JP2912490B2 - Method for stabilizing isocyanate compound and stabilized isocyanate composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizing method for suppressing yellowing and white turbidity of an isocyanate compound due to aging, and to an isocyanate composition stabilized by the method. The material is particularly useful as a raw material for urethane resin for optics such as a plastic lens which requires colorless transparency.

[0002]

2. Description of the Related Art Isocyanate compounds have the disadvantage that they are unstable due to the high reactivity of the isocyanate groups and are liable to color or self-polymerize during storage. Therefore, it is essential to add a stabilizer that suppresses coloring and self-polymerization. Conventionally, various compounds are known as stabilizers for isocyanate compounds, and typical stabilizers include phenols such as 2,6-di-tert-butyl-p-cresol (US Pat. No. 3,715,381), Phenyl phosphite
Phosphite esters such as 5-33438) are known. In addition, ureas, carbamates, acid amides (JP-B-45-7044, JP-A-50-36546),
Acidic substances (Ger. 2,837,770) such as perchloric acid and trifluoromethanesulfonic acid, carbon dioxide and sulfur dioxide (US Pat. No. 3,247,236), organic amines (JP-A-50-101344), acid chloride (JP-A- 63-
179917), siloxane (Berg. 85892)
Numerous stabilizers such as 1), organotin compounds (EP 203874), acyl isocyanate compounds (JP-B 48-3825) are known.

[0003] Compounds known as phenolic stabilizers related to the present application include pyrogallol, catechol,
Guaiacol, eugenol, pentachlorophenol (JP-B-48-3825, JP-B-45-7044),
2,6-ditert-butyl-p-cresol, meta-cresol (JP-A-51-48619), other alkyl-substituted phenols and bisphenols (JP-B-46-27)
594, Pol 100154, Brit. 1315
520, US Pat. No. 3,682,902, JP-A-59-9805.
0).

However, even with these stabilizers, it is difficult to simultaneously suppress coloration of the isocyanate compound and clouding due to self-polymerization, and satisfactory results have not yet been obtained. In particular, aliphatic polyisocyanates, in particular xylylene diisocyanate, are 1-
It is known that cloudiness is likely to occur due to the formation of a nylon-type polymer [Journal of the Chemical Society, Vol. 82, p. 866 (1960)]. I found out that I couldn't do it. Therefore, development of a stabilizer that simultaneously suppresses yellowing and white turbidity of the isocyanate compound for a long period of time has been desired.

[0005]

The first object of the present invention is to provide a stabilizing method for simultaneously suppressing the yellowing and white turbidity of an isocyanate compound for a long period of time, and the second object of the present invention is to provide a stabilized isocyanate compound. And providing a natto composition.

[0006]

Means for Solving the Problems As a result of intensive search for a stabilizer for an isocyanate compound, the present inventors have found that phenols are relatively effective, and among them, phenol exhibits an excellent coloring and clouding suppression effect. Was found. Particularly unstable xylylene diisocyanate can be stably stored at 20 ° C. for 6 months or more by adding phenol. Heretofore, it has been known that phenols are effective as stabilizers, but surprisingly, such an excellent stabilizing action of the simplest compound, phenol, has not been known at all. That is, the first aspect of the present invention is a method for stabilizing an isocyanate compound, which comprises adding 10 to 5000 ppm of phenol to the isocyanate compound.
In the second invention, phenol is added to the isocyanate compound.
It is an isocyanate composition to which 5000 ppm has been added.

The amount of phenol to be added to the isocyanate compound is suitably from 10 to 5000 ppm.
2000 ppm is preferred. If the amount is less than 10 ppm, a sufficient stabilizing effect is not exhibited. If the amount exceeds 5,000 ppm, coloring of the isocyanate compound may be accelerated rather than preferable. Examples of isocyanate compounds to which phenol can be used as a stabilizer include monoisocyanate compounds such as methyl isocyanate, butyl isocyanate, phenyl isocyanate, and benzyl isocyanate.

