JPH10195164A - Premix liquid for producing rigid polyurethane and / or polyisocyanurate foam, method for producing the same, and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard polyurethane and / or polyisocyanurate foam product produced by using water as a blowing agent without using a blowing agent Freon at all, a problem that the flyability is large and the adhesive strength is reduced. Further, there is a strong demand for a solution to the problem of fuming during combustion and generation of toxic compounds. SOLUTION: A premix solution obtained by precipitating a phosphate of a polyethylene polyamine in a solution containing a polyol and water is used for producing a rigid polyurethane and / or polyisocyanurate foam.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a premix solution useful for producing rigid polyurethane and / or polyisocyanurate foam. More specifically,
A premix solution excellent in flame retardancy, in which a phosphate of a polyethylene polyamine is highly dispersed, and a hard polyurethane and / or a foaming agent using the same without using a freon.
Or, it relates to a method for producing a polyisocyanurate foam.

[0002]

2. Description of the Related Art Rigid polyurethane foams are widely used as heat insulating materials for electric refrigerators, freezer warehouses, building materials, etc. because of their excellent heat insulating properties. Conventionally, rigid polyurethane foam is a polyol, a catalyst, a foam stabilizer, a foaming agent, a flame retardant and, if necessary, a premix liquid obtained by mixing other auxiliaries and a polyisocyanate liquid, and after stirring,
The mixture is poured into an appropriate mold or dispersed on a face material, sprayed and foamed. As the foaming agent, CFC-based trichloromonofluoromethane (CFC-11) having excellent heat insulation properties and dichloromonofluoroethane (HCFC-141b), which is an alternative CFC, are used. As the flame retardant, halogen-based tris (2-chloropropyl) phosphate, tris (2-chloroethyl) phosphate and the like are generally used for building materials, and recently bromine-based compounds have begun to be used. Further, a so-called rigid polyisocyanurate foam, in which isocyanate is excessively reacted during production of a rigid polyurethane foam and a heat-resistant high nurate ring which is a trimer of isocyanate is introduced into the foam, is also required to have flame retardancy. Use in the building materials field is spreading.

[0003]

In recent years, in the production of rigid polyurethane and / or polyisocyanurate foams, there has been a strong demand for the elimination of the blowing agent Freon and the improvement of flame retardancy in building materials. Since the blowing agent Freon causes destruction of the ozone layer, at present, the specified Freon C
FC-11 was abolished and HCFC-141b began to be used instead. However, HCFC-141b has begun to be totally abolished because it also destroys the ozone layer to a considerable extent. That is, there has been a demand for a decarbonated foamed product.

At present, studies have been made on foaming formulations using water as a foaming agent. However, foams produced by a formulation using a large amount of water as a foaming agent have a low curing speed and a low foaming rate.
The brittleness (flyability) of the rubber surface is increased, and the self-adhesion to the face material, which is an essential requirement of the rigid polyurethane foam heat insulating material, is remarkably deteriorated. The deterioration of flyability in water foaming is remarkably exhibited in polyisocyanurate foam.

[0005] Further, in foam products, especially building materials, importance has been placed on flame retardancy and safety due to smoking during combustion in order to comply with the Product Liability (PL) Law and Responsible Care (RC). Tris used as a flame retardant (2
-Chloropropyl) phosphate and the like have a high fuming property,
There is also a concern about the generation of highly toxic halogen compounds during combustion. That is, the demand for non-halogen flame retardants is gradually increasing. In contrast, inorganic metal salts,
Metal hydroxides such as aluminum hydroxide, calcium hydroxide, sodium nitrate, calcium nitrate, sodium silicate, and alumina have been studied as non-halogen flame retardants. However, the inorganic type has a problem in dispersion stability in the polyol premix liquid,
Because of sedimentation, it is difficult to stably produce a foam. Further, in order to obtain a certain flame retardancy, a large amount is required, and as a result, there is a drawback that mechanical foam properties are liable to be reduced. The above-mentioned rigid polyisocyanurate foam having a nurate ring introduced therein is expected to be a production method using no flame retardant. However,
In order to increase the flame retardancy, it is produced by increasing the excess amount of isocyanate. However, there is a problem that the amount of unreacted isocyanate increases and the flyability of the foam product deteriorates. Further, a production method using a monoethanolamine salt of a metal phosphate as a flame retardant has been studied (see JP-A-7-300557). However, an amine salt of a metal phosphate is dissolved in a large amount of water. Since a foam product is manufactured using the premixed solution, there is a concern that remarkable deterioration in flyability may occur.

