KR101251262B1 - Poly Urethane Form Containing Absorbent - Google Patents

Abstract

The present invention relates to a polyurethane foam comprising a porous silica adsorbent. The present invention can effectively reduce the amine compound, which is a main component that causes yellowing and an unpleasant odor in the polyurethane foam, and at the same time can reduce the generation of volatile organic substances, and when used in a car seat or the like, Odor can be removed, and can also prevent new car syndrome.

Description

Polyurethane Form Containing Absorbent

The present invention relates to a polyurethane foam for preventing discoloration and odor generation.

The initial color of the seat cover made of 100% fiber or artificial leather is gradually changed due to various causes such as alteration of the surrounding environment such as sunlight, high heat, or the compound used in the manufacturing process and other materials in close contact. It doesn't matter if the color change of the car seat cover is gradual so that it can't be recognized by consumers during the 10 years of the car's end of life. The impact is very large.

Accordingly, the present inventors analyze a material that causes yellowing and odor of the polyurethane foam and provide a polyurethane foam including an adsorbent for selectively adsorbing the material, thereby preventing discoloration of the car seat cover, odor and volatile organic compounds (Volatile Organic Compounds (VOC).

The present invention relates to a polyurethane foam comprising a porous silica adsorbent represented by the following formula (1).

[Formula 1]
_{Al 2 Si 2 O 5 (OH} ) x · M y

However, in Formula 1, M is P, Ca, Zn, Fe, K, Mn, Mo, Ag, Mg or Ti, x is 6 to 7, y is 4 to 5.

The present invention can effectively reduce the amine compound, which is the main component that causes yellowing in the polyurethane foam and causes an unpleasant odor, and at the same time can reduce the generation of volatile organic substances, and when used in a car seat or the like, Odor can be removed, and can also prevent new car syndrome.

1 is a view schematically showing the extraction process of the yellowing material.
Figure 2 is a scanning electron microscope (SEM) image of the adsorbent used in the present invention.
3 is a diagram showing an approximate process of Experimental Example 2.
4 shows gas chromatography-mass spectrometer (GC-MSD) analysis results of Comparative Examples and Examples 2 to 4. FIG.

Hereinafter, the present invention will be described in more detail.

First, the cause of yellowing of the polyurethane foam was analyzed in the following manner. Both sides of the polyurethane foam were slightly melted with a 200 ° C. flame, and then yellowed by artificially standing at a temperature of 50 ° C. and a humidity of 50% for 36 hours in a thermo-hygrostat. The yellowed and non-generated foams were extracted with methanol solvent and the components were detected by gas chromatography-mass spectrometry (GC-MSD). Figure 1 schematically shows the extraction process. Table 1 shows the results of component analysis.

Non-yellowing polyurethane foam Yellowing Polyurethane Foam 1,2-dichloro-ethane 1,2-dichloro-ethane methoxy benzene methoxy benzene alpha-chloroethyl chloroformate 4-methyl-1,3-benzenediamine 3,4,5-trimethoxybenzoldehyde oxime 1,3-dihydro-5-methyl-2H-benzimidazol-2-one s-butylmethylethylphosphonate s-butylmethylethylphosphonate 1,2,5-thiodiozole-3-carboxamide 1,2,5-thiodiozole-3-carboxamide - 2,4-diisocyanato-1-methyl-benzene - 5-chloro-2-methyl-benzoxazole

As a result of analysis, the yellow color among the components detected only in the yellowed polyurethane foam was 2,4-diisocyanato-1-methyl-benzene, 4-methyl-1,3-benzenediamine, 1,3-dihydro-5 -methyl-2H-benzimidazol-2-one and 5-chloro-2-methyl-benzoxazole. In view of these results, the yellowing material is mainly derived from toluene diisocyanate (TDI) and the amine component, and is considered to be liberated from the isocyanate and the catalyst forming a hard segment in the polyurethane foam manufacturing process. Especially, in case of 5-chloro-2-methyl-benzoxazole, it is a benzoxazole type, which is a representative structure used as a fluorescent brightener, and is known to generate reversible yellowing by protonation under acidic conditions. have.

In addition, the compound analyzed as a yellowing substance is one of the causes of new car syndrome as a component causing an unpleasant odor.

The present invention is intended to prevent discoloration and odor of the polyurethane foam by including the adsorbent of the cause of the yellowing and odor generation in the polyurethane foam.

Specifically, the present invention relates to a polyurethane foam comprising a porous silica adsorbent represented by the following formula (1).

 [Formula 1]

_{Al 2 Si 2 O 5 (OH} ) x · M y

However, in Formula 1, M is P, Ca, Zn, Fe, K, Mn, Mo, Ag, Mg or Ti, x is 6 to 7, y is 4 to 5.

In more detail, in Formula 1, M is Zn, x is 7, and y is more preferably 5.

The hydroxy group (-OH) on the surface of the porous silica adsorbent chemically adsorbs the yellowing agent and physically adsorbs the pores of the porous silica as a carrier material, thereby preventing yellowing and odor of the polyurethane foam. It becomes possible to prevent it.

The content ratio of the porous silica adsorbent is preferably 0.2 to 0.5% by weight of polyurethane foam. If less than 0.2% by weight, there may be a problem that the adsorption performance is not sufficient, if more than 0.5% by weight may be a problem that prevents the growth of the polyurethane foam when foaming polyurethane foam. More preferably, it is 0.3 to 0.4 weight%.

In addition, the polyurethane foam according to the present invention may further include a surfactant, a catalyst, a flame retardant, and the like commonly used in the art.

