JPH06145280A - Production of modified polyisocyanurate foam - Google Patents

Abstract

PURPOSE:To easily obtain the subject foam having high expansion ratio in a short time without using a volatile foaming agent such as fluorocarbon by reacting an organic polyisocyanate with a polyol and water in the presence of three specific kinds of catalysts. CONSTITUTION:The objective foam is produced by reacting an organic polyisocyanate with a polyol and water as a foaming agent in the presence of (A) a trimerizing catalyst for isocyanate (preferably the compound of formula I, etc.), (B) a carbodiimidizing catalyst consisting of a phospholene oxide of formula II or formula III (R1 is alkyl, phenyl, etc.; R2 to R7 are H, Cl, etc.) (preferably 3-methyl-1-phenyl-2-phospholene oxide, etc.) and (C) a urethane-urea forming catalyst consisting of a tertiary amine (preferably the compound of formula IV, etc.) satisfying the formula K2/K1>=1 wherein K1 is catalytic constant of the reaction of NCO with alcoholic OH at 30 deg.C and K2 is catalytic constant of the reaction of NCO with water.

Description

Detailed Description of the Invention

The present invention relates to a method for producing a modified polyisocyanurate foam, and more particularly to a modified polyisocyanate suitable for continuous production of laminated boards and siding boards, which does not require the use of an evaporative foaming agent such as Freon. It relates to a method for producing a nurate foam.

A method for producing a modified polyisocyanurate foam by using an organic polyisocyanate and a polyol together with an isocyanurate-forming catalyst and a carbodiimidating catalyst in the presence of a foaming agent is known (for example, Japanese Patent Publication No. 46-4).
591). Further, a modified polyisocyanurate foam is produced by using an organic polyisocyanate and a polyol together with methanol, furfuryl alcohol or phosfluorene oxide (carbodiimidization catalyst) and an alkali metal salt (trimerization catalyst) in the presence of a foaming agent. A method of doing so has also been proposed (see US Pat. No. 4,166,164, JP-A-2-245013). Furthermore, JP-A-50-95397 and JP-A-50-12499.
7, JP-A-51-75799, JP-A-51
-76395, JP-A-51-80393,
JP-A-51-102098 discloses a method of obtaining a modified polyisocyanate foam using a tertiary amine and an alcohol such as amino alcohol as a cocatalyst, and a method of catalytically using Mannich polyol, phosphorus-containing polyol and the like. ,
A method using S-triazine and phenol has been reported.

In the production of these (modified) polyisocyanurate foams, it is general to use freon as a blowing agent, but freon has a problem of ozone layer depletion, and freon will not be used in the near future. It is in the direction of being totally banned. As a substitute for CFCs, a method of using carbon dioxide gas generated by the reaction of water and isocyanate can be considered, but if the amount of water used is increased to reduce the density of the foam (obtain high foam). , Generated urea bond (-NC
O + H ₂ O → -NH ₂ + CO ₂ ↑, -NH ₂ + OCN- →-
There is a problem that the amount of NHCONH-) becomes large, the strength is low, the dimensional stability is poor, and only a foam having poor adhesion to the face material can be obtained. Further, in the above-mentioned method of using a conventional isocyanurate-forming catalyst and a carbodiimidizing catalyst in combination, when water is used as a foaming agent, it is difficult to control the reaction, and it is particularly required for a laminate board or a siding board. It is not possible to produce cured high foams with densities below 40 kg / m ³ at economical rates.

The inventors of the present invention have prepared a highly foamed modified polyisocyanurate foam having a density of 40 kg / m ³ or less from an organic polyisocyanate and a polyol without using an evaporative foaming agent typified by Freon. As a result of extensive studies on industrially applicable methods that can be produced, this time, when a certain combination of a specific trimerization catalyst and a carbodiimidization catalyst is used together with water, the polyisocyanate is trimerized. The reaction and carbodiimidization reaction, the reaction between water and polyisocyanate, etc. proceed rapidly in a well-balanced manner, and even without using an evaporative blowing agent such as CFC, 4
It was found that a modified polyisocyanurate foam having a low density of 0 kg / m ³ or less can be obtained in a short time, and the present invention has been completed.

