JPH0455223B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized polyurethane composition, and more particularly to a polyurethane composition that is stabilized against discoloration and deterioration caused by outside air conditions, combustion gases, and light, and at the same time has improved dyeability. In general, polyurethane products such as polyurethane elastic yarns, foams, elastomers, synthetic leathers, etc. have the disadvantage that they tend to discolor when exposed to an atmosphere of hydrocarbon combustion gas, nitrogen oxide gas, or outside air conditions for a long time. It also has the drawback of discoloration and deterioration due to light. The present invention aims to overcome these drawbacks of polyurethane and at the same time improve the dyeability of polyurethane. In the case of polyurethane that has urea bonds, urethane bonds, ether bonds, or ester bonds in its molecules, it is generally considered essential to add antioxidants and in some cases ultraviolet absorbers to stabilize it against light and heat. These additives tend to promote coloring caused by combustion gas, etc. Many proposals have been made as gas coloring inhibitors, but few have satisfactory performance, and even if they have excellent gas coloring resistance, they may impair other properties or lack durability. There are very few things that can be put to practical use. On the other hand, in order to improve the dyeability of urethane polymers, tertiary amine compounds are generally added or copolymerized. For example, Tokkosho
N,N-dialkyl-β-aminoethyl methacrylate polymers, such as those proposed in Japanese Patent Publication No. 36-19491 and Japanese Patent Publication No. 46-2904, bleed out onto the surface of the urethane polymer and form scum during the spinning process. The disadvantages include that the resulting elastic yarn is easily yellowed due to gas, and the resulting elastic yarn is prone to gas yellowing. The inventors of the present invention have arrived at the present invention as a result of intensive studies in consideration of such problems. That is, the present invention is based on the following chemical formula () A tertiary nitrogen-containing polymer in which the terminal isocyanate groups are end-capped with a monoamine and/or dialkyl hydrazine is prepared from the reaction product of a tertiary nitrogen-containing diol represented by the formula and an excess amount of an organic diisocyanate, and is used as a polyurethane. This is a polyurethane composition containing a stabilizing amount. According to the present invention, not only the resistance to gas yellowing of polyurethane is significantly improved, but also the dyeing properties are significantly improved, and a strong and vivid dyed product can be obtained. Furthermore, it also had the characteristic that the light resistance stability was synergistically improved when used in combination with an antioxidant, a light stabilizer, etc.
In addition, when molding a molded product from the composition, there are many things such as not causing trouble during the molding process or during post-processing of the molded product, no deterioration in physical properties or whiteness, and no uneven dyeing due to heat history. It also has the following features. Furthermore, ethyl-substituted products are characterized by superior light resistance and gas yellowing resistance compared to other alkyl-substituted products, as well as an excellent balance between these properties, dyeability, chlorine resistance, and color fastness. Examples of organic diisocyanates used in producing a tertiary nitrogen-containing polymer using a tertiary nitrogen-containing diol represented by the chemical formula () of the present invention include 4,4'-diphenylmethane diisocyanate, 1,4 - phenylene diisocyanate,
Aromatic diisocyanates such as 2,4-tolylene diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate,
Examples include aliphatic diisocyanates such as 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and 3,3'-dimethylpentane diisocyanate. These internal aliphatic diisocyanates are preferred. Furthermore, the amount of organic diisocyanate added when producing a tertiary nitrogen-containing polymer using the diol represented by formula () is in excess of the diol represented by formula (); The amount is 1.02 to 2.0, preferably 1.05 to 2.0, per 1 diol component in molar ratio.
It is 1.7. When this molar ratio is less than 1.02, the effect is insufficient, and when it is more than 2.0, it is not preferable because it causes scum to be generated during the molding process and during the post-processing of the molded product when molding the composition. After reacting the above excess diisocyanate with the diol represented by the formula (), the terminal isocyanate group in the reaction product is reacted with a monoamine and/or dialkylhydrazine to perform terminal blocking. Examples of monoamines used as terminal blocking agents include diethylamine, diisobutylamine, di-n-butylamine, diisocypropylamine, allylethylamine, dicyclobutylamine, piveridine, ethyleneimine, and propyleneimine. Examples include primary amines such as primary amines, ethylamine, n-butylamine, and laurylamine, and the total number of carbon atoms in the primary to secondary amines is preferably up to about 20.
