JPH036177B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to polyurethane compositions. The polyurethane compositions of the present invention have improved dyeability and color fastness, and at the same time are stabilized against discoloration due to ambient conditions or combustion gases. Moreover, these performances are maintained even after undergoing treatments such as product processing and commercial dry cleaning. Therefore, the composition of the present invention can be used in a wide range of polyurethane products such as elastic fibers, foams, and synthetic leathers. [Prior Art] In general, polyurethane does not have an effective dyeing seat in its constituent molecules, so it usually has the disadvantage of being difficult to dye with dyes. Since polyurethane is often used in combination with other materials such as nylon, polyester, cotton, and wool, its resistance to dyeing is a major problem in textile products. For example, in textile products using covered yarns, core yarns, etc., when the product is stretched, undyed polyurethane appears, which is a drawback that degrades the quality of the product. In order to improve the dyeability of polyurethane, it is generally known to add or copolymerize a tertiary nitrogen compound. Since the latter method of introducing a tertiary nitrogen compound into the polymer molecule tends to cause deterioration of the physical properties of polyurethane, the former method of adding a compound having tertiary nitrogen is preferred. However, even in this method of improving dyeability by adding a dyeability improver, there are side effects associated with the addition, and many proposals have been made so far.
A satisfactory additive has not yet been found. For example, the N,N-dialkyl-β-aminoethyl methacrylate polymer proposed in Japanese Patent Publication No. 46-2904 bleeds out onto the polyurethane surface, forms scum, and causes frequent thread breakage. However, since additives that act as a dyeing seat bleed out onto the surface, they inevitably have drawbacks such as poor dye fastness. In addition, JP-A-59
The tertiary nitrogen-containing polyurethane proposed in Publication No. 221355 has problems such as a decrease in elastic properties, especially elongation recovery, when using a high molecular weight material that is difficult to extract with dry cleaning solvents such as perchlorethylene. It has its drawbacks. [Problems to be solved by the invention] As described above, many proposals have been made as dyeability improvers for polyurethane, but even if the dyeability is improved, other performances may be impaired or the durability There are problems such as lack of energy and sagging. In other words, it bleeds out onto the surface and generates scum.
This causes a decrease in workability and color fastness.
Moreover, it has an adverse effect on physical properties such as a decrease in elongation recovery. In addition, they fall off during product processing and dry cleaning, reducing the improvement effect and resulting in poor durability. The present inventors have conducted extensive research into additives that improve the dyeability of polyurethane, which do not generate scum, do not reduce elongation recovery, are not extracted by perchlorethylene, etc., and have excellent dye fastness. As a result of repeated research, it was discovered that a specific polymer containing tertiary nitrogen having a maleimide structure has no side effects, has good durability, and can improve the dyeing properties of polyurethane, leading to the present invention. [Means for solving the problems] That is, the present invention has the following features:

A polyurethane composition is provided in which a stabilizing amount of a tertiary nitrogen-containing polymer comprising a repeating unit represented by the formula and a repeating unit represented by the following general formula () is blended into polyurethane. (However, in the formula, R ₁ represents an alkylene group having 2 to 6 carbon atoms, and R ₂ and R ₃ are the same or different and have 1 to 6 carbon atoms.
6 shows the alkyl group. ) The polyurethane composition of the present invention has the characteristics that the dyeability and color fastness are significantly improved, and not only bright to fast dyed products can be obtained, but also resistance to gas yellowing is improved. Furthermore, when conventionally known antioxidants, light stabilizers, etc. are used in combination, light embrittlement resistance is also improved. The polyurethane composition of the present invention is

It can be obtained by blending a stabilizing amount of a polymer consisting of a repeating unit represented by the formula (hereinafter referred to as isobutylene unit) and a repeating unit represented by the above general formula (hereinafter referred to as maleimide unit) into polyurethane. . This polymer consisting of isobutylene units and maleimide units is a polymer of isobutylene and maleic anhydride.