Thus, according to the present invention, an organic polyisocyanate, a polyol and water are added to (a) an isocyanate trimerization catalyst and (b) a formula.

[0006]

[Chemical 2]

In the formula, R ₁ represents a substituted or unsubstituted alkyl, phenyl, naphthyl or benzyl group,
_{R 2, R 3, R 4} , R 5, R 6 and R ₇ are each H, an alkyl group of Cl or C ₁ -C _4, in carbodiimidization catalyst and consisting of phosphonium alkylene oxide represented (c) Urethane composed of a tertiary amine having a ratio K ₂ / K ₁ of the catalyst constant K ₁ in the reaction between an isocyanate group and an alcoholic hydroxyl group at 30 ° C. and the catalyst constant K ₂ in the reaction between an isocyanate group and water is 1 or more. -A method for producing a modified polyisocyanurate foam characterized by reacting in the presence of a urea catalyst.

The present invention will be described in more detail below.

The organic polyisocyanate used as a raw material in the method of the present invention may be of any type such as an aliphatic type, an alicyclic type, an aromatic type and a mixed type thereof. Those used in the production of polyurethane and polyisocyanurate can be similarly used. Specifically, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
Aromatic diisocyanates such as crude tolylene diisocyanate, methylene diphenyl diisocyanate and crude methylene diphenyl diisocyanate; aromatic triisocyanates such as 4,4 ′, 4 ″ -triphenylmethane triisocyanate and 2,4,6-tolylene triisocyanate Isocyanate;
4,4'-Dimethyldiphenylmethane-2,2'-5,5'-
Aromatic tetraisocyanates such as tetraisocyanate; Aliphatic isocyanates such as hexamethylene-1,6-diisocyanate; Alicyclic isocyanates such as hydrogenated methylene diphenyl diisocyanate;
-Phenylene diisocyanate, naphthylene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, 4,4'-biphenylene diisocyanate, 3,
Examples thereof include 3'-dimethoxy-4,4'-biphenyldiisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, and among them, 2,4-tolylene diisocyanate and 2,6-tridiisocyanate. Diisocyanate, crude tolylene diisocyanate, methylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate,
Hexamethylene-1,6-diisocyanate, hydrogenated methylenediphenyl diisocyanate and the like are preferable. The above organic polyisocyanates may be used alone or in combination of two or more.

As the polyol, compounds such as polyether polyol, polyester polyol, castor oil, etc., such as aliphatic series, sugar series, aromatic series and mixtures thereof having two or more hydroxyl groups in one molecule. And those conventionally used in the production of polyurethanes can be used as well. Such a polyol may have a low molecular weight or a high molecular weight, and specifically, for example, as a polyether polyol, an alkylene is added to an active hydrogen-containing compound such as polyhydric alcohol, polyhydric phenol, amines and polycarboxylic acid. An example is a compound having a structure to which oxide is added. As polyhydric alcohol,
For example, ethylene glycol, propylene glycol,
Dihydric alcohols such as 1,4-butanediol, 1,6-hexanediol, diethylene glycol and neopentyl glycol; 3 such as pentaerythritol and sucrose
Examples include polyhydric alcohols having a valency or more. Examples of polyvalent phenols include polyvalent phenols such as pyrogallol and hydroquinone, bisphenols such as bisphenol A, and condensation products of phenol and formaldehyde. Amines include ammonia, mono-, di-
-, And alkanolamines such as triethanolamine, isopropanolamine, aminoethylethanolamine; C ₁ -C ₂₂ alkylamines, C ₂ -C ₆
Aromatic amines such as alkylenediamine, polyalkylenepolyamine and aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, diphenyletherdiamine, alicyclic amines such as isophoronediaminecyclohexylenediamine, hetero Examples thereof include cyclic amines. As the polycarboxylic acid, aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, maleic acid and dimer acid, aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid, etc. Two or more of these active hydrogen-containing compounds can be used.
Examples of the alkylene oxide added to the active hydrogen-containing compound include propylene oxide, ethylene oxide, butylene oxide, and tetrahydrofuran. These alkylene oxides may be used alone or in combination of two or more, and in the latter case, they may be block-added or random-added.
Examples of polyester polyols include polyhydric alcohols (the above dihydric alcohols, trimethylolpropane, glycerin, etc.) and carboxylic acids (the above polycarboxylic acids, etc.)
A condensed polyester polyol obtained by reacting with
Examples thereof include a polyester polyol obtained by ring-opening polymerization of a lactone, and a recovered polyester to which an ethylene oxyd adduct of nonylphenol is added. Among these, in particular, aliphatic, aromatic, aliphatic or aromatic amine, pentaerythritol, sucrose polyether polyols; aromatic or aliphatic carboxylic acid polyester polyols; lactone polyester polyols and the like are preferable. Is. The above polyols can be used alone or in combination of two or more kinds.

