JP2001072738A - Nonyellowing polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane foam being excellent in water resistance and not undergoing discoloration by sunlight by reacting an aliphatic polyisocyanate with a polyol component containing a polyoxyalkylene polyol having a specified or lower content of oxyethylene units in the presence of a catalyst selected from a guanidine derivative, etc., so as to form a cured product having a specified degree of swelling. SOLUTION: The oxyethylene units content of the polyoxyalkylene polyol is at most 18 wt.% based on the polyol. The catalyst is selected from a guanidine derivative, a 1,8-diazabicyclo-5,4,0-undecene-5 (salt), a 1,5- diazabicyclo-4,3,0-nonene-5 (salt), a salt of a diazabicycloalkene catalyst, and an alkali metal salt of a weak acid. The obtained foam has a degree of swelling defined by the formula of at most 15% when measured on a sample having been immersed in a 0.5-wt.% aqueous solution of an alkali detergent at 25 deg.C for 24 hr and kept immersed in the solution. If necessary, the foam may contain an antioxidant, an ultraviolet absorber, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the present invention, which is stable for a long period of time even when exposed to light such as sunlight, is hardly discolored, and has little swelling even when immersed in water or an aqueous solution of detergent. There are no wrinkles due to deformation, and there is little outflow of stabilizers such as antioxidants due to swelling, so there is little decrease in heat resistance, strength, etc., and especially non-woven fabrics suitable for clothing such as shoulder pads, bra cups, etc. Related to yellowing polyurethane foam.

[0002]

2. Description of the Related Art Polyurethane foam is lightweight.
Also, it has excellent rubber elasticity and excellent heat retention, so it is widely used for clothing. However, a general polyurethane foam uses an inexpensive aromatic polyisocyanate such as toluene diisocyanate, so that a foam obtained by reacting this with a polyol may be discolored by light such as sunlight, particularly yellowing. There are many. Therefore, when it is used for clothing, it is used only in a part that cannot be seen from the outside, or it is used by applying a coating on the surface of the product so that discoloration is not conspicuous.

On the other hand, aliphatic polyisocyanates (meaning polyisocyanates having no isocyanate group directly bonded to an aromatic ring) are generally expensive,
Foams made using this polyisocyanate are light-stable and do not discolor over time. Therefore, it is suitable for a part where discoloration of the foam is a problem in clothing use. However, since aliphatic polyisocyanates generally have lower reactivity than aromatic polyisocyanates, it is known that a special catalyst is required when a flexible polyurethane foam is produced (Japanese Patent Publication No. Sho 52). -30437).

Further, in practice, not only the above-mentioned special catalyst is used, but also a highly reactive polyol, that is, a polyol having a primary hydroxyl group terminal is generally used in a high proportion. Examples of such a highly reactive polyol include the following.

Polyfunctional active hydrogen compounds, such as glycerin and trimethylolpropane, are used as starting materials, and polyester polyols obtained by condensing and polymerizing adipic acid and diethylene glycol, or polyfunctional active hydrogen compounds, such as glycerin Starting from
A polyether polyol obtained by subjecting this to addition polymerization of propylene oxide alone or partially with ethylene oxide, and polymerizing an appropriate amount of ethylene oxide at the end of the reaction is generally used.

[0006] The use of special catalysts and specific polyisocyanates and polyols as described above can solve the problem of discoloration, but when the foam thus obtained is used for clothing, it is difficult to wash. Other problems such as swelling and deterioration may occur. That is, the foam using the polyester polyol described above deteriorates when the washing is repeated using a normal detergent, and the strength and the like are reduced. Specifically, there is a problem that the foam gradually turns into a powder state due to repetition of washing, drying and the like, and in severe cases, the foam disappears. Further, the foam using the above polyether polyol, depending on the type of detergent, swells due to repeated washing, swelling does not recover even after drying, wrinkles remain, etc. , And the heat resistance, durability and the like may be reduced.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and is mainly a polyurethane foam which is hardly discolored and is used in the field of clothing such as a shoulder pad or a bra cup. A yellowing polyurethane foam that has excellent water resistance and is unlikely to swell even when immersed in water or an aqueous solution of a detergent.Especially, even when washing is repeated, swelling, generation of wrinkles, reduction in strength, powdering, etc. An object of the present invention is to provide a non-yellowing polyurethane foam excellent in durability that does not occur.