Further, as dialkylhydrazine, N,N-dimethylhydrazine, N,N-diisopropylhydrazine, N-methylN-ethylhydrazine, N-
Examples include methyl N-laurylhydrazine, but the total number of carbon atoms is preferably up to about 20. If the number of carbon atoms is too large, the proportion of the end-blocking agent in the tertiary nitrogen-containing polymer increases, which not only requires a large amount of compounding for stabilization, but also causes the drawback that compatibility with polyurethane decreases. . Particularly preferred endcapping agents are diethylamine and dimethyl hydroxide. The amount of the above-mentioned tertiary nitrogen-containing polymer of the present invention added to polyurethane is a stabilizing amount in order to obtain resistance to gas yellowing, and it can be used in an appropriate amount depending on the required performance, but usually the tertiary nitrogen concentration is as
10 to 400 milliequivalents/Kg of polymer is suitable.
If the amount is less than this, sufficient performance cannot be obtained, and if it is too much, the dyeing properties are too high, causing problems such as a decrease in color fastness. If the concentration of tertiary nitrogen in the tertiary nitrogen-containing polymer is low, a large amount of tertiary nitrogen must be added, which deteriorates the physical properties of polyurethane. It is necessary to increase the concentration of tertiary nitrogen. Usually, the amount of the tertiary nitrogen-containing polymer is preferably 0.1 to 20% by weight, particularly 0.2 to 10% by weight, and therefore the compounding polymer contains an amount of tertiary nitrogen corresponding to this amount. It is preferable to contain. The polyurethanes used in the present invention are 4,4'-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4, One type of diisocyanate such as 4'-dicyclohexylmethane diisocyanate or xylylene diisocyanate or a mixture thereof, preferably 4,4'-diphenylmethane diisocyanate, and a substantially diisocyanate having a molecular weight of 600 to 7000 having hydroxyl groups at both ends. linear polymers such as polytetramethylene ether diol, polycaprolactone diol, and ethylene glycol, 1,4-butane diol,
One or a mixture of glycols such as 1,6-hexanediol and neopentyl glycol and succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, β-methyladipic acid, hexahydro A dicarboxylic acid having a melting point of 60°C or less, preferably produced from one or a mixture of aliphatic dicarboxylic acids such as terephthalic acid, and a dicarboxylic acid which may also partially contain aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. Polyester diols below 40°C, or mixtures thereof, and polyfunctional active hydrogen compounds such as hydrazine, ethyleneamine, 1,2
- Polyamines such as propylene diamine, hexamethylene diamine, xylylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-diphenylmethane disemicarbazide, β-aminopropionic acid hydrazide, carbodihydrazide, water, ethylene glycol , 1,4-butanediol, etc., or a mixture thereof, and is an elastic polymer having urethane bonds in the molecule. The composition of the present invention may further contain an antioxidant such as a hindered phenol antioxidant or a hindered amine antioxidant and/or a UV absorber such as a benztriazole UV absorber, if desired. I can do it. In this case, it is particularly important to select additives that do not reduce gas discoloration resistance.
Examples of hindered phenol antioxidants that do not reduce gas discoloration resistance include compounds represented by the following general formulas () and/or (),
The synergistic effect with the tertiary nitrogen-containing polymer of the present invention improves light resistance. (However, in the formula, R ₄ represents an alkyl group, a cycloalkyl group, a neopentyl group, or an aralkyl group,
R ₅ and R ₆ represent a group selected from a hydrogen atom, an alkyl group and an alkoxy group. ) Examples of the phenolic compound represented by the general formula () are 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid, 1,3,5- Tris (4
-sec-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanate, 1,3,5-
Tris(4-neopentyl-3-hydroxy 2,
Examples include 6-dimethylbenzyl)isocyanuric acid. 1,3,5-tris(4-t-butyl-3-
Hydroxy-2,6-dimethylbenzyl)isocyanuric acid. Further, a particularly preferred example of the phenolic compound represented by the general formula () is a compound in which R ₄ is branched and has 4 carbon atoms.
~8 alkyl group, cycloalkyl group, neopentyl group or aralkyl group,
More specific examples include Γ10-(2',6'-dimethyl-4'-t-butyl-3'-
hydroxybenzyl)-9,10-dihydro-9
-Oxa-10-Phosphor Afenethrene-10
-oxide Γ6-methyl-10-(2',6'-dimethyl-4'-t-
Butyl-3'-hydroxybenzyl)-9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Γ6-methoxy-10-(2',6'-dimethyl-4'-t
-butyl-3'-hydroxybenzyl)-9,10
-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Γ10-(2',6'-dimethyl-4'-cyclohexyl-
3′-Hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Γ10-{2′,6′-dimethyl-4′-(α,α-dimethylbenzyl) -3′-hydroxybenzyl}-9,
10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Γ10-(2',6'-dimethyl-4'-neobentyl-
Examples include 3'-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. The amount of these phenolic compounds is a stabilizing amount against light, which is normally compared to polyurethane.
