JPS62156117A - Production of polyisocyanurate foam - Google Patents

Abstract

PURPOSE:To obtain the titled foam having high heat-resistance and flame- retardance and low smoking tendency and brittlenes, by using plural kinds of specific trimerization catalysts and carrying out trimerization and foaming of an organic polyiso-cyanate and a compound containing active hydrogen atom. CONSTITUTION:(A) An organic polyisocyanate (e.g. ethylene diisocyanate) is mixed with (B) a compound containing active hydrogen atom (e.g. ethylene glycol) at an NCO/OH equivalent ratio of preferably 2-13. The mixture is added with (C) trimerization catalysts consisting of (i) 0.1-20wt% compound containing carbonyl group (e.g. 1-naphthylaldehyde) (based on the component A), (ii) 0.1-20wt% compound containing glycidyl group (based on the component A), (iii) 1-100m-mol of a tertiary amine compound (based on 100pts.wt. of the component A) and (iv) 0.05-10wt% aziridine compound (based on the component A). The composition is further added with a foaming agent and foamed to obtain the objective foam.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention: The present invention relates to the production of urethane-modified polyin cyanurate foams having heat resistance, flame retardancy, low smoke emission, and low drying properties.

BACKGROUND ART Conventionally, polyisocyanurate foams have been produced by using trimerization catalysts in combination with polyisocyanates in order to produce foams having flame resistance and low smoke-emitting properties. Due to its excellent properties, polyisocyanurate foam has been widely used as heat insulating materials, lightweight structural materials, sound absorbing materials, etc. In addition, by introducing an isocyanurate ring into the polyurethane crosslinking, it exhibits high heat resistance, hydrolysis resistance, and further dimensional stability. Unfortunately, however, its use is limited because of the large amount of smoke produced during combustion during high-temperature heating.

For this reason, studies are being conducted to improve flame retardancy by adding flame retardants such as inorganic hydrous compounds to urethane foam. However, although this method provides good flame retardancy, it has the disadvantage that the smoke density increases over time as the foam burns. Further, there is a drawback that mechanical properties are also deteriorated.

If a larger amount is used, there is a problem in the storage stability of the reaction mixture, and it is not economical.

In addition, in order to impart high flame retardancy to the foam, attempts have been made to increase the index (Neo10H ratio) to contain incyanurate rings at a high concentration and to have the heat resistance and flame resistance inherent to isocyanurate bonds. However, with conventional trimerization catalysts, there is a limit to how high the N (:! It also had the disadvantage of exploding when exposed to flame.It also had the disadvantage of being extremely brittle, which is a characteristic inherent to isocyanurate bonds.

Until now, urethane-modified isocyanurate 7 ohm has a high N
It was considered that manufacturing with the C010H ratio was relatively difficult. That is, the reason for this is that while the urethanization reaction is rapidly achieved in the presence of an appropriate catalyst, the incyanurate reaction is quite difficult to carry out uniformly, especially within the time constraints during each forming reaction process. This is because, in the foam manufacturing process, these two different reaction mechanisms are not formed to fully satisfy the 7-ohm characteristic. Therefore, it is necessary to select a catalyst to carry out the urethanization and incyanuration reactions effectively and uniformly at the same time. When exposed below, it tended to decompose easily. This tendency is particularly seen in alkali metal salt catalysts, and the foam itself is also cancer-repellent (F
riability).

When producing a foam that can be used as a quasi-nonflammable material, conventional catalysts have not been able to eliminate both deformation and cracking during combustion, and have also been unable to reduce smoke generated during forced combustion. Therefore, no foam with excellent flame retardant and heat resistance has been found in the past, and simply adding commonly known flame retardants such as halogen compounds, phosphorus compounds, and antimony compounds is far from meeting the standards for passing the above flame retardant test. There wasn't.

Problems to be solved by the invention: As mentioned above, each of the conventional methods has major drawbacks.
As a result of intensive research in order to solve these problems, the present inventors have found that by trimerizing and foaming organic polyisocyanate in the presence of a specific trimerization catalyst, the present inventors have succeeded in achieving the conventional method without impairing the foam properties. It significantly reduces smoke generation, which had been considered difficult, and at the same time has the characteristics of low brittleness, heat resistance, and high flame retardancy, and is compliant with JISA-1321.
We have developed a method for manufacturing incyanurate foam that passes the second class flame retardant test (quasi-noncombustible material).

