WO2008023690A1

WO2008023690A1 - Urethane-modified diphenylmethane isocyanate composition

Info

Publication number: WO2008023690A1
Application number: PCT/JP2007/066166
Authority: WO
Inventors: Takeo Takeda; Tomomitsu Yoshihara; Tatsuya Yamaguchi; Kenji Tagami; Yoshiyuki Kanbara
Original assignee: Nippon Polyurethane Industry Co., Ltd.
Priority date: 2006-08-22
Filing date: 2007-08-21
Publication date: 2008-02-28
Also published as: CN101516958A; CN101516958B; JPWO2008023690A1

Abstract

A urethane-modified diphenylmethane isocyanate composition, produced by adding phosphoric acid or a phosphoric ester to an isocyanate resulting from urethane modification of diphenylmethane isocyanate wherein 50 ppm or more of iron is contained. Accordingly, there can be provided a urethane-modified diphenylmethane isocyanate composition that despite containing 50 ppm or more of iron, would inhibit any viscosity increase as long as the time elapsed is within a given period. It is preferred that the iron content be 110 ppm or less. Further, it is preferred that the ratio of viscosity increase of the urethane-modified diphenylmethane isocyanate composition exhibited at the storage for 28 days at 45°C be 15% or below.

Description

Specification

Urethane modified diphenylmethane isocyanate composition Technical Field

[0001] The present invention relates to a urethane-modified diphenylmethane-based isocyanate composition which is a raw material for various polyurethane products.

Background art

[0002] For the production of various polyurethane products, as a raw material, diphenylmethane-based isocyanate that has been modified with urethane by reacting a part of the isocyanate group with a hydroxyl group-containing compound (Rose, urethane-modified diphenylmethane-based isocyanate). Sometimes used. This urethane-modified diphenylmethane isocyanate is preferable as, for example, a rigid urethane foam.

Examples of such urethane-modified diphenylmethane isocyanate are disclosed in Patent Documents 1 and 2 below.

[0004] Patent Document 1: Japanese Patent Publication No. 63-40382

Patent Document 2: Japanese Patent Publication No. 3-55514

Disclosure of the invention

Problems to be solved by the invention

[0005] Diphenylmethane isocyanate produced in a continuous production plant usually does not affect the properties desired for the diphenylmethane isocyanate (eg, reactivity and mechanical properties in the final polyurethane resin). A product with a slight iron content (low iron content) will be produced. However, products that are obtained immediately after regular repairs, etc. of this plant occasionally have high iron content (high iron content).

[0006] When the diphenylmethane-based isocyanate used in Patent Documents 1 and 2 is a high iron content as described above, the urethane-modified diphenylmethane-based isocyanate obtained by urethane modification of the diphenylmethane-based isocyanate is over time ( In particular, when it is easy to thicken (for example, under a constant high temperature of 45 ° C) There was a case.

[0007] Therefore, an object of the present invention is to provide a urethane-modified diphenylmethane isocyanate composition capable of suppressing the thickening within a predetermined period despite containing 50 ppm or more of iron.

Means for solving the problem

[0008] The urethane-modified diphenylmethane isocyanate composition of the present invention is a urethane-modified diphenylamine which has been subjected to urethane modification by reacting a part of the isocyanate group with a hydroxyl group-containing compound using a diphenylmethane isocyanate containing 50 ppm or more of iron as a raw material. It has a composition obtained by adding phosphoric acid or a phosphoric acid ester to a dimethanic isocyanate. The iron content is preferably 1 lOppm or less! /.

[0009] In the urethane-modified diphenylmethane isocyanate composition of the present invention, the phosphorus concentration force S in the phosphate ester is preferably 5% or more in one molecule.

[0010] In the urethane-modified diphenylmethane isocyanate composition of the present invention, it is preferable that the hydroxyl group concentration force S bonded to the phosphorus atom in the phosphate ester is 5% or more in one molecule.

[0011] In the urethane-modified diphenylmethane isocyanate composition of the present invention, the phosphoric acid ester strength polyoxyethylene alkyl ether phosphate, 2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, mono One or more selected from octyl phosphate, bis (2-ethinorehexinole) phosphate, butinorea acid phosphate, and ethenorea acid phosphate are preferable.

