JPS6237654B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyester ether that can be used as a raw material for a polyurethane elastomer having good dyeability, color retention, light resistance, gas yellowing, and yarn package unwinding properties. Conventionally, methods have been known in which tertiary nitrogen atoms and the like are introduced into polymer chains for the purpose of improving the dyeability of polyurethane elastomers. Although it is true that some of these methods yield excellent dyeable polymers, it has been difficult to suppress the deterioration of the physical properties of the polymers. For example, in Special Publication No. 39-23097,

The compound represented by the formula is used in combination with hydrazine. Furthermore, in Japanese Patent Publication No. 11651/1984, various glycols having tertiary nitrogen atoms are used as a component of polyurethane copolymers. However, although the dyeability of the polymers obtained by these methods is improved, it is still not sufficient. The reason for this is thought to be that the tertiary nitrogen atoms introduced by these methods are relatively close to the high-melting point crystalline part in the polymer chain, making them less efficient as a dyeing seat. The details are not clear. On the other hand, as a method for improving the low-temperature properties of polyurethane elastomers, there is a method of using a polyhydric hydroxy compound with a relatively small molecular weight in order to prevent the low-melting point amorphous portion from crystallizing at low temperatures. The elastic body produced by this method has a disadvantage in that the elastic recovery rate at room temperature is extremely poor. Therefore, the present inventors believe that in order to improve the dyeability, it is necessary to introduce a specific group into the low melting point amorphous part where the molecular movement is the most intense in the polymer chain, that is, where it is easily attacked by dyes. Based on inference, the repeating unit is the following general formula [] [However, A is

[expression] or

[Formula], R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₂ and R ₃ represent hydrogen or a linear alkyl group having 1 to 4 carbon atoms. ] A tertiary nitrogen-containing polyester diol consisting of a tertiary nitrogen-containing diol residue and a dicarboxylic acid residue can be used in place of or as a part of a high molecular weight polyhydric hydroxy compound that is generally used as a raw material for the soft segment of a polyurethane elastomer. We considered using it as a. The elastic body obtained by this method had better dyeability and physical properties than the one obtained by the method of Japanese Patent Publication No. 39-23097. In order to increase the polyester diol, it is necessary to use a large amount of the polyester diol, which has the disadvantage that it is easily hydrolyzed under severe conditions during processes such as scouring, bleaching, and dyeing. Further, a polyurethane elastomer using a polyester diol obtained by polymerizing the diol of the general formula [] as a part of the high molecular weight polyhydric hydroxy compound was also investigated. Although this product has been improved in the above-mentioned points, it has the disadvantage that light resistance and gas yellowing resistance are reduced, and when the proportion of the polyether diol is increased, the unwinding property of the elastic yarn package is reduced. was. In view of these points, the present inventor further studied raw materials for obtaining a polyurethane elastomer with improved dyeability without deteriorating other properties, and as a result, arrived at the present invention. In other words, the present invention is based on the general formula [] and the general formula []
and/or has units represented by [], and the units are randomly bonded with ether bonds,
and a tertiary nitrogen-containing polyester ether diol having a molecular weight of 500 to 6000. (However, A:

[expression] or

[Formula] B: (-CH ₂ )- _n or

[Formula] R ₁ : Alkyl group, cycloalkyl group, aryl group, aralkyl group, or

[Formula] R ₂ , R ₃ : each hydrogen or lower alkyl group, R ₄ : alkylene group, R ₅ , R ₆ : each alkyl group, X: alkylene group having 2 to 15 carbon atoms

【formula】

【formula】

[expression] or

[Formula], l is an integer from 1 to 10, j+k is an integer from 2 to 20, and (j+
k)/l: 0.1 to 2, m: an integer of 0 to 15, n: 1
Represents an integer between ~30. Further, R ₇ and R ₈ each represent hydrogen or a lower alkyl group. ) Since the polyester ether diol of the present invention has a high concentration of tertiary nitrogen therein, a small amount of the high molecular weight polyhydric hydroxy compound used as the soft segment component of the polyurethane elastomer is added to the polyester ether diol. By replacing it with , dyeability is sufficiently improved, and undesirable drawbacks such as hydrolyzability and unwinding property do not occur. The polyester ether diol according to the present invention is mainly produced by polymerizing the polyester diol of the general formula [] or the diol with the general formula [] and/or the general formula []. [However, A and B represent the same as in the above formula (), and X is an alkylene group having 2 to 15 carbon atoms,

【formula】

【formula】

[expression] or

[Dye used]