Means for solving the problem: That is, the present invention provides a method for trimerization in producing polyin cyanurate foam by adding a trimerization catalyst to a production stock solution containing an organic polyisonanate and an active hydrogen-containing compound as main components. This invention relates to a method for producing a polyisocyanurate foam, characterized in that a combination of four catalysts is used: (1) a carbonyl group-containing compound, (2) a glycidyl group-containing compound, (2) a tertiary amine compound, and (1) an aziridine compound as a catalyst. be.

The production of incyanurate foam according to the method of the present invention can be carried out by conventional foaming means, using additives as necessary when carrying out the above-mentioned method.

Effects of the Invention By using a carzenyl group-containing compound, the incyanurate reaction is promoted, and the foam has a significant effect on smoke generation.

On the other hand, when the N0O10H ratio is high, by using the catalyst system of the present invention, the reaction is carried out smoothly and selectively, so the incyanurate ring content increases, and a foam with flame resistance and thermal stability can be obtained. Therefore, the desired properties as a semi-nonflammable material can be obtained.

The isocyanurate foam of the present invention includes an organic polyisocyanate, a polyol, a carzenyl group-rich compound as a trimerization catalyst, a glycidyl group-containing compound 13ML aba/based compound, a 4N combination system of an aziridine compound, a foam stabilizer, a blowing agent, etc. Produced by conventional foaming means (with optional additives).

The organic polyisocyanates used in the present invention include aliphatic, alicyclic, aromatic, and aromatic-substituted aliphatic polyisocyanates, such as ethylene diinocyasute, 1.6- Hexamethylene diisocyanate, 2+2+4- or 2,2,6-1-dimethylhexamethylene-1,6-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1
, 4-cyclohexane diisocyanate, inphorone diisocyanate, 2,4- or 2,6-tolylene diisocyanate, P-phenylene diisocyanate, crude tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, tris(4-isocyanate phenyl) methane, 2
, 4.6-) relene triisocyanate, 4.4'-
Dimethyldiphenylmethane-2,2'.

5.5'-tetraisocyanate, naphthylene-1,5
-diisocyanate, 1-methoxyphenyl-2,4-
Diisocyanate, diphenylmethane-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4
, 4'-phenyl diisocyanate, 4-methoxy-1
, 3-phenylene diisocyanate, cumene-2,4-
Diisocyanate, 4-methoxy-1,3-7 22 diisocyanate, 4-chloro-1,3-7 22 diisocyanate, 4-, Pcomo-1,3-phenylene diisocyanate, 4-ethoxy- 1,3-phenylene diisocyanate, 2,4'-diisocyanate diphenyl ether, 5,6-dimethyl-1,3-phenylene diisocyanate, 4,4'-diisocyanate diphenyl ether, benzidine diisocyanate, 4,6-dimethyl-1,3-phenyl ether 9-
10-anthracene diisocyanate, 4,4'-dibenzyl diisocyanate, 3,3'-dimethyl-4,4
'-diisocyanate diphenylmethane, 2,6-dimethyl-4,4'-diisocyanate diphenyl, xylylene diisocyanate, other diisocyanates from dimer acids, carboxyl group-containing polyisocyanates, and diphenylmethane diisocyanates that are liquid at room temperature and have carbodiimide groups, uretoimine groups, etc. There are also polyisocyanates containing urea bonds, allophanate bonds, biuret bonds, incyanurate ring structures, and isocyanate group-terminated prepolymers obtained by reacting with active hydrogen compounds. It can be used as a species or a mixture of two or more.

In trimerizing the above-mentioned organic polyisocyanate compounds, the present invention uses a combination catalyst of four types of a carzenyl group-containing compound, a glycidyl group-containing compound, a tertiary amine compound, and an aziridine compound as a trimerization catalyst, thereby achieving the desired desired result. This provides polyisocyanurate foam properties that have the performance of a quasi-nonflammable material.

Here, examples of the car-737nyl-containing compound used in the present invention include aldehydes and lactones.