It can be easily obtained by reacting an amine of the formula. Polymers of isobutylene and maleic anhydride with different ratios can be produced by selecting the polymerization method, monomer ratio, etc.; Polymers that are alternately copolymerized [see below ()] are preferred. Generally, the reaction of this polymer with an amine is
The polymer before and after the reaction is dissolved and the boiling point is
Solvents that do not inhibit the reaction at temperatures above 100℃, e.g.
N,N-dimethylacetamide, N-methyl-2
- Carry out in pyrrolidone. In the reaction, first, a maleic anhydride unit and an amine are reacted to form an amic acid, and then dehydration and ring closure are performed at a high temperature to imidize the unit. The first stage reaction takes place at a temperature range of 50 to 100℃.
It will last for 2 hours. In the second stage, the mixture is heated under reflux at 130 to 180°C for 1 to 2 hours, and then heated for 4 to 5 hours while distilling off water from the system. In addition, if water is present during the reaction time, it will react with the maleic anhydride units, so it is necessary to avoid bringing water into the system as much as possible, but the presence of some water cannot be avoided, and the isobutylene units and maleimide units Some units other than that are generated. Therefore, it is preferable to suppress the amount to at least 5% or less. used in reaction

〔Effect of the invention〕

The polyurethane composition of the present invention does not produce scum that leads to deterioration of workability, and has significantly improved dyeability and color fastness without deteriorating physical properties such as elongation recovery, and can produce bright and durable dyed products. It will be done. Furthermore, it is stabilized against coloring due to outside air conditions or combustion gases. Furthermore, this type of performance is maintained even after product processing and dry cleaning, resulting in excellent durability.
Although the reason for this effect is not clear, the dye improving agent used in the production of the polyurethane composition of the present invention has a chemical structure in which the main skeleton is composed of maleimide units and isobutylene units that are relatively poorly soluble in urethane. Due to its high molecular weight and high molecular weight, it is easy to phase separate in polyurethane and exist as an aggregate, so there is no formation of scum due to migration to the surface, it does not affect elongation recovery, and it is easy to extract and The desired improvement in dyeability and prevention of gas discoloration can be achieved by the use of tertiary nitrogen, which is difficult to fall off and is distributed in large numbers on the surface of the aggregate, as a dyeing seat and as an absorbing seat for nitrogen oxide gas, etc. [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. In addition, parts and % in an example show a weight part and a weight %. Further, the characteristic values in the examples were measured as follows. Dyeability test After scouring 40 denier polyurethane fiber, dye it under the following conditions and check its dyeability and washing fastness (JIS L
-0844, A-2 method, cloth stain, cotton stain line). Bath composition: Kayanol Milling Xiamin 5R 3% owf Levelan NKN 1% owf PH 4 Bath ratio: 1:50, dyeing at 100°C for 60 minutes The dyeability was compared with the degree of dyeing of nylon fibers and evaluated using the following criteria. . 〇: Stained to almost the same extent as nylon △: Slightly dyed, but inferior to nylon ND made by Nippon Denshoku Kogyo Co., Ltd.
It was measured with a -101DC type color difference meter, and the degree of discoloration was expressed as the change (Δb). Scum test 40 denier polyurethane fiber rolled into a cheese shape is passed through a double covering machine (Kataoka Kikai KK). The yarn feed speed was 5 m/min, the elongation rate between the feed roll and the first roller was 100%, and the first
The elongation rate between the roller and the second roller is 250%,
After 24 hours of continuous operation, the degree of contamination on the surface of the second roller was visually inspected and classified into five ranks: 1st grade if the second roller was not contaminated at all, and 5th grade if it was significantly contaminated. Elongation recovery measurement 40 denier polyurethane fiber was measured using Tensilon (manufactured by Toyo Baldwin Co., Ltd.), and the sample length was 5.
cm, and immediately returned after 300% elongation at a tensile speed of 50 cm/min, and the residual elongation Δl (%) immediately after recovery was determined. Durability test Each sample was placed in perchlorethylene at 40℃ for 1 hour.
After soaking for a time and air drying, each property was measured and durability was evaluated. Example 1 Synthesis of dyeing improver 40 parts of an alternating copolymer of isobutylene and maleic anhydride having an average molecular weight of about 60,000 (isoban-04 manufactured by Clareisoprene Chemical Co., Ltd.), 33.8 parts of diethylaminopropylamine, and dimethylacetamide. 160 parts of the mixture were charged into a reaction vessel equipped with a reflux device, and the maleic anhydride unit in the first stage was reacted with the amine at 50°C for 1 hour and then at 100°C for 1 hour under a nitrogen stream. Next, the temperature was raised to 180°C, and heated under reflux for 1 hour, and for 4 hours while distilling off the produced water, to perform the second imidization reaction, to form the desired tertiary compound consisting of isobutylene units and maleimide units. A nitrogen-containing polymer was obtained. In order to confirm the product, a polymer was taken out from the reaction solution and its infrared absorption spectrum was measured. The results are shown in FIG. In a similar manner, various additives were also synthesized by changing the types of polymers of isobutylene and maleic anhydride used as starting materials and the types of amines to be reacted with the polymers. Table 1 shows the contents and symbols representing the additives. Incidentally, B-1 to B-4 are the synthesis of additives outside the scope of the present invention. B-1 is a case in which an amine in which R ₂ and R ₃ are alkyl groups having 7 or more carbon atoms was used, and a homogeneous solution was obtained during the reaction, but phase separation occurred when the number of R 2 and R 3 was 50 to 60 or less. B-3 is a case where R ₁ uses an amine with an alkylene group having 7 or more carbon atoms, and also 50 to
Phase separation occurred at temperatures below 60°C.