Anthraquinone Blue - SWF (Color Index 62055) [Dyeing method] After scouring and bleaching the samples obtained in each example,
Anthraquinone blue SWF 0.3 parts, formic acid 2.8 parts
Dissolved in 1000 parts of water, the dye solution was adjusted to 80°C and 10 parts (by weight) of the sample was dyed for 1 hour. [Measurement of dyeing amount] After dissolving the dyed material in 20 parts of dimethylformamide, the precipitate was separated using an ultracentrifuge, and the absorption of the upper layer solution at 570 mμ was measured using a spectrophotometer. The amount of dyeing was determined by comparing it with a previously prepared calibration curve.
Other characteristic measurement methods are as follows. [Propane combustion gas exposure test] A gas burner was placed in a 0.5 ^m3 chamber with a circular vent hole of 8 cm in diameter at the top, and propane gas was completely burned at a rate of 800 c.c./min to reduce the temperature inside the chamber. The sample was exposed therein for 10 hours while being maintained at 60°C. Changes in b value before and after exposure were measured using a Nippon Denshoku Kogyo ND-101D color difference meter. [Nitrogen oxide gas exposure test] Exposure was performed for 2 hours according to JIS-L-1055, and changes in b value were measured in the same manner as above. [Lightfastness test] Irradiated for 40 hours with a food-o-meter,
Changes in b value were measured. Example 1 1227 parts of 4-methyl-4-aza-2,6-heptanediol, 487 parts of adipic acid and phosphorous acid
Put 16.4 parts into a polymerization pot with a stirrer and bring the internal temperature to 160℃.
The temperature was raised from to 210°C for 1.5 hours while distilling off the reaction water, then 197 parts of hexamethylene glycol dissolved at 60°C was added, the internal temperature was raised to 220°C, and the reaction water was heated for another 3 hours. Condensation was carried out at normal pressure while distilling off. Thereafter, the pressure was reduced to 10 mmHg over 1 hour, and condensation was further carried out at 220° C. and 10 mmHg for 30 minutes to obtain 1610 parts of polyester-ether diol having an OH value of 86.3 and a molecular weight of 1300. The basic nitrogen content of this polyester-ether was 6.32 (wt%), the saponification value was 230, and it was a clear viscous liquid at room temperature (20°C) with Hazen No. 50. FIG. 1 shows an infrared absorption spectrum of this polyester-ether diol. “In the figure, an absorption peak attributed to an ether bond can be seen at 1110 cm ^-1.As the peak is small, it seems that the sequence of diol units exists in a small form.From the analysis values of the polymer, the Adipic acid residue is 2.7 (mol), 4
-Methyl-4-aza-2,6-heptanediol residue was 6.0 (mol) and hexamethylene glycol residue was 1.3 (mol). The values of l and j+k calculated from these values are:
The average values are 2.7 and 3.6, respectively. ” A total of 1320 parts of this polyester-ether diol and polyoxytetramethylene glycol (molecular weight 1320) in the proportions shown in Table 1, 500 parts of methylene bis(4-phenyl isocyanate) and 75 parts of
The reaction was carried out without solvent at ℃ for 1 hour to obtain a prepolymer having isocyanate end groups. This prepolymer was dissolved in dimethylformamide to make a 35% solution, and after cooling to 3°C, 74 parts of a dimethylformamide solution of 1,2-propylenediamine was gradually added with stirring until the solution viscosity was 1000. When poise was reached, 9.1 parts of monoethanolamine was added followed by 1.2 parts of acetic acid to stabilize the solution. The resulting polyurethane solution was spun to obtain an elastic yarn, which was dyed with anthraquinone blue SWF under the aforementioned dyeing conditions, the amount of dyeing was measured, and the modulus when the elastic yarn was stretched by 300% was measured.

[Table] Comparative Example 1 1320 parts of polyoxytetramethylene glycol (molecular weight 1320) and 500 parts of methylene bis(4-phenyl isocyanate) were reacted at 75°C for 1 hour without solvent to form a prepolymer having isocyanate end groups. Obtained. This prepolymer was dissolved in dimethylformamide to make a 35% solution and cooled to 3°C. Make 6 batches of this prepolymer solution and mix with H ₂ NCH (CH ₃ ) CH ₂ NH ₂ (diamine A) while stirring.
H ₂ NCH ₂ CH ₂ CH ₂ N (t-C ₄ H ₉ ) CH ₂ CH ₂ CH ₂ NH ₂
(Diamine B) and the mixture were dropped into the prepolymer solution. When the solution viscosity reached 1000 poise, the end was stopped and stabilized. The obtained polymer solution was spun to obtain an elastic thread. The obtained elastic yarns are No. 2 to 6.
had good stainability, but modulus (300
(during extension) was significantly reduced. The results are shown in Table 2.