Polyols such as those mentioned above are generally 20-60.
0 mgKOH / g, preferably 25-500 mgKOH
/ G, more preferably 50 to 400 mg KOH / g.

According to the method of the present invention, a polyisocyanurate foam is produced by reacting the above-mentioned organic polyisocyanate and polyol with water as a foaming agent. In this reaction, the use ratios of the organic polyisocyanate, the polyol and the water are not strictly limited, and can be varied over a wide range depending on the desired physical properties and intended use of the modified polyisocyanurate foam of the final product. However, in general, NCO / O
Isocyanate index shown by H equivalent ratio is 1.8 or more,
It is preferable to mix and react the above components so that the amount is preferably in the range of 1.8 to 5.0, particularly 2.0 to 4.0.

The amount of water used as a foaming agent can be adjusted according to the desired density of the modified polyisocyanurate foam of the final product. In particular, the method of the present invention is characterized in that a product having a high expansion ratio can be produced only with water without using an evaporative foaming agent such as CFC. According to the method of the present invention, for example, , 0.3-1.8% by weight, preferably 0.8-1.5% by weight, based on the total weight of the organic polyisocyanate, polyol and water
By adding an amount of water within the range, the free foam density is generally 40 kg / m ³ or less, and particularly 20 to 35 kg / m ^3.
It is possible to easily manufacture a foam having a high expansion ratio without using an evaporative foaming agent.

The method of the present invention is characterized in that the reaction for producing a modified polyisocyanurate foam from the above-mentioned organic polyisocyanate, polyol and water is carried out by (a) a trimerization catalyst of isocyanate, (b) a formula

[0015]

[Chemical 3]

In the formula, R ₁ represents a substituted or unsubstituted alkyl, phenyl, naphthyl or benzyl group,
_{R 2, R 3, R 4} , R 5, R 6 and R ₇ are each H, an alkyl group of Cl or C ₁ -C _4, in carbodiimidization catalyst and consisting of phosphonium alkylene oxide represented (c) The ratio K ₂ / K ₁ of the catalyst constant K ₁ in the reaction between the isocyanate group and the alcoholic hydroxyl group at 30 ° C. and the catalyst constant K ₂ in the reaction between the isocyanate group and water is 1.0.
The point is to carry out in the presence of the urethane-ureaization catalyst composed of the tertiary amine as described above.

The isocyanate trimerization catalyst used in the method of the present invention is not particularly limited, and as such, it has been conventionally used in the production of polyurethane, polyisocyanurate, polyurethane-polyisocyanurate resin and the like. Known isocyanate trimerization catalysts can likewise be used, examples of which include:

[0018]

[Chemical 4]

[0019]

[Chemical 5]

Among these trimerization catalysts, the above (1),
The compounds of (3), (4), (7) and (9) are preferably used.