【table】 \
R ₃
Example 2 1800 parts of polytetramethylene ether glycol having an average molecular weight of 1800 was reacted with 450 parts of 4,4'-diphenylmethane diisocyanate at 80°C for 2 hours to obtain a prepolymer having diisocyanate groups at both ends. 4000 parts of dimethylacetamide was added and dissolved to make a homogeneous solution. Add this solution to 20
Cool dimethylacetamide to °C with stirring.
A solution consisting of 1000 parts of ethylenediamine, 44.64 parts of ethylenediamine, and 8.17 parts of diethylamine was added to carry out a chain extension reaction. The obtained polymerization solution having a solid content of 31.5% and a viscosity of 2500 poise at 30°C is designated as A dope.
Dyeing improver A synthesized in Example 1 to this A dope
-1. Adding 3 parts and 4 parts of titanium oxide to 100 parts of polymer, and a small amount of blue-tinged pigment,
After vacuum decooling, dry spinning was performed using a conventional method to obtain a 40-denier polyurethane elastic fiber. The results of the dyeability test, gas discoloration test, scum test, and elongation recovery measurement of the obtained fibers are shown in Table 2 together with Example 3 and Comparative Examples 1 to 3. Example 3 The dye improving agent A-2 synthesized in Example 1, titanium oxide, and the antioxidant 1,3,5-tris(4-t-butyl-3-hydroxy- 2.5 parts and 4 parts of 2,6-dimethylbenzyl)isocyanuric acid, respectively, per 100 parts of polymer.
1.5 parts and a small amount of blue tinting pigment were added, and a 40 denier polyurethane fiber was obtained by dry spinning. Comparative Examples 1 to 3 Dyeing improver A-2 in the blended dope of Example 3
(Comparative Example 1), when 3 parts of poly(N-diethylaminoethyl methacrylate) was added as a dyeing improver to 100 parts of polymer to the blended dope of Comparative Example 1 (Comparative Example 2),
2-ethyl-2 as a dye improving agent in the blended dope of
-dimethylamino-1,3-propanediol and
A polyurethane solution prepared by adding 3 parts of a tertiary nitrogen-containing polyurethane with an average molecular weight of about 13,000 synthesized from 4.4'-dicyclohexylmethane diisocyanate (Comparative Example 3) was dry-spun in the same manner as in Examples 2 to 33. A 40 denier polyurethane fiber was obtained.