That is, in the case of a rigid polyurethane and / or polyisocyanurate foam product produced using water as a blowing agent without using a blowing agent Freon at all, there is a problem that the flyability is large and the bonding strength is reduced, and furthermore, when burning, There is a strong demand for a solution to the problem of smoke emission and the generation of toxic compounds.

[0007]

Means for Solving the Problems The present inventors have intensively studied to solve the above problems. As a result, when a phosphate of polyethylene polyamines as a flame retardant is synthesized under a specific composition composition in a polyol, a premix liquid having excellent dispersion stability of precipitated salt can be obtained. It has been found that when used for the production of rigid polyurethane and / or polyisocyanurate foams, foam products are obtained which have low flyability and which can improve the problems of smoke emission and the generation of toxic compounds on combustion. The invention has been reached.

That is, the present invention provides a premix liquid for producing a rigid polyurethane and / or polyisocyanurate foam obtained by precipitating a phosphate of a polyethylene polyamine in a solution containing a polyol and water, a method for producing the same, and a method for producing the same. And a method for producing a rigid polyurethane and / or polyisocyanurate foam.

Hereinafter, the present invention will be described in detail.

The premix solution of the present invention comprises a polyol,
It is manufactured by mixing and stirring water, polyethylene polyamines and phosphoric acid. The following can be used as each raw material.

As the polyol, generally known polyether polyol, polyester polyol, polymer polyol, phenol-based polyol or a mixture thereof can be used. Known polyether polyols include, for example, polyhydric alcohols such as glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, sucrose, ammonia, aliphatic amine compounds such as ethylenediamine, toluenediamine, diphenylmethane-4, Polymer polyols obtained by addition reaction of ethylene oxide or propylene oxide alone or with a mixture of aromatic amine compounds such as 4'-diamine as an initiator. As the polymer polyol, the polyether polyol and an ethylenically unsaturated monomer, for example, butadiene, acrylonitrile,
Polymer polyols obtained by reacting styrene or the like in the presence of a radical polymerization catalyst are exemplified. As the polyester polyol, usually, a compound derived from a dibasic acid and a polyhydric alcohol, for example, adipic acid, terephthalic acid, isophthalic acid or phthalic anhydride, dimethyl terephthalate,
Examples thereof include polyester polyols derived from polyethylene terephthalate, and also include polyester polyols produced from polyethylene terephthalate-based waste and dimethyl terephthalate-based process waste. Lactone-based polyester polyols obtained by ring-opening polymerization of cyclic esters such as ε-caprolactone and methylvalerolactone are also included. Phenol-based polyols include novolak resins obtained from phenol and formalin, polyols obtained by reacting alkylene oxides with a resole resin, and Mannich-based polyols obtained by reacting alkylene oxides with phenols and alkanolamines and formalin. Is mentioned. Of these, preferred are polyether polyols and polyester polyols, and more preferred are polyether polyols and polyethylene glycols containing 10% by weight or more of polyethylene glycol.
A mixed polyol of a polyether polyol containing not less than% by weight and a phthalic acid-based polyester polyol is preferably used. Polyethylene glycol effectively acts to improve the dispersion stability of the polyethylene polyamine phosphate precipitated in the premix solution and to improve the flyability of foam products. As the molecular weight of polyethylene glycol increases, the effect of improving the flyability increases, but the strength of the foam decreases. Therefore, the molecular weight is 1,000
Those having a molecular weight of 0 or less are preferable, and those having a molecular weight of 150 to 600 are more preferable. A phthalic acid-based polyester polyol has an effect of increasing flame retardancy. The average hydroxyl value of these mixed polyols is 150 to 800 mg.
KOH / g can be used, but preferably it has a low viscosity and is effective for improving the flyability of foam products.
A mixed polyol of 0 to 400 mgKOH / g is preferably used.