[0008]

According to the present invention, in a non-yellowing polyurethane foam, the swelling ratio when immersed in a detergent solution or the like is suppressed to prevent the outflow of stabilizers and the like, and A non-yellowing polyurethane foam excellent in heat resistance and durability is provided by preventing deformation. The non-yellowing polyurethane foam of the first invention comprises reacting an aliphatic polyisocyanate (meaning a polyisocyanate having no isocyanate group directly bonded to an aromatic ring) with a polyol component in the presence of a catalyst, In the non-yellowing polyurethane foam obtained by curing, the polyol component contains at least a polyoxyalkylene polyol, and when the polyoxyalkylene polyol is 100% by weight, the content of oxyethylene units is 18% by weight or less. And the catalyst comprises (a)
1,8-diazabicyclo-5,4,0-undecene-5
And salts thereof, (b) 1,5-diazabicyclo-4,3,
One or more compounds selected from the group consisting of 0-nonene-5 and salts thereof, (c) salts of diazabicycloalkene catalysts, (d) guanidine derivatives, and (e) alkali metal salts of weak acids. The above non-yellowing polyurethane foam is mixed with a 0.5% by weight aqueous solution of an alkaline detergent.
After immersing the specimen at 5 ° C. for 24 hours, the swelling ratio represented by the following equation measured in a state of being immersed in the aqueous solution of the alkaline detergent is 15% or less. Swelling ratio (%) = {(length of specimen after immersion−length of specimen before immersion) / length of specimen before immersion} × 100

The non-yellowing polyurethane foam of the second invention comprises an aliphatic polyisocyanate (meaning a polyisocyanate having no isocyanate group directly bonded to an aromatic ring) and a polyol component in the presence of a catalyst. In the non-yellowing polyurethane foam obtained by reacting and curing, the polyol component contains at least a polyoxyalkylene polyol, and the proportion of primary hydroxyl groups in the hydroxyl groups of the polyoxyalkylene polyol that reacts with isocyanate groups is 50%. Wherein the catalyst comprises (a) 1,8-diazabicyclo-5,4,0-undecene-5 and a salt thereof, (b) 1,5-diazabicyclo-4,3,0-nonene-5 and a salt thereof A salt, (c) a salt of a diazabicycloalkene catalyst, (d) a guanidine derivative, and (e) an alkane of a weak acid. One or more compounds selected from the group consisting of metal salts. The non-yellowing polyurethane foam is prepared by immersing a specimen in a 0.5% by weight aqueous solution of an alkaline detergent at 25 ° C. for 24 hours. The swelling ratio represented by the above equation measured in a state of being immersed in an aqueous solution of the alkaline detergent is 15% or less.

The shape of the test piece is preferably a plate-like body having a square or rectangular planar shape, and the swelling ratio may be a value measured for one side of a square or a rectangle. Alternatively, the average value of two or more different sides may be obtained. A third invention is characterized in that in the non-yellowing polyurethane foam of the second invention, the content of oxyethylene units is 18% by weight or less when the polyoxyalkylene polyol is 100% by weight. A fourth invention provides the non-yellowing polyurethane foam of the first, second or third invention, wherein (A) a radical chain inhibitor and / or
Or one or two selected from the group consisting of an antioxidant comprising a peroxide decomposer, (B) a benzotriazole ultraviolet absorber, (C) a benzophenone ultraviolet absorber, and (D) a hindered amine light stabilizer. It is characterized by containing a stabilizer comprising the above compound.

The "aliphatic polyisocyanate" includes HDI (hexamethylene diisocyanate), LDI
Aliphatic diisocyanate such as DI (lysine diisocyanate), IPDI (isophorone diisocyanate), hydrogenated XDI [hydrogenated xylene diisocyanate (H
6XDI)], hydrogenated MDI [hydrogenated diphenylmethane diisocyanate (H12MDI)], and alicyclic diisocyanates such as CHDI (cyclohexyl diisocyanate). In addition, lysine ester triisocyanate, 1,8-diisocyanate-4-
Use isocyanate-free polyisocyanates such as triisocyanates such as isocyanate methyloctane, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate, and modified products thereof. You can also.

