JPH02135212A - Polyurethane composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which is used in shoes, motor vehicles and furniture, because it has excellent yellowing resistance by adding a specifically modified yellowing resistant isocyanate to a polyurethane composition containing yellowing type isocyanates. CONSTITUTION:The subject composition is obtained by adding (A) 2 to 18wt.% of a yellowing-resistant isocyanate compound such as hexamethylene diisocyanate or the like to (B) a polyurethane composition containing a yellowing isocyanate such as 2,4-tolylene diisocyanate and a polyol compound such as polyethylene adipate polyol or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a polyurethane composition, more specifically 1.
This invention relates to a polyurethane composition with excellent yellowing properties.

(vt rice technique @) Various polyurethanes have been known for a long time, and polyurethanes made from aromatic isocyanate compounds have excellent reactivity and physical properties, but it is said that they are susceptible to discoloration (W discoloration) due to light and heat. It has its drawbacks.

On the other hand, polyurethanes made from aliphatic and alicyclic isocyanate compounds have excellent yellowing resistance, but are slow in reactivity, have poor physical properties such as solvent resistance, water resistance, and hydrolysis resistance, and are also susceptible to fumes (fuss). The drawback was that it was expensive.

In order to solve such conventional problems, for example, in JP-A-54-127500, a smaller amount, approximately 0.0
It has been proposed to use 5 to 0.85 moles of aromatic (yellowing type) isocyanate compounds. However, the same publication states that if more than about 0.85 mole of aromatic isocyanate compound is used, the resulting polyurethane will have yellowing, and the important feature is to use an excessive amount of non-yellowing type isocyanate compound. .

Further, resistance to yellowing can be obtained by coating the surface with a non-yellowing paint, but in this case a coating step is required, increasing the number of steps and equipment costs.

(Problems to be Solved by the Invention) An object of the present invention is to provide a polyurethane composition having excellent yellowing resistance by using a small amount of a non-yellowing type isocyanate compound.

Another object of the present invention is to provide a polyurethane composition having excellent yellowing resistance by a simple method that does not require a coating process or the like.

(Means for Solving the Problems) The present invention provides a polyurethane composition containing a tora-variable isocyanate compound and a polyol compound.
The present invention relates to a polyurethane composition characterized in that it contains % by weight of a modified non-yellowing type isocyanate compound.

In the present invention, by using a modified non-yellowing type isocyanate compound, the desired excellent yellowing resistance can be obtained, and the amount of the non-yellowing type isocyanate compound used is also small. Therefore, there are no problems in terms of physical properties and reactivity. Although it is not fully clear why the present invention has excellent yellowing resistance, the modified non-yellowing type isocyanate compound does not substantially react,
This is thought to be due to blooming on the surface of polyurethane. On the other hand, when a non-yellowing type isocyanate compound that is not modified is used, there is almost no yellowing resistance effect, although the reason is not fully clear.

In the present invention, the yellowing type isocyanate compound is 2,4- or 2,6-)rylenenoisocyanate (
TDI), 4,4'-nophenylmethane diincyane) (MDI), xylylene diisocyane) (XDI)
and aromatic isocyanate compounds such as chlorophenylene diisocyanate.

As non-yellowing type isocyanate compounds modified in the present invention, those modified by urethane modification, urea modification, nurate modification, and other modification methods can be used, and both ends of the modified product may be NGO. Alternatively, the NGO groups at both ends may be capped by reacting with alcohol, amine, etc. Non-yellowing type isocyanate compounds include hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), cyclohexane diisocyanate, methylcyclohexane noisocyanate (HTDI), and dicyclohexylmethane noisocyanate (HMDI). , inpropylidenenocyclohexyl diisocyanate (I
Aliphatic and alicyclic isocyanate compounds such as PDI) and gimaric acid monocyane (DDI) can be mentioned. As a representative example of a specific modified product, IPD I-
T1890/100 (Hüls, Nurate modified IPD
I), Dulaney) 24A-100 (Asahi Kasei Co., Biulet modified l]DI), and the like.