[0012] In the urethane-modified diphenylmethane isocyanate composition of the present invention, the viscosity change rate after 28 days at 45 ° C is preferably 15% or less. More preferably, it is 10% or less.

The invention's effect

[0013] According to the above configuration, it is possible to provide a urethane-modified diphenylmethane isocyanate composition capable of suppressing thickening within a predetermined period even though it contains 50 ppm or more of iron. Further, according to the urethane-modified diphenylmethane isocyanate composition of the present invention, for example, when used in rigid urethane foam, the panel physical properties are phosphoric acid or phosphoric acid. This is the same as the case of using les, nales, and low iron products with addition of an acid ester (le, wa, generally used! /, Urethane-modified diphenylmethane isocyanate compositions).

BEST MODE FOR CARRYING OUT THE INVENTION

[0014] The diphenylmethane isocyanate composition according to an embodiment of the present invention will be described below.

[0015] The diphenylmethane-based isocyanate composition according to the present embodiment is a urethane-modified diphenylsilane that is subjected to urethane modification by reacting a part of the isocyanate group in the diphenylmethane-based isocyanate containing 50 ppm or more of iron with a hydroxyl group-containing compound. It has a composition obtained by adding phosphoric acid or phosphoric acid ester to rumethane isocyanate. Examples of the hydroxyl group-containing compound herein include those disclosed in Patent Documents 1 and 2 above.

[0016] The iron content here refers to an iron content present in an isocyanate composition and measured by an analytical method such as atomic absorption analysis. Examples of analysis methods include, for example, a method in which isocyanate is dissolved in a solvent (for example, methylisoptyl ketone), and then iron is detected by flame atomic absorption spectrometry or ICP (inductively coupled plasma) measurement. By using a flameless atomic absorption spectrometer to measure the iron content of an isocyanate composition dissolved in a solvent such as acetone or a solvent, or by ion chromatography of an aqueous solution in which the isocyanate composition has been treated by a known method. One method force ^s to detect the iron.

In the present invention, it is preferably applied to a urethane-modified diphenylmethane isocyanate composition having an iron content of 10 ppm or less. l Diphenylmethane-based isocyanate compositions containing iron in excess of lOppm have a large increase in viscosity after the urethanization reaction, making it difficult to obtain the originally desired urethane-modified diphenylmethane diisocyanate. . In addition, when a urethane reaction is carried out on diphenylmethane isocyanate containing iron in an amount exceeding l lOppm, in some cases, the viscosity rises violently, resulting in a viscosity exceeding the desired level or in the form of a gel. End up.

[0018] Diphenylmethane isocyanate is a mixture (polyphenylene polymer) of binuclear MDI (diphenylmethane diisocyanate) and trinuclear or higher polynuclear (MDI condensate). Tylene polyisocyanate). This diphenylmethane isocyanate can be obtained by converting the amino group of a condensation mixture (polyamine) obtained by the condensation reaction of aniline and formalin to an isocyanate group by phosgenation or the like. In addition, by changing the raw material composition ratio and reaction conditions during the condensation, it is possible to control the composition (nuclear distribution and isomer composition ratio) of the final diphenylmethane isocyanate.

[0019] In addition, diphenylmethane isocyanate is different in reaction conditions and separation conditions such as reaction liquid after conversion to isocyanate group, removal of solvent from the reaction liquid, and bottom liquid obtained by distilling and separating some MDI. It may be a mixture of several kinds. It is also possible to mix MDI with commercially available diphenylmethane isocyanate! / ヽ.

[0020] The ratio of MDI in the diphenylmethane isocyanate according to the present embodiment is 25 to

The power is preferably 70% S, more preferably 35-45%. The ratio of MDI here is a ratio determined from the peak area ratio of MDI by GPC (gel permeation chromatography).

[0021] MDI, which is a binuclear body, is composed of three isomers: 4, 4 'MDI, 2, 2'- MDI, and 2, 4'- MDI. The composition ratio of isomers can be determined from a calibration curve based on the area percentage of each peak obtained by GC (gas chromatography).