Further, XDI and TMXDI (tetramethylxylene diisocyanate) as polyisocyanates having an aromatic ring but having an isocyanate group not directly bonded to the aromatic ring and capable of obtaining a foam which is hardly yellowed are obtained. Etc. can be used. In addition, among the above various polyisocyanates, HDI, IPDI and their modified products contain a primary isocyanate group and have no steric hindrance, and therefore have relatively high reactivity as compared with those having steric hindrance. Particularly preferred.

The above "polyoxyalkylene polyol"
Usually, those comprising an oxypropylene unit and an oxyethylene unit are used. In the first invention, when the content of the oxyethylene unit in the polyol exceeds 18% by weight, the water resistance is reduced, and the polyol easily swells when immersed in water or an aqueous solution of a detergent (at the time of washing), and becomes stable. Due to outflow of the agent and the like, the strength and the like of the foam may be reduced, and the foam may remain swelled even after drying, causing wrinkles or deterioration of the foam and powdering. In the second invention, the same problem occurs when the proportion of primary hydroxyl groups among the hydroxyl groups that react with isocyanate groups exceeds 50%.

In the present invention, the above-mentioned "polyol component" is constituted by a stabilizer such as a foaming agent, a catalyst, a foam stabilizer and an antioxidant, and a light stabilizer in addition to the above-mentioned specific polyoxyalkylene polyol. Is done. Incidentally, even when a plurality of polyols are used in combination, the total content of oxyethylene units and the proportion of primary hydroxyl groups in the total amount of the plurality of polyols are within the range specified in the present invention, regardless of the type of polyol. , The effect of the present invention is expected.

Further, water is generally used as the foaming agent, and a silicone-based foaming agent can be used as the foam stabilizer. Examples of the catalyst include (a) 1,8-diazabicyclo-5,4,0-undecene-5 and a salt thereof, and (b) 1,5-diazabicyclo in order to increase the reactivity between the aliphatic polyisocyanate and the polyol. -4,3,0-nonene-5 and a salt thereof, (c) a salt of a diazabicycloalkene catalyst, (d) a guanidine derivative,
(E) One or more compounds selected from the group consisting of alkali metal salts of weak acids (carbonic acid, phenol, benzoic acid, etc.) are used.

Further, as the catalyst, the above (a) to (e)
In general, amine catalysts and metal catalysts that are commonly used can be used in combination with the special catalysts described in (1). In the present invention, it is particularly preferable to use a catalyst selected from the above (a) to (c) in combination with a metal catalyst such as a tin-based metal, and use it in combination with an alkali metal salt of a weak acid such as phenol. By combining the catalyst and the like in this manner, the reactivity between the low-reactivity aliphatic polyisocyanate and the polyoxyalkylene polyol having a low content of oxyethylene units can be increased to a level at which there is no practical problem. . As the catalyst selected from (a) to (c), 1,8-diazabicyclo-5,4,0-undecene-5 is particularly preferably used.

Various stabilizers can be used. Examples of the antioxidant include radical chain inhibitors such as phenol and amine (primary antioxidants) and peroxide decomposers such as sulfur and phosphorus (secondary antioxidants).
When the radical chain inhibitor and the peroxide decomposer are used in combination, a synergistic effect can be obtained. As the light stabilizer, a benzotriazole-based or benzophenone-based ultraviolet absorber, or a light stabilizer such as a hindered amine having a hindered piperidine skeleton called so-called HALS can be used.

In the present invention, it is preferable to use a stabilizer which has high heat resistance and hardly leaks out by washing or the like, and a phenol-based antioxidant and a benzotriazole-based ultraviolet absorber are preferred. Conventionally, both antioxidants and ultraviolet absorbers were added at about 2000 ppm, but in the present invention, each of the above stabilizers can be added in a larger amount, and 5000 ppm or more of each can be added. it can. This can more effectively suppress a decrease in heat resistance, durability, and the like due to repeated washing.