Examples of the polyisocyanate compound include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and 2,2 ′. -Dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-
1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate 4-isocyanatomethyloctane, 2,5,7-trimethyl-
1,8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butyleneglycoldipropylether-α, α′-diisocyanate, lysinediamine Isocyanate methyl ester, lysine triisocyanate, 2-isocyanatoethyl 2,6
-Diisocyanatohexanoate, 2-isocyanatopropyl 2,6-diisocyanatohexanoate, xylylene diisocyanate, bis (isocyanatoethyl)
Benzene, bis (isocyanatopropyl) benzene,
α, α, α ′, α′-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesylate Tyrylene triisocyanate, 2,6-di (isocyanatomethyl) furan, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethyl Methane diisocyanate, 2,2'-dimethyldicyclohexyl methane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, diisocyanate diisocyanate, 2-iso Anatomechiru-3- (3
-Isocyanatopropyl) -5-isocyanatomethyl-
Bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane,
2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2
1] -heptane, 2-isocyanatomethyl-2- (3-
Isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5- (2-
Isocyanatoethyl) -bicyclo- [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [2,2 1] -Heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5
(2-isocyanatoethyl) -bicyclo- [2,2
1] -heptane, 2-isocyanatomethyl-2- (3-
Isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [2,2,1] -heptane, 2,5
(Or 6) -bis (isocyanatomethyl) -bicyclo [2,2,1] -heptane, thiodiethylene diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl Aliphatic polyisocyanates such as diisocyanate, dithiodiethyldiisocyanate, dithiodipropyldiisocyanate, phenylene diisocyanate, tolylene diisocyanate, ethyl phenylene diisocyanate, isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate Nate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate , Methylnaphthalene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-
Diisocyanate, bibenzyl-4,4'-diisocyanate, bis (isocyanatophenyl) ethylene, 3,
3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethane triisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane 2,4,4'-triisocyanate, 3-
Methyldiphenylmethane-4,6,4'-triisocyanate, 4-methyl-diphenylmethane-3,5
2 ', 4', 6'-pentaisocyanate, phenylisocyanatomethylisocyanate, phenylisocyanatoethylisocyanate, tetrahydronaphthalenediisocyanate, hexahydrobenzenediisocyanate, hexahydrodiphenylmethane-4,4'-di Isocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate,
Diethylene glycol diphenyl ether diisocyanate, dibenzofurandi isocyanate, carbazole diisocyanate, ethyl carbazole diisocyanate, dichlorocarbazole diisocyanate, diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate Nath, 3,3 '
-Dimethoxy-4,4'-diisocyanatodibenzylthioether, bis (4-isocyanatomethylphenyl)
Sulfides, aromatic isocyanates having a sulfide bond such as 4,4'-methoxyphenylthioethylene glycol-3,3'-diisocyanate, diphenyl disulfide-4,4'-diisocyanate, 2,2'-
Dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-6,6'-diisocyanate,
4,4'-dimethyldiphenyl disulfide-5,5 '
-Diisocyanate, 3,3'-dimethoxydiphenyl disulfide-4,4'-diisocyanate, 4,4 '
Aromatic diisocyanates having a disulfide bond, such as dimethoxydiphenyl disulfide-3,3'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidine Sulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate, 4-methyldiphenylsulfone-2,
4'-diisocyanate, 4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3 '
-Dimethoxy-4,4'-diisocyanatobenzyldisulfone, 4,4'-dimethyldiphenylsulfone-3,
3′-diisocyanate, 4,4′-di-tert-butyldiphenylsulfone-3,3′-diisocyanate, 4,4′-methoxyphenylethylenesulfone
Aromatic isocyanates having a sulfone bond such as 3,3'-diisocyanate, 4,4'-dicyclodiphenylsulfone-3,3'-diisocyanate, 4-methyl-3-isocyanatophenylsulfonyl-4 Aromatic isocyanates having a sulfonic acid ester bond, such as' -isocyanatophenol ester and 4-methoxy-3-isocyanatophenylsulfonyl-4'-isocyanatophenol ester, 4-methyl-3-isocyanatophenylsulfonylanilide- 3'-methyl-4'-isocyanate, diphenylsulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-methoxyphenylsulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3 -Isocyanatophenylsulfonylanilide-4-methyl And aromatic polyisocyanates such as aromatic isocyanates having a sulfonic acid amide bond such as -3'-isocyanate. Moreover, a sulfur-containing heterocyclic compound such as thiophene-2,5-diisocyanate, and other 1,4-dithiane-2,5-diisocyanate are also exemplified.