[0022] The average number of functional groups of the diphenylmethane isocyanate according to the present embodiment is preferably 2.2 or more, and more preferably 2.2 to 3-1. Further, Isoshianeto group content of diphenylmethane-based Isoshianeto, more preferably preferably be a 27 to 33 weight ^_0/0 device is 27. 5-31. 5% by weight.

[0023] In addition, the acidity of the diphenylmethane-based isocyanate according to the present embodiment is preferably 0.05% by mass or less, more preferably 0.04% by mass or less.

[0024] Examples of phosphoric acid esters include bis (2-ethylhexyl) phosphate, butoxysilane acid phosphate, diisodecyl phosphate, methyl acid phosphate, ethinorea acid phosphate, butinorea acid phosphate, butinorea acid phosphate, dibutyl phosphate , Monobutyl phosphate, monooctyl phosphate, oleore acid phosphate, tetracosyl acid phosphate, 2-ethyl hexyl acid phosphate, isodecino rare acid phosphate, monoisodecinorephosphate, laurinorely Acid, polyoxyethylene lauryl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene alkyl (C12-15) ether phosphate, polyoxyethylene stearyl ether phosphate, polyoxyethylene stearyl ether phosphate, polyoxyethylene Stearyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphoric acid, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene dialkyl phenyl Ether phosphoric acid, polyoxyethylene dialkyl phenyl ether phosphoric acid, polyoxyethylene dialkyl phenyl ether phosphoric acid, polyoxyethylene phenyl ether phosphoric acid Polyoxyethylene anolenoquinole (C 12-14) ether phosphate, polyoxyethylene sec alkyl (C 12-14) ether phosphate, 2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, ethylene glycol Acid phosphate, polyoxyethylene alkyl (C12-14) ether phosphoric acid, polyoxyethylene sec alkyl (C12-14) ether phosphoric acid, polyoxyethylene alkyl (C12) ether phosphoric acid, etc. One or more types are used. These phosphate esters are compounds in which a hydroxyl group, two, or three are directly bonded to the phosphorus atom. These phosphoric esters can be used by selecting only one of them, or can be used as a mixture of two or more.

[0025] In the present invention, from the viewpoint that the desired storage stability can be ensured, phosphoric acid or a series of these phosphoric acid esters having a phosphorus concentration of 5% or more in one molecule is used. It is preferable to select one or more types and include them in the urethane-modified diphenylmethane isocyanate according to this embodiment.

[0026] Further, in the present invention, from the viewpoint that the desired storage stability can be secured, the concentration of the hydroxyl group bonded to the phosphorus atom in phosphoric acid or a series of these phosphoric esters is 5 per molecule. It is preferable to select one or more of those having a concentration of at least% (more preferably at least 10%) and including them in the urethane-modified diphenylmethane isocyanate according to this embodiment.

[0027] Furthermore, in the present invention, phosphoric acid, polyoxyethylene alkyl ether phosphoric acid, 2-ethylhexyl phosphate, di (2 From the viewpoint of the excellent compatibility (homogeneous mixing when added) of diphenylmethane isocyanate, which is preferably used alone or in combination. Alkyl ether phosphoric acid is preferably contained in the urethane-modified diphenylmethane isocyanate according to this embodiment.

[0028] It should be noted that the phosphoric acid ester according to the present invention may be one in which a hydroxyl group is directly bonded to a phosphorus atom and V is mixed with a compound as an accessory component.

[0029] According to the above configuration, it is possible to provide a urethane-modified diphenylmethane isocyanate composition capable of suppressing the increase in viscosity within a predetermined period despite containing 50 ppm or more of iron. In addition, according to the urethane-modified diphenylmethane isocyanate composition of the present invention, for example, even when used as a rigid urethane foam, the panel properties were added with phosphoric acid or phosphoric acid ester, and a low iron content was used. Same as the case.

Example

Next, the present invention will be described using examples.

[0031] The isocyanate group content (hereinafter abbreviated as "NCO content" in the examples and comparative examples described below. In the following table, described as "NCO% (mass%)") is shown below. It measured by the measuring method.

(1) Add approximately 0.5 to the sample to be measured for NCO content.!

(2) Add 20 ml of 0.5 mol / l dibutylamine monochlorobenzene solution to the above Erlenmeyer flask and gently stir for 15 minutes.