On the other hand, in the above formula (I) or (II) used in combination with the trimerization catalyst, the alkyl group represented by R ₁ may be linear or branched. Further, a part of them may be substituted with halogen or another functional group. Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, 2-phenylethyl, 2-chloroethyl, 2-methoxyethyl groups and the like.
The substituted or unsubstituted phenyl, naphthyl and benzyl groups include benzyl, phenyl, o-, p- or m-tolyl, xylyl, naphthyl, 4-diphenyl,
Examples thereof include o-, p- or m-chlorophenyl. R ₁ may preferably be a C ₁ -C ₄ alkyl group, a phenyl group and a benzyl group. Examples of R _{2 to} R ₇ in the formula (II) or (III) include hydrogen, chlorine, methyl, ethyl, propyl, isopropyl and butyl, and hydrogen and methyl are preferable.

The following are specific examples of the phosfluorene oxide of the formula (I) or (II).

1-Methylphosphorus oxide, 3-methyl-1-phenylphosphorus oxide, 3-methyl-
1-benzylphosphorus oxide, 3-methyl-1-ethylphosphorus oxide, 3-methyl-1-ethylphenylphosphorus oxide, 1-phenyl-3- (4-
Methyl-3-pentenyl) phosphorene oxide, 1-
Phenyl-3-chlorophosphylene oxide etc. Among these phosphorene oxides, especially 3-methyl-1-
Phenyl-2-phosfluorene oxide and 3-methyl-1
-Phenyl-3-fuosfluorene oxide is preferably used. These phosfluorene oxides are known per se as catalysts for accelerating the reaction of forming a carbodiimide compound from an organic isocyanate (see, for example, Japanese Patent Publication No. 46-4591).

Further, as the urethane-urea catalyst composed of a tertiary amine used in combination with the above-mentioned trimerization catalyst and phospholene oxide, a urethane-urea catalyst having an excellent urea formation ability rather than a urethane formation ability is selected. That is, when the catalyst constant in the reaction between the isocyanate group and the alcohol group at 30 ° C. is K ₁ and the catalyst constant in the reaction between the isocyanate group and water is K ₂ , the catalyst constant ratio represented by K ₂ / K ₁ is One or more, for example, one within the range of 1 to 5 is used. Here, the catalyst constant is A. Farkes et al. [J. A. C. S. 82 , 642 (1960)]
Can be obtained by Specific examples of the tertiary amine having K ₂ / K ₁ of 1 or more include the following.

[0025]

[Chemical 6]

Among the above-mentioned tertiary amines, especially (1),
The compounds of (2) and (5) are preferably used. When the tertiary amine used has a catalyst constant ratio represented by K ₂ / K ₁ of less than 1, it is usually difficult to obtain a low-density foam due to resinification.

The present invention is an isocyanate trimerization catalyst as a catalyst for producing a modified polyisocyanurate foam from an organic polyisocyanate, a polyol and water.
Phosphorene oxide (carbodiimidization catalyst) of the above formula (I) or (II) and a catalytic constant k in the reaction between an isocyanate group and an alcoholic hydroxyl group at 30 ° C.
Catalytic constant k ₂ in the reaction of ₁ with an isocyanate group and water
Is characterized in that using a specific combination of - (urea catalyst urethanes) ratio k ₂ / k ₁ of the tertiary amine is 1 or more. As a result, the modified polyisocyanurate foam having a high expansion ratio was successfully produced by an industrially applicable method without using a problematic effervescent foaming agent such as CFC.

The respective amounts of isocyanate trimerization catalyst, phosfluorene oxide of formula (I) or (II) (carbodiimidization catalyst) and tertiary amine as urethane-ureaization catalyst are strictly limited. The amount of the trimerization catalyst is generally in the range of 0.2 to 5% by weight, and particularly 0.4 to 3% by weight, based on the weight of the entire reaction system, although it may vary depending on the reaction conditions used. The carbodiimidization catalyst is generally used in an amount of 0.05-5
It is suitable to use it in the range of% by weight, especially 0.1 to 2% by weight. Also, the urethane-urea catalyst is generally less than 0.1.
It is preferably used in the range of 05 to 5% by weight, particularly 0.1 to 3% by weight.

