (3)

(57) [Claims] 1. In all amide units, 60 to 100 mol% is a phosphonium sulfoisophthalic amide unit represented by the following formula 1, and 40 to 0 mol% is a monoaminomonocarboxylic acid represented by the following formula 2. A thermoplastic synthetic polymer modifier comprising a modified polyamide which is an acid amide unit and / or a dicarboxylic acid amide unit represented by the following formula 3: (Equation 1) (Equation 2) (Equation 3) [In the formulas 1 to 3, R ^{1 to} R ⁴ : an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 18 carbon atoms which are the same or different at the same time R ⁵ : H or —N (CH ₃ ) ₂ A ¹ To A ³ : the same or different divalent organic group n: an integer of 4 to 10] 2. The thermoplastic synthetic polymer modifier according to claim 1, wherein 20 to 40 mol% of all amide units are monoaminomonocarboxylic acid amide units represented by the formula (2). 3. A thermoplastic synthetic polymer comprising the modifier for a thermoplastic synthetic polymer according to claim 1 or 2 and a thermoplastic synthetic polymer having no sulfonic acid group in the molecule. A polymer composition comprising a filler in an amount of 0.1 to 10% by weight as a phosphonium sulfoisophthalic acid amide unit represented by the formula 1.