The amount of water used is 2 to 10% by weight in concentration in the premix solution, and if it is less than 2% by weight, the fluidity of the slurry of the polyethylene polyamine phosphate precipitated in the premix solution is reduced. Workability may deteriorate. In addition, the stability of the phosphate of polyethylene polyamine is poor, and the foaming reactivity during foam production is reduced. On the other hand, when the content is 10% by weight or more, the flyability of the foam product is extremely deteriorated. Water reacts with the polyisocyanate at the time of foam production to generate carbon dioxide gas and serves as a foaming agent. Therefore, the density of the foam product is determined according to the amount of water used.

The polyethylene polyamines include, for example, ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, and pentaethylenehexamine or higher amines. It may contain an amine having the same number of nitrogen atoms partially having a certain piperazine skeleton. Of these, ethylene diamine, which does not affect the foaming reactivity during foam production and has good structural stability as a phosphate, is particularly preferred.

The phosphoric acid may be either hydrous phosphoric acid or phosphoric anhydride, but is preferably 85% phosphoric acid for industrial use.

The molar ratio of the polyethylene polyamines to phosphoric acid is not particularly limited, but the molar ratio is preferably in the range of 0.2 to 0.6 phosphoric acid to 1 nitrogen atom of the polyethylene polyamine, and more preferably phosphorus to polyethylene polyamine. A molar ratio range in which the amount of the acid added does not become 7 or less as the pH of the premix solution is preferable.

The amount of the phosphate of the polyethylene polyamine synthesized in the polyol in this way is not particularly limited. If the amount is too large, the flame retardancy of the foam product is improved. The rise may cause a decrease in the fluidity of the liquid. Therefore, the amount of the polyethylene polyamine phosphate is preferably 50 parts by weight or less based on 100 parts by weight of the polyol.

As a method for producing a premix solution, for example, a predetermined amount of polyol, water and polyethylene polyamines are charged into a suitable container or a reaction vessel, and after adjusting the temperature to a predetermined temperature, phosphoric acid is added dropwise while stirring, and polyethylene is added. The polyamine phosphate is precipitated. Alternatively, a predetermined amount of polyol, water and phosphoric acid may be charged into an appropriate container or reaction vessel, and after adjusting the temperature to a predetermined temperature, polyethylenepolyamines may be dropped while stirring to precipitate polyethylenepolyamine phosphate. The temperature is not particularly limited, but is preferably in the range of 20 to 80C. Stirring is preferably performed by a stirrer capable of stirring a high-viscosity liquid, and examples thereof include a homogenizer and a stirrer having a Max Blend type blade. The dropping time of phosphoric acid is a time required for dropping at a rate not exceeding the above temperature range.

On the other hand, a polyethylene polyamine phosphate is synthesized in a solvent other than the production method of the present invention, for example, in a solvent such as methanol or water, dried and pulverized, and the obtained powder is used in the present invention. In a premix solution produced by dispersing in a polyol, the crystal stability of the salt is high and the sedimentation is quick because the crystal particle size of the salt is large and the cohesion is high.

The above-mentioned production method describes a method for producing a premix liquid to be used in the production of a foam product described below. May be mixed with other polyols and used as a premix liquid for producing foam products.

The premix liquid of the present invention is reacted with a polyisocyanate to form a hard polyurethane and / or
Alternatively, a polyisocyanurate foam can be produced. The premix solution of the present invention may contain other auxiliary agents required for producing rigid polyurethane and / or polyisocyanurate foam, such as a catalyst and a foam stabilizer, for dispersion stability of phosphate, structural stability and foam product. It may be preliminarily mixed with the premix liquid as long as the flame retardancy is not deteriorated.