In the polyoxyalkylene polyol used in the present invention, when a polyoxyalkylene polyol having a high content of oxyethylene units or a polyhydroxyalkylene polyol having a high proportion of primary hydroxyl groups is used, the resulting foam is generally The water resistance is reduced, and swells easily in water. Moreover, the swellability of the foam in an aqueous detergent solution tends to be much greater than that of water. When the content of oxyethylene units in the polyol exceeds 18% by weight, the swellability of the foam in the aqueous detergent solution sharply increases. Get higher. As a result, wrinkles are generated in the foam, and various stabilizers easily flow out, so that heat resistance, durability and the like are reduced.

The cause of deterioration of the non-yellowing polyurethane foam used for clothing such as bra cups is as described above, due to the swelling of the foam due to the decrease in water resistance, the stabilizer flows out, and the hydrolysis of the polyurethane chain occurs. And oxidative decomposition is promoted. And in the present invention,
In order to solve the above-mentioned problem, a specific polyoxyalkylene polyol having a small content of oxyethylene units or a low proportion of primary hydroxyl group terminals is used.
In this case, the reactivity usually decreases and the formability of the foam deteriorates, but this problem is solved by using the above-mentioned specific catalyst.

When the water resistance of the foam is further increased and the swelling of the foam is reduced by using the specific polyoxyalkylene polyol as described above, the various stabilizers are hardly physically moved in the foam, and the It is thought that it becomes difficult to flow out, and a decrease in strength or the like is suppressed. Therefore, in order to suppress the deterioration of the foam, it is effective to select a stabilizer having a structure that is essentially difficult to flow, in addition to the use of the above specific polyol, It is preferable to select a stabilizer having high performance. Further, the deterioration of the foam can be reduced or prevented by increasing the amount of the stabilizer having such excellent performance.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be specifically described based on examples and comparative examples. In addition, each component such as a polyol used in the following examples and the like is specifically as follows.

Polyol 1: Polyoxypropylene triol having a oxyethylene unit content of 0% by weight, a ratio of primary hydroxyl group terminals of 0%, and a number average molecular weight of 3,000 (manufactured by Sanyo Kasei Co., Ltd. under the trade name of "SUNNIX") GP30
00 ") Polyol 2: Content of oxyethylene units; 0% by weight, ratio of primary hydroxyl group terminals; 0%, number average molecular weight;
000 polyoxypropylene triol (trade name: "Preminol 3005", manufactured by Asahi Glass Co., Ltd.)

Polyol 3: Polyoxypropylene triol having a oxyethylene unit content of 5% by weight, a ratio of primary hydroxyl group terminals of 2%, and a number average molecular weight of 3000 (manufactured by Sanyo Chemical Co., Ltd. under the trade name of "SUNNIX") GP30
30 ") Polyol 4: Content of oxyethylene units; 17% by weight, ratio of primary hydroxyl terminal; 22%, number average molecular weight;
2300 polyoxypropylene triol (trade name “FA225” manufactured by Sanyo Chemical Industries, Ltd.)

Polyol 5: Polyoxypropylene triol having a content of oxyethylene units of 20% by weight, a ratio of primary hydroxyl group terminals of 53% and a number average molecular weight of 2600 (trade name "FA226" manufactured by Sanyo Chemical Industries, Ltd.) Polyol 6: content of oxyethylene units; 22% by weight, proportion of primary hydroxyl groups; 55%, number average molecular weight;
4800 polyoxypropylene triol (trade name "SBU Polyol 0" manufactured by Sumitomo Bayer Urethane Co., Ltd.)
350 ")

Crosslinking agent: ethylene glycol Catalyst 1: 50% by weight aqueous solution of sodium salt of phenol Catalyst 2: diazabicycloundecene Catalyst 3: dibutyltin dilaurate Foam stabilizer: trade name "SH19" manufactured by Toray Silicone Co., Ltd.
0 "Stabilizer 1: Ciba Geigy Co., Ltd., trade name" Irganox 1010 "Stabilizer 2: Ciba Geigy Co., Ltd., trade name" Tinuvin 765 "Aliphatic polyisocyanate: IPDI

Example 1 prepared using each of the above components
Table 1 shows the composition and amount ratio of the foam raw materials of Comparative Examples 1 to 4 and Comparative Examples 1 and 2. In Table 1, each numerical value represents parts by weight when the polyol is 100 parts by weight.