[Table] Example 2 Adipic acid, 1,4-butanediol, 2,2
-Dimethylpropanediol-1,3-polyester glycol (glycol molar ratio 80/
20, OH value 62.2, acid value 0.7, molecular weight 1785) and polyester ether diol (adipic acid/4-ethyl-4-aza-2,6-heptanediol/1,
Charge molar ratio of 6-hexanediol 1/3/1,
(molecular weight: 1300, tertiary nitrogen content: 6.0% by weight) in the proportions shown in Table 3 to make a total of 500 parts. This was dehydrated for 1 hour at 5 mmHg, and 140 parts of methylene-bis(4-phenyl isocyanate)
and reacted at 110°C for 90 minutes under a nitrogen atmosphere. The prepolymer with isocyanate end groups prepared in this way was dissolved in 1340 parts of dimethylformamide and the solution was rapidly cooled to 0°C. 20.7 parts of 1,2-propylene diamine dissolved in 200 parts of dimethylformamide were slowly added to the cold solution with vigorous stirring. After the viscosity of the solution reached 2000 poise (25°C), the addition of diamine was stopped, 15 parts of di-n-butylamine was added, and then 3.2 parts of glacial acetic acid were added to stabilize the solution viscosity. After spinning the above polyurethane solution, it was dyed with anthraquinone blue-SWF. The yarn that could be spun was dyed in a deep color and had excellent washing fastness. The modulus (at 300% extension) was also excellent.

[Table] Example 3 A total of 250 parts of polylactone diol with a molecular weight of 1250 obtained by addition polymerizing ε-caprolactone using 1,4-butanediol as an initiator and polyester ether diol whose monomer composition is shown in Table 4 (polylactone diol) When 100 parts of methylene bis(4-phenyl isocyanate) and 350 parts of dimethylformamide were mixed with diol: polyester ether diol = 96.5:3.5) and 50 ppm of diptyltin dilaurate was added as a catalyst, heat was immediately generated.
The reaction was completed in 20 minutes at ℃. The solution was rapidly cooled 265
dimethylformamide was added to dilute the mixture.
To this cold solution, 1,2-propylene diamine dissolved in 200 parts of dimethylformamide was added little by little with vigorous stirring. Then a small amount of g-
The viscosity of the solution was adjusted to around 2300 poise (25°C) by adding n-butylamine. When the above polyurethane solution was spun and then dyed with anthraquinone blue SWF, all the fabrics were dyed in a deep color and had excellent washing fastness.

【table】

[Table] Example 4 Polyoxytetramethylene glycol (molecular weight
1320) and 42.6 parts of polyester ether diol (molecular weight 1600, tertiary nitrogen content 6.37%) obtained in the same manner as in Example 1 were mixed with 500 parts of methylene bis(4-phenyl isocyanate) at 70°C. The reaction was carried out without solvent for a period of time to obtain a prepolymer having isocyanate end groups. After dissolving this prepolymer in dimethylformamide, a solution of 74 parts of 1,2-propylenediamine in dimethylformamide was gradually added under stirring, and when the solution viscosity reached 1000 poise, 9.1 parts of monoethanolamine was added. and then 1.2 parts of acetic acid were added to stabilize the solution. The obtained polyurethane solution was spun to obtain an elastic thread containing 100 mmol/Kg of tertiary nitrogen.
(This is called elastic yarn A) The characteristics of this yarn are as follows.
It is shown in Table 7. Comparative Example 2 Polyoxytetramethylene glycol (molecular weight
1320) 1320 parts and 4-methyl-4-aza-2,6-
Heptanediol and hexamethylene glycol (2:1 molar ratio) were mixed using a phosphorous acid catalyst.
37.6 parts of polyether diol obtained by dehydration co-condensation at 230°C (molecular weight 1600, tertiary nitrogen content
7.2% by weight) was reacted and spun in the same manner as in Example 1 to obtain an elastic yarn containing 100 mmol/Kg of tertiary nitrogen (this will be referred to as elastic yarn B). The properties of this yarn are shown in Tables 5-7. Comparative Example 3 Polyoxytetramethylene glycol (molecular weight
1320) 1320 parts and 4-methyl-4-aza-2,6
-Heptanediol and 46.8 parts of polyester diol obtained from adipic acid (molecular weight 1600, tertiary nitrogen content 5.8% by weight) were reacted in the same manner as in Example 1, and spun, and 100 m of tertiary nitrogen was added.
An elastic yarn containing mol/Kg was obtained. (This is referred to as elastic yarn C.) Table 5 shows the amount of dyeing when elastic yarns A, B, and C were dyed in the same bath with anthraquinone blue SWF under the dyeing conditions described above.

[Table] Table 6 shows caustic soda 10g/, Neugen 2
g/, the strength retention rate when treated at 100°C for 60 minutes at a bath ratio of 1:40.

[Table] Table 7 also shows the measurement results of yellowing and light resistance due to propane combustion gas and nitrogen oxide gas.