(3) Place 100 ml of methanol and 1 drop of bromophenol blue indicator in the above Erlenmeyer flask, and perform back titration on the flask contents using 0.5 mol / l hydrochloric acid standard solution. At this time, the titer of the hydrochloric acid standard solution required for the titration of the sample is A (ml).

(4) The same operation as in the above (1) to (3) is performed to obtain a “blank” sample. The blank is titrated in the same manner as (3) above. At this time, the titration volume of the hydrochloric acid standard solution required for the blank titration is B (ml).

(5) The end point of the titration is the point where the indigo color of the bromophenol blue indicator turns yellow . (6) Calculate the NCO content using the following formula.

NCO content (mass%) = [(B-A) X42X0.5Xf] X 100+ (S X 1000)

A: Titration of 0.5 mol / l hydrochloric acid standard solution required for titration of sample (ml)

B: Titration of 0.5 mol / l hydrochloric acid standard solution required for blank titration (ml)

f: Factor of 0.5 mol / l hydrochloric acid standard solution

S: Sampling amount (g)

Respectively.

[0032] Viscosities of Examples and Comparative Examples described below were measured by a method according to JI SK2283 (1980) using a Cannon Fenceke viscometer. The outline of the measurement method is as follows.

(1) Place a sample whose viscosity is to be adjusted to 25 ° C in a Canon Fenceke viscometer and place it vertically in a constant temperature bath adjusted to 25 ° C for a predetermined time.

(2) After the sample in the viscometer reaches the specified temperature, measure the outflow time t (s) by the method shown in JIS K2283 (1980).

(3) Calculate the kinematic viscosity by the following formula

V = CXt

In the above formula,

V: Kinematic viscosity (cSt) {mm ² / s}

C: Viscometer constant (cSt / s) {mmVs ² }

t: Outflow time (s)

Respectively.

(4) Calculate the static viscosity (mPa's) by multiplying the kinematic viscosity obtained by the above equation by the specific gravity of the sample.

[0033] (Example ;! to 3)

As the diphenylmethane isocyanate used in Examples 1 to 3, the following diphenylmethane isocyanate was prepared.

Iron content = 75ppm

Acidity = 0.015 mass%

MDI (binuclear) peak area ratio = 43.5% * MDI peak area ratio was calculated from GPC.

4, Α 'MDI content in MDI (binuclear body) = 99%

* 4,4 '—MDI content in MDI was calculated from GC.

Isocyanate group content = 30.6 mass%

[0034] The iron content is determined by diluting and dissolving the sample to be measured in methylisoptyl ketone (dilution ratio: 70 to 150 times), and then flame atomic absorption photometer (manufactured by Shimadzu Corporation) 6800) was measured by the standard addition method.

[0035] The inside of a 2 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen seal tube, and a cooling tube was purged with nitrogen. To this, 1,800 g of the above-mentioned diphenylmethane isocyanate was charged, and the temperature rise and stirring of the liquid was started. When the liquid temperature reached 75 ° C, 56 g of “Reosolve PE M—700N (trade name, polyethylene glycol monomethyl ether, number of active hydrogen-containing groups = 1, number average molecular weight = 700, manufactured by Lion Corporation)” was added. and, under a nitrogen atmosphere, and reacted by stirring and mixing for 3 hours at 80 ° C, a urethane-modified Jifue two Rume Tan system Isoshianeto (Isoshianeto group content = 29.2 wt ^_0/0, the viscosity at 25 ° C = 187mPa's) was obtained.

[0036] Next, 500 g of urethane-modified diphenylmethane isocyanate extracted from this was added as an additive to “Phosphanol RA-600 (trade name, polyoxyethylene alkyl ether phosphate, estimated phosphorus concentration = 6%, Toho Chemical Industries, Ltd.) (Made by Co., Ltd.) ”and a urethane-modified diphenylmethane isocyanate composition (Example 1) prepared in the same manner as in Example 1 and“ Phosphanol RA-600 ”as an additive. A urethane-modified diphenylmethane isocyanate composition (Example 2) prepared by adding OOppm and “phosphoric acid (89% phosphoric acid (trade name, phosphoric acid 89% aqueous solution, phosphorus concentration = 28%, bonded to phosphorus atom) A urethane-modified difurethane isocyanate composition (Example 3) prepared by adding 25 ppm of hydroxyl group concentration = 46%, manufactured by Rasa Industry Co., Ltd.) was prepared. For each of the urethane-modified diphenylmethane isocyanate compositions according to these examples;! To 3, the NCO content and viscosity change over time (from 0 weeks to 4 weeks every week) were set to 45 ° C by the methods described above. —Measured in a constant atmosphere. The results for Examples 1 to 3 are shown in the following Tables 1 to 3 in order.