The relative ratio of the trimerization catalyst to the carbodiimidization catalyst or the urethane-ureaization catalyst can be varied within a wide range depending on the desired physical properties of the final product. Weight ratio is generally 0.5
It is preferable to be in the range of 10, especially 2 to 6, and the weight ratio of trimerization catalyst / urethane-ureaization catalyst is 2 to
It is preferably in the range of 30, especially 5 to 20. For example, if the weight ratio of trimerization catalyst / carbodiimidization catalyst is less than 0.5, the carbodiimidization reaction precedes and the trimerization is hindered, so that the curing of the foam tends to be slow, while if it is greater than 10, trimerization occurs. , It tends to be impossible to obtain a foam having a low density. If the weight ratio of trimerization catalyst / urethane-urea catalyst is smaller than 2, the cream time is shortened.
On the other hand, it tends to be unsuitable for production by a continuous line. On the other hand, when it exceeds 30 on the other hand, the progress of the urethane-urea reaction is delayed, and the curing of the foam is likely to be delayed.

Furthermore, in the method of the present invention, if necessary, a foam stabilizer (eg, dimethylsiloxane-polyether block copolymer), a cross-linking agent (eg, ethylene glycol, propylene glycol, 1,4-butanediol). 1,6-hexanediol, diethylene glycol, triethanolamine, diethanolamine,
Ethylenediamine, toluenediamine, etc.), flame retardant (for example, triphenyl phosphite, triethyl phosphite, trimethyl phosphate, cresyl diphenyl phosphate, tris cresyl phosphite, tris chloroethyl phosphite, Tris dichloropropyl phosphonate, tris-β-chloropropyl phosphonate, tris-β-chloroethyl phosphonate, tris (2,3-dibromopropyl) phosphonate, tris (bromocresyl) phosphonate, melamine, antimony trioxide, etc. ), A colorant, and other additives can be used together in the amounts usually used.

As a method for producing a modified polyisocyanurate foam from each of the above components, for example, an isocyanate component composed of the above-mentioned organic polyisocyanate or an isocyanate prepolymer obtained by previously reacting an organic polyisocyanate with a polyol is used. Polyol component obtained by adding a foam stabilizer, a cross-linking agent, a flame retardant, a colorant and other additives to the above-mentioned polyol, water, trimerization catalyst, carbodiimidization catalyst and urethane-ureaization catalyst as necessary. There is a method of preparing and, mixing both components at the time of use, rapidly stirring and mixing, and then foam-curing.

The reaction temperature is usually room temperature, but in some cases, it may be heated up to about 90 ° C.

The present invention will be described in more detail below with reference to examples.

[0034]

【Example】

Examples 1 to 14 and Comparative Examples 1 to 6 25 g of a polyol component prepared by mixing predetermined amounts of polyol, water, catalyst, foam stabilizer and flame retardant shown in Table 1 below (however, in the case of Example 14). Is 50g),
Crude MDI (diphenylmethane diisocyanate) 75 g
(However, 50 g in the case of Example 14) was mixed and stirred with a hand drill (2200 rpm, stirring blade 30 mmφ) for 5 seconds. 80g of the mixture is added to 150x150x15
It was poured into a 0 mm wooden box and the cream time and rise time were measured. The time from the liquid state to the start of foaming was defined as the cream time, and the time when the foaming was completed was defined as the rise time. After 1 minute, the foam was touched to determine the cured state of the surface. About 1 at the center of the cured foam
It was cut into 00 × 100 × 100 mm, and the free foam density was calculated from its volume and weight.