[Table] From Table 2, Comparative Example 1 without dyeing improver,
The polyurethane composition of the present invention was compared with Comparative Example 2 in which a conventional dye improving agent was added which caused a lot of scum formation and poor dye fastness, and Comparative Example 3 in which a conventional dye improving agent was added which caused poor elongation recovery properties. In the case of materials, there is no scum formation, no deterioration in elongation recovery,
It can be seen that excellent dyeing properties, washing fastness, and gas discoloration resistance can be obtained. Example 4 A 40 denier polyurethane fiber was obtained from a dope containing 3 parts of the dye improving agent A-3 in place of the dye improving agent A-2 in the formulation of Example 3. Dyeability test of the obtained fibers before and after perchlorethylene treatment,
The gas discoloration test results are shown in Table 3 together with Comparative Example 4. Comparative Example 4 In the formulation of Comparative Example 3, the average molecular weight was approximately
A 40 denier polyurethane fiber was obtained from a dope containing a polyurethane having the same composition and an average molecular weight of about 3,700 instead of a tertiary nitrogen-containing polyurethane of 13,000.

[Table] From Table 3, the polyurethane composition of the present invention has excellent dyeing properties, compared to Comparative Example 4 in which a low-molecular-weight tertiary nitrogen-containing polyurethane that has no effect on elongation recovery properties is blended. It can be seen that gas discoloration resistance is maintained even after perchlorethylene treatment. Examples 5 to 7 In the formulation of Example 2, A-4 (Example 5), A-5 (Example 6),
A dope containing A-6 (Example 7) was dry-spun to obtain a 40-denier polyurethane elastic fiber.
The results of the dyeability test and gas discoloration test before and after the perchlorethylene treatment of each of the obtained fibers are shown in Table 4 together with Comparative Examples 5 to 8. Comparative Examples 5 to 8 Similarly, in the formulation of Example 2, dyeing improver A
Dyeing improver agent B-1 (Comparative Example 5) in which R ₂ and R ₃ are an alkyl group having 7 carbon atoms instead of -1, and a dyeing in which an amino group in which R ₁ is zero and a tertiary nitrogen are directly connected Dyeing improver B-2 (Comparative Example 6), Dyeing improver B-3 (Comparative Example 7) in which R ₁ is an alkylene group having 7 carbon atoms, Dyeing improver B-4 having an average molecular weight of 7300 (Comparative Example 8)
Each dope containing the above was dry-spun to obtain a 40-denier polyurethane elastic fiber.

[Table] From Table 4, compared with Comparative Example 5 with poor washing fastness, Comparative Example 6 with poor gas discoloration resistance, Comparative Example 7 with poor gas discoloration resistance, and Comparative Example 8 with poor performance after perchlorethylene treatment. The results show that the polyurethane composition of the present invention has excellent dyeability, color fastness, and gas discoloration resistance, and also maintains its performance even after perchlorethylene treatment.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum diagram of improving agent A-1 of Example 1.

Claims (1)

[Claims] 1. A polyurethane obtained by blending into polyurethane a stabilizing amount of a tertiary nitrogen-containing polymer having a molecular weight of 8,000 or more and consisting of a repeating unit represented by the formula and a repeating unit represented by the following general formula. Composition. (However, in the formula, R ₁ represents an alkylene group having 2 to 6 carbon atoms, and R ₂ and R ₃ are the same or different groups with 1 carbon number.
~6 alkyl group is shown. 2. The polyurethane composition according to claim 1, wherein the tertiary nitrogen-containing polymer is a polymer in which repeating units represented by the formula and repeating units represented by the general formula are alternately repeated.