0.1-10% by weight, preferably 0.5-8% by weight. Blending into polyurethane to obtain the composition of the present invention can be carried out by adding it at any stage of producing polyurethane, but it is preferable to mix it after the completion of polyurethane polymerization and before the molding stage. Furthermore, the composition of the present invention may optionally contain inorganic fine particles such as barium sulfate, silicates, and zinc chloride, anti-blocking agents such as calcium stearate, magnesium stearate, polytetrafluoroethylene, and organopolysiloxane, and antifungal agents. , a coloring agent, and other compounding agents may be appropriately blended. The polyurethane composition thus obtained can be formed into fibers, tapes, films, etc. by dry, wet, or melt molding, and can also be used for foams, elastomers, synthetic leather, paints, etc.; Useful in fiber and tape applications. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the scope of these Examples. Note that parts and % in the examples indicate parts by weight and % by weight. In addition, the characteristic values in the Examples were measured as follows. Gas discoloration test for polyurethane fibers A 3-unit strength test was conducted in accordance with JIS L 0855-1976, and the b value before and after the test was calculated using Nippon Denshoku Kogyo Co., Ltd.
Measurement was performed using a ND-101D color difference meter, and the degree of discoloration was expressed as the change (Δb). Dyeability test for polyurethane fibers After scouring 40 denier polyurethane fibers, dyeing was carried out under the following conditions, and the dyeing examples and washing fastness (JIS L
-0844-1976, A-2 method, fabric staining, cotton staining, silk staining). CI Ashitsuredo 6 1% owf Newbon TS (Level dyeing agent manufactured by Nicca Chemical Co., Ltd.) 5% owf PH 3.5 Light resistance test of dyed polyurethane fiber at bath ratio 1:50, 100℃ x 60 minutes 40 denier polyurethane fiber with Neugen HC
After scouring 1 g of (nonionic activator manufactured by Dai-ichi Kogyo Co., Ltd.) in an aqueous solution at 80°C for 20 minutes, irradiation was performed using a fade-o-meter for 20 hours, 40 hours, 60 hours, and 80 hours, and measurement was performed using a Tensilon meter. The irradiation time (T1/2) at which the intensity was reduced by half was determined from the intensity change curve obtained. Chlorine resistance test of polyurethane fibers 40 denier polyurethane fibers were exposed to running tap water (containing 0.15 ppm chlorine) for 24 and 36 hours.
After 48 hours of treatment, the tensile strength was measured, and the retention rate was calculated from the strength obtained, and the chlorine resistance was expressed as the total value of the retention rates for 24 hours, 36 hours, and 48 hours. Example 1 1950 parts of polytetramethylene ether glycol having a molecular weight of 1950 and 500 parts of 4,4'-diphenylmethane diisocyanate were reacted at 70°C for 60 minutes to obtain a prepolymer having isocyanate groups at both end groups. 4478 parts of dimethylformamide was added to this and dissolved to make a homogeneous solution. This solution was cooled to 0°C and a 46% paste of titanium oxide pigment containing a small amount of blue-tinting pigment dispersed in dimethylformamide was prepared.
145 parts of the reaction mixture were added, and a solution of 74 parts of 1,2-propylene diamine dissolved in 983 parts of dimethylformamide was added first and slowly at the end while stirring to carry out a chain extension reaction. 90% of the 1,2-propylene diamine solution was added to reach 2500 poise at 25°C. At this point dimethylformamide 72
The free isocyanate in the polymer solution was quenched by adding 12 parts of monoethanolamine dissolved in 72 parts of dimethylformamide.
10 parts of acetic anhydride was added to stabilize the viscosity of the polymer solution. The obtained polymer solution having a solid content of 32% and a viscosity of 2200 poise at 25°C is designated as A dope. On the other hand, 86.5 parts of 4-ethyl-4-aza-2,6
250.0 parts of dimethylformamide was added to heptanediol and mixed with stirring, the temperature was raised to 65-70°C, and while stirring was continued, 156.2 parts of 4,4'-dicyclohexylmethane diisocyanate was gradually added. After the addition was completed, the reaction was carried out at 65 to 70°C for about 20 hours, and then 7.3 parts of dimethylhydrazine was ^gradually added.
After confirming that absorption by NCO groups has disappeared, the reaction is terminated, and the tertiary nitrogen-containing polymer (molecular weight
4000) was obtained. The resulting tertiary nitrogen-containing polymer solution was dissolved in A dope so that the tertiary nitrogen content was 80 milliequivalents per 1 kg of polyurethane, and 1,3,5-tris(4-t-butyl-
0.32 parts of 3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid was added to 100 parts of the above dope, and this was dry-spun in a conventional manner to obtain a 40-denier polyurethane elastic fiber. The results of the gas discoloration test, dyeing test and light fastness test of the obtained fibers are shown in Example 2 and Comparative Examples 1 and 2.