As the catalyst, an amine catalyst, a metal catalyst or the like can be used. Examples of the amine catalyst include a compound having a tertiary amino group or a quaternary ammonium salt. As the compound having a tertiary amino group, for example,
Trimethylamine, triethylamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N ', N " , N "
-Pentamethyldiethylenetriamine, N, N, N ',
N ", N" -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ', N ", N" -pentamethyldipropylenetriamine, N, N, N', N'-tetramethylguanidine, 1 , 3,5-Tris (N, N-
Dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, N, N, N ', N'-tetramethylhexamethylenediamine, N-methyl-N '
-(2-dimethylaminoethyl) piperazine, N, N '
-Dimethylpiperazine, N-methylpiperazine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-
Tertiary amine compounds such as 2-methylimidazole and 1-dimethylaminopropylimidazole, N, N-dimethylaminoethanol, N, N-dimethylaminoisopropanol, N, N-dimethylaminoethoxyethanol, N, N, N '-Trimethylaminoethylethanolamine, N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether, N, N-bis (3
Alkanolamines such as -dimethylaminopropyl) -N-isopropanolamine, N- (3-dimethylaminopropyl) N, N-diisopropanolamine, N- (2-hydroxyethyl) -N'-methylpiperazine, and dimethylamino Examples thereof include amines having primary and secondary amino groups such as propylamine and bisdimethylaminopropylamine. Also, salts of these with organic acids can be used. The quaternary ammonium salt is a compound obtained by reacting a salt of the compound having a tertiary amino group with an organic acid with an alkylene oxide, and the organic acid is a carboxylic acid having 1 or more carbon atoms, for example, , Formic acid,
Acetic acid, propionic acid, 2-ethylhexanoic acid and the like, and examples of the alkylene oxide include ethylene oxide and propylene oxide. Examples of the metal-based catalyst include organometallic compounds.Specifically, stannas diacetate, stannas dioctoate, stannas dioleate, stannas dilaurate, dibutyl tin oxide, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl Examples include tin dichloride, dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate and lithium, sodium and potassium salts of carboxylic acid. Among them, a catalyst mainly comprising a compound having a tertiary amino group is preferably used for the production of a rigid polyurethane foam, while a quaternary is used for the production of a rigid polyisocyanurate foam in which a polyisocyanate is excessively reacted. A catalyst mainly comprising an ammonium salt and / or an organometallic compound is preferably used. The amount of the catalyst used is not particularly limited, but is preferably 0.01 to 100 parts by weight of the polyol.
20 parts by weight.

The foam stabilizer is not particularly limited, and examples thereof include nonionic surfactants such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers, and mixtures thereof. The amount used is usually 0.1 part by weight per 100 parts by weight of polyol.
To 10 parts by weight.

The polyisocyanate is not particularly restricted but includes, for example, toluene diisocyanate (TDI), 4,4'- or 4,2'-diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, xylylene diisocyanate and the like. Aromatic polyisocyanates, cycloaliphatic polyisocyanates such as isophorone diisocyanate and norbornane diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, or free isocyanate-containing prepolymers by reaction of them with polyols, modification such as carbodiimide modification Examples thereof include polyisocyanates, and mixed polyisocyanates thereof. Of these, TDI and its derivatives or MDI and its derivatives are preferred, and these may be used in combination. TDI
And its derivatives include 2,4-TDI and 2,6-TD
Mention may be made of mixtures of I or terminal isocyanate prepolymer derivatives of TDI. Examples of MDI and its derivatives include a mixture of MDI and its polymer, polyphenylpolymethylene diisocyanate, and / or a diphenylmethane diisocyanate derivative having a terminal isocyanate group. Of these, diphenylmethane diisocyanate, which is effective for improving the flyability of foam products, and crude diphenylmethane diisocyanate, which is a derivative thereof, are preferred. The amount of the polyisocyanate used is determined according to the purpose of producing the rigid polyurethane and / or polyisocyanurate foam. When represented by an isocyanate index (molar ratio of an OH group-containing compound capable of reacting isocyanate groups with isocyanate groups, water x 100), rigid polyurethane foams usually have a range of 70 to 120, while rigid polyisocyanurate foams For the production, a polyisocyanate is usually used in the range of 120 to 400. If the isocyanate index is less than 70, the unreacted terminal alcohol is large and the foam properties deteriorate. On the other hand, if it exceeds 400, the isocyanate trimer increases and the flame retardancy increases, but the amount of unreacted isocyanate increases and the flyability of the foam product deteriorates. In order to maintain these in a good balance, the range is preferably about 110 for the production of a rigid polyurethane foam, while the range of 150 to 300 is preferred for the production of a rigid polyisocyanurate foam.