Representative examples of aldehydes include 1-naphthylaldehyde, 2-naphthylaldehyde, P
- tolylaldehyde, 2-phenanthrylaldehyde,
α,β-diphenylpropionaldehyde, o-yenylbenzaldehyde, P-phe2,6-dimethylbenzaldehyde, β-phenylpropionaldehyde, 1-
Aromatic or aromatic substituted aldehydes such as anislylaldehyde P, or linear aliphatic aldehydes, branched aliphatic aldehydes or alicyclic aldehydes such as n-nonylaldehyde, n-decanealdehyde, n-tetradealdehyde, cyclohexanealdehyde, Diethylacetaldehyde, 3,3-dimethylbutyraldehyde, or unsaturated aliphatic aldehydes such as acrolein, crotonaldehyde, β-methylcrotonaldehyde, γ-methylcrotonaldehyde, methacrolein, n-hexenaldehyde, 2-1+-2-hexene Coumarin-3- as an aldehyde, octenaldehyde, etc. or a heterocyclic-substituted aldehyde.
Aldehydes such as furfural, 3-, furfurylaldehyde, and 5-methylfurfural; alicyclic unsaturated aldehydes such as 2-cyclohexenaldehyde and 2-cyclopentenaldehyde; P13-cyclooctenaldehyde; and aromatic substituted unsaturated aldehyde derivatives such as cinnamic aldehyde. , α-phenylcinnamaldehyde, α
- Methylcinnamaldehyde, etc., or aromatic aldehyde substituted with amino, hydroxyl, or alkoxy groups, such as O-
Anisaldehyde, P-7=y, 7 Lua'human, m-anisaldehyde, salicylaldehyde, P-dimethylaminobenzaldehyde, P-ethoxybenzaldehyde, 〇-ethoxybenzaldehyde, 3,4-jethoxybenzaldehyde, m-benzoylbenzaldehyde , resorcyl aldehyde, etc., or hydroxybilbic aldehyde derivatives containing hydroxyl groups and alkoxy groups.
, f IJ colaldehyde, α-hydroxypropionaldehyde, methoxyacetaldehyde, etc., and fats such as acetaldehyde, propionaldehyde, isobutyraldehyde, butyraldehyde, nogleraldehyde, isobutyraldehyde, benzaldehyde, ethylbenzaldehyde, cyclopropyl aldehyde, etc. Group, aromatic, and alicyclic aliphatic aldehydes are also effective.

In addition, lactones include γ-butyrolactone, β-butyrolactone, ε-caprolactone, δzecalactone γ
-enantholactone, δ-enantholactone, α-methylenebutyrolactone, γ-laurolactone, and similar compounds thereof.

Glycidyl group-containing compounds, which are a type of catalyst that can be used in the present invention, include those having one or more glycidyl groups in the molecule, or those obtained by reacting an alkoxysilane compound with glycidol. Hereinafter, in this specification, simply "glycidyl group-containing compound"
If it is written as , it shall mean both of the above.゛Here, examples of the glycidyl group-containing compound which is one of the trimerization catalysts used in the present invention include butercricidyl ether, phenylglycidyl ether, allylglycidyl ether, glycidyl methacrylate, butylphenylglycidyl ether, styrene oxide, butadiene oxide. , dimethylpentane dioxide, 3
(pentadecyl) phenyl glycidyl ether, cyhinylbenzene oxide, resorcin diglycidyl ether, 2.6-cyclophenyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, neopentyl glycidyl ether, neopentyl glycidyl ether, cidyl ether, 1,6-hexanesiol diglycidyl ether, polyalkylene glycol diglycidyl ether represented by the formula: (R is an alkyl group, n is an integer of 1 or more), butanediol cricidyl ether , glycerin diglycidyl ether, trimethylolpronoζ triglycidyl ether, hydrogenated hisphenol A diglycidyl ether, 2,2-dibromoneopentyl glycol, diglycidyl ether, cyfuromocresyl glycidyl ether, N-N diglycidyl orthotoluidine Alkylphenol monoglycidyl ether, 3.4-
Epoxycyclohexylmethane, 3,4-epoxycyclohexanecalzexylate bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, bis(3,4-epoxycyclohexyl)adipate, N, N, N', N '-tetraglycidyl meta-xylylene diamine olefin oxide,
Cyclohexane vinyl monooxide, vinyl cyclohexane dioxide, polyepichlorohydrin, glycidol, 3,4-epoxy-6-methylcyclohexylmethyl 3/,4'-epoxy-6'-methylcyclohexanecal! -+ sylate, 3,4'-evoquinhexahydropenzal, 3',4/-epoxycyclohexane-1/, 1/-dimethatol, N,N'-diglycidyl-dimethylnoidantoin, etc., and similar compounds thereof Orgalysilicates represented by the general formula R'n5i(OR)41 (where R' represents an alkyl group having 1 to 20 carbon atoms or has a reactive group, more specifically preferably denotes a mixed aliphatic-aromatic hydrocarbon group having active groups which can be replaced by isocyanate-reactive groups, R denotes an alkyl group having 1 to 15 carbon atoms, and n is O or 1 to (an integer of 3) with glycidol may also be used. Examples of these compounds include methyltri(glycidyloxy)silane, tetraglycidyloxysilane, phenyltri(glycidyloxy)silane, and the like.