[0037] [Table 1] NCO% Change rate Viscosity Change rate

0 weeks 29.2 0% 185 0%

1 week 28.9 -1% 188 2%

2 weeks 28.9 -1% 193 4%

3 weeks 28.9 -1% 198 7%

4 weeks 28.9 -1% 194 5%

[Table 2]

[Table 3]

(Comparative Example 1, Example 4)

The urethane-modified diphenylmethane isocyanate used in Examples 1 to 3 (without any additives) (Comparative Example 1) and the urethane-modified diphenylmethane isocyanate similar to that used in Examples 1 to 3 “JP—508 (trade name, 2-ethyl hexyl phosphate (mono: di = 1: 1 (estimated molar ratio)), estimated phosphorus concentration = 11%, bonded to phosphorus atom! /, Hydroxyl group Estimated concentration = 11%, manufactured by Johoku Chemical Industry Co., Ltd.) ”and the urethane-modified diphenylmethane isocyanate composition (Example 4) prepared by adding 50 ppm! /, The same method as in Examples 1-3 NCO content and viscosity change over time (0 to 4 weeks) Was measured at 45 ° C in a constant atmosphere. The results for Comparative Example 1 and Example 4 are shown in the following Tables 4 and 5 in order.

[0039] [Table 4]

[Table 5]

[0040] From Tables 4 and 5, the sample of Example 4 has a tendency to suppress the rate of change in viscosity compared to Comparative Example 1. Moreover, it can be seen from Tables:! To 3 that Examples:! To 3 are suppressed within an allowable range even after 4 weeks, although they are thickened.

[0041] (Examples 5 to 7)

The diphenylmethane isocyanate shown below was prepared as the diphenylmethane isocyanate used in Examples 5-7.

Iron content = 101ppm

Acidity = 0.015 mass%

MDI (dinuclear) peak area ratio = 42.8%

* MDI peak area ratio was calculated from GPC.

4, 4 'MDI content in MDI (binuclear body) = 99%

* 4, A '— MDI content in MDI was calculated from GC. Isocyanate group content = 30.6 mass%

[0042] The inside of a 2 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen seal tube, and a cooling tube was purged with nitrogen. To this, 1,800 g of the above-mentioned diphenylmethane isocyanate was charged, and the temperature rise and stirring of the liquid was started. When the liquid temperature reached 75 ° C, 56 g of “Reosolve PE M-700N” was added and reacted by stirring and mixing at 80 ° C for 3 hours under a nitrogen atmosphere, and urethane-modified diphenylmethane isocyanate (isocyanate). Group content = 29.1% by weight, viscosity at 25 ° C. = 198 mPa ′s).

[0043] Next, a urethane-modified diphenylenomethane isocyanate composition (Example 5) prepared by adding 50 ppm of "phosphanol RA-600" as an additive to 500 g of urethane-modified diphenylmethane isocyanate collected from this In the same manner as in Example 1, a urethane-modified diphenylmethane isocyanate composition (Example 6) prepared by adding lOOppm of “Phosphanol RA-600” as an additive and urethane prepared by adding 25 ppm of phosphoric acid. A modified diphenylmethane-based isocyanate composition (Example 7) was prepared. For each of the urethane-modified diphenylmethane isocyanate compositions according to Examples 5 to 7, in the same manner as in Examples 1 to 3, the NC content and viscosity change rate over time (from 0 weeks to 4 weeks every week) ) Was measured at 45 ° C in a constant atmosphere. The results for Examples 5 to 7 are shown in order in Tables 6 to 8 below.