In the production of the rigid polyurethane and / or polyisocyanurate foam of the present invention, other auxiliaries can be used if necessary. As a foaming agent other than water, a physical foaming agent and / or a chemical foaming agent other than Freon can be used, and there is no particular limitation. Examples of the physical foaming agent include hydrocarbons such as pentane and cyclopentane having a low boiling point, and gases such as air, nitrogen and carbon dioxide, and low-temperature liquids. Examples of the chemical foaming agent include water, organic acids, inorganic acids such as boric acid, alkali carbonates, cyclic carbonates, and dialkyl carbonates.Examples include those that generate a gas by reacting with a polyurethane resin component or decomposing by heat or the like. Can be Further, a coloring agent, an antioxidant and other additives can be used. The types and amounts of these additives can be sufficiently used within the range usually used.

The rigid polyurethane and / or polyisocyanurate foam of the present invention is a method for producing a foam molded product by rapidly mixing and stirring a premix solution and a polyisocyanate solution to cause a reaction.
For mixing and stirring, a general stirrer and a dedicated polyurethane foaming machine may be used. High pressure and low pressure machines can be used as the polyurethane foaming machine, and a spray machine can also be used.

The molded product of the rigid polyurethane and / or polyisocyanurate foam of the present invention can be widely used as a heat insulating material for freezing warehouses and building materials.

[0027]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Examples 1 to 8 and Comparative Examples 1 to 4 Polyethylenepolyamine phosphates were produced in polyols, and the dispersion stability of the obtained premix liquid was evaluated.

The premix solution was prepared by charging about 100 g of polyol, a predetermined amount of water and polyethylenepolyamine in a 200 ml three-necked glass flask, and rotating at 7 rpm with a stirrer having three blade screw stirring blades.
After adjusting the temperature to about 25-30 ° C, 85% phosphoric acid
Manufactured while dropping in 0 minutes. From the obtained premix liquid, the fluidity and dispersion stability of the slurry liquid, the crystal particle diameter of the precipitated salt, and the cohesiveness of the crystal were evaluated. Comparative Example 1 was an example using monoethanolamine which is an amine other than polyethylene polyamine, and Comparative Example 4 was prepared by synthesizing a phosphate of ethylenediamine in a methanol solvent, followed by separation, drying and pulverization. Example using a premix liquid obtained by mixing and stirring with polyols and a predetermined amount of water in a three-necked flask, Comparative Example 5 mixed 16 g of aluminum hydroxide with polyols and a predetermined amount of water in a three-necked flask as described above. This is an example in which a premix solution obtained by stirring was used, and was evaluated at the same time. The raw materials used and the evaluation method are shown below.

A. Raw material used a-1. Polyol Polyol A: sorbitol-based polyether polyol, SO-300 (manufactured by Takeda Pharmaceutical Co., Ltd., hydroxyl value 300 mg)
KOH / g) Polyol B: Terephthalic acid-based polyester polyol, PL-305 (manufactured by Toho Rika Co., Ltd., hydroxyl value 317 mg)
KOH / g) polyethylene glycol: molecular weight 150, molecular weight 600
(First-class reagent) a-2. Polyethylene polyamine EDA: Ethylenediamine (manufactured by Tosoh Corporation) DETA: Diethylenetriamine (manufactured by Tosoh Corporation) TETA: Triethylenetetraamine (manufactured by Tosoh Corporation) a-3. Other raw materials Phosphoric acid: 85% phosphoric acid (primary reagent) MEA: monoethanolamine (primary reagent) Aluminum hydroxide (primary reagent) b. Evaluation method b-1. Fluidity of the slurry liquid The flow state of the premix liquid in a three-necked flask in a stirring state was visually observed and determined as follows. …: Completely stirred state △: Upper part of liquid does not flow slightly ×: Liquid does not flow at all b-2. Dispersion stability of the slurry liquid The premix liquid after the synthesis was transferred to a 100 ml graduated measuring cylinder in an amount of just 100 ml, and after a predetermined number of days, the height of the slurry layer of the precipitated salt was read from the graduated scale of the measuring cylinder. The numerical value was directly used as the dispersion stability (%). b-3. Crystal particle size of precipitated salt and cohesiveness of crystal The salt precipitated in the premix solution was photographed with an optical microscope (manufactured by Nikon Corporation), and the average particle size of the crystal was measured and the cohesiveness was observed. The cohesiveness was determined as follows. …: Crystal particles are completely dispersed.