In the present invention, polyester polyols, polyether polyols, and other types of polyols can be used as the polyol compound. Examples of polyester polyols include aliphatic dicarboxylic acids having 4 to 20 carbon atoms such as 7 nobic acid, superic acid, sebacic acid, and brassylic acid, terephthalic acid, and isophthalic acid as acid components, and ethylene glycol, propylene glycol, and neopentyl glycol. , aliphatic diols having 1 to G carbon atoms such as hexamethylene glycol, ether glycols such as diethylene glycol and noprobylene glycol, spiroglycol M, N-furkylnoalkali/-ruamines such as N-methyljetanolamine, etc. as polyol components. Polyester polyols or polycaprolactone polyols can be used, and specific examples include anovate polyols such as polyethylene anovate polyol, polybutylene anovate polyol, and polyethylene propylene adipate polyol, and terephthalic acid polyols (e.g., Toyo Polyol). Examples include Bosekisha, trade name Byron RUX1 Byron Rv-20OL), HoIJ caprolactone polyol (eg, Gycel Chemical, trade names Plaxel 210, Plaxel 212, Plaxel 220), and the like.

Specific examples of polyether polyols include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, and the like.

Examples of the polyol in the pond include polycarbonate polyol (eg, West Germany, Bayer AG, trade name Desmoreen 2020E), castor oil polyol, and the like. These polyols can be used alone or in combination of two or more.

In the present invention, a chain extender may be used if necessary, and examples of the chain extender include, for example,
Examples thereof include hexafunctional short-chain polyols and diamines having a molecular weight of 500 or less and a secondary terminal amino group of 7 groups. Suitable chain extenders include, for example, ethylene glycol, noethylene glycol, propylene glycol, dipropylene glycol, butanol, hexaneol, glycerin, trinotyrolpropane, pentaerythritol, nlubitol,
Polyols such as 1,4-cyclohexaneol, 1,4-cyclohexane dimetatool, and xylylene glycol (b) Diamines such as hydranone, ethylene oxide, tetramethylenezamine, hexamethylene diamine, and 1,4-cyclohexanoamine (e) Flukanolamines such as ethanolamine, jetanolamine, triethanolamine, etc. (d) Hydroquinone, pyrrolol, 4,4'-imbropylidenephenol, aniline, and the above polyols and diamines , Furka/
-Molecular weight 500 obtained by adding propylene oxide and/or ethylene oxide to ruamiso in any order
Examples include the following polyols. Moreover, other known additives can also be added.

The polyurethane composition of the present invention is obtained using each of the above components, and the modified non-yellowing type isocyanate compound is used in an amount of about 2 to 18% by weight in the composition. If it is less than 2%, the yellowing prevention effect is insufficient;
%, there will be problems in terms of physical properties such as tear strength and bending properties. In the polyurethane composition of the present invention, the NGO index is generally preferably in the range of 0.95 to 1.05. In this case, NCO of non-yellowing type isocyanate compound
Groups, whether modified or unmodified, are not taken into account.

The polyurethane composition of the present invention can be cured by a known method, such as by mixing a polyol component and an isocyanate component in separate tanks, or by heating the composition.

Incidentally, the polyurethane composition of the present invention can be used for various purposes, but especially for polyurethane foam elastomers,
For example, it is useful in the fields of shoes, automobiles, and household goods. In particular, the direct urethane sole (DOS) sole using the urethane of the present invention is characterized by excellent adhesion to the shoelace, especially initial adhesion.

(Example) Examples and comparative examples will be described below.

Example I IPDI (2.2 mol) and Nibolane N-4042
(Polyol, 1.0 mol) at 80°C under nitrogen gas flow.
The mixture was reacted for 3 hours to obtain polyol-modified non-yellowing isocyanate A containing approximately 3.7% NGO.

On the other hand, M D I (10,2 mol) and Nibolane N
4042 (1.0 mol) was similarly reacted at 70° C. for 2 hours to obtain a yellowed isocyanate prepolymer B having an NCO content of about 17%.

Niraporan N4042 as a polyol component of the curing agent
(92.0 parts), ethylene glycol (8.4 parts), water (0.35 parts), silicone foam stabilizer (Toshi Silicon S H
-193.0.3 parts), antioxidant (BHT, 1.0 part), ultraviolet absorber (181S), titanium white toner (4 g) and catalyst [) lyethylene diamine: ethylene glycol (weight ratio) = 1: 2.1.4 parts) to obtain polyol component C.