[0044] [Table 6]

[Table 7] NCO% Change rate Viscosity Change rate

0 weeks 29.1 0% 194 0%

1 week 29.1 0% 198 2%

2 weeks 29.0 -1% 202 4%

3 weeks 28.9 -1% 203 5%

4 weeks 28.9 -1% 206 6%

[Table 8]

[0045] (Comparative Example 2, Example 8)

The urethane-modified diphenylmethane isocyanate used in Examples 5 to 7 (without additives) (Comparative Example 2) and the urethane-modified diphenylmethane isocyanate similar to that used in Examples 5 to 7 About JP-508 added with 50ppm (Example 8), change rate over time of NCO content and viscosity in the same way as Example;! Was measured at 45 ° C. in a constant atmosphere. The results for Comparative Example 2 and Example 8 are shown in the following Tables 9 and 10 in order.

[0046] [Table 9]

NCO% Change rate Viscosity Change rate

0 weeks 29.1 0% 198 0%

1 week 28.9 -1% 254 28%

2 weeks 28.4-2% 304 54%

3 weeks 28.3 -3% 349 76%

4 weeks 28.2 -3% 415 1 10% [Table 10]

From Tables 9 and 10, it can be seen that Example 8 has a tendency to suppress the rate of change in viscosity compared to Comparative Example 2. In addition, from Tables 6 to 8, Examples 5 to 7 are thickened, but are suppressed within an allowable range even after 4 weeks! The

[0048] (Examples 9 and 10)

The diphenylmethane isocyanate shown below was prepared as the diphenylmethane isocyanate used in Examples 9 and 10.

Iron content = 102ppm

Acidity = 0.014 mass%

MDI (dinuclear) peak area ratio = 42.8%

* MDI peak area ratio was calculated from GPC.

4, 4 'MDI content in MDI (binuclear body) = 99%

* 4,4 '—MDI content in MDI was calculated from GC.

Isocyanate group content = 30.6 mass%

[0049] The inside of a 2 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen seal tube, and a cooling tube was purged with nitrogen. To this, 500 g of the above-mentioned diphenylmethane isocyanate was charged, and the liquid was heated and stirred. When the liquid temperature reached 75 ° C, 56g of “Reosolve PEM — 700N” was added and reacted by stirring and mixing at 80 ° C for 3 hours under a nitrogen atmosphere, resulting in urethane-modified difurmethane-based isocyanate (isocyanate). Group content = 28.9 mass%, viscosity at 25 ° C. = 198 mPa ′s).

[0050] Next, the urethane-modified diphenylmethane prepared by adding 50 ppm of "Phosphanol RA-600" as an additive to the urethane-modified diphenylmethane isocyanate obtained from this. A rumethane-based isocyanate composition (Example 9) and a urethane-modified diphenylmethane-based isocyanate composition (Example 10) prepared by adding 25 ppm of phosphoric acid were prepared. With respect to each urethane-modified diphenylmethane isocyanate composition according to Examples 7 and 8, in the same manner as in Examples;! To 3, N0 content and rate of change over time (0 weeks to 4 weeks every week) Was measured at 45 ° C in a constant atmosphere. The results for Examples 9 and 10 are shown in the following Tables 11 and 12 in order.

11]

[Table 12]

[0052] (Comparative Example 3, Example 11)

The urethane-modified diphenylmethane isocyanate used in Examples 9 and 10 itself (without additives) (Comparative Example 3) and the urethane-modified diphenylmethane isocyanate similar to that used in Examples 4 to 6 About JP-508 with 50 ppm added (Example 1 1), change over time in NCO content and viscosity (0 weeks to 4 weeks every week) in the same manner as in Examples 1 to 3 Was measured at 45 ° C. in a constant atmosphere. The results for Comparative Example 1 and Example 11 are shown in the following Tables 13 and 14 in order.

[0053] [Table 13] NCO% Change rate Viscosity Change rate

0 weeks 29.0 0% 198 0%

1 week ^ j 28.7 -1% 254 28%

2 weeks 28.5 -2% 300 52%

3 weeks 28.2 -3% 382 93%

4 weeks 27.1 1 6% 1022 416%

[Table 14]

[0054] From Table 13, it can be seen that the sample of Comparative Example 3 tends to increase in viscosity with time. On the other hand, from Tables 11 and 12, it can be seen that those of Examples 9 and 10 are suppressed within an allowable range even after 4 weeks although they are thickened. Also, from Table 14, it can be seen that Example 11 has a tendency to suppress the rate of change in viscosity compared to Comparative Example 3.