[Table] Example 5 2023 parts of N,N'-bis(β-hydroxypropyl)piperazine, 472.4 parts of succinic acid, and 20 parts of phosphorous acid were placed in a polymerization pot equipped with a stirrer, and the internal temperature was adjusted to 160°C.
The temperature was raised from 210°C to 210°C over 1.5 hours while distilling off the reaction water, then 236.4 parts of hexamethylene glycol dissolved at 60°C was added, the internal temperature was raised to 220°C, and the reaction water was heated for another 3 hours. Condensation was carried out at normal pressure while distilling off. Thereafter, the pressure was reduced to 10 mmHg over 1 hour, and condensation was further carried out at 220° C. and 10 mmHg for 30 minutes to obtain 2,360 parts of polyester ether diol having an OH value of 73.8 and a molecular weight of 1,520.
The basic nitrogen content of this polyester ether was 10.95% (by weight), and it was a very viscous liquid at room temperature (20°C) of Hazen No. 75. 24.5 parts of this polyester ether diol was reacted with 1320 parts of polyoxytetramethylene glycol (molecular weight 1320) in the same manner as in Example 5, and the chain was extended with 1,2-propylene diamine. When the solution viscosity reached 1000 poise, The solution was stabilized by adding 9.1 parts of monoethanolamine followed by 1.2 parts of acetic acid. The obtained polyurethane solution was spun to obtain an elastic thread containing 100 mmol/Kg of basic nitrogen. Table 8 shows the results of various yellowing tests of this elastic yarn in the same manner as in Example 4.

[Table] Table 9 also shows that the elastic yarn of Example 5 was dyed with anthraquinone blue SWF under the above-mentioned dyeing conditions.
The amount of dyeing was measured, and the modulus when the elastic yarn was stretched 300% was measured.

[Table] Example 6 Polyester ether diol obtained in Example 1
1300 parts of 2,4-tolylene diisocyanate
The mixture was reacted with 348 parts at 75° C. for 1 hour without solvent to obtain a prepolymer having isocyanate end groups. This prepolymer was dissolved in dimethylformamide to make a 35% solution, and after cooling to 3°C, 60 parts of a 35% dimethylformamide solution of ethylenediamine was gradually added under stirring to form a polyurethane solution with a solution viscosity of 150 poise. Obtained. This polyurethane solution (referred to as polyurethane solution D). Separately, 1320 parts of polyoxytetramethylene glycol (molecular weight 1320) was reacted with 500 parts of methylene bis(4-phenyl isocyanate) at 75°C for 1 hour without a solvent to obtain a prepolymer having isocyanate end groups. This prepolymer was dissolved in dimethylformamide to make a 35% solution, and after cooling to 3°C, 74 parts of a 35% solution of propylene diamine in dimethylformamide was gradually added dropwise with stirring to adjust the solution viscosity.
When 1000 poise was reached, 9.1 parts of monoethanolamine was added followed by 12 parts of acetic anhydride to stabilize the solution. (This is referred to as polyurethane solution E) Polyurethane solution D was added to polyurethane solution E at 3%, mixed, and the resulting elastic yarn was spun and dyed with anthraquinone blue SWF. It was dyed in a deep color and was difficult to wash. It had excellent robustness. Example 7 Hexamethylene glycol in Example 1
Condensation was carried out under the same conditions except that 197 parts were replaced with 241 parts of 1,4-cyclohexanedimethanol (cis-trans mixture). 1650 g of polyester ether diol having an OH value of 92.7 corresponding to a molecular weight of 1210 was obtained. In addition,
This polyester ether diol had a basic nitrogen content of 6.17 (wt%), a saponification value of 226, and was a clear viscous liquid at room temperature with Hazen No. 80. The amount of tertiary nitrogen content polyester ether in the high molecular weight hydroxyl compound in Example 1 was
When carried out at 2.56% by weight, the dyeing amount was 32.1
(mg/g), and the modulus was 92 (Kg/cm ² ).

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrogram of the polyester ether diol obtained in Example 1.

Claims (1)

[Claims] 1 It has the general formula [] and units represented by the general formula [] and/or [], the units are randomly bonded with ether bonds, and the molecular weight is
A tertiary nitrogen-containing polyester ether diol having a molecular weight of 500 to 6000. (However, A: [Formula] or [Formula] B: (-CH ₂ ) - _n or [Formula] R ₁ : Alkyl group, cycloalkyl group, aryl group, aralkyl group, or [Formula] R ₂ , R ₃ : each hydrogen or lower alkyl group, R ₄ : alkylene group, R ₅ , R ₆ : each alkyl group, X: alkylene group having 2 to 15 carbon atoms,
[Formula] [Formula] Represents [Formula] or [Formula], l: an integer from 1 to 10, j+k: an integer from 2 to 20, and (j+
k)/l: 0.1 to 2, m: an integer of 0 to 15, n: 1
Represents an integer between ~30. Further, R ₇ and R ₈ each represent hydrogen or a lower alkyl group. )