It is shown in Table 1. Example 2 68.4 parts of 4-ethyl-4-aza-2,6-heptanediol was mixed and dissolved in 200.0 parts of dimethylformamide, heated to 65 to 70°C, and then 124.7 parts of 4,4' was added while stirring. - Gradually add dicyclohexylmethane diisocyanate, and then
The reaction was carried out under stirring at 65 to 70°C for 20 hours, and after the reaction, 6.9 parts of diethylamine was gradually added to react, and the reaction was completed after confirming that the isocyanate absorption peak at 2250 cm ^-1 in the infrared spectrum disappeared. Polymers containing tertiary nitrogen (molecular weight approx.
4000) was obtained. The obtained tertiary nitrogen-containing polymer solution was dissolved in the A dope described in Example 1 so that the content of tertiary nitrogen per 1 kg of polyurethane was 80 meq. -dimethyl-4'-t-butyl-3'-hydroxybenzyl)
-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added in an amount of 0.32 parts to 100 parts of the above A dope, and by dry spinning.
A 40 denier polyurethane elastic fiber was obtained. Comparative Example 1 Comparative Example 1 is a case in which when the diol represented by the chemical formula () and the diisocyanate are reacted, the amount of the diisocyanate is not in excess of the diol, and furthermore, the terminals are not blocked with a monoamine or hydrazine. That is, 60.8 parts of 4-ethyl-
Dissolve 4-aza-2,6-heptanediol in 150 parts of dimethylformamide, gradually add 89.2 parts of 4,4'-dicyclohexylmethane diisocyanate while stirring and heating to 65-70°C, and then
The reaction was carried out at 70°C for 20 hours to obtain a solution of a tertiary nitrogen-containing polymer (molecular weight approximately 4000). The obtained tertiary nitrogen-containing polymer solution was dissolved in the A dope described in Example 1 so that the content of tertiary nitrogen was 80 milliequivalents per 1 kg of polyurethane, and further 1,3,5-
Tris(4-t-butyl-3-hydroxy-2,
0.32 part of 6-dimethylbenzyl)isocyanuric acid was added to 100 parts of the above A dope, and this was dry spun to obtain a 40 denier polyurethane elastic fiber. Comparative Example 2 A 40-denier polyurethane elastic fiber was obtained by dry spinning the A dope of Example 1 without adding any additives.

[Table] As a result, according to the present invention, polyurethane elastic fibers with significantly improved gas yellowing resistance, dyeability and light fastness, and good washing fastness were obtained.
On the other hand, a comparative example using a tertiary nitrogen-containing polymer without using an excess of organic diisocyanate or an end-capping agent had poor gas yellowing resistance, as well as poor light fastness, dyeability, and washing fastness. Example 3 The tertiary nitrogen-containing polymer solution used in Example 1 was mixed with a tertiary nitrogen content of 80% per 1 kg of polyurethane.
It was dissolved in A dope to give a milliequivalent weight, and this was dry-spun by a conventional method to obtain a 40-denier polyurethane elastic fiber. The obtained fibers were subjected to a gas discoloration test, a dyeing test, a light fastness test, and a chlorine resistance test, and the results shown in Table 2 were obtained. Also, 4-methyl-4-aza-2,6-heptanediol and 4-isopropyl-4-aza-2,6-heptanediol were used instead of 4-ethyl-4-aza-2,6-heptanediol. A tertiary nitrogen-containing polymer was produced in the same manner, polyurethane elastic fibers were spun in the same manner as in the examples, and comparative tests were conducted. The results are also shown in Table 2.

[Table] As a result, the polyurethane elastic fiber according to the present invention was found to be excellent in gas yellowing resistance, dyeing property, light resistance, and chlorine resistance, and was a fiber with well-balanced properties.

Claims (1)

[Scope of Claims] 1. A tertiary compound in which the terminal isocyanate group of the reaction product of a tertiary nitrogen-containing diol represented by the following chemical formula () and an excess amount of organic diisocyanate is blocked with a monoamine and/or dialkylhydrazine. A polyurethane composition characterized in that a nitrogen-containing polymer is blended into polyurethane in a stabilizing amount. 2. The polyurethane composition according to claim 1, wherein the reaction molar ratio of the tertiary nitrogen-containing diol and the organic diisocyanate is 1:1.02 to 1.7. 3. The polyurethane composition according to claim 1, wherein the tertiary nitrogen-containing polymer is a tertiary nitrogen-containing polymer having a molecular weight of 1,000 to 8,000. 4 Claim 1 additionally containing a stabilizing amount of an ultraviolet absorber and/or an antioxidant
The polyurethane composition according to any one of Items 1 to 3.