[0055] (Comparative Example 4, Examples 12 to 14)

The diphenylmethane isocyanate shown below was prepared as the diphenylmethane isocyanate used in Comparative Example 4 and Examples 12 to 14;

Iron content = 155ppm

Acidity = 0.015 mass%

MDI (dinuclear) peak area ratio = 43.3%

* MDI peak area ratio was calculated from GPC.

4, 4 'MDI content in MDI (binuclear body) = 99%

* 4,4 '—MDI content in MDI was calculated from GC.

Isocyanate group content = 30.5 mass%

[0056] Inside a 2L 4-neck flask equipped with a thermometer, stirrer, nitrogen seal tube, and cooling tube Was replaced with nitrogen. To this, 1,800 g of the above-mentioned diphenylmethane isocyanate was charged, and the temperature rise and stirring of the liquid was started. When the liquid temperature reached 75 ° C, 56 g of “Reosolve PE M-700N” was added and reacted by stirring and mixing at 80 ° C for 3 hours under a nitrogen atmosphere, and urethane-modified diphenylmethane isocyanate (isocyanate). Group content = 28.9 mass%, viscosity at 25 ° C. = 198 mPa ′s).

[0057] Next, the urethane-modified diphenylmethane isocyanate (collected with no additive) collected from this (Comparative Example 4) and the above-mentioned diphenylmethane isocyanate ("Phosphanol RA-600") as an additive. Modified diphenylmethane isocyanate composition (Example 12) prepared by adding 50 ppm of styrene and urethane-modified diphenylmethane isocyanate composition prepared by adding 50 ppm of “JP-508” as an additive (Example 13) And a urethane-modified diphenylmethane isocyanate composition (Example 14) prepared by adding 25 ppm of phosphoric acid. With respect to each urethane-modified diphenylmethane isocyanate composition according to Comparative Example 4 and Examples 12 to 14; Was measured at 45 ° C in a constant atmosphere. The results for Comparative Example 4 and Examples 12 to 14 are shown in the following Tables 15 to 18 in order.

[0058] [Table 15]

NCO% Change rate Viscosity Change rate

0 weeks 28.4 0% 345 0%

1 week 28.3 0% 375 9%

2 weeks 28.2 -1% 378 10%

3 weeks 28.1 -1% 433 26%

4 weeks 27.5 —3% 669 94%

[Table 17]

[Table 18]

[0059] From Table 15, it can be seen that Comparative Example 4 tends to increase in viscosity with time. On the other hand, it can be seen that Tables 16 to 18 and those of Examples 12 to 14 tend to suppress the rate of change in viscosity as compared with Comparative Example 4.

[0060] (Comparative Example 5, Examples 15 to 18)

As the diphenylmethane isocyanate used in Comparative Example 5 and Examples 15 to 18, the following diphenylmethane isocyanate was prepared.

Iron content = 104ppm

Acidity = 0.015 mass% MDI (dinuclear) peak area ratio = 43.3%

* MDI peak area ratio was calculated from GPC.

4, Α 'MDI content in MDI (binuclear body) = 99%

* 4,4'-MDI content in MDI was calculated from GC.

Isocyanate group content = 30.5 mass%

[0061] The inside of a 2 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen seal tube, and a cooling tube was purged with nitrogen. To this, 1,800 g of the above-mentioned diphenylmethane isocyanate was charged, and the temperature rise and stirring of the liquid was started. When the liquid temperature reached 75 ° C, 56 g of “Reosolve PE M-700N” was added and reacted by stirring and mixing at 80 ° C for 3 hours under a nitrogen atmosphere, and urethane-modified diphenylmethane isocyanate (isocyanate). Group content = 28.9% by weight, viscosity at 25 ° C. = 164 mPa ′s).