(3) There are crystal particles that are slightly aggregated.

X: There are large aggregates.

The results are shown in Table 1.

[0034]

[Table 1]

As a result, as shown in Examples 1 to 8 in Table 1, the premix liquid obtained by producing the phosphate of polyethylene polyamine in the polyol of the present invention was obtained by the flow of the slurry liquid. The dispersion properties of the slurry were excellent, and the crystal particle diameter of the precipitated salt was small and there was no cohesion.

On the other hand, the slurry liquid produced using monoethanolamine, which is an amine other than the polyethylene polyamine of Comparative Example 1, has a large crystal particle diameter of the precipitated salt and has a cohesive property. Poor properties, resulting in faster settling of precipitated salts.

Comparative Example 2 was an example in which water was not used. The dispersion stability of the slurry was good, but the fluidity of the slurry was not at all.

Comparative Example 3 is an example in which a phosphate of ethylenediamine was synthesized in a methanol solvent to prepare a premix solution. However, since the precipitated salt has a large crystal particle diameter and is cohesive, the dispersion stability of the slurry liquid is stable. Sex was bad.

Comparative Example 4 is an example in which aluminum hydroxide was used as a premix liquid, but the dispersion stability of the slurry liquid was poor and sedimentation was quick.

Examples 9 to 17 and Comparative Examples 5 to 9 The above-prepared premix solution and polyisocyanate were mixed and stirred to foam a rigid polyurethane foam and / or a polyisocyanurate foam. sex,
The foam properties were evaluated.

A predetermined amount of the premix solution, the catalyst, and the foam stabilizer were placed in a 200 ml polyethylene cup, and after preliminary stirring,
The liquid temperature was 25 ° C. A predetermined amount (index change) of the polyisocyanate separately adjusted to 25 ° C.
The mixture was stirred with a high-speed stirrer (Labor Disper, manufactured by Tokushu Kika Co., Ltd.) at 6000 rpm (5 seconds), and then quickly poured into a mold to foam and harden. The foaming reactivity during foaming and the foam properties of the molded foam were measured and evaluated. Raw materials used,
The measurement and evaluation methods for the properties of the foam are described below.