[0028]

[Table 1]

(Example 1) The polyol component shown in Table 1 and polyisocyanate were mixed and stirred to produce a flexible polyurethane foam, and the cream time and rise time during foam production were measured. Further, the density of the obtained foam was measured according to JIS K6401. Further, this foam was cut into a 5 cm square, 5 cm square and 5 mm thick, and was added at 25 ° C. to a 0.5% by weight aqueous solution of an alkaline detergent (trade name “Ultra Ariel” manufactured by Procter & Gamble Far East). For 24 hours, and the wet swelling ratio was measured.

The swelling ratio when wet is a value obtained by measuring the swelling ratio in the vertical and horizontal lengths while the foam is immersed in an aqueous solution of a detergent, and averaging the measured values. The immersed foam was taken out of the aqueous solution, washed with water, and naturally dried at room temperature, and then the swelling ratio during drying was determined in the same manner.

Further, in order to simulate adverse effects on the foam such as generation of wrinkles and pulverization when washing is repeated, a 15 × 15 × 1 cm specimen was prepared by using the above-mentioned detergent adjusted to 50 ° C. After immersing in a 0.5% by weight aqueous solution for 16 hours, taking out, washing with water, and drying at 80 ° C. for 8 hours, the process was repeated 20 times, and the color and appearance of the foam were visually observed, and a tensile test was conducted according to JIS K6301. And measured the breaking strength and elongation. As described above, the cream time and the rise time are also shown in Table 1, and the results of the density, swelling property, simulated washing test and tensile test are shown in Table 2.

[0032]

[Table 2]

(Examples 2 to 4 and Comparative Examples 1 and 2) The same procedures as in Example 1 were carried out except that the kinds of the polyols and the amounts of the blowing agent, the catalyst and the polyisocyanate were slightly changed as shown in Table 1. To produce a polyurethane foam.
Each characteristic was evaluated in the same manner. The results are shown in Tables 1 and 2.

According to Table 1, the cream time and rise time at the time of foam production do not change so much depending on the kind of the polyol, the catalyst, and a small amount of variation of the polyisocyanate and the like. Did not. According to Table 2, although the density of the foam is slightly higher or lower, it is in a range that does not cause any particular problem. still,
In each of Examples and Comparative Examples, since aliphatic polyisocyanate was used, almost no discoloration was observed in the simulated washing test.

Further, according to the results shown in Table 2, Examples 1 and 2 using a polyol having a oxyethylene unit content of 0% by weight and a primary hydroxyl group terminal ratio of 0%, and the oxyethylene unit content In Example 3 using a polyol having a content of 5% by weight and a ratio of primary hydroxyl group terminals of 2%,
It can be seen that the swelling ratio in both wet and dry conditions is very small, and the water resistance is excellent. In addition, in the results of the simulated washing test, in each case, not only no discoloration, but also no occurrence of wrinkles, powdering, etc. were observed, the appearance was good, and even in the results of the tensile test, the breaking strength, The elongation was almost the same as before the mock test, indicating that the foam had excellent durability.

When the content of oxyethylene units is 17
Example 4 in which a polyol having a considerably high ratio of 22% by weight of primary hydroxyl groups, which is close to the upper limit of the first invention, is used.
Then, the swelling ratio when wet is 14%, which is close to the upper limit of the present invention,
The swelling ratio during drying is 7%, which is higher than the other examples. The swelling ratio of Example 4 indicates that in the present invention, the swelling ratio increases as the content of oxyethylene units and the ratio of primary hydroxyl group terminals increase.

On the other hand, when the content of oxyethylene units is 20
Comparative Example 1 using a polyol containing 53% by weight of a primary hydroxyl group terminal and a polyol containing 22% by weight of an oxyethylene unit and containing 55% of a primary hydroxyl terminal. In Example 2, it can be seen that the swelling ratio in both wet and dry states is extremely large, and the water resistance is poor. For this reason, in the results of the simulated washing test, although there was no discoloration, wrinkles were conspicuous on the surface of the foam, and the corners of the sample were cut off and rounded due to powderization, and the thickness of the entire sample was also reduced. Also, the results of the tensile test show that both the breaking strength and the elongation are greatly reduced, indicating that the durability is poor.