Next, as the 3M amine compounds, triethylamine, tributyl aban, N-methylmorpholine, N-methylmorpholine, N-laurylmorpholine, triethylenediamine, 3-methoxy-N,N'dimethylpropylamine,
N, N, N', N'-tetramethylethylenediamine,
N-methyl-N'-dimethylaminoethylpiperazine,
N,N,N'-trimethylisopropylpropylenediamine, N,N,N',N'-tetraethylpropylenediamine, N,N-dimethylbenzylamine, bis-
(N, N-diethylaminoethylazihe-)), N, N
-diethylcyclohexylamine, pentamethyldiethylenetriamine, N.

N'-dimethylcyclohexylamine, N, N, N',
N'-tetramethyl-1,3-butanediamine,
N,N-dimethyl β-phenylethylamine, 1.8-
-)7f-biscyclo(5,4,6)undecene-1,
2,4,6-tris(dimethylaminomethyl)phenol, 2-(dimethylaminomethyl)phenol, dimethylaniline, pyridine, etc., and similar compounds thereof, as well as tertiary amine compounds having active hydrogen that can react with isocyanate groups. For example, triethanolamine, triisopronogenolamine, N-methylgetanolamine, N-ethylgetanolamine, N
, N-dimethylethanolamine, and compounds obtained by reacting these compounds with alkylene oxide compounds are also effective.

Also used are silamines having carbon-silicon bonds. Examples include 2,2,4-)limethyl-1,2-silamorpholine and 1,3-diethylaminomethyltetramethyldisiloxane.

Furthermore, as aziridine compounds, N-butylethyleneimine, 2-hydroxyethylethyleneimine, trimethylolpropane-triβ-aziridinylpropinate, 1-phenyl-2-aziridineethanol, 2-(1
-aziridinylnethyl acrylate) (N-N'-diphenylmethane-4,4'bis(1-aziridinecarzexamide)]]tert-butylaziridinetetramethylolmethane-triβ-aziridinylpropinate, 2- (1-aziridinyl)ethyl methacrylate,
Trimethylolpropane-mono-β-aziridinylpropionate diacrylate, tetramethylolmethane-
Mono °β-aziridinylpropinate diacrylate, N-N'hexamethylene-1,6-bis(1-aziridinecarzexamido)propyleneimine, diphenylmethane-bis-4,4', N,N'-diethylene It is one type or a mixture of urea and the like.

Thus, by producing a urethane-modified polyisocyanurate foam using the above four types of trimerization catalysts, a foam molded product having the desired performance as a quasi-nonflammable material can be obtained.

However, by arbitrarily selecting the amounts of the above-mentioned four types of trimerization catalysts, the properties of the polyisocyanurate foam vary greatly, so the amounts added can be arbitrarily adjusted depending on the required properties of the foam and workability.

The amount of the carzenyl group-containing compound added here is preferably 0.1 wt% to 2 wt% based on the isocyanate compound.
0 wt%t', more preferably 0-5 wt%~
It is in the range of 10wt.