Hereinafter, the present invention will be described in detail with reference to specific examples, but the scope of the present invention is not limited to these examples.

Example  1 to 4 and Comparative example

The polyol, the flame retardant, the surfactant, and the catalyst were added in the amounts shown in Table 2 below and stirred and mixed at 3000 rpm for 30 seconds, and then the adsorbent was added in the amounts shown in Table 2 and mixed for 20 seconds. Thereafter, the blowing agent and the isocyanate were added in the amounts shown in Table 2 below, mixed for 5 seconds, poured into a mold, and the foam was grown. The adsorbent used in Example 1 is shown in FIG.

Content (g) Polyol G-Polyol (KPX Chemical, P-3022) 40 POP-Polyol (KPX Chemical, FA-410) 20 LF-Polyol (KPX Chemical, KE-874N) 40 Flame retardant Phosphorus-halogen-based (Nine Chemical, CR-530) 16 Surfactants Silicon based (Nine Chemical, BF-2470) One catalyst Amine series-1 (Nine Chemical, A-1) 0.07 Amine series-2 (Nine Chemical, A-33) 0.05 Tin system (Nine Chemical, T-9) 0.1 blowing agent Methylene Chloride 5 Distilled water - 3.6 Isocyanate Toluene Diisocyanate (OCI) 48 Example 1 absorbent Al ₂ Si ₂ O ₅ (OH) ₇ Zn ₅ 0.1 Example 2 Al ₂ Si ₂ O ₅ (OH) ₇ Zn ₅ 0.3 Example 3 Al ₂ Si ₂ O ₅ (OH) ₇ Zn ₅ 0.5 Example 4 Al ₂ Si ₂ O ₅ (OH) ₇ Zn ₅ 1.0 Comparative example - 0

Experimental Example  1: Cream / Rising  Time measurement

The cream time and the rising time of the manufacturing processes of Examples 1 to 4 and Comparative Examples were measured and shown in Table 3 below.

Adsorbent Content (g) Cream Time (s) Rising Time (s) Example 1 0.1 7 265 Example 2 0.3 7 255 Example 3 0.5 8 249 Example 4 1.0 10 243 Comparative example 0 7 271

As the result of Table 3, as the content of the adsorbent increases, the cream time is slowed down, the rising time is fastened, and it can be seen that the adsorbent interferes with the growth of the foam. In view of the above results, it is determined that the content ratio of the adsorbent should be less than 0.5% by weight, more preferably less than 0.4% by weight relative to the total polyurethane foam.

Experimental Example  2: volatile organic substance analysis test

After pretreatment of 4.8 g of the polyurethane foam prepared in Examples 2 to 4 and Comparative Examples, each of them was put in a 3L odor bag and sealed. After filling with 1 L of odorless high purity nitrogen gas, it was put in a dryer and heated at 100 ° C. for 2 hours. It was taken out of the dryer and precooled for 1 hour. After the odor bag was filled with odorless high purity nitrogen gas, gas chromatography-mass spectrometry (GC-MSD) analysis was performed. 3 shows the general process of Experimental Example 2. Figure 4 is a gas chromatography-mass spectrometer (GC-MSD) analysis results of Comparative Examples and Examples 2 to 4 from the top, respectively, and are shown in Table 4 below.

Detection material Comparative example Example 2 Example 3 Example 4 0g 0.3 g 0.5 g 1.0 g Concentration (ppb) Concentration (ppb) Concentration (ppb) Concentration (ppb) Dimethylamine 50.50 - - - 2-Butene 2.85 - - - Acetonitrile 75.81 66.21 26.54 22.32 Cyclobutylamine 622.80 475.02 304.87 192.92 Carbon disulfide 11.86 9.62 - - 2-Butenal 14.09 7.62 - - Trichloromethane 22.50 22.50 8.24 11.94 1,2-Dichloroethane 196.87 116.30 121.41 98.54 1-Butanol 24.05 12.64 6.02 3.12 Benzene 2.93 2.91 - - 1,3,5-Cycloheptatriene 198.91 76.21 36.21 35.19 Ethylbenzene 7.42 3.21 1.02 0.56 o-Xylene 14.41 11.35 2.06 1.94 Styrene 143.08 136.52 33.98 36.20 2,2'-azobis Propanenitrile 347.80 303.24 267.15 186.83 Isobutyl nonyl oxalic acid 5.32 3.95 0.56 0.32 2,2-dimethyl-octane 2.89 - - - Hexadecane 3.04 2.65 0.32 - 3,4-Dimethyl-decane 26.51 24.30 5.21 6.05 O-decyl-Hydroxylamine 12.98 11.64 3.69 3.05

As can be seen in Table 4, in the case of the polyurethane foam containing the adsorbent of the present invention, it is possible to suppress the occurrence of the yellowing agent, and at the same time it was confirmed that it can reduce the occurrence of unpleasant odor and various volatile organic substances .

Claims (3)

Polyurethane foam for absorbing the yellowing agent and the volatile organic substance comprising a porous silica adsorbent represented by the formula (1).
[Formula 1]
_{Al 2 Si 2 O 5 (OH} ) x · M y
(In Formula 1, M is P, Ca, Zn, Fe, K, Mn, Mo, Ag, Mg or Ti, x is 6-7, y is 4-5)
delete The polyurethane foam according to claim 1, wherein the content ratio of the porous silica adsorbent is 0.2 to 0.5 wt% based on the total polyurethane foam.

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