JPS6036560A - Polyurethane composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent stability against the discoloration and deterioration with atmosphere and combustion gas and the deterioration with chlorine, by compounding a polyurethane with a tert-nitrogen- containing urethane polymer blocked at the terminal with a sucrose fatty acid ester. CONSTITUTION:100pts.wt. of a polyurethane is compounded with 0.01-15pts.wt. of a tert-nitrogen-containing urethane polymer blocked at the terminal with a sucrose fatty acid ester. The urethane polymer can be produced by reacting 1mol of an amine diol with 1.02-1.9mol of an organic polyisocyanate (preferably aliphatic diisocyanate), and reacting the product with a sucrose fatty acid ester.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stabilized polyurethane composition, and more particularly to a polyurethane composition stabilized against discoloration and deterioration due to outside air conditions or combustion gas, deterioration due to chlorine, and the like.

In general, polyurethane products such as polyurethane elastic threads, foams, elastomer sheets, synthetic leather, and polyurethane resin-treated fiber products tend to discolor when exposed to an atmosphere of hydrocarbon combustion gas, nitrogen oxide gas, or outside air conditions for a long time. There are drawbacks.

Furthermore, in the case of polyurethane having raw bond, urethane bond 1, ether bond, or ester bond in the molecule, it has drawbacks such as discoloration and deterioration even when exposed to light or heat. Normally, it is essential to add antioxidants and sometimes ultraviolet absorbers to polyurethane in order to stabilize it against light and heat, but these additives actually promote coloration due to combustion gas or nitrogen oxide gas. There is a tendency.

Many proposals have been made for gas coloring inhibitors, but few have satisfactory performance, and even if they have excellent resistance to coloring, they may impair other properties.
There are few known materials that can be put to practical use due to their lack of durability.

The present inventors took these problems into consideration and arrived at the present invention as a result of intensive research to improve the gas coloring resistance of polyurethane. In other words, the present invention provides polyurethane with
It is characterized by containing a stabilizing amount of a tertiary nitrogen-containing urethane polymer end-capped with a sucrose fatty acid ester.

The tertiary nitrogen-containing urethane polymer used in the present invention is, for example, a terminal isocyanate group-containing polyurethane consisting of a tertiary nitrogen-containing bifunctional compound, a tertiary nitrogen-containing diol, and an excess amount of an organic polyisocyanate. An example is a urethane polymer having a structure in which incyanate groups are blocked by sucrose fatty acid esters. The tertiary nitrogen-containing diol to be used is not particularly limited, but the following are exemplified as preferred compounds.

(However, in the formulas represented by general formulas (I), (II), and (III), R represents an alkyl group having 1 to 12 carbon atoms, and R
1 may form a heterocycle with an alkyl group having 1 to 4 carbon atoms of the same size or with a nitrogen atom in instant contact with R1 of 2&l. ) (In the formula represented by general formula (IY), R2, R3, R4,
R5 and R6 represent hydrogen or the same or different alkyl groups having 1 to 4 carbon atoms. ) (In the general formula (V), R7 is an alkyl group having 1 to 4 carbon atoms, or 5 with two R? and a nitrogen atom in instant contact)
~6-membered ring may be formed, and oxygen or nitrogen may be included in the ring. R8 alkyl group having 1 to 4 carbon atoms tR
9 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, which may be the same or different. ) Organic polyisocyanates are also not particularly limited, but include, for example, 4,4'-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2
Aromatic diisocyanates such as +4-tolylene diisocyanate, knack diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate,
Examples include aliphatic diisocyanates such as hexamethylene diisocyanate and 3,3'-dimethylbencune diisocyanate. Among these, aliphatic diisocyanates are preferred.

The sucrose fatty acid ester used for end-capping the tertiary nitrogen-containing urethane polymer contains 1 to 1 fatty acid per molecule of sucrose.
It is a compound in which three molecules are bonded through ester bonds, and a compound represented by the general formula (Vl) is exemplified.

(However, in the formula, RIO, R11, and R12 represent hydrogen or an acyl group having the same or different carbon atoms from 12 to 18, and at least one central member of RIO, R11, and R12 is an acyl group.) Specific The following compounds are exemplified as fatty acid esters of sucrose. Namely, monolaurate and monomyristate of sucrose.