The results are shown in Table 1 below.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

Note (1): Polyol Polyol A: Phthalate ester-based polyol, hydroxyl value = 315 (APP-315 manufactured by Union Carbide) Polyol B: Pentaerythritol-based polyol, hydroxyl value = 410 (410NE manufactured by Asahi Glass Co., Ltd.) Polyol C: Shruger aromatic amine polyol, hydroxyl value = 410 (manufactured by Sanyo Kasei Co., RX-403) Polyol D: Aliphatic polyol, hydroxyl value = 400
(GP-400 manufactured by Sanyo Kasei Co., Ltd.) Polyol E: Aliphatic polyol, hydroxyl value = 28.
5 (manufactured by Sanyo Kasei Co., FA-718)

[0040]

[Chemical 7]

[0041]

[Chemical 8]

3-Methyl-1-phenyl-2-phosfluorene oxide:

[0043]

[Chemical 9]

3-Methyl-1-phenyl-3-phosfluorene oxide:

[0045]

[Chemical 10]

Chiyurine 52: Note (3): Foam stabilizer dimethylsiloxane-polyale block copolymer (SZ-1627 manufactured by Nippon Unicar) Note (4): Flame retardant tris (β-chloropropyl) phosphate (manufactured by Stouf Chemical) Further, the results of measuring the physical properties of the modified polyisocyanurate foam obtained in Example 5 were as shown in Table 2 below.

[0047]

[Table 4]

Example 15 The procedure of Example 1 was applied to an actual siding board continuous production line.

Foaming machine: low-pressure foaming machine (forced stirring system), G
-05 type (made in-house), discharge rate 2.0 kg / min.

Double conveyor: conveyor length 18 m, conveyor speed 10 m / min.

Cutter: Traveling circular saw cutter, cut 2 minutes and 20 seconds after injection.

Molded product: Face material (front) aluminum decorative plate 0.32
mmt, (back) aluminum kraft paper.

Molded product (width) 350 mm, (thickness) 18 m
m.

Temperature conditions: polyol component 25 ° C., isocyanate component 40 ° C., face material temperature 20 ° C., conveyor temperature 7
5 ° C.

When the continuous molding was carried out under the above conditions, there were no problems in filling property, curability and cutting property, and the molded product had no particular problems in warpage, shrinkage, adhesion to paper, aluminum and the like.

Main physical properties of continuously produced product: Form density 38 kg / m ³ Peel strength (paper) 2.2 kg / 10 cm Oxygen index 24 Compressive strength 1.6 kg / cm ²

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 11, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

The present inventors have developed a highly foamed modified polyisocyanurate foam having a density of 40 kg / m ³ or less from an organic polyisocyanate and a polyol without using an evaporative foaming agent represented by Freon. As a result of extensive studies on industrially applicable methods that can be produced, this time, when a certain combination of a specific trimerization catalyst, a carbodiimidization catalyst and a urethane- ureaization catalyst is used with water. , The polyisocyanate trimerization reaction and carbodiimidization reaction, the reaction of water and polyisocyanate, etc. proceed rapidly in a well-balanced manner, and have a low density of 40 k / m ³ or less without using an evaporative blowing agent such as Freon. It was found that the modified polyisocyanurate foam of 1) can be obtained in a short time, and the present invention has been completed.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

As the urethane-urea catalyst comprising a tertiary amine used in combination with the above-mentioned trimerization catalyst and phospholene oxide, a urethane-urea catalyst which is more excellent in ureanization ability than urethanization ability is selected. That is, when the catalyst constant was K ₂ catalytic constants in the reaction of isocyanate groups with alcoholic water acid groups at 30 ° C. in the reaction of K ₁ isocyanate groups and water, the catalyst constant represented by K 2 _/ K ₁ Those having a ratio of 1 or more, for example, those in the range of 1 to 5 are used. Here, the catalyst constant is A. Fark
es et al. [J. A. C. S. 82 , 642 (196
0)]. Specific examples of the tertiary amine having K ₂ / K ₁ of 1 or more include the following.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