A comparison of the swelling ratio and the results of the tensile test between Example 4 and Comparative Examples 1 and 2 reveals that the content of the oxyethylene unit specified in the first invention or the primary hydroxyl group specified in the second invention is It can be seen that the swelling ratio sharply increases from the terminal ratio, and when the swelling ratio exceeds the upper limit of 15% of the present invention, the breaking strength and the elongation are greatly reduced, and it is found that there is a practical problem.

[0039]

Industrial Applicability The non-yellowing polyurethane foam of the present invention is suitable for clothing such as shoulder pads and bra cups, has no discoloration due to sunlight or the like, has excellent water resistance, and can be used in aqueous solutions of water or detergent. Since it does not easily swell even when immersed and there is little outflow of the stabilizer or the like from the foam, a decrease in strength or the like is suppressed. Further, even when repeatedly washed, there is no generation of wrinkles due to swelling, and no powdering or the like occurs.

Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court II (Reference) // (C08G 18/20 101: 00) (72) Inventor Motoo Matsuo 3-36 Imaikecho, Anjo-shi, Aichi Prefecture No. Innoac Corporation Anjo Business Office (72) Inventor Koji Yamamoto 3-1-1, Imaikecho, Anjo-shi, Aichi Prefecture Inoac Corporation Anjo Business Office

Claims (4)

[Claims] Claims 1. An aliphatic polyisocyanate (which means a polyisocyanate having no isocyanate group directly bonded to an aromatic ring) and a polyol component are reacted and cured in the presence of a catalyst. In the yellowing polyurethane foam, the polyol component contains at least a polyoxyalkylene polyol, and when the polyoxyalkylene polyol is 100% by weight, the content of oxyethylene units is 18% by weight or less. (A) 1,8-diazabicyclo-5,4,
0-undecene-5 and a salt thereof, (b) 1,5-diazabicyclo-4,3,0-nonene-5 and a salt thereof, (c)
At least one compound selected from the group consisting of a salt of a diazabicycloalkene catalyst, (d) a guanidine derivative, and (e) an alkali metal salt of a weak acid. After immersing the specimen in a 0.5% by weight aqueous solution of a detergent at 25 ° C. for 24 hours, the swelling ratio represented by the following equation measured in a state of being immersed in the aqueous solution of the alkaline detergent is 15% or less. Non-yellowing polyurethane foam characterized by the following. Swelling ratio (%) = {(length of specimen after immersion−length of specimen before immersion) / length of specimen before immersion} × 100 2. A reaction product obtained by reacting and curing an aliphatic polyisocyanate (which means a polyisocyanate having no isocyanate group directly bonded to an aromatic ring) and a polyol component in the presence of a catalyst. In the yellowing polyurethane foam, the polyol component contains at least a polyoxyalkylene polyol, and a ratio of a primary hydroxyl group in a hydroxyl group of the polyoxyalkylene polyol that reacts with an isocyanate group is 50% or less. a) 1,8-diazabicyclo-5,4,4
0-undecene-5 and a salt thereof, (b) 1,5-diazabicyclo-4,3,0-nonene-5 and a salt thereof, (c)
At least one compound selected from the group consisting of a salt of a diazabicycloalkene catalyst, (d) a guanidine derivative, and (e) an alkali metal salt of a weak acid. After immersing the specimen in a 0.5% by weight aqueous solution of a detergent at 25 ° C. for 24 hours, the swelling ratio represented by the following equation measured in a state of being immersed in the aqueous solution of the alkaline detergent is 15% or less. Non-yellowing polyurethane foam characterized by the following. Swelling ratio (%) = {(length of specimen after immersion−length of specimen before immersion) / length of specimen before immersion} × 100 3. The polyoxyalkylene polyol according to claim 1,
The non-yellowing polyurethane foam according to claim 2, wherein the content of oxyethylene units is 18% by weight or less when the content is 00% by weight. 4. An antioxidant comprising (A) a radical chain inhibitor and / or a peroxide decomposer, (B) a benzotriazole UV absorber, (C) a benzophenone UV absorber, and (D) a hindered amine light. Stabilizer,
The non-yellowing polyurethane foam according to claim 1, 2 or 3, further comprising a stabilizer comprising one or more compounds selected from the group consisting of: