JP2005047854A - Stabilizer-containing organic polyisocyanate composition and stabilizer composition for organic polyisocyanate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic polyisocyanate composition containing a specific phenolic compound, to provide a stabilizer composition for organic polyisocyanate comprising the specific phenolic compound and an organic phosphite, more specifically, to provide the organic polyisocyanate composition effectively prevented from discoloration, and to provide the stabilizer composition capable of preventing an organic polyisocyanate from discoloration. <P>SOLUTION: The organic polyisocyanate composition comprises an organic polyisocyanate compound and a specific hindered phenolic compound. The stabilizer composition for organic polyisocyanate comprises the specific hindered phenolic compound and the organic phosphite. Thus, discoloration of the organic polyisocyanate composition can effectively be prevented even without using BHT(butylated hydroxytoluene), and among others, the new organic polyisocyanate composition with high storage stability at high temperatures can be provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an organic polyisocyanate composition containing a specific phenolic compound and a stabilizer composition for organic polyisocyanate comprising a specific phenolic compound and an organic phosphite. More specifically, the present invention relates to an organic polyisocyanate composition that effectively prevents discoloration and a stabilizer composition that can prevent discoloration of the organic polyisocyanate.

  Organic polyisocyanate compounds are highly reactive substances and are used in a wide range of production as raw materials for polyurethane foams, elastomers, adhesives and paints.

  However, these organic polyisocyanates have a problem that they are easily yellowed except for some non-yellowing and non-yellowing isocyanates, and the tendency is particularly remarkable when storage at a high temperature is required. .

  In contrast, conventionally, attempts have been made to prevent discoloration by adding a stabilizer such as an antioxidant to an organic polyisocyanate. Examples of such stabilizers include phenol compounds, phosphorus compounds, sulfur compounds, amine compounds, and mixtures thereof. Among these, 2,6- (di-tert-butyl) -p having a substituent having a steric hindrance action at both ortho positions of phenolic hydroxyl groups, called phenolic compounds, particularly both hindered phenol compounds. -Cresol (hereinafter also referred to as BHT) has been widely used.

  However, this BHT changes its structure in the presence of NOx and causes discoloration itself, and has relatively high volatility. When polyurethane is produced from an organic polyisocyanate compound to which BHT is added, There is a problem in that the volatilized BHT moves to a material (for example, cloth, artificial leather, etc.) covering the periphery of the material, and as a result, the surface of the covering material turns yellow.

  In order to solve such problems of BHT, development of an alternative material for BHT is desired. For example, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid ester has conventionally been used for organic polyisocyanate. It has been proposed to be used as an antioxidant (see Patent Document 1).

  Further, as a stabilizer for preventing discoloration, various hindered phenol compounds such as O, O-di-n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate alone or as a mixture, or Polyisocyanates containing various phosphite compounds such as triphenyl phosphite alone or in combination as a mixture in addition to the hindered phenol compound have been disclosed (see Patent Document 2).

  However, the field of BHT substitute materials has not yet been established, and in addition to the above materials, it is desired that a wide variety of substitute materials be developed by approaches from various angles.

As a result of diligent research in view of such circumstances, the present inventors can effectively prevent discoloration of the obtained organic polyisocyanate composition by adding a specific hindered phenol compound to the organic polyisocyanate compound. The present inventors have found that discoloration of the surface of a covering material of a polyurethane foam produced using an organic polyisocyanate composition as a raw material can be prevented, thereby completing the present invention.
Special Table 2002-507594 U.S. Pat. No. 4,064,157

  The present invention provides an organic polyisocyanate composition containing a phenolic compound different from BHT as a stabilizer, and more specifically, as a BHT substitute material, the ortho- and para-positions of both phenolic hydroxyl groups are three-dimensional. An object of the present invention is to provide an organic polyisocyanate composition having excellent stability using a hindered phenol compound having a group having a hindering action. Furthermore, this invention makes it a subject to provide the novel stabilizer composition for organic polyisocyanate containing this phenol type compound and organic phosphite.

  The organic polyisocyanate composition according to the present invention is characterized by containing an organic polyisocyanate compound and a compound represented by the following formula (I). ;

  Further, the organic polyisocyanate composition of the present invention preferably contains an organic phosphite in addition to the phenolic compound.

  In the present invention, the compound represented by the formula (I) is desirably contained in the organic polyisocyanate composition in an amount of 10 to 2500 mg with respect to 1000 g of the organic polyisocyanate compound.

  Moreover, the stabilizer composition for organic polyisocyanate according to the present invention comprises the compound represented by the formula (I) and an organic phosphite.

  According to the present invention, discoloration of an organic polyisocyanate composition can be effectively prevented without using BHT, and in particular, a novel organic polyisocyanate composition having excellent storage stability during heating can be provided.

Furthermore, using the organic polyisocyanate composition of the present invention as an isocyanate raw material,
When a polyurethane foam is produced, it is possible to prevent yellowing of the material surface covering the polyurethane foam.

  Moreover, according to the stabilizer composition for organic polyisocyanate of the present invention, discoloration of the organic polyisocyanate can be effectively prevented.

  Hereinafter, the present invention will be specifically described.

  The organic polyisocyanate composition according to the present invention is characterized by containing an organic polyisocyanate compound and a compound represented by the formula (I).

First, each component which comprises the organic polyisocyanate composition of this invention is demonstrated, Then, the organic polyisocyanate composition of this invention and the stabilizer composition for organic polyisocyanates are demonstrated.
<Organic polyisocyanate compound>
The organic polyisocyanate compound used in the present invention is not particularly limited, and aliphatic polyisocyanate, alicyclic polyisocyanate, araliphatic polyisocyanate, aromatic polyisocyanate and the like that are usually used for the production of polyurethane and the like. Can be mentioned.

  Specific examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, and 2,3-butylene diisocyanate. 1, aliphatic diisocyanates such as 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate; lysine ester triisocyanate, 1,4, 8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate Hexane over preparative, 2,5,7 and aliphatic triisocyanates such as trimethyl-1,8-diisocyanate-5-isocyanatomethyl octane.

Specific examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, and 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate. 4,4'-methylenebis (cyclohexyl isocyanate), methyl-
Alicyclic diisocyanates such as 2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or mixtures thereof, norbornane diisocyanate; Triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatemethyl) -bicyclo (2,2,1) heptane, 2- (3-isocyanatopropyl) ) -2,6-di (isocyanatomethyl) -bicyclo (2,2,1) heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2,2,1) heptane , 5- (2-Isocyanate) L) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2,2,1) heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl)- Bicyclo (2,2,1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2,2,1) -heptane, 6- (2-isocyanate) Ethyl) -2-isocyanatomethyl-2- (3-isocyanatepropyl)
-Alicyclic triisocyanates such as bicyclo (2,2,1) heptane.

Specific examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω′-diisocyanate-1,
Aromatic aliphatic diisocyanates such as 4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene (also referred to as tetramethylxylylene diisocyanate) or mixtures thereof; 1,3,5 -Aro-aliphatic triisocyanates such as triisocyanate methylbenzene.

Specific examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate,
1,5-naphthalene diisocyanate, 2,4- or 4,4′-diphenylmethane diisocyanate (hereinafter also referred to as MDI) or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate (hereinafter also referred to as TDI). ) Or a mixture thereof, 4,4'-
Aromatic diisocyanates such as tolidine diisocyanate, 4,4′-diphenyl ether diisocyanate; triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,
Aromatic triisocyanates such as 3,5-triisocyanate benzene and 2,4,6-triisocyanate toluene; aromatic tetraisocyanates such as 4,4′-diphenylmethane-2,2 ′, 5,5′-tetraisocyanate, etc. Is mentioned.

  These organic polyisocyanate compounds may be used alone or in combination of two or more.

Of these, aromatic diisocyanates are preferred from the viewpoint that the effect of preventing discoloration according to the present invention can be more effectively achieved, and TDI, MDI, and the like are preferably used.
<Compound represented by formula (I)>
The organic polyisocyanate composition of the present invention contains a compound represented by the following formula (I).

  Unlike BHT, this compound has a bulky tert-butyl group at both the ortho positions adjacent to the phenolic hydroxyl group, and also has a structure having a large substituent including a tert-butyl group at the para position. Yes.

The compound represented by the formula (I) can be synthesized by a known method, but a commercially available product can also be used as it is. Specifically, Irganox 3114 (manufactured by Ciba Specialty Chemicals) and the like can be used. Can be used.
<Other ingredients>
The organic polyisocyanate composition according to the present invention may contain other components in addition to the organic polyisocyanate compound described above and the phenol compound represented by the formula (I).

  As other components, known stabilizers used for organic polyisocyanate compounds, specifically, for example, described in US Pat. No. 3,715,381, US Pat. No. 4,064,157, etc. In addition, antioxidants such as dialkyldiphenylamine, phenothiazine, and organic phosphite, ultraviolet absorbers, heat deterioration inhibitors and the like can be mentioned.

  Among these, an organic phosphite is preferable. In addition to the phenolic compound represented by the formula (I), the organic polyisocyanate composition further contains an organic phosphite. Discoloration can be prevented more effectively.

  The organic phosphite is not particularly limited, and those conventionally used as phosphorus antioxidants can be widely used. Specific examples thereof include triphenyl phosphite and diphenylisodecyl phosphite. , Phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite. Of these, triphenyl phosphite can be preferably used.

In addition, these organic phosphites may be used individually by 1 type, and may be used in combination of 2 or more type.
<Organic polyisocyanate composition>
The organic polyisocyanate composition of the present invention can be produced using each of the above components. Specifically, the phenolic compound represented by the formula (I) is added to and mixed with the organic polyisocyanate compound, or the phenolic compound represented by the formula (I) and other components (preferably The organic polyisocyanate composition of the present invention can be obtained by adding and mixing the organic phosphite).