The amount of the glycidyl group-containing compound added here is preferably in the range of 0.1 to 20 wt%, more preferably in the range of 0.5 to 1Qwt, based on the isocyanate compound. Addition of an appropriate amount of a glycidyl group-containing compound has the effect of promoting the nurate reaction in a high yield and with high selectivity even when the resol state has progressed, that is, in the late stage of the reaction, and the internal heat generated during the reaction further promotes the nurate reaction. promote.

Furthermore, the amount of the tertiary amine compound added is preferably 1 mmol to 10 parts by weight per 100 parts by weight of the isocyanate compound.
0 mmol, more preferably 5 mmol-5
It is 0 mmol. If a large amount of tertiary amine is used, the urethanization reaction will be extremely accelerated, and the resol state of the foam solution will increase rapidly in the initial stage, thereby inhibiting the second-stage reaction, which is the nurating reaction.

The amount of the aziridine compound added is 0.05 wt% to 10 wt%, more preferably 2 wt% to 5 wt%, based on the isocyanate compound. The added amount of the aziridine group-containing compound has the role of promoting the trimerization reaction of the tertiary amine compound and the glycidyl group-containing compound catalyst, and the effect is exhibited by adding the minimum optimum amount.

However, due to the optimal addition amount of the trimerization catalyst of the present invention, N
Even when the OOlo H ratio is high, the nurate reaction has a selective high yield, and the reaction proceeds smoothly in a stepwise manner, so it has very excellent workability.

As a result, the foam has a high content of isocyanurate rings, so there is little weight loss even when heated at high temperatures for long periods of time, and even when the foam is exposed to flame, it has heat resistance that hardly deforms the back side of the foam and the surrounding area where the flame hits. 7 ohms are obtained.

Conventional catalysts cannot eliminate both deformation and cracking during combustion, and cannot reduce the smoke generated during forced combustion, so commonly known methods of adding flame retardants have been tried, but they have not produced sufficient results. However, the urethane-modified polyiso/annulate foam composition of the present invention has properties such as low smoke emission, heat resistance, low brittleness, flame retardance, and excellent physical properties of the foam. A molded body that also produces sound can be obtained. This is an unprecedented characteristic.

Further, in the present invention, in order to impart physical properties to the polyisocyanurate foam, an active hydrogen compound capable of reacting with the organic polyisocyanate may be optionally used.

When manufacturing polyin cyanurate foam by using one part of organic polyisocyanate and one polyol, in order to obtain a foam with excellent heat resistance, flame retardance, smoke emitting property, brittleness, etc., it is necessary to It is necessary to generate a large amount of cyanurate ring structure, and for that purpose, NCo10H
The equivalent ratio must be between 2 and 13, preferably between 3 and 1
It is 1.

Compounds containing active hydrogen that react with organic polyisocyanates include polyols, polyamines, polyamides, polymercaptans, etc., and polyol compounds are particularly suitable. As the polyol compound, polyether polyols, polyester polyols, acrylic polyols, polyepoxide resins, phosphorus-containing polyols, thioether-containing polyols, and similar compounds thereof may be used singly or in mixtures.

A more preferably used polyol is a polyalkylene polyether polyol, which is a polymerization product of a polyfunctional alcohol and an alkylene oxide compound.

Here, the polyfunctional alcohol is ethylene glycol, 1
, 3-propylene glycol, 1,2-propylene glycol, 1. ! >-ethylene glycol, 1.3-
Butylene glycol, 1,2-butylene glycol%
115-hentanediol, 1,7-hebutane glycol, glycerin, trimethylolpropane, trimethylolethane, hexane-1,2,6-triol, α
- Methyl glucoside, pentaerythritol, sorbitol, sugar alcohols such as sucrose, glucose, fructose, bisphenol A, etc. and similar compounds thereof, alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, etc. The molecular weight of the random or (7:t-block copolymers obtained with these compounds) may be as low as the molecular weight of the polyin The preferred range is 200 to 3,000, although it varies depending on the required characteristics of the cyanurate foam.