Using the PECMU-203H type urethane foam rock (manufactured by Polyurethane Ennonearing Co., Ltd.), add the above C to the liquid tank.
Ingredients: (1) The above A and B components were placed in a liquid tank and the temperature of the liquid in the tank was adjusted to 40°C. The 1ffl temperature of the foamed rock discharge part at an air temperature of 20°C was 35°C. Adjust the gear pumps for liquid ■ and liquid ■ so that NGO index = 1.0 and discharge the mixed liquid of liquid liquid and liquid ■ to 45 g/Sec, and mix and discharge at mixer rotation speed of 5000 rpm. I let it happen. Molded product dimensions are 200 re mX +
Material thickness 2 to be 50+a+n X G Inur
Using a 0 cov aluminum mold, apply a release agent on the contact surface of the urethane, and at a mold temperature of 48 to 52°C, 20 parts of the A component and 1 part of the B component were added to the urethane foam from the urethane foam.
A total of 81 g was injected at a ratio of 0.00 parts and 100 parts of C component, and the mold was demolded after 5 minutes. The content of modified non-yellowing isocyanate is 9.1%. The average density of the obtained polyurethane foam is determined by the weight of the molded article ffi (g)/volume of the molded article (cc
) is calculated from r. The hardness of this sample was measured at 20° C. using an ASKERC type hardness meter (manufactured by Kobunshi Keiki Co., Ltd., compliant with Japan Rubber Association standard SRI S-0101). Furthermore, the breaking strength (TB, kH/can')
, elongation at break (EI3.96) and tear strength (Tr,
kg-c+n) was measured using JISK [330+1]. The bending properties (Demarcher type bending test! 9 waves, 75 x 19 strokes, 21 notches, 100,000 times) and the degree of yellowing (color difference meter Model TC-1500MC, Tokyo Shinshoku) were also investigated. T [3, EB.

Tr is Autograph U TM manufactured by Toyo Baldwin.
-4-200. In the yellowing test, fluorescent lamps (next summer, daylight color 40W, ' F L R40S -W
-E/M, distance +5c+++), Weather-O-meter (WOM, made by Sushikeniso, WUE, L-2 type, precipitation conditions 12 minutes/60 minutes, black panel temperature 63 ± 3 ° C,
Number of carbon electrodes: 2), sun lamp (next summer, FL20SE
, 20W1 distance 30e+m) was used. In addition, the initial adhesion of the sample was determined after 3 minutes of demolding, 2 minutes, 3 minutes, 5 minutes, and 10 minutes.
After a few minutes, the pre-molded artificial leather (2 c, 1 in) was heated to 25°C using a spring scale (Yawata Kogyo, 20 kg).
Measurements were made by performing a 180° peel test. The results are shown in Table 1.

Examples 2 to 7 Polyurethane compositions were obtained in the same manner as in Example 1 using the components listed in Table 1, and their properties were investigated. 1st
In the table D: HXD I (2.2 mol) and Nibolane N
NGO obtained from -4042 (1.0 mol) is about 3.
6% polyol modified non-yellowing isocyanate.

C: IP D l-T1890/100 nurate modified non-yellowing isocyanate.

F: Durane) 24A-100 Biuretz modified non-yellowing isocyanate.

G: IPI')I Non-yellowing insiaquitomo/
Polyol modified with approximately 4.0% NGO obtained from Mer 1 (: IIXDr non-yellowing inanate mo/mer 1: T MX I) I (2.2 mol) and Niraporan N-4042 (1.0 mol) Non-yellowing isocyanate.

Comparative Examples 1 to 5 Polyurethane compositions were obtained in the same manner as in Example 1 using each component listed in Table 2, and their properties were investigated. Results! ! ' Shown in Table S2.

Part 1 table

Claims (1)

[Claims] (1) A polyurethane composition characterized in that about 2 to 18% by weight of a modified non-yellowing type isocyanate compound is blended into a polyurethane composition containing a yellowing type isocyanate compound and a polyol compound.