  In this case, the phenol compound represented by the formula (I) is usually 10 to 2500 mg, preferably 10 to 1000 mg, with respect to 1000 g of the organic polyisocyanate compound in the organic polyisocyanate composition of the present invention. It is desirable to add to the organic polyisocyanate compound in an amount. When the phenolic compound is contained in the organic polyisocyanate composition of the present invention in an amount within the above range, at least an effect of preventing discoloration comparable to that of BHT, and an effect of preventing discoloration superior to that of BHT when heated. Can play.

Further, when the organic polyisocyanate composition of the present invention also contains an organic phosphite in addition to the phenolic compound, the organic phosphite is incorporated into the organic polyisocyanate composition in the formula (I). It is desirable that the compound is generally contained in a ratio of 1: 0.01 to 1: 500 in a weight ratio of the compound represented by formula (1): organic phosphite. More specifically, the organic phosphite is added to the organic polyisocyanate compound so that it is usually contained in the organic polyisocyanate composition of the present invention in an amount of 10 to 2500 ppm, preferably 10 to 1000 ppm. Is desirable. When the organic polyisocyanate composition of the present invention contains an organic phosphite in a proportion within the above range in addition to the phenolic compound, the anti-discoloration effect can be further improved and the long-term stability can be improved. An excellent organic polyisocyanate composition can be obtained.

  The mixing of each constituent component can be performed by a known method, and is not particularly limited, but can be generally performed at 0 to 100 ° C. under normal pressure. In addition, the said phenol type compound may be added directly to an organic polyisocyanate compound, and may be added in a system in the manufacturing process of an organic polyisocyanate compound.

  Moreover, when the organic polyisocyanate composition of the present invention also contains an organic phosphite, the organic phosphite may be added before the phenolic compound is added, or the phenolic compound is added. You may add later and may add simultaneously.

In addition, although the organic polyisocyanate composition of the present invention uses the phenolic compound as a BHT substitute material, it is preferable that the organic polyisocyanate composition does not contain BHT originally, but further contains BHT in the present invention. Of course, it is possible. By doing so, the usage-amount of BHT can be reduced compared with the past, and discoloration of the coating | covering material surface can be reduced. Therefore, the present invention does not exclude such an embodiment including BHT.
<Stabilizer composition for organic polyisocyanate>
The stabilizer composition for organic polyisocyanate of the present invention comprises the compound represented by the formula (I) and an organic phosphite.

This stabilizer composition for organic polyisocyanate is obtained by mixing and stirring the phenolic compound represented by the formula (I) and the organic phosphite at the ratio described above using the known means described above. When the organic polyisocyanate compound is added and mixed, the phenolic compound and the organic phosphite are used so as to have the above-described concentrations.
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following examples and comparative examples, “%” means “wt%” unless otherwise specified.

First, materials used in Examples and Comparative Examples are shown below.
<Organic polyisocyanate compound>
・ TDI-80;
2,4-tolylene diisocyanate: 2,6-tolylene diisocyanate = 80: 20% mixture (Mitsui Takeda Chemical Co., Ltd.)
<Phenolic compound represented by the formula (I)>
・ A1;
1,3,5-tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) -S
-Triazine-2,4,6- (1H, 3H, 5H) trione <Organic phosphite>
・ B1;
Triphenyl phosphite <Others>
・ BHT

  The organic polyisocyanate composition of the present invention was obtained by adding and mixing A1 with TDI-80 (100 g) so as to be contained in the amount shown in Table 1.

<Discoloration evaluation of organic polyisocyanate composition>
The obtained organic polyisocyanate composition was put into a transparent sample bottle with an inner cap made of polyethylene, and the gas phase portion was replaced with nitrogen or air, and then sealed, under nitrogen atmosphere (23 ° C., 50 ° C.) and under air (23 ° C., 50 ° C.) for 30 days.

  Subsequently, the number of colors (APHA) was visually measured according to JIS K-1556.

  The results are shown in Table 1.

[Examples 2 to 4 and Comparative Examples 1 to 4]
In Example 1, it carried out like Example 1 except having changed the compound added to TDI-80, and its quantity according to Table 1. FIG.

  The results are summarized in Table 1.

[Comparative Example 5]
As a blank, only TDI-80 was evaluated for discoloration in the same manner as in Example 1.

  The results are shown in Table 1.

Claims (4)

An organic polyisocyanate composition comprising an organic polyisocyanate compound and a compound represented by the following formula (I): ;
  The organic polyisocyanate composition according to claim 1, wherein the organic polyisocyanate composition further contains an organic phosphite.   The compound represented by the formula (I) is contained in the organic polyisocyanate composition in an amount of 10 to 2500 mg with respect to 1000 g of the organic polyisocyanate compound. The organic polyisocyanate composition described. A stabilizer composition for organic polyisocyanate, comprising a compound represented by the following formula (I) and an organic phosphite;