Monopalmitic acid ester, monostearic acid ester, monooleic acid ester, monolinoleic acid ester,
Monopalmitic acid ester, monosinolic acid ester,
Dilauric acid ester, dimylinutic acid ester, cibalmitic acid ester, distearic acid ester, dioleic acid ester.

trilauric acid ester, trimyristate ester,
These include tribalmitic acid ester, tristearic acid ester, and trioleic acid ester.

The above sucrose fatty acid esters can be used alone or as a mixture of two or more.

An excess amount of the organic polyisocyanate is used relative to the amine diol represented by the above general formulas (1) to (V). Particularly preferred is 1.02 to 1.9 mol of organic polyisocyanate per 1 mol of amine diol.

A urecne polymer with terminal incyanate groups is obtained by the reaction of amine diol and polyisocyanate,
This terminal incyanate group is reacted with a sucrose fatty acid ester to obtain a tertiary nitrogen-containing urethane polymer having a sucrose fatty acid ester terminal group. A portion of the sucrose fatty acid ester may be present in an unreacted state.

The amount of the tertiary nitrogen-containing urethane polymer thus obtained is a stabilizing amount, and it can be used in an appropriate amount depending on the required performance, but it is usually 0.01 to 151 parts per 100 mff of polyurethane.
Parts by weight are preferred, and 0.1 to 5 parts by weight are particularly preferred. If the amount is too small, the effect will be insufficient, and if the amount is too high, it will cause scum during molding of the composition and post-processing of the molded product, which is inappropriate.

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. . In this case, it is particularly important to select additives that do not reduce gas discoloration resistance.

In particular, the following general formula (■) and/or (
V#) is exemplified.

(Similar formula 1, R13 is an alkyl group, a cycloalkyl group,
It represents a neopentyl group or an aralkyl group, and HI3 and R15 represent a group selected from a hydrogen atom, an alkyl group, and an alkoxy group. ) -i Examples of phenolic compounds represented by formula (■) include 1,3.5-) lis(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid, 1, 3.5-) lis(4-butyl-3-hydroxy-2,6-dimethylpenzyl)isocyanuric acid,
1.3.5-) lis(4-neopentyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid and the like. Particularly preferred in terms of production and effectiveness is 1,3.5-)IJs(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid.

Particularly preferable examples of the phenolic compound represented by the general formula (■) are compounds in which R13 is a branched alkyl group having 4 to 8 carbon atoms, a cycloalkyl group, a neopentyl group, or an aralkyl group. teeth.

・10-(2',6'-dimethyl-4'-t-butyl-3'-hydroxypenzyl)-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10
-oxide 6-lomethyl-10- (2',6'-dimethyl-47
-1-butyl-3'rhydroxybenzyl) -9,1
0-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide 06-medoxy10- (2',6'-dimethyl-4
'-tert-butyl-3'-hydroxybenzyl) -9°10-dihydro-9-oxa-10-phosphonophenanthrene-10-ogicide-1,0-(2/,6'-dimethyl-47- cyclohexyl-3'-hydroxybenzyl)-9,10-dihydro-9-oxa-10-humesphaphenanthrene-1
0-oxide 10- (2', 6'-dimethyl-4'-(σ, α-
dimethylbenzyl)-3'-hydroxybenzyl)-9
210-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 010- (2', 6'
-dimethyl-4'-neopentyl-37-hydroxybenzyl) -9,10-dihydro-9-oxa-10-
Examples include fumesphaphenanthrene-10-oxide.

The amount of these phenolic compounds is a stabilizing amount against light, and is usually 0.1 to 10% by weight, preferably 0.5 to 8% by weight, based on the polyurethane.

The polyurethane to which the present invention is applied is not particularly limited, and includes, for example, substantially linear polymers having active hydrogen-containing groups at both ends and having a molecular weight of 500 to 7,000, such as polyether diol, polyester diol, and polycarbonate dimer. .

Polylactone diol, polyamide diol, polyamide diamine etc. and polyfunctional incyanate such as 4,4
'-Diphenylmethane diisocyanate, 1.4-phenylene diisocyanate, 2.4-)! J diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, xylylene diisocyanate, inphorone diisocyanate.

4.4'-dicyclohegycylmethane diisocyanate, etc. and polyfunctional low-molecular active hydrogen compounds such as hydrazine, ethylenediamine, 1,2-propylenediamine,
Hexamethylene diamine, β-aminopropionic acid hydrazide, carbodihydrofuide.

Examples include polyurethanes having urethane bonds in the molecule obtained by reacting water, ethylene glycol, 1,4-butanediol, and the like.

The tertiary nitrogen-containing urethane polymer of the present invention can be added to polyurethane at any stage of producing polyurethane, but it is preferably mixed after the completion of polyurethane polymerization and before the molding stage.

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 leathers, paints, glass fiber sizing agents, etc. Particularly useful in clothing fiber and tape applications.

The polyurethane composition obtained by blending the tertiary nitrogen-containing urethane polymer of the present invention has a characteristic that resistance to yellowing due to outside air conditions or gases such as combustion gas, and discoloration and deterioration due to chlorine are significantly improved.

It also has the advantage of improved moldability, peelability, dyeability, 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 the examples are parts by weight and weight fi%.
shows. In addition, the characteristic values in the examples were measured as follows.

Gas discoloration test for polyurethane fibers A strong test was conducted on 3 units in accordance with JIS L 0855-1976, and the b value before and after the test was measured using an ND-101D color difference meter manufactured by Nippon Gunshoku Kogyo Co., Ltd., and the change (Δb
) represents the degree of discoloration.

A 40-denier polyurethane fiber was placed in a glass tube with an inner diameter of about 8 mm and a length of about 1 m, and one end was closed.

Regular tap water containing about 0.1 to 0.5 ppm of sterilizing chlorine was continuously flowed at a flow rate of about 2 bu/h, and each sample was washed 12 hours, 24 hours, 36 hours, and 48 hours after the start of the test. After taking it out and drying it at 80° C. for 2 hours, the breaking strength was measured using a tensilon measuring machine, and the test time (T I/2) at which the strength was halved was determined from the strength change curve.

Example 1 1950 m of polytetramethylene ether glycol having a molecular weight of 1950 and 500 parts of 4,4'-diphenylmethane diisocyanate were polished at 70°C for 60 minutes to obtain a prepolymer having incyanate groups at both end groups. 4478 parts of dimethylformamide was added to this and dissolved to form a homogeneous solution. This solution was cooled to 0°C, 145 parts of a 46% paste of titanium oxide pigment containing a small amount of blue pigment dispersed in dimethylformamide was added, and the mixture was further stirred to 1 and then dissolved in 983 parts of dimethylformamide. A chain extension reaction was carried out by adding 74 parts of a solution of 1,2-propylene diamine first and then slowly at the end. ] Add 90% of the 2-propylene diamine solution to 250 ml at 25°C.
Reached 0 voices. At this point, dimethylformamide 7
The free incyanate in the polymerization ff' solution is quenched by adding 12 parts of monoethanolamine dissolved in 2 parts;
Thereafter, 10 parts of acetic anhydride dissolved in 72 parts of dimethylformamide were added to stabilize the viscosity of the polymer solution.

The obtained polymer solution having a solid content of 32% and a viscosity of 2200 voids at 25° C. is designated as A dope.

Separately, 1109 parts of 4,4' dicyclohexylmethane diisocyanate was dissolved in 500 parts of dimethylformamide b1. After adding 10-2 parts of dibutyltin diacetate, the temperature was raised to about 62°C with stirring, and while maintaining that temperature, 55.1 parts of 2-ethyl-2-dinothylamino-1,3- Propanediol was gradually added, and after all additions were completed/ζ, the reaction was stirred at 62° C. for an additional 5 hours. Furthermore, 59 parts of sucrose fatty acid ester was added to this reaction mixture, and the mixture was reacted at 62°C for about 3 hours with stirring. The sucrose Vi fatty acid esters used at this time were monoester and di-sucrose.