A. Raw material used a-1. Premix liquid Premix liquids obtained in Examples 1 to 8 and Comparative Examples 1 to 5 (indicated by symbols in Table 2). Further, a premix liquid having the following symbols. N: 80 parts by weight of polyol A, 20 parts by weight of polyethylene glycol (molecular weight 150), 5 parts by weight of water, Tris (2
A mixture of 16 parts by weight of (-chloropropyl) phosphate O: a mixture of 80 parts by weight of polyol A, 20 parts by weight of polyethylene glycol (molecular weight 150), and 5 parts by weight of water a-2. Catalyst C-1: N, N, N ', N'-tetramethylhexamethylenediamine (TOYOCAT-M manufactured by Tosoh Corporation)
R) 75% and N, N, N ', N ", N" -pentamethyldiethylenetriamine (TOYOCA manufactured by Tosoh Corporation)
C-2: Potassium octylate (reagent) 61.4%, ethylene glycol 26.3% and N, N, N ', N ", N"
Mixture with pentamethyldiethylenetriamine (TOYOCAT-DT manufactured by Tosoh Corporation) 12.3% a-3. Other raw materials: foam stabilizer: silicone-based foam stabilizer L-5420 (manufactured by Nippon Unicar, L-5420) polyisocyanate: crude MDI, NCO concentration 3
1.1% (manufactured by Nippon Polyurethanes, MR-200) b. Measurement of foaming reactivity 2 with polyethylene film inner bag attached inside mold
The following time is measured during the foam foaming process when the mixture is poured into an aluminum mold (mold temperature 45 ° C.) having a size of 2 × 26 × 5 cm and foamed and cured. Cream time; starting time of forming (second) Gel time; Resining time (sec) Tack free time; time when tackiness on the foam surface is eliminated (sec) Rise time; time when foam reaches the maximum foaming height (sec) c. Measurement and evaluation of foam properties The following items were measured and evaluated from the foam cured. <Flyability> The surface of the foam 10 minutes after foaming was pressed with a finger, and the brittleness of the foam surface was evaluated as follows. ◎: No brittleness ○: Slightly brittle △: Brittle ×: Very brittle <Foam density> The central part of the foam-cured foam was 15
It was cut to a size of × 15 × 2.5 cm, and the foam density was calculated from the weight and volume. <Flame Retardancy of Foam> The oxygen index and smoke density were measured from a foam density measurement sample. The oxygen index is an index indicating the flame retardancy of the foam, but the combustion test method is ASTM D
It carried out according to 2863D-74. The smoke concentration was measured using a smoke tester NBS (manufactured by Toyo Seiki Seisaku-sho, Ltd.), and the test method was the maximum amount of smoke generated by the flaming combustion method per foam weight (Dmax) according to ASTM E-662.
/ G).

Table 2 shows the results.

[0044]

[Table 2]

As a result, as shown in Examples 9 to 17 in Table 2, the rigid polyurethane foam and / or polyisocyanurate foam produced using the premix solution of the present invention had a reduced foaming reactivity. It had excellent flyability and cured quickly. Also, the foam had high flame retardancy and low smoke density.

On the other hand, the foam produced from the premix solution using monoethanolamine, which is an amine other than the polyethylene polyamine of Comparative Example 5, had a reduced foaming reactivity, was slow in curing, and exhibited some flyability. .

Comparative Example 6 is an example of a foam produced from a premix solution without using water, but the precipitated salt has poor structural stability, has a low foaming reactivity, is hardened slowly, and has a little flyability. Was done.

Comparative Example 7, which is an example of a foam produced from a premix liquid mixed with aluminum hydroxide as a flame retardant, had low flame retardancy and high smoke density.

Comparative Example 8 is an example of a foam produced from a premix liquid mixed with tris (2-chloropropyl) phosphate as a flame retardant, but the smoke density was extremely high.

Comparative Example 9 is an example of a foam produced without using a flame retardant and increasing the excess amount of polyisocyanate to increase the flame retardancy. However, although the flame retardancy is high, the flyability is extremely high. Bad and brittle foam.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G 101: 00)

Claims (7)

[Claims] 1. A premix solution for producing a rigid polyurethane and / or polyisocyanurate foam obtained by precipitating a phosphate of a polyethylene polyamine in a solution containing a polyol and water. 2. The premix liquid according to claim 1, wherein the polyol contains 10% by weight or more of polyethylene glycol. 3. The method according to claim 1, wherein the amount of water is 2 in concentration in the premix solution.
The premix liquid according to claim 1 or 2, wherein the amount is 10 to 10% by weight. 4. The premix liquid according to claim 1, wherein ethylene diamine is used as the polyethylene polyamine. 5. The method according to claim 1, wherein after adding the polyethylene polyamine to the solution containing the polyol and water, phosphoric acid of the polyethylene polyamine is precipitated while dropping phosphoric acid with stirring. 5. The method for producing a premix liquid according to any one of 4. 6. The method according to claim 1, wherein after phosphoric acid is added to the solution containing the polyol and water, the polyethylene polyamine phosphate is precipitated while dropping the polyethylene polyamine under stirring. 5. The method for producing a premix liquid according to any one of 4. 7. The premix solution according to claim 1, which is reacted with a polyisocyanate in the presence of a catalyst, a foam stabilizer and, if necessary, other auxiliaries. A method for producing a rigid polyurethane and / or polyisocyanurate foam.