[0062] Next, urethane-modified diphenylmethane-based isocyanate itself (without any additives) (Comparative Example 5) and 500 g of the above-mentioned diphenylmethane-based isocyanate were added as additives to JP-502 (trade name, et al.). Till acid phosphate (mono: di = 1: 1 (estimated molar ratio)), estimated phosphorus concentration = 22%, estimated hydroxyl group concentration to phosphorus atom = 19%, manufactured by Johoku Chemical Co., Ltd.) Urethane-modified diphenylmethane-based isocyanate composition (Example 15) prepared by adding 50 ppm and “JP—504 (trade name, butyl acid phosphate (mono: di = 1: 1 (estimated molar ratio)) as an additive. ), Estimated phosphorus concentration = 17%, estimated concentration of hydroxyl group bound to phosphorus atom = 15%, manufactured by Johoku Chemical Co., Ltd.)) 50 ppm of the nate composition (Example 16) and “monooctyl phosphate (phosphorus concentration = 16%, hydroxyl group concentration bound to phosphorus atom = 16%)” as an additive were prepared. Urethane-modified diphenylmethane isocyanate composition (Example 17) and additive “bis (2-ethylhexyl) phosphate (phosphorus concentration = 10%, hydroxyl group bound to phosphorus atom = 5%)” A urethane-modified diphenylmethane isocyanate composition (Example 18) prepared by adding 50 ppm and a urethane-modified diphenylmethane isocyanate composition (Example 19) prepared by adding 50 ppm of phosphoric acid. . For each of the urethane-modified diphenylmethane isocyanate compositions according to Comparative Example 5 and Examples 15 to 19; The change rate of viscosity with time (from 0 weeks to 4 weeks every week) was measured at 45 ° C in a constant atmosphere. The results for Comparative Example 5 and Examples 15 to 19 are shown in the following Tables 19 to 24 in order.

[Table 19]

[Table 22] Viscosity change rate

0 weeks 164 0%

1 week 1 64 0%

2 weeks 1 74 6%

3 weeks 1 76 7%

4 weeks 1 78 9%

[Table 23]

[Table 24]

[0064] From Table 19, it can be seen that the sample of Comparative Example 5 tends to increase in viscosity with time. On the other hand, Tables 20 to 24, et al. Examples 15 to 19 show that although they are thickened, they are suppressed within an allowable range even after 4 weeks.

[0065] From each of the above Examples and Comparative Examples, diphenylmethane-based isocyanate containing iron It can be seen that the present invention, which is a urethane-modified diphenylmethane isocyanate composition obtained from the sulfonate, can suppress thickening within a predetermined period.

Note that the present invention can be modified in design without departing from the scope of the claims, and is not limited to the above-described embodiments and examples.

Industrial applicability

[0067] The urethane-modified diphenylmethane isocyanate composition of the present invention can be applied to the field of rigid polyurethane foam. It can also be applied to fields such as flexible or semi-rigid polyurethane foams, paints, adhesives and elastomers.

Claims

The scope of the claims

[1] A urethane-modified diphenylmethane characterized by having a composition obtained by adding phosphoric acid or a phosphoric acid ester to an isocyanate obtained by urethane-modifying diphenylmethane-based isocyanate containing 50 ppm or more of iron Isocyanate composition.

[2] The urethane-modified diphenylmethane isocyanate composition according to [1], wherein the iron content is lO ppm or less.

[3] The urethane-modified diphenylmethane isocyanate composition according to claim 1 or 2, wherein the phosphorus concentration in the phosphate ester is 5% or more in one molecule.

[4] The urethane-modified diphenyl methane isocyanate composition according to claim 1 or 2, wherein the concentration of hydroxyl groups bonded to phosphorus atoms in the phosphate ester is 5% or more in one molecule. .

[5] Phosphoric ester strength Polyoxyethylene alkyl ether phosphoric acid, 2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, monooctyl phosphate, bis (2-ethylhexyl) 3. The urethane-modified diphenylmethane isocyanate composition according to claim 1 or 2, wherein the urethane-modified diphenylmethane isocyanate composition is one or more selected from among phosphate, butyl acid phosphate, and ethyl acid phosphate.

[6] Urethane-modified diphenylmethane isocyanate according to any one of claims 1 to 5, wherein the rate of change in viscosity after 28 days at 45 ° C is 15% or less. Composition.