It was a mixture of triesters, and the fatty acids included stearic acid and palmitic acid. The resulting tertiary nitrogen-containing polymer was a light brown solution with 2.5 centivoids at 30°C.

The tertiary nitrogen-containing urethane polymer thus obtained has a tertiary nitrogen content of 80% per 11ψ of polyurethane.
1 and 1.3.
5-Tris(4-t-butyl-3-hydroxy-2,
0.32 parts of 6-dimethylbenzyl)isocyanuric acid was added to 100 parts of the above dope, and dry spinning was performed by a conventional method to obtain a 40 denier polyurethane fiber. The results of the gas discoloration test and chlorine embrittlement test of the obtained fibers are shown in Example 2.
3 and Comparative Example 1.2.3 are shown in Table 1.

Example 2 471 parts of 4,4' dicyclohexylmethane diisocyanate was dissolved in 1112 parts of dimethylformamide, and after adding 0.15 parts of dibutyltin diacetate, the temperature was raised to about 65°C, and the temperature was maintained while stirring. 221
1 part of 4-methyl-4-aza-2,6-hebutanediol was gradually added, and after the entire amount had been added, the mixture was kept at about 65°C for about 6 hours with stirring once, and then 420 parts of sucrose fatty acid ester was added. In addition, the third
A urethane polymer containing grade nitrogen was obtained. This polymer solution was brown in color and had about 1.9 voids at 30°C.

The tertiary nitrogen-containing urethane polymer thus obtained has a tertiary nitrogen content of 8 per 1 kp of polyurethane.
Added to A dope so that it becomes 0 mm, and further 1.0
- (2',6'-dimethyl-4'-t-butyl-3'
-hydroxybenzyl) -9,10-dihydro-9-
Add 0.32 parts of oxa-10-phosphonoaphenanthrene-10-oxide to 100 parts of the above dope.
Polyurethane fibers of 40 denier were obtained by dry spinning using three methods.

Example 3 437 parts of 4,4' dicyclohexylmethane diisocyanate were dissolved in 910 parts of dimethylformamide,
After adding NQ of 0.15 parts of dibutyltin diacetate,
1! fj: Raise the temperature to about 63°C while stirring, and add 242 parts of 4-ethyl-4-aza-2 while maintaining the temperature.
, 6-hebutanediol was gradually added, and after the entire amount had been added, the mixture was kept at about 60°C for about 5 hours while stirring once, and then 231 parts of sucrose fatty acid ester was added and reacted at 60°C while stirring for 3 hours. I let it happen. The obtained tertiary nitrogen-containing urethane polymer was a viscous solution with 2.5 voids at 30°C.

This tertiary nitrogen-containing urethane polymer is
Addition of 10-(2',6'-dimethyl-47-cyclohexyl-3'-hydroxybenzyl)-9,10-dihydro -9-oxa-10-phosphenthrene-10-oxide A beef 10
A 40-denier polyurethane fiber was obtained by dry spinning by adding 0.32 parts to 0 parts.

Comparative Examples 1 to 2 When no additive is added to the hedope of Example 1 (Comparative Example 1
), when 1,3.5-tris(4-t-butyl-8-hydroxy-2,6-dimethylbenzyl)isocyanuric acid alone is added as an additive to 1100 parts of A-Bee and 0.32 part is added. (Comparative Example 2) In addition to Comparative Example 2, poly(N-diethylaminoethyl methacrylate) was added per polymer, and the tertiary chamber content was 80 ytl. / kP (Comparative Example 3), each was dry-spun in the same manner as Examples 1 to 3 to obtain a 40-denier polyurethane fiber.

Table 1 From the above results, it can be seen that the polyurethane composition of the present invention has a remarkable effect on gas discoloration caused by outside air conditions and chlorine deterioration.

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Scope of Claims] 1. A polyurethane composition comprising a stabilizing amount of a tertiary nitrogen-containing urethane polymer embedded in polyurethane and end-capped with sucrose fatty acid ester. 2. The polyurethane composition according to claim 1, wherein the amount of the tertiary nitrogen-containing urethane polymer is 0.01 to 15 parts by weight per 100 parts by weight of the polyurethane.