More preferred polyester polyols include, for example, ethylene glycol 1, diethylene glycol, trimethylene glycol, ], ]2-propylene glycol trimethylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol. , Tecamethylene Glycol, Glycerin, Trimethylolpropane, Pentaerythritol,
At least a little bit, such as sorbitol, bisphenol A, etc.
'One or two compounds having two or more hydroxyl groups
t11! The above and marron peel, maleic acid, phosphoric acid, adipic acid 1. Shiseki Hang, pimelic acid, sepacic acid,
Shu rice, phthalic acid, terephthalic acid, azelaic acid, trimellitic N2, glutaconic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylgeltanic acid, α, β-diethylsuccinic acid, hemimelittic acid , 1,4-Cyclohexanesicalargenic acid and the like can be prepared using two or more types of compounds having at least two carboxyl groups by a known method.

Next, the expression 1 (zl agent and I-teji,
Water or a low boiling point liquid that evaporates due to the heat of reaction generated during foam formation. The blowing agent that can be used is an inert liquid having a boiling point of 125 to 50°C, preferably 115 to 50°C.
Blowing agents with a boiling point of 40°C are preferred. Examples are inter alia alkanes, alkenes, halokene-substituted alkanes, alkenes, dialkyl ethers. For example, carbon number 1~
Seven saturated or unsaturated hydrocarbon compounds, imbutylene, butadiene, isoprene butane, pentane, petroleum ether, and halogen-substituted saturated unsaturated hydrocarbon compounds, such as methylene chloride, fluorotrichloromethane, difluorodichloromethane, These are trifluorochloromethane, chloroethane, vinyl chloride, vinylidene chloride, and the most effective blowing agent is trichlorofluoromethane.

Suitable blowing agents that may be added also include acetone, ethyl acetate hexane, diethyl ether.

Also, as a compound that can generate gas at temperatures above room temperature,
Azo compounds such as azoisobutyric acidonitrile may also be used. Furthermore, CO2, N2, air, etc. can be mixed in for use.

The amount of blowing agent used is appropriate depending on the type of blowing agent.

The foam stabilizer used in the present invention may be any conventionally known foam stabilizer, such as silicone surfactants such as organopolysiloxanes, polyoxyalkylene copolymers, polyalkenylsiloxanes having polyoxyalkylene side chains, and cationic foam stabilizers. Surfactants of the surfactant type, anionic type, and nonionic type can also be used.

The amount of foam stabilizer used is appropriate depending on the type of foam stabilizer.

In addition, in the present invention, flame retardants, hollow inorganic materials such as glass balloons and shirasu balloons, inorganic brightening agents (such as alumina, alumina, calcium carbonate, and aluminum hydroxide), and other fibrous substances (such as glass fibers,
Carbon fiber, etc.) may also be added.

As a means for producing polyisocyanurate 7 ohm from the above-mentioned raw materials, any device that can mix uniformly may be used, such as a small experimental mixer or a foaming machine that is generally used when producing urethane foam. It can be easily obtained by uniformly mixing the raw materials using a .

However, the polyin cyanurate foam obtained according to the present invention has excellent flame resistance when exposed to flame, has little deformation and cracking even when forced combustion, has little smoke emission, and has excellent flame resistance, heat resistance, A foam molded article having excellent mechanical properties can be obtained.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following nine examples as long as the gist of the invention is not exceeded.

Production Example 1 Synthesis of Catalyst A cooling unit equipped with a stirrer, a thermometer, and a reflux device was set in a 4-IL flask. Next 4 Lofras: 7K
MTS-32 (methyltriethoxysilane'i374
, Prepare. Further, 43B2 of glycidol and 0.12 of thallium oxide as a catalyst were added, and the temperature was gradually raised to 80°C. 8
After 30 minutes have passed after reaching 0°C, reflux is started and the transesterification reaction is carried out. When the internal temperature is maintained at 80°C x 5hrg, the rapid flow stops and the reaction is completed. Next, the reaction solution was rectified under reduced pressure to remove volatile components, and the reaction product was a yellow transparent liquid with a specific gravity of 1.19 (20/20°C) [methyltri(glycidyloxy)silane].
obtained as.