Furthermore, can be applied to the isocyanate compound having a Isochioshia Na preparative group, such as 1-isocyanato-3-isothiocyanato-propane, 1-isocyanato-5-isothiocyanato-pentane, 1-isocyanato -
Aliphatic or alicyclic compounds such as 6-isothiocyanatohexane, isothiocyanatocarbonyl isocyanate, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3 Aromatic compounds such as isocyanato-1-isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, and 4-isocyanato-
Compounds containing a sulfur atom in addition to an isothiocyanato group such as 4'-isothiocyanatodiphenyl sulfide and 2-isocyanato-2'-isothiocyanatodiethyl disulfide are exemplified.

In the method for stabilizing an isocyanate compound according to the present invention, the isocyanate compound may be used in an amount of 10 to 5000 p.
Regarding the addition method when adding phenol of pm,
No special measures need to be taken. However, it is preferable to adjust the amount to be added depending on the type and storage period of the target isocyanate compound, storage method, storage atmosphere, and the like.

The stabilized isocyanate composition of the present invention may be used in combination with a known stabilizer used for an isocyanate compound, as long as the effect of the present invention is not impaired. The stabilized isocyanate composition of the present invention exhibits favorable storage stability even at a high temperature condition such as 80 ° C., as shown in Examples described later.

As described above, the isocyanate composition to which the phenol of the present invention is added in an amount of 10 to 5000 ppm suppresses coloring due to aging and white turbidity due to self-polymerization and exhibits excellent storage stability. In particular, phenol exhibits an outstanding stabilizing effect on unstable xylylene diisocyanate as compared with known stabilizers. Further, as shown in Table 2, the decrease in purity of the isocyanate compound is also suppressed by the addition of phenol, and the effect is remarkable with respect to the aliphatic polyisocyanate.

[0013]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Examples 1-3 and Comparative Examples 1-31 m-xylylene diisocyanate (purity 99.8%, hydrolyzable chlorine 0.010%, 5.1 of JIS K1556)
The stabilizer shown in Table 1 was added to APHA 10), and the glass container was replaced with nitrogen and sealed and stored at 20 ° C. The presence or absence of cloudiness and APHA were measured visually every week, and the results were as shown in Table 1. The storage test was stopped when visual turbidity or APHA exceeded 20, and the test period was a maximum of 24 weeks.

[0014]

[Table 1]

[0015]

[Table 2]

Examples 4 to 12 and Comparative Examples 32 to 40 Samples of 500 ppm phenol and 500 ppm phenol with respect to various isocyanate compounds of APHA10 having a purity of 99.8% or more were prepared by using a glass container, nitrogen replacement, and sealing. Stored under the condition of ° C. Each day, 1 g was sampled and dissolved in 20 ml of toluene, and the number of days until cloudiness was observed was measured. For those for which no cloudiness was observed for 6 days or more, APHA and purity were measured on the 6th day,
The test period was up to 10 days. The results are shown in Table 2.

[0017]

[Table 3]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 323/45 C07C 323/45 331/20 331/20 (56) References JP-A-6-92925 (JP, A) (58) 6) Fields investigated (Int. Cl. ⁶ , DB name) C07C 265/04 C07C 263/18 C07C 265/12 C07C 265/14 C07C 317/26 C07C 323/45 C07C 331/20 CA (STN)

Claims (6)

(57) [Claims] 1. The method according to claim 1, wherein said isocyanate compound is 10 to 5000.
A method for stabilizing an isocyanate compound, which comprises adding ppm of phenol. 2. The method according to claim 1, wherein the isocyanate compound is an aliphatic polyisocyanate. 3. The method according to claim 2, wherein the aliphatic polyisocyanate is xylylene diisocyanate. 4. A composition comprising 10 to 5000 ppm of phenol and 99.5 to 99.999% of an isocyanate compound.
An isocyanate composition in which yellowing and cloudiness are suppressed. 5. The isocyanate composition according to claim 4, wherein the isocyanate compound is an aliphatic polyisocyanate. 6. The isocyanate composition according to claim 5, wherein the aliphatic polyisocyanate is xylylene diisocyanate.