The present invention relates to an isocyanate trimerization catalyst as a catalyst for producing a modified polyisocyanurate foam from an organic polyisocyanate, a polyol and water .
Phosphorene oxide (carbodiimidization catalyst) of the above formula (I) or (II) and a catalytic constant k in the reaction between an isocyanate group and an alcoholic hydroxyl group at 30 ° C.
Catalyst constant k in the reaction of ₁ with an isocyanate group and water
Is characterized in that using a specific combination of - (urea catalyst urethanes) ₂ ratio k _{2 /} k ₁ tertiary amine is 1 or more. As a result, the modified polyisocyanurate foam having a high expansion ratio was successfully produced by an industrially applicable method without using a problematic effervescent foaming agent such as CFC.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

[0034]

EXAMPLES Polyol of Examples 1-16 and Comparative Example 1 to 5 The following predetermined amount shown in Table 1, water, catalyst, foam stabilizer and the polyol component 25g, prepared by mixing a flame retardant (However, embodiments In the case of Example 16 , 50 g),
Crude MDI (diphenylmethane diisocyanate) 75 g
(However, 50 g in the case of Example 16 ) was mixed and stirred with a hand drill (2200 rpm, stirring blade 30 mmφ) for 5 seconds. 80g of the mixture is added to 150x150x15
It was poured into a 0 mm wooden box and the cream time and rise time were measured. The time from the liquid state to the start of foaming was defined as the cream time, and the time when the foaming was completed was defined as the rise time. After 1 minute, the foam was touched to determine the cured state of the surface. About 1 at the center of the cured foam
It was cut into 00 × 100 × 100 mm, and the free foam density was calculated from its volume and weight.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

[0046] Note (3): Foam stabilizer dimethylsiloxane - Porie Te le block copolymer (manufactured by Nippon Unicar Co., SZ-1627) Note (4): a flame retardant tris (beta-chloropropyl) phosphates (Stowe Sulfur Chemical Co., Fuairoru PCF) The results of measuring the physical properties of the modified polyisocyanurate foam obtained in Example 5 were as shown in Table 2 below.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

[0048] was applied to the procedure of Example 17 Example 5 to the actual Saide Lee Ngubodo continuous production line.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area C08L 75:04

Claims (8)

[Claims] 1. An organic polyisocyanate, a polyol and water are added to (a) an isocyanate trimerization catalyst, and (b) a compound represented by the formula: In the formula, R ₁ represents a substituted or unsubstituted alkyl, phenyl, naphthyl or benzyl group, and R ₂ , R ₃ ,
R ₄ , R ₅ , R ₆ and R ₇ are each H, Cl or C _{1 to} C ₄
A carbodiimidization catalyst consisting of a phosphorene oxide represented by the formula: and (c) a catalyst constant K ₁ in the reaction between an isocyanate group and an alcoholic hydroxyl group at 30 ° C. and a catalyst in the reaction between the isocyanate group and water. A process for producing a modified polyisocyanurate foam, which comprises reacting in the presence of a urethane-ureaization catalyst composed of a tertiary amine having a constant K ₂ ratio K ₂ / K ₁ of 1 or more. 2. Phosphorene oxide is 3-methyl-
The method according to claim 1, which is 1-phenylphosphoren oxide. 3. The polyol is 20 to 600 mg KOH /
The method according to claim 1, which is at least one polyol having a hydroxyl value within the range of g. 4. The method according to claim 1, wherein the blending ratio of the organic polyisocyanate, the polyol and the water is 1.8 or more in terms of the isocyanate index represented by the NCO / OH equivalent ratio. 5. Water in an amount of 0.3 to 1.8% by weight based on the total weight of the organic polyisocyanate, the polyol and the water.
The method according to claim 1, which is used in an amount of. 6. The free foaming density of the modified polyisocyanurate foam produced is 40 kg / m ³ or less.
The method described. 7. A catalyst system for isocyanate polymerization, which comprises an isocyanate trimerization catalyst, a phosphorene oxide represented by formula (I) or (II) according to claim 1, and a tertiary amine according to claim 1. . 8. A polyol composition comprising a polyol, water and the catalyst system of claim 7.