Examples 1 to 7 Each of the reaction mixtures Ai and B shown in Table 1 was heated to a temperature of 2.
After adjusting the temperature to 0°C ± 1°C, it was weighed into a 21 polyethylene beaker and placed in a stirring mixer (rotation speed 5000 rpm + n).
The mixture was stirred and mixed for 3 to 5 seconds, and free foaming was carried out in a polyethylene bag set in a 25 x 25 x 25 crn aluminum box that had been previously kept at 40°C. All of the obtained foam specimens had test results showing heat resistance, low smoke emission, and flame retardancy.

Examples 8 to 14 Similarly, each of the reaction mixtures A and B shown in the second coating was adjusted to a liquid temperature of 20±1°C, then weighed into a polyethylene beaker No. 21, and placed in a stirring mixer (rotation speed: 500 rpm).
) for 3 to 5 seconds, then 46 x 46 x 2.
An A1 aspal surface material was spread and fixed on the lower mold of a 5 crn aluminum mold, and after being preheated to 50° C., it was poured into the aluminum mold.

Immediately thereafter, a 0.27 gourd color plate material was set on top of the foam, the top lid was closed, and the material was pressed and cured at 50°C for 15 minutes at 1v1. Thereafter, the mold was demolded to obtain a sandwich panel.

JIS-A1321 Building Interior Material Combustion Test The 7 ohm obtained by the above method was 220m long and 220m wide, 25f thick.
Cut at i to obtain a specimen. The specimen is placed in a heating furnace and heated for a prescribed time using propane gas as a secondary heat source and an electric heater as the main heat source, and the presence or absence of cracking/deformation of the specimen and its degree, after heating is completed. afterflame time,
Measure the exhaust temperature curve and calculate the calorific value (
(temperature time area Tdθ°C x minutes) Each item is measured regarding the smoke generation coefficient (CA), and the combustion of the material is determined by a perforation test and a surface test.

Heat resistance test The 7 ohm obtained by the method described above is
A specimen was obtained by cutting at 0℃M and a thickness of 5crn, and JIS
Tested according to A9511.

AdhesivenessThe sandwich panel obtained by the above-mentioned method was entirely used,
The surface material and foam were separated and adhesion was examined.

Table notes ■ Lactone polyol (D, manufactured by Daicel) Polyether polyol, manufactured by Asahi Glass Co., Ltd. ■ Polyether polyol, manufactured by Nippon Nyukazai ■ Abbreviation for ethylene oxide adduct to trimethylolpropane, manufactured by Nippon Nyukazai (■ Abbreviation for diethylene glycol (ω Union) , made of carbide, polyester polyol ■ Made by Mitsui Fluorochemical ■ Nippon Nikajo ■ Nippon Shokubai Kagaku System 1ω Abbreviation for dimethylcyclohexylamine ■ Manufactured by A.I.C.O Yodo Chemical Co., Ltd., abbreviation for tertiary butylphenyl glycidyl ether O Glycidyl meth Abbreviation for acrylate [Phase] Polyphenylmethane polyisocyanate $ JIS A9514 JIS A1321 manufactured by Nippon Polyurethane ■

Claims (1)

[Scope of Claims] 1. In producing a polyisocyanurate foam by adding a trimerization catalyst to a production stock solution containing an organic polyisocyanate and an active hydrogen-containing compound as main components, as a trimerization catalyst, I, carbonyl A method for producing a polyisocyanurate foam, which comprises using a combination of four types of catalysts: a group-containing compound, II, a glycidyl group-containing compound, III, a tertiary amine compound, and IV, an aziridine compound. 2. The manufacturing method according to claim 1, wherein a stock solution containing a foaming agent and a foam stabilizer is used. 3. The manufacturing method according to claim 1 or 2, wherein a compound having one or more glycidyl groups in the molecule is used as the glycidyl group-containing compound. 4. As a glycidyl group-containing compound, general formula R'_nS
i(OR)_4_-_n (wherein R' represents an alkyl group having 1 to 20 carbon atoms or a mixture having a reactive group and an active group which can be replaced by an isocyanate-reactive group) aliphatic
represents an aromatic hydrocarbon group, R represents an alkyl group having 1 to 15 carbon atoms, and n is 0 or 1 to 3
3. The manufacturing method according to claim 1 or 2, which uses a reaction product of an organosilicate represented by (which is an integer of ) and glycidol.